JP5056114B2 - Sheet thin film forming apparatus and method for manufacturing sheet with thin film - Google Patents

Description

  The present invention relates to a sheet thin film forming apparatus and a method for manufacturing a sheet with a thin film.

2. Description of the Related Art Conventionally, a metal vapor-deposited film serving as a material for film capacitors, magnetic recording tapes, packaging films, and the like has been manufactured by forming a thin film on an electrically insulating sheet exemplified by a plastic film. For this production, for example, a roll-up type vapor deposition apparatus (for example, Non-Patent Document 1) is used in which a plastic film as a roll is unwound in a vacuum chamber, and is formed again after being formed into a thin film.

  The outline will be described with reference to FIGS. FIG. 10 is a diagram showing components of a thin film forming apparatus for continuously forming a thin film on a sheet such as a plastic film. FIG. 10 shows only the main part, and the decompression chamber and the intermediate roll for housing the structure are omitted. FIG. 11 is a schematic configuration diagram of the apparatus viewed from the right hand of FIG. In FIG. 10, a long electrically insulating sheet 1 is fed from a raw roll body 2 and rotated at a required winding angle by intermediate rollers 4 and 5 on a cylindrical sheet guide surface 3 that rotates along the traveling direction of the sheet. It is conveyed in a wound state and wound up as a winding roll body 6. When the electrically insulating sheet 1 is conveyed onto the sheet guide surface 3, the vapor 10 evaporated from the vapor deposition material 8 in the induction heating crucible 7 adheres to the sheet 1, and as shown in FIG. A thin film 13 is formed thereon. The evaporation includes, for example, a method of heating the vapor deposition material using the principle of induction heating or resistance heating, and a method of heating the vapor deposition material by irradiating the vapor deposition material with an electron beam. The sheet guide surface 3 mainly has a role of conveying the sheet 1 without wrinkles and a role of efficiently releasing the heat load received by the sheet 1. For this reason, for example, it is controlled to a required temperature by temperature control by circulation of a known heat medium. In addition, not only a cylinder but also a method of conveying a sheet on a belt body can be seen.

  However, when there is a large portion where the temperature of the sheet 1 is excessively increased due to the thermal load received by the sheet 1 on the sheet guide surface 3 or when there is a portion where the sheet 1 and the sheet guide surface 3 are not in contact with each other, 1 may cause thermal deformation (heat loss). In particular, when wrinkles occur in the sheet 1 on the sheet guide surface 3, the wrinkle-generating portion may not come into contact with the sheet guide surface 3, and the wrinkle shape may be thermally deformed (heat loss). The main heat load received by the sheet 1 in this case includes radiant heat received from the induction heating crucible 7 and the like, and condensation heat received from the deposited thin film 13.

  In order to prevent thermal deformation as described above, when forming a conductive thin film, it is formed on the sheet 1 in order to efficiently release the heat received by the sheet 1 to the sheet guide surface 3 during vapor deposition. A potential difference is applied between the thin film 13 and the sheet guide surface 3 by the DC power source 14 via the intermediate roller 5 in contact with the thin film 13, and the sheet 1 is fed into the sheet by electrostatic force acting between the thin film 13 and the sheet guide surface 3. A technique (for example, Patent Document 1) that strongly sticks to the guide surface 3 is used. Thus, when a potential difference is provided between the thin film 13 and the sheet guide surface 3, as shown in FIG. 11, the width of the opening 12 of the mask member 11 is the sheet guide surface even when a potential is applied to the thin film 13. Usually, it is set at least smaller than the sheet width so that the vapor 10 does not adhere to 3 and the thin film 13 and the sheet guide surface 3 are electrically short-circuited.

  In this example, a DC power supply 14 is provided between the sheet guide surface 3 and the thin film 13 and a potential difference is given between them. However, there is a case in which one is grounded and a voltage is applied only to the other. In this example, the potential of the thin film 13 is lower than that of the sheet guide surface 3, but there is also a case in which it is reversed. FIG. 13 shows the behavior of charges when a potential difference is applied between the thin film 13 and the sheet guide surface 3 as shown in the example of FIG. When the negative polarity side of the DC power source 14 is connected to the thin film 13 via the intermediate roller 5, and the positive polarity side of the DC power source 14 is connected to the sheet guide surface 3, the electrically insulating sheet 1 is sandwiched on the sheet guide surface 3. Thus, a positive charge is induced on the sheet guide surface side, and a negative charge is induced on the thin film 13. The electrostatic force works between these positive and negative charges, and the sheet 1 and the sheet guide surface 3 are in close contact with each other. This electrostatic force acts between the thin film formation start point 31 where the thin film starts to be formed on the sheet 1 and the peel point 32, and between the winding point 33 and the thin film formation start point 31 and downstream of the peel point. Since the distance between the thin film 13 to which the potential difference is applied and the sheet guide surface 3 is increased, the thin film 13 does not work.

  However, this method of applying a voltage between the sheet guide surface and the thin film is effective when the thin film forms a conductive film such as a metal film, but is formed of a semiconductor or an electrical insulator. In the thin film, sufficient electric charge is not induced in the thin film, so that a potential difference between the thin film and the sheet guide surface does not occur, and the sheet cannot be strongly adhered to the sheet guide surface.

  On the other hand, as a method for allowing the sheet to be attached to the sheet guide surface not only when the thin film is formed of a metal film but also when formed of a semiconductor or an electrical insulator, the sheet is formed before the formation of the thin film. There is known a technique (for example, Patent Documents 2 and 3) in which a sheet is strongly attached to a sheet guide surface by an electrostatic force acting by the charging. This method will be described with reference to FIG. FIG. 12 is a diagram showing components of a thin film forming apparatus that continuously forms a thin film on a sheet such as a plastic film. Note that components having the same or equivalent functions as those in FIG. 10 are given the same numbers, and detailed descriptions thereof are omitted. A major difference from the example shown in FIG. 10 is that the charged particle source 22 irradiates the surface of the sheet 1 before forming the thin film with charged particles 23 to charge the surface of the sheet 1. An electron beam irradiation apparatus or an ion beam irradiation apparatus is applied to the specific charged particle source 22. By charging the surface of the sheet 1 in this manner, an electrostatic force acts between the sheet 1 and the sheet guide surface 3, and both of them strongly adhere to each other, and there is an effect of releasing the heat received by the thin film formation to the sheet guide surface 3. is there. Further, even when the thin film is electrically conductive or electrically insulative, an electrostatic force acts between the sheet 1 and the sheet guiding surface 3, and the heat received by the thin film formation is released to the sheet guiding surface 3. It is said that there is.

  FIG. 14 shows the charge behavior in the method of charging the surface of the sheet 1 by irradiating the charged particles 23 before the thin film is formed on the sheet guide surface 3 as shown in the example of FIG. ing. In the example of FIG. 14, negative charged particles 23 are irradiated toward the sheet 1 from the charged particle source 22 between the winding point 33 of the sheet guide surface 3 and the thin film formation start point 31. At this time, negatively charged particles remain on the surface and inside of the sheet 1 and the sheet 1 is charged. At this time, positive charged particles are induced on the surface of the sheet guide surface 3 so as to supplement the negative charged particles of the sheet 1. The electrostatic force works between these positive and negative charges, and the sheet 1 and the sheet guide surface 3 are in close contact with each other. According to the knowledge of the inventors, between the thin film formation start point 31 and the peeling point 32, the charged particles on the very surface of the sheet 1 are within the thin film 13 when the evaporated particles arrive at the surface of the sheet 1. The thin film 13 is formed so that charged electrons such as free electrons (especially in the case of a conductive thin film) with a small amount of electrons and ions existing in the evaporated particle group supplement the charged charge, and the charge is apparently erased. However, since the charged particles 23 enter the inside of the sheet 1 and near the boundary with the sheet guide surface, static electricity is generated between the charged particles 23 and the charged particles 23 guided to the sheet guide surface 3. The force works and the state where the sheet 1 and the sheet guide surface 3 are in close contact with each other continues.

  However, according to the knowledge of the present inventors, the electron beam irradiation apparatus and ion beam irradiation apparatus, which are the aforementioned charged particle sources, generally apply an acceleration voltage of several [kV] to several tens [kV] to apply electrons. Alternatively, charged particles of ions are irradiated toward the sheet thin film forming surface, so that the charged particles are driven into the sheet, and the charged particles remain in the sheet even after the thin film is formed, and the sheet is wound while being strongly charged. It was like that. In this way, when the sheet remains charged, the sheet and the conveying roller adhere to each other by electrostatic force to form wrinkles in the subsequent process, or the thin film forming surface and the unformed surface of the sheet are static In some cases, the film is brought into close contact by force, and when the film is rewound, the thin film is peeled off, so-called blocking. In addition, the sheet static elimination method (for example, patent document 6) which applied plasma discharge is known in the thin film formation apparatus in a pressure-reduced atmosphere. This is because charged particles such as electrons and ions generated by the plasma are induced by an electric field formed by negative and positive charged charges existing on the sheet, and charged particles of opposite polarity to the charged charges arrive at the sheet surface. This is based on the principle that charging is neutralized. However, even if it tries to remove the charged charge that has been injected into the sheet, the charged particles from the plasma reach the surface of the sheet but do not reach the inside, so the charge cannot be neutralized. There are cases where it cannot be sufficiently suppressed. Also, in static elimination after forming a conductive or semiconductive thin film, free electrons in the thin film are induced in the electric field formed from the inside of the sheet, and no electric field is formed outside the sheet. In some cases, it is not induced, that is, not neutralized. As described above, there are cases where the conventional static elimination method is insufficient to neutralize the charged charges driven into the sheet. When using an electron beam irradiation apparatus, in order to irradiate electrons in the width direction of the sheet, a method of scanning an electron beam in the width direction of the sheet at several tens to several hundreds [Hz] is generally used. According to the knowledge of the inventors, when charging is performed while running at a sheet speed of 500 [m / min] or more, charging unevenness due to the scanning frequency is neglected by 10 [cm] or more in the sheet running direction. Occurred at intervals that could not be achieved, causing uneven heat loss. Further, according to the knowledge of the present inventors, Patent Document 7 describes an example in which charging is performed with an acceleration voltage of 200 [V] of an electron beam irradiation apparatus, but when scanning an electron beam as described above, In this case, the distance between the sheet and the electron beam irradiation apparatus is increased by several hundred [mm]. In this case, electrons do not sufficiently reach the sheet at an acceleration voltage of 200 [V], and particularly at a high speed of 50 [m / min] or more. In the case of conveying a sheet by forming, charging may be insufficient. Although the amount of charge can be increased by bringing the electron beam irradiation device closer to the sheet or arranging a plurality of electron beam irradiation devices in the width direction of the sheet, uneven charging due to the arrangement of the electron beam irradiation device occurs, resulting in uneven heat loss. May occur. Furthermore, since electron beam irradiation devices and ion beam irradiation devices mainly emit charged particles of either polarity, the charged particles diffuse in a reduced-pressure atmosphere and charge the structure in the sheet and the reduced-pressure chamber outside the charging unit. There is a case where a malfunction occurs.

Further, in the sheet on the upstream side of the sheet guide surface, a technique for charging the surface opposite to the surface on which the thin film is formed (for example, Patent Document 4), or charging of opposite polarities is applied to both surfaces of the sheet. A technique (for example, Patent Document 5) is known. In these technologies, since the surface opposite to the surface on which the thin film is formed is charged, especially when the thin film is formed on the sheet guide surface, the sheet is guided by the electrostatic force acting on the sheet. It is effective to make it stick strongly. However, even in these methods, after the thin film is formed, strong charge remains on the surface opposite to the surface on which the thin film is formed, so that wrinkles are generated at the time of sheet conveyance and winding downstream of the sheet guide surface, In some cases, problems such as blocking may occur in post-processing.
JP 59-147023 A JP-A-2-247383 JP-A-6-158319 JP-A-63-219570 JP 2004-43569 A JP-A-8-176822 JP-A-2-239428 Ken Ihouchi et al., “Polymer films and functional membranes”, Gihodo Publishing, April 1991, p. 198-203

  As described above, in the prior art, particularly when an electrically insulating thin film is formed, it is difficult to form a thin film without sticking the sheet to the sheet guide surface and leaving no charge on the sheet after forming the thin film. there were. In view of the above-described problems of the prior art, an object of the present invention is to provide a thin film forming apparatus that does not leave a charge on a sheet and that hardly causes thermal deformation in the sheet, particularly when an electrically insulating thin film is formed. It is providing the manufacturing method of a sheet | seat with a thin film.

In order to achieve the above object, according to the present invention, in a reduced pressure atmosphere, fine particles flying from a fine particle generation source are deposited on an electrically insulating sheet conveyed in the conveying direction while contacting the sheet guide surface. A method of manufacturing a sheet with a thin film for forming a thin film, wherein a charged particle of any polarity among charged particles supplied from a plasma generating source is generated on the sheet thin film forming surface on the sheet guide surface. The sheet thin film forming surface is charged by applying and guiding a potential difference of 10 [V] or more and 1000 [V] or less between the source and the sheet guide surface, and then the sheet thin film forming surface is charged. the method for manufacturing a thin-film sheet characterized by forming the thin film on the sheet film formation surface on the sheet guiding surface and the same said sheet guide surface is provided using the time

Further, according to another embodiment of the present invention, in a reduced pressure atmosphere, the fine particles flying from the fine particle generation source are deposited on the electrically insulating sheet conveyed in the conveying direction while contacting the sheet guide surface, A method of manufacturing a sheet with a thin film for forming a thin film, wherein charged particles of any polarity among charged particles supplied from a plasma generation source are applied to the sheet thin film forming surface on the sheet guiding surface. by inducing impart potential difference 10 [V] or more and 1000 [V] or less between the opposed the electrodes, after charging the sheet film formation surface, when charging the sheet film forming surface A method for producing a sheet with a thin film is provided, wherein the thin film is formed on the sheet thin film forming surface on the same sheet guiding surface as the sheet guiding surface used in the above .

  Moreover, according to the preferable form of this invention, the manufacturing method of the sheet | seat with a thin film which uses a sheet surface non-contact type as said electrode is provided.

  Moreover, according to the preferable form of this invention, the manufacturing method of the sheet | seat with a thin film which uses a sheet surface contact type thing as said electrode is provided.

  Further, according to a preferred embodiment of the present invention, the potential difference is applied so that the potential of the sheet guide surface is higher than the potential of the plasma generation source or the electrode, and negative charge is applied to the thin film forming surface of the sheet. A method for producing a sheet with a thin film for inducing particles is provided.

  According to a preferred embodiment of the present invention, the thickness of the sheet is 1 [μm] or more and 100 [μm] or less, and the potential difference per 1 [μm] of the sheet thickness is 10 [V / μm] or more and A method for producing a sheet with a thin film of 100 [V / μm] or less is provided.

Further, according to a preferred embodiment of the present invention, the thin film formed on the sheet thin film forming surface has a surface resistance of 10 ³ [Ω / □] to 10 ¹⁴ [Ω / □]. A method is provided.

According to another aspect of the present invention, there is provided a decompression chamber and a sheet guide surface that conveys the sheet while being in contact with the sheet in the decompression chamber, and conveys the sheet as the sheet guide surface moves. A sheet conveying unit; a particle generation source that scatters particles toward the sheet on the sheet guide surface to form a thin film on the sheet; and a charging unit that charges the sheet on the sheet guide surface. In the sheet thin film forming apparatus, the charging unit disposed upstream of the fine particle generation source in the sheet traveling direction includes a plasma generation unit configured to generate plasma inside the casing, and a plasma from the casing. in the generated charged particles the housing outlet for discharging to the outside of the sheet proposals are arranged to face the particulate source and the plasma generation means Located 10 [V] is composed of a or more and 1000 [V] a potential difference applying means for the following potential can be imparted, and the sheet guiding surface and the discharge port is opposed between the surface and the same said sheet guide surface Thus, a sheet thin film forming apparatus is provided.

According to another aspect of the present invention, there is provided a decompression chamber and a sheet guide surface that conveys the sheet while being in contact with the sheet in the decompression chamber, and conveys the sheet as the sheet guide surface moves. A sheet conveying unit; a particle generation source that scatters particles toward the sheet on the sheet guide surface to form a thin film on the sheet; and a charging unit that charges the sheet on the sheet guide surface. In the sheet thin film forming apparatus, the charging unit disposed upstream of the fine particle generation source in the sheet traveling direction includes a plasma generation unit configured to generate plasma inside the casing, and a plasma from the casing. in generated and the charged particle outlet for discharging to the outside of the housing, wherein the sheet guiding surface and the same said sheet being disposed opposite to the particulate source Apparatus for forming a thin film sheet and having a potential difference imparting electrode for imparting a potential difference of 10 [V] or more and 1000 [V] or less between the inner surface are provided.

  Moreover, according to the preferable form of this invention, the thin film forming apparatus of the sheet | seat whose said electric potential difference provision electrode is the said sheet surface non-contact type is provided.

  Moreover, according to the preferable form of this invention, the thin film forming apparatus of the sheet | seat whose said electric potential difference provision electrode is the said sheet surface contact type is provided.

  Moreover, according to the preferable form of this invention, the said plasma generation means provides the thin film formation apparatus of the sheet | seat which excites plasma with an alternating voltage.

  Furthermore, according to a preferred embodiment of the present invention, there is provided a sheet thin film forming apparatus in which a ratio of the discharge port to the surface area of the housing is 0.1 [%] or more and 3 [%] or less. The

  According to a preferred embodiment of the present invention, there is provided a sheet thin film forming apparatus in which a distance between the sheet guide surface and the discharge port is 1 [mm] or more and 100 [mm] or less.

  In the present invention, “under reduced pressure atmosphere” refers to a pressure at which a vacuum deposition method, a sputtering method, an ion plating method, and a CVD method, which are thin film forming methods to which the present invention is applied, are preferably applied. ] Refers to the following pressure environment.

  Typical examples of the electrically insulating sheet to which the present invention is preferably applied include a sheet such as a plastic film and paper, and a sheet. In particular, a plastic film having high electrical insulation is suitable for applying the present invention. Examples of the material of the plastic film include polyolefins such as polyethylene and polypropylene, and polymer plastic films such as polyester, polycarbonate, polyimide, polyphenylene sulfide, aramid, and nylon. The plastic film may be a single layer or a laminate film having two or more layers.

  Examples of the thin film forming method of the present invention include a vacuum deposition method, a sputtering method, an ion plating method, and a CVD method, which have a large thermal load applied to the electrically insulating sheet of the substrate. In particular, the vacuum deposition method has a high film formation rate of several hundreds [nm / s], and the sheet conveyance speed is as high as several hundreds [m / min]. Therefore, it is difficult to heat the sheet and cool the sheet. From the above, it is suitable as an object of the present invention.

  In the present invention, the term “fine particles” refers to a thin film material that comes and adheres to a sheet when the thin film is formed on the sheet in the above-described thin film forming method. For example, in the vacuum deposition method, it means vapor particles of a thin film material heated and evaporated in a crucible which is a so-called evaporation source. As an evaporation source of the vacuum deposition method, there are a resistance heating method, an electron beam method, etc. in addition to the induction heating method, and any of them can be applied.

  In the present invention, the “sheet guide surface” is a component of a thin film forming apparatus that conveys a sheet while contacting a surface opposite to the thin film forming surface of the sheet when forming a thin film on the sheet in the above-described thin film forming method. Say. This “sheet guide surface” mainly serves to convey the sheet without wrinkles and to efficiently release the heat received by the sheet. As a typical one, there is a cylindrical one as shown in FIGS. 10 and 11, which conveys a sheet while rotating around this axis. In addition, not only the cylindrical shape but also a method of conveying a sheet on a belt body is known, but any one is effective in the present invention. In order to impart a stable potential difference between the thin film and the thin film, the surface of the sheet guide surface or the vicinity thereof preferably has conductivity. Further, a thin film of an insulating material may be formed on a conductive base material or drum.

  In the present invention, the “sheet thin film forming surface” refers to a surface on the side where the thin film is formed on the sheet guide surface. Regardless of whether or not a thin film is formed, the surface on which the film is formed is called in this way.

  In the present invention, “dispose to face the sheet guide surface” means to place the sheet guide surface on the side in contact with the sheet and on the sheet on the sheet thin film forming surface side.

  In the present invention, the “plasma generation source” means that an electric field is applied to gas molecules existing in a reduced pressure atmosphere and a glow discharge accompanied by light emission is generated, whereby at least a part of the gas molecules in the atmosphere is converted into electrons and ions. The process of ionizing. Further, in the present invention, “plasma generating means” refers to applying a voltage such as direct current, alternating current, or rectangular wave to a conductive electrode under a reduced pressure atmosphere to cause glow discharge of the gas around the electrode, This is a device that at least partially ionizes electrons and ions, and in particular, the electrode itself that applies voltage does not emit red light or light, and it has the principle of glowing only the gas atmosphere around the electrode to emit light. Point to.

  In the present invention, the “charged particle” means an ion or electron generated by ionization of a part of a gas atom or molecule or a cluster particle in which a plurality of atoms or molecules are integrated by a plasma generating means. . This also includes electrons and ions that are secondarily generated when these electrons and ions collide with other atoms, molecules, and cluster particles.

  In the present invention, the “potential of the plasma generation source” refers to a structure covered with a conductive casing provided with an opening for discharging charged particles around the plasma generated by the plasma generation source. Means the average value of the potential of the casing; otherwise, it means the average value of the voltage applied to the electrode for generating plasma. The average value of the voltage means a time average value, and is an average value in a time span of at least 1 second or more. When an AC voltage having a frequency of 1 [Hz] or higher with respect to the ground potential is applied to the electrode for generating plasma, the “plasma generation source potential” refers to the ground potential.

  In the present invention, the “non-contact type” means a configuration in which a predetermined distance is provided between the electrode disposed opposite to the sheet guide surface, the sheet guide surface, and the sheet on the sheet guide surface. Further, in the present invention, the “contact type” is a configuration in which the electrode is arranged in a state where a part of the electrode arranged to face the sheet guide surface is in contact with the sheet guide surface or the sheet on the sheet guide surface. Say something. As an example, there is a configuration in which the electrode is cylindrical and can be rotated around the center of the cylinder, and the electrode rotates while the sheet on the sheet guide surface and the cylindrical surface of the electrode are in contact with each other.

In the present invention, “alternating voltage” refers to a voltage whose voltage always varies with time. In general, the voltage value changes in a sine wave shape with time, but other examples in which the voltage value changes in a rectangular wave shape or a pulse wave shape are also exemplified.
The thin film forming material in the present invention is not particularly limited, and any of metal, metal alloy, metal compound, and the like may be used. Specifically, examples of the single metal include Al, Cu, Zn, Co, Fe, and Sn. Examples of the metal alloy include Al—Zn, Al—Cu, and Co—Cr, and examples of the metal compound include AlOx, CuOx, ZnS, ZnO, SiOx, and ITO.

  According to the present invention, thermal deformation (heat loss) is unlikely to occur in the electrically insulating sheet during the formation of the thin film, and after the thin film is formed, charging inside the sheet remains, or after wrinkles or blocking caused by the charging. It is possible to obtain a thin film forming apparatus and a method for manufacturing a sheet with a thin film, which are less prone to process problems.

  Hereinafter, an example in which the example of the best embodiment of the present invention is applied to a winding type vapor deposition apparatus will be described as an example with reference to the drawings.

  FIG. 1A is a schematic cross-sectional view of a first embodiment in which the present invention is applied to a wind-up type vapor deposition apparatus. FIG. 1A shows only the main part, and the decompression chamber and the intermediate roll for housing the structure are omitted. Note that components having the same or equivalent functions as those of the conventional example are denoted by the same reference numerals, and detailed description thereof is omitted.

  A major difference from the prior art device shown in FIG. 10 is that, as shown in FIG. 1A, an alternating voltage based on the ground potential as a charge supply source is applied to generate plasma from the plasma discharge region 27. Means for charging the sheet 1 on the sheet guide surface 3 by providing a plasma electrode 18 to be generated, a DC power source 14 for applying a potential difference between the plasma electrode 18 and the casing 19 of the plasma electrode and the sheet guide surface 3 It is a point that has.

  The plasma electrode 18 generates positive and negative charged particles by generating a plasma discharge in a gas under a reduced pressure atmosphere. As a form of a plasma generation source that can operate in a reduced pressure atmosphere suitable for this embodiment, rods, pipes, and plate-like long conductive electrodes are arranged at a substantially constant interval from the sheet in the sheet width direction. And a case where a high voltage is applied between a case around the electrode or a grounded object and the electrode. When the sheet width is long, the conductive electrodes may be divided and arranged in the sheet width direction. Magnetron-type electrodes with built-in magnets, hollow cathode type electrodes in which combination electrodes with a predetermined interval and hole electrodes with a predetermined hole diameter are evenly arranged in the sheet width direction also sustain plasma discharge stably. It is suitable as an electrode. Each plasma generation source is based on the principle of applying a voltage to a conductive electrode and generating an electric field around the electrode, thereby ionizing the gas around the electrode and generating a glow discharge. Has the characteristic of generating positive and negative charged particles in a substantially balanced manner. Among them, the magnetron type plasma electrode can be made compact, can operate in a relatively wide pressure range under a reduced pressure atmosphere, and can form a plasma with a high ionization degree at a relatively low applied voltage. Is preferred. The plasma electrode is generally non-contact with the sheet, but may be of a contact type. Conventionally, such plasma electrodes are commonly used in vacuum processes today. As one of the uses, it has been used to charge a sheet, but has not been used to charge a sheet. The mechanism of charge removal is that positive and negative charged particles generated at the plasma electrode are induced by an electric field formed by negative and positive charged charges existing on the sheet, and charged particles of opposite polarity arrive at each charged charge. This neutralizes the charge. The present inventors reversely use the principle that the charged particles are induced by an electric field, and bring the positive and negative charged particles generated from the plasma electrode in the vicinity of the sheet thin film forming surface so as to guide the sheet to the surface of the sheet. It has been found that an electric field is forcibly formed to charge the sheet. In addition, since the positive and negative charged particles diffuse almost equally in areas other than the area where the above-mentioned forced electric field is formed, there is a problem that the sheet or the structure in the decompression chamber is charged except for the portion to be charged. This also has the advantage of using plasma electrodes.

  However, the pressure in the vacuum chamber of the vacuum vapor deposition apparatus is often kept at several tens [Pa] or less, and when plasma is generated in such a vacuum atmosphere, the plasma diffuses inside the vacuum chamber. Even if a potential difference is applied between the two objects in such a state where the plasma is diffused, a current flows through the plasma, and thus there is a case where the potential difference cannot be stably applied. Even in the case of the present embodiment, when the sheet guide surface for applying a potential difference for inducing electric charges to the sheet thin film forming surface is directly exposed to the plasma, the voltage may not be stably applied. In order to maintain a stable state, it is effective to spatially isolate the plasma and the object to which a potential difference is applied in a casing maintained at a predetermined potential by grounding or the like. For these reasons, it is preferable to devise a technique that prevents plasma from leaking to other regions from the region in which the vicinity of the plasma electrode and the sheet thin film forming surface are charged. In FIG. 1A, the charged particle radiation port 25 integrated with the plasma electrode housing 19 is brought close to the surface of the sheet 1, and the plasma discharge region 27 is formed from the gap between the charged particle radiation port 25 and the sheet 1. 19 and the charged particle radiation port 25 are prevented from leaking outside. The gap between the charged particle radiation port 25 and the sheet 1 at this time is preferably 1 [mm] or more and 10 [mm] or less. If the distance is too close, there is a possibility that the charged particle emission port 25 may come into contact with the sheet 1, and in that case, the sheet 1 may be damaged. On the other hand, if it exceeds 10 [mm], the plasma discharge region 27 may leak out of the casing 19 and the charged particle radiation port 25.

  Further, as a plasma electrode suitable for the present embodiment, as described in Patent Document 6, for example, the electrode portion is surrounded by a grounded casing, and plasma discharge is generated within the casing, thereby the casing In addition, a configuration in which charged particles are emitted from an opening such as a slit or a pinhole provided in a part of the substrate is also included. FIG. 1B is a schematic cross-sectional view showing an application example in which a charged particle radiation port 25 formed by a slit or a pinhole is provided in a part of the casing 19 of the plasma electrode. FIG. 1B shows only the main part, and the decompression chamber and the intermediate roll for housing the structure are omitted. Note that components having the same or equivalent functions as those in FIG. 1A are given the same reference numerals, and detailed descriptions thereof are omitted. By using such a plasma generation means, the plasma discharge region 27 does not leak from the plasma electrode casing 19 and discharges positive and negative charged particles from the charged particle emission port 25. The charged particles of any polarity are induced on the surface of the sheet 1 by the potential difference applied between the grounded plasma electrode housing 19 and the sheet guide surface 3 to which the DC power supply 14 is connected. 1 is charged, and the sheet 1 and the sheet guide surface 3 can be brought into close contact with each other. The width of the plasma electrode 18 in the sheet width direction (longitudinal direction) is preferably wider than the width of the sheet to be charged, and the charged particle radiation ports 25 are preferably arranged uniformly in the width of the sheet to be charged. Thereby, charged particles can be discharged uniformly in the width direction of the sheet, and can be uniformly charged in the width direction and the running direction of the sheet.

In addition, the amount of charge supply can be adjusted by changing the size of the slit or pinhole. The ratio of the opening area of the slit or pinhole to the surface area of the casing of the plasma electrode is preferably 0.1 [%] or more and 3 [%] or less. The surface area of the casing of the plasma electrode refers to the surface area of the outer periphery of the casing. The inner surface of the casing (the surface in contact with the plasma discharge region) and both end faces in the sheet width direction (for example, the paper surface method of FIG. The surface area of the members at both end faces in the line direction is not included. If the surface area of the housing is larger than 3%, the plasma in the housing leaks outside the housing, and the voltage applied between the sheet guide surface and the plasma electrode housing is unstable. May vary. On the other hand, if it is smaller than 0.1 [%], the amount of charged particles released to the outside of the housing is reduced, and charging may be insufficient.
In order to maintain a pressure environment in which plasma discharge is easy to occur in the plasma electrode casing 19, gas can be introduced into the casing to adjust the pressure in the casing. The gas can be selected from an inert gas such as nitrogen gas, carbon dioxide gas, argon gas, helium gas, or oxygen. A mixed gas of these gases can also be used. The optimum amount of the gas introduced varies depending on the pressure of the atmosphere that generates the plasma discharge region 27, the conductance of the charged particle emission port 25, the length of the plasma electrode 18 in the sheet width direction, and the like. A suitable condition can be set as appropriate from the condition that light emission can be brightened and the condition that the voltage applied to the plasma electrode 18 can be kept low. The voltage applied to the plasma electrode 18 may be either direct current or alternating current, but alternating current is preferable in terms of sustaining stable discharge. In addition, when a DC voltage is applied to the plasma electrode 18, the electric field due to the DC voltage may affect the electric field for inducing charged particles to the surface of the sheet 1. In order to separate the function from the potential difference for inducing particles, it is preferable to apply an AC voltage with reference to the ground potential to the plasma electrode 18. In addition to the AC voltage that changes in a sine wave shape, a plasma power source that generates a steep voltage change such as a rectangular wave shape or a pulse wave is also commercially available, but any of them may be used. When a sinusoidal AC voltage is used, the AC voltage applied to the plasma electrode is within the range of voltage amplitude 100 to 1,000 [V] and frequency 50 [Hz] to 50 [MHz]. It can select suitably according to pressure environment. The current flowing through the plasma electrode (root mean square value in the case of alternating current) is preferably 10 [mA] or more per 10 [cm] width in the sheet width direction (longitudinal direction) of the electrode. Alternatively, the power supplied to the plasma electrode is preferably 2 [W] or more per 10 [cm] of the electrode width. When the current or the input power is low, the amount of charged particles generated may be small and charging may be insufficient, or the plasma may become unstable in time and uneven charging may occur.
Moreover, the range of 1-100 [mm] is suitable for the distance of the charged particle radiation opening 25 and the sheet | seat 1. FIG. If it is too close, there is a possibility of contact with the sheet 1, in which case the sheet 1 may be damaged. Moreover, when it becomes larger than 100 [mm], the charged particles are not sufficiently supplied to the sheet 1.
The potential difference applied between the sheet guide surface 3 and the casing 19 of the plasma electrode may be either positive or negative, but is more preferably a polarity that induces negative charged particles to the sheet 1. According to the inventors' knowledge, negatively charged particles are mainly electrons and positively charged particles are ions in a reduced-pressure atmosphere, but electrons are smaller in mass than ions. In order to move charged particles, electrons are easier to control. Therefore, it is preferable to induce electrons, which are main negatively charged particles, to the surface of the sheet 1 because the charging efficiency is higher than that to induce ions. For this purpose, a potential difference may be provided between the sheet guide surface and the counter electrode so that the potential of the sheet guide surface is higher than the potential of the plasma electrode housing. The potential difference applied between the sheet guide surface and the casing of the plasma electrode is suitably in the range of 10 [V] to 1,000 [V]. If it is too low, the charge cannot be sufficiently attracted, and if it is higher than 1000 [V], abnormal discharge may occur between the sheet and the sheet. Further, when a voltage higher than 1000 [V] is applied, charged particles are driven into the surface of the sheet 1 at the same voltage as the acceleration voltage of the conventional electron beam irradiation apparatus or ion beam irradiation apparatus, and after the thin film is formed. Charge may remain in the sheet, which is not preferable.

  Further, when the sheet thickness is 1 [μm] or more and 100 [μm] or less, the potential difference between the sheet guide surface and the plasma electrode housing per sheet thickness of 1 [μm] (that is, the sheet guide surface and the plasma electrode housing). The value obtained by dividing the potential difference between the body and the sheet by the sheet thickness is preferably 10 [V / μm] or more and 100 [V / μm] or less. According to the inventors' knowledge, the degree to which the sheet is in close contact with the sheet guide surface is substantially proportional to the potential difference between the sheet guide surface and the plasma electrode housing, and inversely proportional to the thickness of the sheet. This can also be inferred from the relationship of equation (2) described later. Therefore, the optimum potential difference can be quantified by the potential difference per 1 [μm] of the sheet thickness. If the potential difference per sheet thickness is smaller than 10 [V / μm], the charge amount may be insufficient. Further, even if it exceeds 100 [V / μm], the amount of charge does not increase any more, and conversely, there is a high probability of causing adverse effects such as abnormal discharge or injection of charged particles into the sheet.

  The thickness of the thin film such as a metal or a metal compound obtained by the present embodiment is particularly effective in the range of 50 [nm] to 500 [nm]. That is, when the thickness of the thin film is 50 [nm] or less, the conventional thin film forming method can often form a film without heat loss. However, in the conventional method, if this film thickness is exceeded, the heat load on the sheet is increased. Film formation becomes difficult. Further, the heat load increases as the film thickness increases. According to the knowledge of the present inventors, when the thickness of the sheet is small even when the thickness is 500 [nm] or more in the method of the present embodiment, the sheet thickness is particularly 10 [μm]. If it falls below, it may lead to heat loss.

  In the example shown in FIG. 1B, a DC power source 14 is connected to the sheet guide surface 3, the plasma electrode housing 19 is grounded, and a potential difference is generated between the sheet guide surface 3 and the plasma electrode housing 19. It is set as the structure to provide. Between the sheet guide surface 3 and the plasma electrode casing 19, a travel path of the electrically insulating sheet 1 that travels while contacting the sheet guide surface 3 is formed. When the sheet 1 is traveling in the sheet conveyance direction 20, positive charged particles and negative charged particles generated by plasma discharge at the plasma electrode 18 are supplied onto the sheet 1. FIG. 8 shows a schematic diagram depicting the movement of the charged particles in FIG. The positive and negative charged particles generated in the plasma electrode 18 are mainly charged particles of any polarity due to the electric lines of force formed by the potential difference between the sheet guide surface 3 and the casing 19 of the plasma electrode. Drawn to the surface of 1. FIG. 8 shows a state in which a positive voltage is applied to the sheet guide surface 3 and negative charged particles are guided to the surface of the sheet 1. In this way, the sheet 1 is negatively charged. As shown in FIG. 1B, the charged sheet 1 is further conveyed in the direction of the sheet conveyance direction 20, and the vapor 10 coming from the evaporation source 7 is deposited on the sheet 1 on the same sheet guide surface 3. A thin film 13 is formed. When the thin film 13 formed at this time is conductive, a positive charge is generated in the thin film 13 so as to cancel the charging of the sheet 1 in the thin film via the intermediate roller 5 that is in contact with the thin film 13 and grounded. The charge of the sheet 1 is apparently removed. Further, even when the thin film 13 to be formed is insulative, according to the knowledge of the present inventors, the ions and electrons of the evaporated particles contained in a trace amount in the vapor 10 are charged on the surface of the sheet 1. The charge is induced and the charge is apparently removed. Thereafter, after the sheet 1 is peeled from the sheet guide surface 3 at the peeling point 32, the sheet 1 is wound around the winding roll body 6 through the intermediate roller 5. At this time, since the charging of the sheet 1 is apparently removed, the adverse effect of causing wrinkles due to the sheets being held together by the intermediate roller 5 and the winding roll body 6 is unlikely to occur.

  According to the knowledge of the inventors, in the case of not using a technique for attaching the sheet to the sheet guide surface with electrostatic force acting between the thin film and the sheet guide surface, most of the thermal deformation during the thin film formation is Is conveyed while sliding slightly on the sheet guide surface, there is a slight gap between the sheet guide surface and the sheet, or the sheet floats locally at the wrinkles that occur when the sheet slides. As a result, it was found that the heat transfer at that portion deteriorated and the sheet was thermally deformed. Therefore, the inventors do not necessarily need to attach the sheet to the sheet guide surface at the portion where the thin film is formed on the sheet guide surface and the portion after the formation as in the prior art. It was found that many of the thermal deformation of the sheet can be suppressed by adhering both at the contact portion between the sheet and the sheet guide surface other than the part and conveying the sheet at the same speed as the sheet guide surface.

  In FIG. 1B, a potential difference is applied between the casing 19 of the plasma electrode and the sheet guide surface 3. In this case, the electric lines of force for inducing charges are voltage as shown in FIG. Is generated between the sheet guide surface 3 to which is applied and a surrounding grounded conductive object such as a vacuum chamber (not shown) other than the plasma electrode housing 19. For the convenience of attachment, when the distance between the plasma electrode casing 19 and the sheet guide surface 3 is increased, in order to efficiently guide the charged particles 23 to the surface of the sheet 1, for example, as shown in FIG. It is more preferable to dispose the counter electrode (potential difference applying electrode) 16 at a position facing the sheet guide surface 3 and a position close to the charged particle radiation port 25 of the plasma electrode 18. Thereby, a potential difference can be applied between the counter electrode 16 and the sheet guide surface 3 with a relatively low voltage, and the effect of inducing charged particles is enhanced. In FIG. 2, the counter electrode 16 is disposed on the downstream side in the traveling direction of the sheet 1 with respect to the plasma electrode 18, but may be disposed on the upstream side in the opposite direction.

  As the form of the counter electrode, a rod, pipe, or plate-shaped long conductive electrode is preferably arranged in the sheet width direction so as to be substantially spaced from the sheet guide surface. More preferably, in the case of a cylindrical sheet guide surface as shown in FIG. 2, for example, in the case of a cylindrical sheet guide surface as shown in FIG. More preferred is a shape facing the surface. In addition, when the sheet width is long, the conductive electrodes may be divided and arranged in the sheet width direction.

  Although depending on the pressure at the place where the sheet 1 is charged, the voltage applied to the counter electrode 16 is 10 [V] or more and 500 [V] or less when the pressure is approximately 1 [Pa] to 100 [Pa]. Is preferred. If the applied voltage is less than 10 [V], charging is insufficient, and if it is greater than 500 [V], abnormal discharge such as spark discharge may occur from the counter electrode 16 itself, and the sheet 1 is made uniform. May not be charged. Further, when the pressure of the charging atmosphere is 1 [Pa] or less, the abnormal discharge as described above is relatively less likely to occur, but an abnormal discharge may still occur at an applied voltage higher than 1 [kV]. Further, according to the knowledge of the inventors, when the charged particles 23 are accelerated with an applied voltage higher than 1 [kV], the charged particles 23 are driven into the sheet 1, and the charge formed in this way will be described later. Even if thin film formation or static elimination is performed, the sheet may remain in the sheet, which may cause adverse effects such as wrinkling and blocking in subsequent processes. Therefore, the applied voltage is preferably 1 [kV] or less.

In the embodiment of FIG. 1B and FIG. 2, when the thin film 13 formed after the sheet 1 is charged is conductive, the surface of the sheet 1 is charged when the thin film is formed. Since it is induced to cancel the charge, it disappears apparently. Therefore, after the thin film is formed, the force for bringing the sheet 1 and the sheet guide surface 3 into close contact with each other is weak, but the sheet 1 and the sheet guide surface 3 are in close contact between the charging processing unit and the thin film formation start point 31. Since both are conveyed at the same speed, an effect that the sheet is not easily wrinkled can be obtained.
FIG. 3A shows an example of another embodiment of the present invention. The difference from FIG. 1B is that the sheet guide surface 3 is grounded and a counter electrode (potential difference applying electrode) 16 is disposed separately from the sheet guide surface 3. The sheet guide surface 3 has a function of optimizing the angle at which the vapor 10 of the vapor deposition material is incident on the sheet 1 while cooling the sheet 1, and is a winding type vapor deposition apparatus applied to the present embodiment. A relatively large structure may be a complicated structure. In such a case, it may be difficult to electrically insulate the sheet guide surface 3 from the ground and to apply a voltage. In this case, it is preferable to dispose the counter electrode 16 separately as shown in FIG. 3A while the sheet guide surface 3 is grounded. FIG. 9 shows a schematic diagram depicting the movement of charged particles in the embodiment of FIG. The positive and negative charged particles generated at the plasma electrode 18 are mainly attracted to the surface of the sheet 1 by the electric lines of force formed between the counter electrode 16 and the sheet guide surface 3. It is done. FIG. 9 shows that the sheet guide surface 3 is grounded, a negative voltage is applied to the counter electrode, and negative charged particles are induced on the surface of the sheet 1. When the counter electrode 16 is arranged separately from the sheet guide surface 3 as shown in FIG. 3A, each charged particle 23 generated from the plasma electrode 18 is sent between the sheet guide surface 3 and the counter electrode 16. It is better to arrange the components. Specifically, it is a preferable embodiment that the charged particle discharge port 25 of the plasma electrode housing 19 is directed between the sheet guide surface 3 and the counter electrode 16. Even when no gas is introduced into the casing 19 of the plasma electrode, gas molecules are likely to diffuse under a reduced pressure atmosphere, so that some of the charged particles leaking from the charged particle discharge port 25 are separated from the sheet guide surface 3. It can diffuse between the counter electrode 16 and charge the thin film forming surface of the sheet. When the gas is introduced into the casing 19 of the plasma electrode, more charged particles are discharged in the direction of the charged particle discharge port 25 due to the differential pressure between the inside and outside of the casing, and the sheet guide surface 3 and the counter electrode 16 are discharged. It is more effective because it is introduced in between. On the other hand, when the charged particles 23 from the plasma electrode 18 are emitted to a place other than between the sheet guide surface 3 and the counter electrode 16, the charged particles 23 are changed to the sheet 1 by the voltage applied to the counter electrode 16. May be repelled in a direction different from the direction toward the surface, and charging may not be performed efficiently. The distance between the counter electrode 16 and the sheet guide surface 3 is preferably as close as possible, and the distance of the shortest portion is preferably 1 [mm] or more and 100 [mm] or less. If the distance is closer than 1 [mm], both may come into contact with each other and damage the surface of the sheet 1 or the sheet guide surface 3. Further, when the distance is longer than 100 [mm], the electric field formed between the sheet guide surface 3 and the counter electrode 16 is formed between the barrier electrode or the vacuum chamber and the counter electrode 16 which are other ground potentials. The electric field cannot be ignored, and the probability that the charged particles 23 generated from the plasma electrode 18 are induced to an object having a ground potential other than the surface of the sheet 1 is increased, and the charging effect of the sheet 1 may be insufficient. In order to increase the charging effect, it is effective to further increase the electric field between the counter electrode 16 and the sheet guide surface 3, and therefore the distance between them is in the range of 1 [mm] to 20 [mm]. More preferably. Further, the length 16a shown in FIG. 9 in which the counter electrode 16 and the sheet guide surface 3 face each other in the conveyance direction of the sheet 1 is preferably in the range of 10 [mm] to 300 [mm]. When the distance is shorter than 10 [mm], the range in which charged particles are guided to the surface of the sheet 1 becomes small, and the charging effect may be insufficient. On the other hand, when the length is longer than 300 [mm], the probability that the charged particles generated from the plasma electrode 18 reach the end of the counter electrode 16 becomes low, and the improvement of the charging effect may not be expected. In FIG. 3A, the counter electrode 16 is disposed on the downstream side in the traveling direction of the sheet 1 with respect to the plasma electrode 18. However, the counter electrode 16 may be disposed on the upstream side. However, when arranged on the upstream side, the sheet 1 is charged in the vicinity of the counter electrode 16, but a part of the charging of the sheet 1 may be neutralized by charged particles emitted from the plasma electrode 18 downstream thereof. If anything, it is preferable to dispose the counter electrode 16 on the downstream side of the plasma electrode 18. The current flowing through the counter electrode is preferably 2 [mA] or less per 10 [cm] width in the sheet width direction (longitudinal direction) of the counter electrode. When a current larger than 2 [mA] flows, a discharge accompanied by light emission (plasma discharge in the present invention) occurs around the counter electrode, and the voltage may not be stably applied to the counter electrode. Further, when plasma discharge is generated around the counter electrode, positive and negative charged particles generated by the plasma discharge diffuse to the periphery, and the sheet immediately after the charging treatment is neutralized, so that the adhesion effect may be insufficient. Furthermore, when the sheet thickness is 1 [μm] or more and 100 [μm] or less, the potential difference between the sheet guide surface and the counter electrode per sheet thickness of 1 [μm] (that is, the potential difference between the sheet guide surface and the counter electrode). Is a value obtained by dividing the sheet thickness by 10 [V / μm] to 100 [V / μm] for the same reason as in the embodiment of FIG.

As shown in FIG. 3A, there is a method in which the counter electrode 16 is not brought into contact with the sheet 1 but can be charged even when brought into contact with the sheet 1. An example is shown in FIG. In FIG. 3B, the counter electrode 16 that is rotatable in a cylindrical shape is disposed so as to be in contact with the surface of the sheet 1 on the sheet guide surface 3, and the counter electrode 16 can be rotated as the sheet 1 is conveyed. Yes. In the example of FIG. 3B, the electric potential of the DC power source 14 is applied to the circumferential surface of the counter electrode 16 through the electric resistance 15, and an electric field is formed between the sheet guide surface 3 and the ground. The charged particles 23 generated at the plasma electrode 18 are guided to the surface of the sheet 1. Since the counter electrode 16 has a cylindrical shape and is in contact with the sheet 1, a narrow gap can be formed between them, and a strong charging effect may be obtained in some cases. Thus, when the cylindrical counter electrode 16 is used, the diameter of the cylinder is preferably in the range of 10 [mm] to 300 [mm]. When it is smaller than 10 [mm], the range in which the charged particles are guided to the surface of the sheet 1 becomes small, and the charging effect may be insufficient. On the other hand, if it is larger than 300 [mm], a large space is required for the attachment of the counter electrode 16, which may make attachment and adjustment difficult. In addition, even when the parallelism between the sheet 1 and the counter electrode 16 is slightly shifted, the circumference of the counter electrode 16 may be covered with a soft material such as rubber so that the sheet 1 and the counter electrode 16 are uniformly contacted in the width direction of the sheet. . In this case, the material to be coated is preferably a conductive material so that the potential of the DC power source 14 can be applied to the surface of the coating material. For example, conductive rubber mixed with conductive powder such as carbon black is exemplified. In this case, the surface resistance of the conductive rubber is preferably 10 ⁶ [Ω / □] or less.

FIG. 15 shows a schematic diagram of a thin film forming apparatus including a decompression chamber in the embodiment of FIG. Most of the winding type vapor deposition apparatuses to which the example of the embodiment of the present invention is applied are divided into a winding chamber 41a for unwinding and winding the film by the partition wall 24 and a vapor deposition chamber 41c for depositing the film, respectively. These chambers are evacuated by the pumps of the winding chamber vacuum pump 42a and the vapor deposition chamber pump 42c. The charging process of this embodiment can be performed in either the winding chamber or the vapor deposition chamber. More preferably, it is preferable to carry out in a chamber whose pressure is 1 [Pa] or less because abnormal discharge is less likely to occur when a potential difference is applied between the counter electrode 16 and the sheet guide surface 3. It is. Further, as shown in FIG. 15, it is more preferable to partition the region where the charging process is performed by the partition wall 24 and to provide the charging process chamber 41b. In that case, the discharge chamber 41a and the vapor deposition are more preferably evacuated by the charge processing vacuum pump 42b so that the pressure in the charge processing chamber 41b is in the range of 0.01 [Pa] to 1 [Pa]. This is preferable because it is not affected by the pressure change in the chamber 41c.
Similarly to the embodiment of FIG. 3A, when the sheet guide surface 3 is grounded and the counter electrode 16 is arranged separately from the sheet guide surface 3, charged particles emitted from the charged particle discharge port 25 of the plasma electrode 18. More preferably, the gas introduction path 29 is provided so that the gas including the gas 23 is efficiently introduced between the counter electrode 16 and the sheet guide surface 3.
FIG. 4 shows an example in which the plasma electrode 18, the charged particle emission port 25, and the counter electrode 16 are configured as a set of devices. In the case of a set of devices as shown in FIG. 4, the casing 19 of the plasma electrode is grounded, and a voltage is applied to the counter electrode 16, so that the charged particle radiation port 25 is an insulating material in order to electrically insulate them from each other. It is necessary to devise such as using.

When the deposited thin film 13 is conductive, a voltage is applied between the thin film 13 and the sheet guide surface 3 to bring the sheet 1 and the sheet guide surface 3 into close contact, so-called electrostatic contact and this embodiment. It can be used in combination. The embodiment is shown in FIGS. FIG. 5 shows an example in which an electrostatic contact technique is used in combination with the embodiment of FIG. A voltage is applied between the sheet guide surface 3 and the intermediate roller 5 to generate an adhesive force between the sheet guide surface 3 and the sheet 1. In this example, the sheet 1 is in close contact with the sheet guide surface by charging of the sheet 1 according to the present embodiment before vapor deposition, and is applied between the thin film 13 via the sheet guide surface 3 and the intermediate roller 5 after vapor deposition. The sheet 1 and the sheet guide surface 3 are in close contact with each other due to the electrostatic force generated by the applied voltage. In this example, since the sheet 1 is conveyed in a state of being in close contact with the sheet guide surface 3, the sheet 1 is unlikely to be wrinkled and wrinkled heat loss is unlikely to occur. FIG. 6 shows an example in which an electrostatic contact technique is used in combination with the embodiment of FIG. In this case, since the sheet guide surface 3 is at ground potential, it is necessary to apply a voltage to the intermediate roller 5 to provide a potential difference between the thin film 13 and the sheet guide surface 3.
On the other hand, when the deposited thin film 13 is insulative, it is impossible to apply a voltage to the thin film 13, and thus the above-described electrostatic adhesion cannot be applied. In such a case, as shown in FIG. 7, the sheet guide on the sheet guide surface 3 after the thin film 13 is formed on the surface of the sheet 1 is again subjected to the charging process of the present embodiment, thereby the sheet guide. The sheet 1 can be conveyed in a state of being in close contact with the surface 3 over a wide range. However, if the charged sheet 1 is continuously conveyed as it is, the sheet 1 remains charged, so that the sheet 1 clings to the sheet guide surface 3 at the peeling point of the sheet guide surface 3, or the winding roll body 6 Sheets may clump together and cause wrinkles. Therefore, as in this embodiment, when the charging process is performed after the thin film is formed, it is necessary to discharge the sheet 1 before the sheet 1 passes the peeling point 32 on the sheet guide surface 3 after the charging process. As a method for discharging the sheet, a method using plasma discharge or a method for forcibly irradiating the gas toward the sheet, which is known as a method for discharging the electrically insulating sheet in vacuum, is known. . FIG. 7 shows an example in which the neutralization plasma electrode 30 is disposed upstream of the peeling point 32 and the surface of the sheet 1 is neutralized.
In addition, about the electroconductivity and insulation of the thin film described here, it can distinguish roughly by the measurement of surface resistance. The electrostatic adhesion technique is effective for a thin film having a surface resistance of 10 ³ [Ω / □] or less. In order to attach the sheet to the sheet guide surface with a thin film of 10 ³ [Ω / □] or more, a method of charging the sheet is effective. However, in the conventional charging method, there are problems in subsequent processes such as charging and blocking of the sheet. It was easy to happen. The charging method of the present embodiment is a method that can hardly cause the influence of charging in the subsequent processing, and can be said to be effective in forming a thin film of 10 ³ [Ω / □] or more. However, in the case of a thin film having a surface resistance higher than 10 ¹⁴ [Ω / □], it may be difficult to apparently remove the charge on the sheet thin film forming surface when forming the thin film, which causes wrinkles and blocking after the thin film is formed. Sometimes.
The surface resistance of the thin film can be measured by the method described in JIS K7194 (1994) and JIS K6911 (1962) after taking out the wound sheet after forming the thin film. If the surface resistance value is 10 ⁶ [Ω / □] or less, the four-probe method described in JIS K7194 is effective. If it is 10 ⁶ [Ω / □] or more, the measurement method using the ring electrode described in JIS K6911 is effective. It is.
According to the knowledge of the inventors, the charging of the sheet depends on the application, but when the absolute value of the charging amount exceeds 30 [μC / m ² ], wrinkles at the time of winding, blocking with a winding roll, etc. There is a high possibility of causing harmful effects. Therefore, it is preferable to wind the sheet after forming a thin film with the charge amount being 30 [μC / m ² ] or less. This charge amount can be measured as follows. First, the electrostatic capacity C [F] per unit area (1 [m ² ]) of a sheet composed of a single layer of a material having a relative dielectric constant ε at a sheet thickness t [m] is expressed by a vacuum dielectric constant ε _0. If [F / m], it is represented by the formula (1).

C = ε ₀ ε / t [F / m ² ] (1)
Further, when the potential value obtained by measuring the charge amount of the sheet with an electrometer is V [V], the maximum value of the charge amount (charge charge density) σ [C / m ² ] calculated from the potential is expressed by the following formula ( 2).

σ = CV
= Ε ₀ εV / t [C / m ² ] (2)
In this case, the electrometer is measured by attaching a sheet so that the thin film forming surface is in close contact with the grounded metal plate, and measuring the potential from the surface of the sheet (the surface on which the thin film is not formed) using a surface electrometer. Is the method. According to the knowledge of the inventors, wrinkles and blocking of the sheet after forming a thin film are likely to occur when the charge amount is larger than 30 [μC / m ² ].

In the following examples and comparative examples, the heat loss, particularly the presence or absence of heat loss generated in the form of wrinkles, was compared. The detection method of heat loss is as follows.
(1) Detection method of heat loss The sheet color after the vapor deposition is run at a speed of several [m / min] so that the sheet passes in front of the plane light source, and the color of the sheet is observed while observing the light of the plane light source passing through the sheet. Observe unevenness and wrinkles visually. The sheet is observed for a length of 100 [m]. Cut out the dark part of the surroundings (the part with low transmittance). The cut sheet piece is gently placed on a desk, and if there is a wrinkled sheet deformation starting from a dark portion, it is determined that the heat is lost.
(2) Measurement of Charge Charge Density on Sheet Non-Thin Film Surface Charged charge density was measured in order to confirm whether the charge on the sheet thin film non-form surface is at a level that affects post-processing. When the charge amount was 30 [μC / m ² ] or less, the range was set so as not to affect post-processing.

The electrically insulating sheet after vapor deposition is 10 [cm] in the sheet running direction, the sheet width direction is cut into a strip shape, and the sheet is attached so that the thin film forming surface is in contact with the grounded metal plate. To a micro-spot type surface potential meter (Monroe model 244 and Monroe probe 1017, opening diameter 1.75 [mm]) with a gap of 3 mm to measure the potential. The potential was measured at intervals of 5 mm while shifting the metal plate in the sheet width direction, and the charge density σ [C / m ² ] was determined from the average potential measurement value V [V] and the formula (2).
(3) Measurement of the voltage amplitude of the high frequency power supply for plasma A high voltage probe (P6015A made by Tektronix) is connected to the output cable of the high frequency power supply for plasma, and the probe is connected to an oscilloscope (TDS1000B made by Tektronix). Was displayed, and the voltage amplitude was measured.
(4) Measurement of the current flowing in the counter electrode For example, the voltage across the electric resistor 15 connected between the counter electrode 16 and the DC power source 14 shown in FIG. ) And the voltage was divided by the resistance value of the electric resistance 15 to obtain the current.
[Example 1]
As an electrical insulating sheet, on one side of a polyethylene terephthalate film (“Lumirror” manufactured by Toray Industries, Inc.) having a thickness of 4.5 [μm] and a width of 620 [mm], a take-up vacuum deposition apparatus shown in FIG. The film was deposited under the following deposition conditions.
(Deposition conditions)
Evaporation source: Induction heating crucible evaporation material: Aluminum evaporation power: 30 [kW]
Vacuum environment: 2 × 10 ⁻² [Pa]
Film thickness: 60 [nm]
Deposition film surface resistance: 0.9 [Ω / □]
(Film transport conditions)
Conveyance speed: 50 [m / min]
(Plasma electrode conditions)
As shown in FIG. 1 (b), a plasma generation source having a magnetron electrode built therein was disposed in a grounded casing. Each condition is as follows.
(1) Length of plasma electrode in sheet width direction: 700 [mm]
(2) Power output of high frequency power supply for plasma: 200 [W]
(3) Voltage amplitude of the high-frequency power source for plasma: 500 [V]
(4) Frequency of plasma high-frequency power supply: 100 [kHz]
(5) Charged particle radiating ports of the plasma electrode housing: Pinholes having a diameter of 2 [mm] are evenly arranged on a straight line in the sheet width direction at intervals of 10 [mm]. Arranged so that the distance between the sheet guide surface and the charged particle emission port is 20 mm.
(6) Direction of the charged particle radiation port: a direction in which the center of the magnetron electrode as a plasma electrode and a straight line extending from the center of the charged particle radiation port are incident on the surface of the cylindrical sheet guide surface substantially perpendicularly.
(Sheet guide surface conditions)
A cylindrical sheet guide surface was used as shown in FIG. Inside the sheet guide surface, a medium for adjusting the temperature of the surface of the sheet guide surface is circulated, and a medium having a constant temperature is introduced from a refrigerant circulation device outside the apparatus. Each condition is as follows.
(1) Diameter of cylindrical sheet guide surface: 500 [mm]
(2) Temperature of medium flowing inside the sheet guide surface: −20 [° C.]
(3) Applied voltage to cylindrical sheet guide surface: +200 [V]
(4) Resistance value of the electrical resistor 15: 1 [kΩ]
As a result of observing the presence or absence of a dark-colored portion of the film that had been vapor-deposited that had a length of 100 [m] and was viewed as being heat-defeated through the backlight source, no heat-loss was observed. Further, the charge density on the surface of the sheet where the thin film was not formed was 13 [μC / m ² ].
[Example 2]
The electrically insulating sheet, vapor deposition conditions, and film transport conditions used were the same as in Example 1, and vapor deposition was carried out under the following vapor deposition conditions using a winding vacuum vapor deposition apparatus shown in FIG.
(Plasma electrode conditions)
As shown in FIG. 3 (a), a plasma generation source having a magnetron electrode built therein was disposed in a grounded casing. Each condition is as follows.
(1) Length of plasma electrode in sheet width direction: 700 [mm]
(2) Power output of high frequency power supply for plasma: 200 [W]
(3) Voltage amplitude of the high-frequency power source for plasma: 500 [V]
(4) Frequency of plasma high-frequency power supply: 100 [kHz]
(5) Charged particle radiating ports of the plasma electrode housing: Pinholes having a diameter of 2 [mm] are evenly arranged on a straight line in the sheet width direction at intervals of 10 [mm]. Arranged so that the distance between the sheet guide surface and the charged particle emission port is 50 mm.
(6) Direction of charged particle radiation aperture: The center of the magnetron electrode, which is a plasma electrode, and a straight line extending from the center of the charged particle radiation aperture are incident at a position approximately halfway between the cylindrical sheet guide surface and the counter electrode. Direction to do.
(Sheet guide surface conditions)
A cylindrical sheet guide surface was used as shown in FIG. As in the first embodiment, the medium is circulated inside the sheet guide surface, and the temperature of the medium is controlled at a constant temperature. In this embodiment, the sheet guide surface is electrically grounded. Each condition is as follows.
(1) Diameter of cylindrical sheet guide surface: 500 [mm]
(2) Temperature of medium flowing inside the sheet guide surface: −20 [° C.]
(3) Voltage application to the sheet guide surface: grounding (0 [V])
(Counter electrode conditions)
As shown in FIG. 3A, a counter electrode made of stainless steel is arranged so as to face the cylindrical sheet guide surface. Each condition is as follows.
(1) Length of counter electrode in sheet width direction: 700 [mm]
(2) Length of counter electrode in sheet running direction: 50 [mm]
(3) Counter electrode thickness: 3 [mm]
(4) Applied voltage: -300 [V]
(5) Resistance value of the electrical resistor 15: 1 [kΩ]
(6) Current flowing through the counter electrode: 0.8 [mA]
(7) Distance from sheet guide surface: 10 [mm]
(8) Shortest distance from the charged particle emission port: 20 [mm]
As a result of observing the presence or absence of a dark-colored portion of the film that had been vapor-deposited that had a length of 100 [m] and was viewed as being heat-defeated through the backlight source, no heat-loss was observed. The charge density on the surface of the sheet where the thin film was not formed was 7 [μC / m ² ].
[Example 3]
The electrical insulating sheet and film transport conditions used were the same as in Example 1, but the film was formed by using the take-up vacuum deposition apparatus shown in FIG. Formed on top.
(Deposition conditions)
Evaporation source: Induction heating crucible evaporation material: Aluminum evaporation power: 29 [kW]
Oxygen introduction amount: 2500 “cc / min”
Vacuum environment: 4 × 10 ⁻² [Pa]
Film thickness: 60 [nm]
Deposition film surface resistance: 2 × 10 ¹² [Ω / □]
(Plasma electrode conditions)
As shown in FIG. 3 (a), a plasma generation source having a magnetron electrode built therein was disposed in a grounded casing. Each condition is as follows.
(1) Length of plasma electrode in sheet width direction: 700 [mm]
(2) Power output of high frequency power supply for plasma: 200 [W]
(3) Voltage amplitude of the high-frequency power source for plasma: 500 [V]
(4) Frequency of plasma high-frequency power supply: 100 [kHz]
(5) Charged particle radiating ports of the plasma electrode housing: Pinholes having a diameter of 2 [mm] are evenly arranged on a straight line in the sheet width direction at intervals of 10 [mm].
(6) Direction of charged particle radiation aperture: The center of the magnetron electrode, which is a plasma electrode, and a straight line extending from the center of the charged particle radiation aperture are incident at a position approximately halfway between the cylindrical sheet guide surface and the counter electrode. Direction to do.
(Sheet guide surface conditions)
A cylindrical sheet guide surface was used as shown in FIG. As in the first embodiment, the medium is circulated inside the sheet guide surface, and the temperature of the medium is controlled at a constant temperature. In this embodiment, the sheet guide surface is electrically grounded. Each condition is as follows.
(1) Diameter of cylindrical sheet guide surface: 500 [mm]
(2) Temperature of medium flowing inside the sheet guide surface: −20 [° C.]
(3) Voltage application to the sheet guide surface: grounding (0 [V])
(Counter electrode conditions)
As shown in FIG. 3A, a counter electrode made of stainless steel is disposed so as to face the cylindrical sheet guide surface. Each condition is as follows.
(1) Length of counter electrode in sheet width direction: 700 [mm]
(2) Length of counter electrode in sheet running direction: 50 [mm]
(3) Counter electrode thickness: 3 [mm]
(4) Applied voltage: -200 [V]
(5) Resistance value of the electrical resistor 15: 1 [kΩ]
(6) Current flowing through the counter electrode: 0.7 [mA]
As a result of observing the presence or absence of a dark-colored portion of the film that had been vapor-deposited that had a length of 100 [m] and was viewed as being heat-defeated through the backlight source, no heat-loss was observed. The charge density on the surface of the sheet where the thin film was not formed was 16 [μC / m ² ].
[Example 4]
The electrical insulating sheet and film transport conditions used were the same as in Example 1, but the film was formed by using the take-up vacuum deposition apparatus shown in FIG. Formed on top.
(Deposition conditions)
Evaporation source: Induction heating crucible evaporation material: Aluminum evaporation power: 35 [kW]
Oxygen introduction amount: 5000 “cc / min”
Vacuum environment: 5 × 10 ⁻² [Pa]
Film thickness: 150 [nm]
Deposition film surface resistance: 4 × 10 ⁻⁸ [Ω / □]
(Plasma electrode conditions)
As shown in FIG. 3 (a), a plasma generation source having a magnetron electrode built therein was disposed in a grounded casing. Each condition is as follows.
(1) Length of plasma electrode in sheet width direction: 700 [mm]
(2) Power output of high frequency power supply for plasma: 200 [W]
(3) Voltage amplitude of the high-frequency power source for plasma: 500 [V]
(4) Frequency of plasma high-frequency power supply: 100 [kHz]
(5) Charged particle radiating ports of the plasma electrode housing: Pinholes having a diameter of 2 [mm] are evenly arranged on a straight line in the sheet width direction at intervals of 10 [mm].
(6) Direction of charged particle radiation aperture: The center of the magnetron electrode, which is a plasma electrode, and a straight line extending from the center of the charged particle radiation aperture are incident at a position approximately halfway between the cylindrical sheet guide surface and the counter electrode. Direction to do.
(Sheet guide surface conditions)
A cylindrical sheet guide surface was used as shown in FIG. As in the first embodiment, the medium is circulated inside the sheet guide surface, and the temperature of the medium is controlled at a constant temperature. In this embodiment, the sheet guide surface is electrically grounded. Each condition is as follows.
(1) Diameter of cylindrical sheet guide surface: 500 [mm]
(2) Temperature of medium flowing inside the sheet guide surface: −20 [° C.]
(3) Voltage application to the sheet guide surface: grounding (0 [V])
(Counter electrode conditions)
As shown in FIG. 4, a counter electrode made of stainless steel is disposed so as to face the cylindrical sheet guide surface. Each condition is as follows.
(1) Length of counter electrode in sheet width direction: 700 [mm]
(2) Length of counter electrode in sheet running direction: 50 [mm]
(3) Counter electrode thickness: 3 [mm]
(4) Applied voltage: -400 [V]
(5) Resistance value of the electrical resistor 15: 1 [kΩ]
(6) Current flowing through the counter electrode: 1.0 [mA]
As a result of observing the presence or absence of a dark-colored portion of the film that had been vapor-deposited that had a length of 100 [m] and was viewed as being heat-defeated through the backlight source, no heat-loss was observed. The charge density on the surface of the sheet where the thin film was not formed was 18 [μC / m ² ].
[Comparative Example 1]
The electrical insulating sheet, vapor deposition conditions, and film transport conditions used were the same as in Example 3, and vapor deposition was performed using a winding vacuum vapor deposition apparatus shown in FIG.
(Sheet guide surface conditions)
(1) Diameter of cylindrical sheet guide surface: 500 [mm]
(2) Temperature of medium flowing inside the sheet guide surface: −20 [° C.]
(3) Voltage application between the sheet guide surface and the guide roll: 0 [V]
As a result of observing pinholes with a length of 100 [m] through a backlight light source on the film after the completion of vapor deposition, 23 heat losses were found. Further, the charge density on the surface of the sheet where the thin film was not formed was 6 [μC / m ² ].
[Comparative Example 2]
The electrically insulating sheet, vapor deposition conditions, and film transport conditions used were the same as in Example 3, and the sheet thin film formation surface on the sheet guide surface before the thin film formation was applied to the electron beam using the winding type vacuum vapor deposition apparatus shown in FIG. Vapor deposition was performed by irradiating electrons from the irradiation device and charging the surface of the sheet. Except for the above, vapor deposition was performed under the following vapor deposition conditions.
(Electron beam irradiation device irradiation conditions)
The sheet thin film forming surface was charged under the following conditions.
(1) Acceleration voltage: 5 [kV]
(2) Cathode current: 20 [mA]
(3) Distance from sheet guide surface: 500 [mm]
(4) Electron irradiation range to the sheet: sheet width direction 650 [mm], sheet traveling direction 100 [mm]
(Sheet guide surface conditions)
A cylindrical sheet guide surface was used as shown in FIG. As in the first embodiment, the medium is circulated inside the sheet guide surface, and the temperature of the medium is controlled at a constant temperature. In this embodiment, the sheet guide surface is electrically grounded. Each condition is as follows.
(1) Diameter of cylindrical sheet guide surface: 500 [mm]
(2) Temperature of medium flowing inside the sheet guide surface: −20 [° C.]
(3) Voltage application to the sheet guide surface: grounding (0 [V])
As a result of observing a pinhole with a length of 100 [m] through a backlight light source, no heat loss was found. However, wrinkles occurred on the wound film roll. The charge density on the surface of the obtained sheet where the thin film was not formed was 70 [μC / m ² ].
[Comparative Example 3]
The electrically insulating sheet, vapor deposition conditions, and film transport conditions used were the same as in Example 3. The aluminum oxide film was placed on the film while introducing oxygen in the vicinity of the evaporation source using the take-up vacuum vapor deposition apparatus shown in FIG. Formed. Except for the above, vapor deposition was performed under the following vapor deposition conditions.
(Sheet guide surface conditions)
A cylindrical sheet guide surface was used as shown in FIG. Inside the sheet guide surface, a medium for adjusting the temperature of the surface of the sheet guide surface is circulated, and a medium having a constant temperature is introduced from a refrigerant circulation device outside the apparatus. Each condition is as follows.
(1) Diameter of cylindrical sheet guide surface: 500 [mm]
(2) Temperature of medium flowing inside the sheet guide surface: −20 [° C.]
(3) Applied voltage to cylindrical sheet guide surface: +200 [V]
(4) Resistance value of the electrical resistor 15: 1 [kΩ]
As a result of observing the presence or absence of a dark portion of the film that had been deposited, which was observed to have a length of 100 [m] and lost heat through the backlight light source, eleven heat losses were found. The charge density on the surface of the sheet where the thin film was not formed was 22 [μC / m ² ].

  The present invention is very suitable as a vacuum vapor deposition method and a wind-up type vacuum vapor deposition apparatus for an electrically insulating plastic film, but can also be applied to a vacuum vapor deposition method for a web such as paper. However, it is not limited to these.

It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention. It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention. It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention. It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention. It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention. It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention. It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention. It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention. It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention. It is the schematic diagram which showed the motion of the charged particle which concerns on one embodiment of this invention. It is the schematic diagram which showed the motion of the charged particle which concerns on one embodiment of this invention. It is a schematic block diagram of the conventional winding type vacuum evaporation system. It is a schematic block diagram of the conventional winding type vacuum evaporation system. It is a schematic block diagram of the conventional winding type vacuum evaporation system. It is the schematic diagram which showed the motion of the charged particle which concerns on the conventional winding type vacuum evaporation system. It is the schematic diagram which showed the motion of the charged particle which concerns on the conventional winding type vacuum evaporation system. It is a schematic block diagram of the winding type vacuum evaporation system which concerns on one embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Sheet 2 Original roll body 3 Sheet guide surface 4 Intermediate roller (unwinding side)
5 Intermediate roller (winding side)
6 Winding roll body 7 Induction heating crucible 8 Vapor deposition material 9 Power supply device 10 Vapor 11 Mask member 12 Opening portion 13 Thin film 14 DC power source 15 Electric resistance 16 Counter electrode 16a Length of counter electrode in running direction 17 High frequency power source for plasma 18 Plasma Electrode 19 Plasma electrode housing 20 Sheet conveyance direction 21 Grounding 22 Charged particle source 23 Charged particle 24 Bulkhead 25 Charged particle emission port 27 Plasma discharge area 29 Gas introduction path 30 Plasma discharge electrode 31 Thin film formation start point 32 Separation point 33 winding Attached point 41 Decompression chamber 41a Winding chamber 41b Charging chamber 41c Deposition chamber 42 Vacuum pump 42a Vacuum pump for winding chamber 42b Vacuum pump for charging chamber 42c Vacuum pump for deposition chamber 43 Valve 44 Gas cylinder 45 Pressure reducing valve

Claims (14)

This is a method for manufacturing a sheet with a thin film in which a thin film is formed by depositing fine particles flying from a fine particle generation source on an electrically insulating sheet conveyed in the conveying direction while being in contact with the sheet guide surface in a reduced pressure atmosphere. Then, charged particles of any polarity among charged particles supplied from the plasma generation source are applied to the sheet thin film forming surface on the sheet guide surface by 10 [V between the plasma generation source and the sheet guide surface. The sheet that is the same as the sheet guide surface used for charging the sheet thin film forming surface after charging the sheet thin film forming surface by applying and inducing a potential difference of 1000 V or less. A method for producing a sheet with a thin film, comprising: forming the thin film on a sheet thin film forming surface on a guide surface. This is a method for manufacturing a sheet with a thin film in which a thin film is formed by depositing fine particles flying from a fine particle generation source on an electrically insulating sheet conveyed in the conveying direction while being in contact with the sheet guide surface in a reduced pressure atmosphere. Then, charged particles of any polarity among charged particles supplied from the plasma generation source are formed on the sheet thin film forming surface on the sheet guide surface with an electrode of 10 [V] between the electrodes arranged opposite to the sheet guide surface. The sheet that is the same as the sheet guide surface used for charging the sheet thin film forming surface after charging the sheet thin film forming surface by applying and inducing a potential difference of 1000 V or less. A method for producing a sheet with a thin film, comprising: forming the thin film on a sheet thin film forming surface on a guide surface. The method for producing a sheet with a thin film according to claim 2, wherein a sheet surface non-contact type is used as the electrode. The method for producing a sheet with a thin film according to claim 2, wherein a sheet surface contact type electrode is used as the electrode. 2. The negative charged particles are induced on the sheet thin film forming surface by applying the potential difference so that the potential of the sheet guide surface is higher than the potential of the plasma generation source or the electrode. To 4. The manufacturing method of the sheet | seat with a thin film in any one of 4. The sheet thickness is 1 [μm] to 100 [μm], and the potential difference per sheet thickness 1 [μm] is 10 [V / μm] to 100 [V / μm]. The manufacturing method of the sheet | seat with a thin film in any one of Claim 1 to 5 characterized by the above-mentioned. 7. The surface resistance of the thin film formed on the sheet thin film forming surface is 10 ³ [Ω / □] or more and 10 ¹⁴ [Ω / □] or less, according to claim 1. Manufacturing method of sheet with thin film. A decompression chamber, a sheet conveying surface that conveys the sheet while being in contact with the sheet in the decompression chamber, and a sheet conveying unit that conveys the sheet along with the movement of the sheet guiding surface; A thin film forming apparatus for a sheet, comprising: a fine particle generation source that scatters fine particles toward a sheet to form a thin film on the sheet; and a charging unit that charges the sheet on the sheet guide surface . The charging means disposed upstream of the particulate generation source in the traveling direction includes plasma generating means for generating plasma inside the casing, and charged particles generated by plasma from the casing to the outside of the casing. a discharge port for discharging, and said plasma generating means and the said are arranged to face the particulate source sheet guiding surface and the same said sheet guide surface The sheet thin film is characterized in that the discharge port and the sheet guide surface are arranged to face each other, and a potential difference applying means capable of applying a potential difference of 10 [V] or more and 1000 [V] or less. Forming equipment. A decompression chamber, a sheet conveying surface that conveys the sheet while being in contact with the sheet in the decompression chamber, and a sheet conveying unit that conveys the sheet along with the movement of the sheet guiding surface; A thin film forming apparatus for a sheet, comprising: a fine particle generation source that scatters fine particles toward a sheet to form a thin film on the sheet; and a charging unit that charges the sheet on the sheet guide surface . The charging means disposed upstream of the particulate generation source in the traveling direction includes plasma generating means for generating plasma inside the casing, and charged particles generated by plasma from the casing to the outside of the casing. a discharge port for discharging, and 10 [V] or more between the particulate source said are arranged opposite sheet guidance surface in the same of the sheet guide surface 000 thin film forming device for a seat characterized in that it has a potential applying electrode for applying a potential difference [V] or less. The sheet thin film forming apparatus according to claim 9, wherein the potential difference applying electrode is a non-contact type on the sheet surface. The sheet thin film forming apparatus according to claim 9, wherein the potential difference applying electrode is of the sheet surface contact type. 12. The sheet thin film forming apparatus according to claim 8, wherein the plasma generating means excites plasma with an alternating voltage. 13. The sheet thin film according to claim 8, wherein a ratio of the discharge port to the surface area of the casing is 0.1 [%] or more and 3 [%] or less. Forming equipment. 14. The sheet thin film forming apparatus according to claim 8, wherein a distance between the sheet guide surface and the discharge port is 1 [mm] or more and 100 [mm] or less.

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