JP5481239B2 - Manufacturing apparatus for sheet with thin film, manufacturing method for sheet with thin film, and cylindrical roll used in these - Google Patents

Description

The present invention relates to an apparatus for manufacturing a sheet with a thin film, a method for manufacturing a sheet with a thin film, and a cylindrical roll used in these.

Conventionally, by forming a thin film on a sheet exemplified by a plastic film,
Metal-deposited films, which are materials such as film capacitors, magnetic recording tapes, and packaging films, are manufactured. 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. 7-1 and 7-2. FIGS. 7-1 and FIGS. 7-2 are the figures which showed the component of the thin film formation apparatus which forms a thin film continuously on sheets, such as a plastic film. FIGS. 7-1 and 7-2 show only main parts, and a vacuum chamber and an intermediate roll for housing the structure are omitted. In FIG. 7A, the long sheet 1 is a raw roll body 2.
From the winding point 33 to the peeling point 32 at a required winding angle determined by the intermediate rollers 4 and 5 on the sheet guide surface 3 which is a surface of a cylindrical metal can that is fed out from the sheet and rotates along the sheet traveling direction. It is conveyed in a wound state and then wound up via the intermediate roller 5 to form a winding roll body 6. When the sheet 1 is conveyed onto the sheet guide surface 3, it is placed in the crucible 7 (evaporation source) in the region between the film formation start point 30 and the film formation end point 31 restricted by the traveling direction mask member 11b. A vapor 10 evaporated from a certain vapor deposition material 8 adheres to the sheet 1, and a first thin film 13 is formed on the sheet 1. The winding roll body 6 wound in this way is then
In FIG. 7-2, it is set on the raw fabric roll body 2 and conveyed so that the surface on which the first thin film 13 is formed is in contact with the sheet guide surface 3, and the second thin film 14 is formed on the opposite surface. , Sheet 1
A sheet with a thin film having thin films formed on both sides can be obtained. 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. 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.

FIG. 8 is a schematic configuration diagram of the apparatus viewed from the right hand of FIG. 7-2. When a potential difference is provided between the second thin film 14 and the sheet guide surface 3 as described above, as shown in FIG. 8, the width of the opening 12 of the width direction mask member 11a is the same as that of the second thin film 14 and the sheet guide. Usually, it is set at least smaller than the sheet width so that the surface 3 is not electrically short-circuited.

A method of forming a second thin film on the other surface of the sheet after forming the first thin film on one surface of the sheet using such a winding vapor deposition apparatus is known. For example, Patent Document 1 discloses a method of forming a metal thin film on both surfaces of a plastic film. Patent Document 2 discloses forming a thin film of metal oxide or hydroxide on both surfaces of a plastic film. In this way, when a thin film is formed on both sides of the sheet, the phenomenon that the sheet loses heat is remarkable particularly when the second thin film is formed on the opposite surface after the first thin film is formed on the first surface. It becomes. The heat loss is when the 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 is large or when there is a portion where the sheet 1 and the sheet guide surface 3 are not in contact with each other. This is a phenomenon in which the sheet 1 undergoes thermal deformation. Note that the main heat load received by the sheet 1 in this case includes radiant heat received from the evaporation source 7 and the like, and solidification heat received from the deposited second thin film 14.

When a conductive first thin film is formed on one side of a sheet that has not yet been formed with a thin film on either side, the heat received by the sheet 1 during deposition is efficiently released to the sheet guide surface 3. As shown in FIG. 7-1, a potential difference is applied between the first thin film 13 and the sheet guide surface 3 by the DC power source 15 through the intermediate roller 5 in contact with the first thin film 13 formed on the sheet 1. The technique (for example, patent document 3) which sticks the sheet | seat 1 strongly on the sheet | seat guide surface 3 with the electrostatic force which acts between the thin film 13 of 1 and the sheet | seat guide surface 3 is used.

However, after forming the first thin film 13 on one side of the sheet 1 and further forming the second thin film 14 on the other side of the sheet 1, the gap between the second thin film 14 and the sheet guide surface 3 is also obtained. Even if a potential difference is applied, the first thin film 13 and the sheet guide surface 3 are electrically at the same potential, so that electrostatic force does not act between the sheet 1 and the sheet guide surface 3, so that the sheet 1 and the sheet Insufficient contact with the guide surface 3 may cause heat loss. In particular, when a second thin film having a thickness of 50 [nm] or more is formed, the heat load applied to the sheet is large, and heat loss is likely to occur. In addition,
A typical form of heat loss that occurs when the sheet 1 does not sufficiently adhere to the sheet guide surface 3 is a wrinkle-like deformation extending in the sheet conveyance direction. The present inventors consider the cause of this occurrence as follows. That is, the sheet 1 is caused by the thermal load that the sheet 1 receives during vapor deposition.
In the sheet conveying direction, a tension for conveying acts on the sheet conveying direction, which acts as a deformation suppressing force. On the other hand, the sheet 1 is formed on the sheet guide surface 3 in the sheet width direction. If the sheet is not in close contact, the restraining force is particularly weak, so the sheet is deformed while sliding slightly on the sheet guide surface. At this time, the sheet occurs between the area subjected to the thermal load and the area not subjected to the sheet conveyance direction. The wrinkle part of the sheet guide surface 3
The heat conduction becomes insufficient because it is not in contact with the surface, and it is locally deformed in the shape of wrinkles. If a close contact force acts between the sheet 1 and the sheet guide surface 3, it is considered that this serves as a suppression force for deformation in the sheet width direction, and no wrinkle-like heat loss occurs.

As a countermeasure against the heat loss, for example, in Patent Document 1, the sheet is run along the circumferential surface of a cylindrical can in which an insulating layer such as alumina is formed on the circumferential surface of the sheet guide surface, and the metal thin film and the cylindrical shape are used. Disclosed is a method for preventing the sheet guide surface and the thin film from having the same potential by providing a potential difference between the can and generating an electrostatic force between the sheet and the sheet guide surface.
This electrostatic force generates an adhesive force between the sheet and the sheet guide surface, which enables double-sided vapor deposition at a higher speed than a sheet guide surface on a metal surface without an insulator layer.

Japanese Patent Laid-Open No. 60-092467 JP 2007-157244 A JP 59-147023 A

Ken Ihouchi et al., “Polymer films and functional membranes”, Gihodo Publishing, April 1991, p. 198-203

However, according to the knowledge of the present inventors, in the manufacturing method as described in Patent Document 1, the same thin film material is formed on the surface of the sheet 1 on which the thin film has not yet been formed, with the same film thickness, and the insulator layer. It was still inferior to the speed achievable when depositing with a sheet guide surface with no metal surface.

Furthermore, according to the knowledge of the present inventors, when the metal oxide thin film described in Patent Document 2 is deposited on both surfaces, an insulator layer is provided on the peripheral surface of the conventional sheet guide surface as described above. In the method, the metal oxide thin film is a film having a higher electrical resistance than the metal thin film, so that it is difficult for current to flow, the electrostatic force acting between the sheet guide surface and the sheet becomes weak, and the sheet is likely to lose heat. was there.

Further, according to the knowledge of the present inventors, in the conventional manufacturing method as described above, the sheet guide surface 3
The characteristics of the insulator layer formed on the peripheral surface of the film greatly affected the quality of the deposited film. One of them is a decrease in thermal conductivity in the insulator layer. For example, in Patent Document 1, alumina is coated as an insulator layer, but alumina, which is a ceramic, has lower thermal conductivity than metal,
It becomes difficult for the heat received by the film by vapor deposition to escape to the sheet guide surface. In addition, the electrostatic force applied between the sheet and the sheet guide surface depends on the characteristics of the insulator layer.
The characteristics of the insulator layer that affect the electrostatic force are mainly the dielectric constant and the coating thickness. As an insulator layer that can be coated on the surface of a cylindrical can, a material that satisfies the characteristics required for a sheet guide surface, such as surface smoothness, surface hardness, and uniform film thickness, can be obtained by thermal spraying. It has been limited to ceramic materials such as alumina and zirconia. In order to improve the thermal conductivity and adhesion between the sheet 1 and the sheet guide surface 3 within the limitation of such material selection, it is advantageous to make the insulator layer as thin as possible. Has been used in a range thinner than 200 [μm]. However, compared to the speed achievable when the same thin film material is formed on the surface of the sheet 1 on which the thin film has not yet been formed, using the sheet guide surface of the metal surface without the insulator layer, with the same film thickness. Since heat loss occurred at a low speed, it was difficult to increase the speed further. As a cause of this, particularly in a ceramic film such as alumina formed by a spraying method, which is employed for an insulator on the peripheral surface of this kind of sheet guide surface, if the film thickness is less than 200 [μm], the sprayed film thickness This is because the unevenness of the film and the unevenness of the film quality cannot be ignored, a part having a low adhesion force is partially formed, and a problem that the heat loss is partially generated may occur. Regarding the unevenness of the film thickness, since the cylindrical sheet guide surface having a diameter of 400 [mm] or more generally includes an error of roundness of about 10 to 20 [μm], the unevenness of the film thickness of the insulator layer. 10 to 20 [μm] exists, and the ratio of the film thickness unevenness to the film thickness increases as the film thickness of the insulator layer decreases. Since the electrostatic force generated when a voltage is applied becomes stronger as the film thickness is thinner, unevenness of the adhesion force occurs due to unevenness of the film thickness, resulting in partial heat loss. On the other hand, the unevenness of the film quality mainly depends on the difference in the density (void) formed at the time of thermal spraying. The portion where there are many voids has a low dielectric constant, and the amount of charge induced when a voltage is applied decreases. As a result, the adhesive strength of the portion is weakened, leading to partial heat loss. On the other hand, if the thickness of the coating is set to 200 [μm] or more so that the unevenness of the sprayed coating is not noticeable, the thermal conductivity is insufficient, and the sheet 1 may easily lose heat. For this reason, the thickness of the insulator layer is reduced to about 100 [μm], and the deposition is performed at a speed range in which this partial heat loss does not occur. For example, when depositing an aluminum thin film on a polyethylene terephthalate film having a thickness of 5 [μm], when depositing the first thin film on an undeposited film on both sides, the deposition rate is 600-7.
Deposition at a rate of 00 [nm / sec] is possible. However, in the case of depositing the second thin film, when using the sheet guide surface of the metal surface, the film formation rate is 200 [nm / sec].
When heat loss occurs at a speed of about, or when a sheet guide surface provided with an insulator layer as described in Patent Document 1 is used, heat loss occurs at a speed of about 400 [nm / sec]. It has occurred. Thus, the film could not be formed at the same speed as the case of depositing the first thin film, and productivity had to be reduced when forming the second thin film.

Moreover, although it is a compound thin film like a metal oxide thin film and surface resistance is higher than a metal thin film, 10 < ¹ >-
In the case of depositing a compound thin film exhibiting conductivity within a range of 10 ⁵ Ω / □ on both surfaces, the conventional method of providing an insulator layer on the peripheral surface of the sheet guide surface, the sheet guide surface and the sheet However, the adhesion is weaker than that of a metal thin film having a surface resistance of less than 10 ¹ Ω / □, and the sheet loses heat compared to the case where a metal thin film is deposited on both sides. In some cases, it became easier. For example, in the case where an aluminum oxide thin film adjusted to have a film thickness of 50 [nm] and a surface resistance of about 10 ⁴ Ω / □ is formed on both sides of a polyester film,
The film formation rate when forming the second thin film was 350 [nm / sec] as the limit even when the sheet guide surface provided with the insulator layer was used.

As described above, in the prior art, after forming the first thin film on one side of the sheet, the second thin film is formed on the other side of the sheet or when the compound thin film showing conductivity is formed. In particular, it has been difficult to form the second thin film without heat loss at a high speed that can be achieved by the formation of the first thin film on the sheet.

Therefore, in view of the problems of the prior art as described above, the present inventors have made characteristics of an insulating layer that can make harmless unevenness of film thickness and unevenness of film quality that cause partial heat loss. As a result of intensive studies, an object of the present invention is to provide an apparatus for manufacturing a sheet with a thin film, a method for manufacturing a sheet with a thin film, and a cylindrical roll used therefor, which form a second thin film at a high speed even for a particularly thin film. To do.

  In order to achieve the above object, the present invention is characterized by the following configurations.

According to the present invention, in a reduced pressure atmosphere, the sheet on which the first thin film is formed on one surface is brought into contact with the surface of the cylindrical roll, and is conveyed along with the rotational movement of the cylindrical roll. A method of manufacturing a sheet with a thin film, wherein metal vapor is blown toward the sheet from an evaporation source in which an evaporation material is melted on the other surface of the sheet, and a second thin film is continuously formed on the sheet. The volume resistance of the cylindrical roll is 10 ⁸ to 10 on the surface of the cylindrical roll.
Applying a voltage in the range of 100 to 400 V between the surface on which the first thin film is formed and the cylindrical roll, using a coating with an insulator layer in the range of ¹¹ Ωcm, A method for manufacturing a sheet with a thin film is provided, in which a second thin film is formed on the other surface of the sheet. Here, “volume resistance is in the range of 10 ⁸ to 10 ¹¹ Ωcm” specifically means 1 × 10 ⁸ to 1 ×.
The range of 10 ¹¹ Ωcm is shown.

Moreover, according to the preferable form of this invention, manufacture of the sheet | seat with a thin film using what the thickness of the said insulator layer coat | covered on the surface of this cylindrical roll exists in the range of 40-200 micrometers as said cylindrical roll. A method is provided.

Moreover, according to the preferable form of this invention, the thickness of the said sheet | seat is 10 micrometers or less, The manufacturing method of the sheet | seat with a thin film whose conveyance speed of the said sheet | seat is 100 m / min or more is provided.

Moreover, according to the preferable form of this invention, a manufacturing method of the sheet | seat with a thin film whose said 1st thin film is a metal compound thin film, and the surface resistance of the said metal compound thin film exists in the range of 10 < ¹ > -10 < ⁵ > ohm / square. Is provided.

Moreover, according to the preferable form of this invention, the manufacturing method of the sheet | seat with a thin film whose said metal compound thin film is aluminum oxide and whose film-forming rate is 600 nm / second or more is provided.

According to another aspect of the present invention, the decompression chamber, and the decompression chamber includes a cylindrical roll that conveys the sheet while being in contact with the sheet, and the sheet is accompanied by a rotational motion of the cylindrical roll. Conveying means, an evaporation source for scattering metal vapor toward the sheet on the cylindrical roll, and a potential difference generating means for generating a potential difference between the sheet and the cylindrical roll. An apparatus for manufacturing a sheet with a thin film that continuously forms a thin film on the sheet, wherein the cylindrical roll is configured by covering a peripheral surface of a cylindrical metal body portion with an insulator layer. There is provided an apparatus for producing a sheet with a thin film, wherein the volume resistivity of the insulator layer is in the range of 10 ⁸ to 10 ¹¹ Ωcm.

Moreover, according to the preferable form of this invention, when the volume resistance of two arbitrary points in the area | region which contacts the sheet | seat of the said insulator layer is set to R1 and R2 (R1 <= R2), the sheet | seat with a thin film which satisfy | fills the following formula | equation A manufacturing apparatus is provided.

          1 ≦ R2 / R1 ≦ 2

Moreover, according to the preferable form of this invention, the manufacturing apparatus of the sheet | seat with a thin film whose thickness of the said insulator layer exists in the range of 40-200 micrometers is provided.

Further, according to a preferred embodiment of the present invention, the sheet has a sheet conveying distance between the guide roll immediately before and immediately after the cylindrical roll and the cylindrical roll both within 200 mm, and the sheet is An apparatus for manufacturing a sheet with a thin film is provided in which the surface in contact with the guide roll is the opposite surface of the surface in contact with the cylindrical roll.

Moreover, according to the preferable form of this invention, in the said electric potential difference generation means, the manufacturing apparatus of the sheet | seat with a thin film containing the electric current suppression circuit which restrict | limits the electric current which flows between the said sheet | seat and the said cylindrical roll to 50 mA or less is provided. Is done.

According to a preferred embodiment of the present invention, the insulator layer is made of a material in which aluminum oxide is a main component and at least one selected from magnesium oxide, silicon oxide, chromium oxide, calcium oxide, and zirconium oxide is mixed. An apparatus for manufacturing a sheet with a thin film is provided.

Here, as a typical sheet applied in the present invention, there are sheets such as a plastic film and paper. In particular, a plastic film is preferably used in 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.

In the present invention, examples of the method for forming a thin film include a vacuum deposition method, a sputtering method, an ion plating method, and a CVD method. Among these, the vacuum evaporation method is preferable because high-speed film formation with a film formation rate of several hundreds [nm / second] is possible. In the evaporation source of the vacuum evaporation method, as a method of heating the material, there are a resistance heating method and an electron beam heating method in addition to the induction heating method, and any of them can be applied. In particular, the electron beam heating method is most suitable as a method for obtaining a uniform metal oxide thin film in the width direction because the evaporation amount can be easily controlled in the sheet width direction.

In the present invention, the “evaporation source” refers to a volume portion that melts a metal material that is a thin film material. A container for containing a metal material, a heat insulating material, a material supply device, a heater for heating, and the like are disposed around the evaporation source. A suitable one is appropriately selected depending on the method of heating the evaporation source. There is no particular limitation.

In the present invention, the “film formation rate” refers to a speed at which the metal oxide is deposited on the surface of the sheet in the sheet film formation region, specifically, the sheet conveyance speed is v [m / sec], When the film thickness of the metal oxide thin film deposited on the sheet surface is d [nm] and the length of the sheet deposition region in the sheet conveyance direction is L [m], it indicates a value represented by the following formula. .

          (Film formation rate) [nm / sec] = (v × d) / L (1)

In the present invention, the “sheet guide surface” refers to a constituent element 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 a thin film is formed on the sheet. 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 FIG. 1 to be described later, which conveys a sheet while rotating around an 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 the present invention, a metal thin film is provided by evaporating the metal material, or a metal compound thin film is provided by introducing oxygen or nitrogen into the metal vapor atmosphere. The material mainly composed of aluminum and / or copper is preferably used because it has a low melting point and is an inexpensive material. Aluminum oxide films and copper oxide films are preferably used because of their good characteristics such as gas barrier properties, rigidity, thermal expansion properties, and productivity. Other materials include Zn, Sn, Si, Ni, Ag, Au, Co, C
Examples of the metal include r, Fe, Mn, Mg, In, Pt, Ta, Ti, and Zr. There are also alloy materials of these. In addition, as a metal compound thin film, AlO _X , AlN, AlF ₃ , Si
_{O X, SiC, SiN X,} CaF 2, CoO, CeO X, CrO X, HfO X, ITO,
_{MgO, MgF 2, NbO X,} SnO X, TaO X, TiO X, TiN, WO X, YO X
, YF ₃ , ZnO, ZnS, ZrO _{2 and the} like are mentioned, but are appropriately selected depending on the use of the sheet with a thin film, and do not limit the application of the present invention.

According to a preferred embodiment of the present invention, the surface of the cylindrical metal roll having a structure for circulating the medium therein is provided with an insulator layer in which aluminum oxide and titanium oxide are mixed, and the surface of the insulator layer A cylindrical roll that conveys a long sheet in contact with a rotary motion, and the insulator layer has a volume resistance of 10 ⁸ to 10 ¹¹ Ωcm, a thickness of 40 to 200 μm,
In addition, a cylindrical roll having a titanium element concentration of 2.2 to 4.0 at% is provided.

Moreover, according to the preferable form of this invention, the film thickness 1 of the insulator layer in the arbitrary positions of the said surface
A cylindrical roll having a dielectric breakdown voltage per 00 μm of 500 V / 100 μm or more is provided.

Further, according to a preferred embodiment of the present invention, the standard deviation of the titanium element concentration in each region divided by a square lattice having 10 μm as one side in an arbitrary cross section of the insulator layer intersecting perpendicularly to its circumferential direction. Is provided with a cylindrical roll having a coefficient of variation of less than 2.0.

According to a preferred embodiment of the present invention, the surface roughness Ra of the insulator layer surface is 0.01-0.
. A cylindrical roll having a surface roughness Ra of 1 μm and a surface roughness Ra of 1 to 3 μm is provided.

According to another aspect of the present invention, the decompression chamber, and the decompression chamber includes a cylindrical roll that conveys the sheet while being in contact with the sheet. Conveying means, an evaporation source for scattering metal vapor toward the sheet on the cylindrical roll, and a potential difference generating means for generating a potential difference between the sheet and the cylindrical roll. An apparatus for manufacturing a sheet with a thin film that continuously forms a thin film on the sheet is provided, wherein the cylindrical roll is any one of the cylindrical rolls described above.

According to another aspect of the present invention, in a reduced pressure atmosphere, a sheet having the first thin film formed on one surface is brought into contact with the surface of the cylindrical roll, and the rotational movement of the cylindrical roll is accompanied. With the thin film attached to the other surface of the sheet being conveyed, metal vapor is blown toward the sheet from an evaporation source in which the evaporation material is melted, and a second thin film is continuously formed on the sheet. A method for producing a sheet, wherein any one of the cylindrical rolls as described above is used as the cylindrical roll, and the surface between the surface on which the first thin film is formed and the cylindrical roll is 100.
A method for producing a sheet with a thin film is provided in which a voltage in the range of ˜400 V is applied to form a second thin film on the other surface of the sheet.

According to the present invention, as is clear from the comparison between Examples and Comparative Examples described later, after the first thin film is formed on one side of the sheet, the second thin film is further formed on the other side of the sheet. If you want to
Even with a relatively thick metal thin film or metal oxide thin film of 50 [nm] or more, a sheet with a thin film can be produced at high speed without losing heat.

FIG. 1-1 is a schematic configuration diagram of a take-up vacuum deposition apparatus showing an embodiment of the production apparatus of the present invention. FIG. 1-2 is an enlarged schematic cross-sectional view of a portion where the metal vapor of FIG. 1-1 is flying. FIG. 2 is a schematic configuration diagram of the apparatus viewed from the right hand of FIG. 1-1. FIG. 3 is a schematic configuration diagram of a take-up vacuum deposition apparatus showing an embodiment of the production apparatus of the present invention. FIG. 4 is a schematic configuration diagram of a take-up vacuum deposition apparatus showing an embodiment of the production apparatus of the present invention. FIG. 5 is a schematic configuration diagram showing a method for measuring the resistance of the insulator layer of the present invention. FIG. 6 is a schematic configuration diagram of a take-up vacuum deposition apparatus showing an embodiment of the production apparatus of the present invention. FIG. 7-1 is a schematic configuration diagram illustrating a method of forming a first thin film using an example of a conventional winding type vacuum deposition apparatus. FIG. 7-2 is a schematic configuration diagram illustrating a method of forming a second thin film using an example of a conventional winding type vacuum deposition apparatus. FIG. 8 is a schematic configuration diagram of the apparatus viewed from the right hand of FIG. 7-2. FIG. 9 is a schematic configuration diagram showing an example of a conventional take-up vacuum deposition apparatus. FIG. 10 is an image of an insulator layer cross section of Example 2. FIG. 11 is an image of an insulator layer cross section of Example 3. FIG. 12 is an image of an insulator layer cross section of Example 4. FIG. 13 is an image of an insulator layer cross section of Comparative Example 3. FIG. 14 is an image of an insulator layer cross section of Comparative Example 4.

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.

FIGS. 1-1 and 1-2 are both schematic cross-sectional views of a winding-type vapor deposition apparatus showing an embodiment of the production apparatus of the present invention. FIG. The vacuum chamber and intermediate roll are omitted. FIG. 1-2 is a schematic cross-sectional view in which the portion where the metal vapor of FIG. 1-1 is flying is enlarged and the positional relationship such as the arrangement of each component is easily understood. further,
FIG. 3 shows an overall schematic diagram illustrating a vacuum chamber and a vacuum pump, omitting details such as an oxygen nozzle, together with FIGS. 1-1 and 1-2. 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.

The roll-up type vapor deposition apparatus shown in FIG. 1-1 has a sheet guide surface 3 that conveys the sheet 1 while in contact with the sheet 1, and accompanies the movement of the sheet guide surface 3 on which the insulator layer 20 is formed. A conveying means such as a cylindrical roll for conveying the sheet 1 and a crucible 7 (evaporation source) for scattering metal vapor toward the sheet 1 on the sheet guide surface 3 are provided. In such an apparatus, the sheet 1 on which the first thin film 13 has already been formed on one side is continuously drawn out from the raw roll 2 and is a cylindrical metal that rotates along the traveling direction of the sheet. At the required wrapping angle determined by the intermediate rollers 4 and 5 on the sheet guide surface 3 which is the surface where the insulator layer 20 is provided in the can made,
It is conveyed in a state of being wound from the winding point 33 to the peeling point 32, and then wound around the intermediate roller 5 to form a winding roll 6. At this time, the metal vapor deposition material 8 in the crucible 7 is evaporated. Thus, when the sheet 1 is conveyed onto the sheet guide surface 3, it is in the crucible 7 in the region between the film formation start point 30 and the film formation end point 31 restricted by the traveling direction mask member 11b. The vapor 10 evaporated from the vapor deposition material 8 adheres to the surface of the sheet 1 on which the thin film has not yet been formed, and the second thin film 14 is formed on the sheet 1.

Moreover, when forming a metal oxide thin film, as shown in FIG. 1-1, the oxygen nozzle 17 which introduce | transduces oxygen in order to make it react with a metal vapor is provided. The oxygen nozzle is configured by arranging a plurality of holes in the sheet width direction, and is disposed on the upstream side and the downstream side of the crucible 7 in the sheet conveyance direction. Each oxygen nozzle 17 introduces oxygen toward a region between the crucible 7 and the sheet guide surface 3. At this time, the vapor deposition material 8 in the crucible 7 is evaporated, and at the same time, oxygen is introduced from the oxygen nozzles 17 provided on the upstream side and the downstream side of the crucible 7 in the sheet conveying direction. As a result, the second thin film 14 is removed from the oxygen nozzle 17.
Oxygen introduced into the metal vapor atmosphere 10 becomes a metal oxide. That is, a second thin film 14 of metal oxide is formed on the surface of the sheet 1.

Furthermore, the formation of the thin film will be described in detail with reference to FIG. When further heated, the metal vapor 10 begins to evaporate from the molten metal surface of the metal material 8. The vapor 10 of the metal thus vaporized flies toward the sheet 1 along the sheet guide surface 3. The metal vapor thus flying is deposited on the sheet surface, and the second thin film 14 is formed. At this time, the surface of the sheet guide surface 3 is applied by applying a voltage between the first thin film 13 already formed on the back surface of the sheet 1 and the sheet guide surface 3 by the DC power source 15 and the current limiting resistor 16. Positive and negative charges are induced across the insulating layer 20 and an electrostatic force is generated between the sheet 1 and the sheet guide surface 3 to act as an adhesion force.

FIG. 2 is a schematic configuration diagram of the apparatus viewed from the right hand of FIG. 1-1. Thus, a voltage is applied between the first thin film 13 and the sheet guide surface 3. Unlike the case of FIG. 8, the insulator layer 20
Since a voltage is applied between the sheet guide surface 3 and the first thin film 13 with the sheet interposed therebetween, the sheet guide surface 3
The first thin film 13 and the sheet guide surface 3 are not electrically short-circuited even if the vapor 10 adheres to the width of the sheet 1, so that the second thin film 14 is formed over the entire width of the sheet 1. May be set larger than the sheet width. However, this is not the case when there is a problem that the vapor deposition material adhering to the sheet guide surface damages the edge of the sheet 1 or the like.

As a method for melting and evaporating a metal, for example, there are a method of heating a 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. That is, a high-frequency induction heating method under reduced pressure, a resistance heating method, an electron beam method, a laser ablation method, and the like can be given. In order to increase the thickness of the metal oxide film, a high frequency induction heating method or an electron beam method is preferably used, and an electron beam method is preferably used if it is a high melting point material, for example, a melting point material of 1500 [° C.] or higher.

Further, 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. Specifically, it is cooled to, for example, about −20 [° C.] using a refrigerant such as ethylene glycol or silicone oil. In addition, a method of conveying a sheet on a belt body is also applicable, not limited to a cylinder.

The major difference between the present invention and the method of forming the second thin film by coating the peripheral surface of the cylindrical sheet guide surface described in Patent Document 1 with the insulator layer is the present invention. 1-1, the volume resistance of the insulator layer 20 provided on the peripheral surface of the cylindrical sheet guide surface 3 is 10 ⁸ to 10.
¹¹ [Ωcm], and by applying a voltage between the already formed first thin film 13 and the sheet guide surface 3, the sheet 1 and the sheet are sandwiched with the insulator layer 20 interposed therebetween. This is a point where an adhesion force is applied to the guide surface 3.

Note that the polarity of the DC power source 15 is not necessarily connected as shown in FIG.

The volume resistance of the insulator layer 20 is preferably in the range of 10 ⁸ to 10 ¹¹ [Ωcm]. In the prior art, a ceramic film such as alumina formed by a thermal spraying method is used for the insulator layer 20 employed for insulation of the peripheral surface of the sheet guide surface 3, but this alumina has a volume resistance of 10 ¹² [ Ωcm] or more, and if a voltage of 300 [V] or more is applied thereto, an electrostatic force acts between the sheet 1 and the sheet guide surface 3, but the force is relatively weak and is sufficiently close to prevent heat loss. In order to obtain a force, it was necessary to apply a voltage of 500 [V] or more. In the case of a winding-type vacuum vapor deposition machine as shown in FIG. 3, the pressure in the vacuum chamber is 10 ⁰ to 10 ⁻³ [Pa
However, if a voltage of about 500 [V] is applied under this pressure, unnecessary discharge may occur in the vacuum chamber. If such a discharge occurs, the voltage is stabilized. In some cases, there was a problem that could not be applied. When the thickness of the insulator layer 20 is less than 200 [μm], the unevenness of the sprayed film thickness and the unevenness of the film quality cannot be ignored, a part having a low thermal conductivity is partially formed, and the heat loss is partially generated. was there. The thickness of the insulator layer 20 is set to 200.
If it is [μm] or more, the thermal conductivity is insufficient, and the sheet 1 may easily lose heat.
Therefore, when the coating material is selected so that the volume resistance of the insulator layer 20 is in the range of 10 ⁸ to 10 ¹¹ [Ωcm] as in the present invention, sufficient adhesion is exhibited even when the applied voltage is 400 V or less. I found out that According to the knowledge of the inventors, this adhesion force is a force called Janssen-Rahbek force, which is different from the conventional electrostatic force. It works. This Jansen-Rahbek force has been applied to electrostatic chuck technology in the film forming process of semiconductors and glass substrates, although it is a different industrial field. The thickness of the insulator layer 20 having such a volume resistance is 200 [μm.
In the following, heat loss is also less likely to occur due to the high adhesion. Furthermore, this Jansen-Rahbek force is based on the principle that charges are induced inside the insulator layer 20 and electrostatic attraction is also generated by the charges inside the insulator layer 20, and unlike the conventional electrostatic force, the insulator layer 2
The dependence on the film thickness and dielectric constant of 0 is small, and largely depends on the volume resistance of the insulator layer 20. Therefore, there is an advantage that unevenness of the adhesion force caused by unevenness of the film thickness of the insulator layer 20 hardly occurs and partial heat loss hardly occurs. Further, since the volume resistance is lower than that of the alumina or zirconia insulator layer of the prior art, the heat conduction of the insulator layer 20 is improved, and thus there is an advantage that heat loss is less likely to occur. Furthermore, the volume resistance of the insulator layer 20 is 10 ⁸ to 10.
By selecting the material of the insulator layer so as to be within the range of ¹⁰ [Ωcm], the applied voltage 3
Even if it is 00 [V] or less, a sufficient adhesion can be obtained, which is more preferable. As described above, the inventors of the present invention are particularly effective in suppressing partial heat loss of the plastic film, which is the subject of the present invention, by selecting a material that generates the Janssen-Rahbek force for the insulator layer. I found it.

However, there are some problems in applying the Janssen-Rahbek force to the winding vacuum deposition apparatus of the present invention. The action of the adhesion force in the wind-up type vacuum evaporation apparatus as in the present invention is mainly due to the fact that the conveyed sheet is more flexible than the electrostatic chuck in the semiconductor film forming process and the glass film forming process. The difference is that the contact force is continuously applied to the other sheet, and the contact force needs to be quickly expressed on the sheet conveyed at high speed. In the semiconductor film forming process and the glass film forming process, the silicon wafer or glass substrate, which is a work, and the electrostatic chuck are attached and detached by turning on and off the applied voltage. In the apparatus, with the voltage applied between the sheet guide surface 3 and the first thin film 13, the sheet is brought into close contact at the sheet winding point 33, and the sheet 1 is removed from the sheet guide surface at the sheet peeling point 32. Remove. This peeling is peeled off from the sheet guide surface by the tension acting on the sheet 1. As a result of the intensive studies by the inventors, the adhesion force acts at a relatively low voltage in order to cause the adhesion force to act quickly after the sheet 1 is wound and to smoothly peel the sheet 1 from the sheet guide surface 3. It has been found that the volume resistance of the insulator layer 20 is preferably in the range of 10 ⁸ to 10 ¹⁰ [Ωcm]. By applying the volume resistance insulator layer 20, when the rotational speed of the sheet guide surface 3 is relatively fast, for example, when the cylindrical sheet guide surface 3 rotates at 50 [rpm] or more,
Even when the sheet 1 is transported at a speed of 100 [m / min] or more, the sheet 1 can be transported in close contact with the sheet guide surface 3 and suppresses problems such as heat loss and wrinkles during peeling. It is effective. Further, on the surface of the sheet guide surface 3 in FIG. 1-1, the sheet is not in close contact between the point 32 where the sheet 1 peels and the point 33 where the sheet starts to be wound. Leaks to the sheet guide surface 3 side. And winding point 3
3, the internal charge of the insulator layer 20 is induced again by the voltage applied between the first thin film 13 and the sheet guide surface 3 when the sheet 1 starts to come into close contact with the sheet 1. Therefore, the adhesion force at the winding point 33 is relatively weak, and the adhesion force between the sheet 1 and the sheet guide surface 3 gradually increases while the sheet 1 is conveyed from the winding point 33 to the film formation start point 30. To increase. For this reason, in order to develop sufficient adhesion from the sheet 1 downstream of the winding point 33 and to prevent the charge of the insulator layer 20 from leaking excessively downstream of the peeling point 32, winding from the peeling point 32 is performed. The distance in the circumferential direction of the sheet guide surface 3 to the point 33 should be as short as possible, and the time during which the sheet guide surface 3 is not in contact with the sheet 1 downstream of the peeling point 32 should be as short as possible. The distance in the circumferential direction between the film formation start points 30 should be as long as possible, and the time during which the sheet 1 is in contact with the sheet guide surface 3 upstream of the film formation start point 30 should be as long as possible. According to the knowledge of the present inventors, specifically, the peeling point 32
The time during which the sheet guide surface 3 from the winding point 33 to the winding point 33 is not in contact with the sheet 1 is within 0.2 [second], or the sheet 1 from the peeling point 32 to the winding point 33 is the sheet guide surface 3. It is preferable that the time of contact with is 0.05 seconds or more. When this is converted into a circumferential distance on the surface of the sheet guide surface 3, the circumferential distance from the winding point 33 to the film formation start point 30 is 0. When the conveyance speed of the sheet 1 is v [m / min]. 05 × v / 60 [m] or more is preferable, and the circumferential distance from the peeling point 32 to the winding point 33 is preferably 0.2 × v / 60 [m] or less. If neither of these conditions is satisfied, the adhesive force between the sheet 1 and the sheet guide surface 3 does not sufficiently act in the film formation region, and the sheet may lose heat.

The sheet 1 applied in the present invention is exemplified by a polymer plastic film such as polyethylene, polypropylene, polyester, etc. In particular, the thickness of the sheet 1 is 10 [μm.
The following plastic films are relatively thin, have a small heat capacity, and are flexible, so that they easily lose heat due to the heat load during vapor deposition.

When the thickness of the sheet 1 is 10 [μm] or less, the sheet guide surface 3 is used for its flexibility.
And the first thin film 13 are easily wound around the sheet guide surface 3. In particular, at the peeling point 32, the sheet 1 cannot be peeled while being in close contact with the sheet guide surface 3, and a trouble of winding is likely to occur. In order to prevent such inconvenience, as shown in FIG. 4, in the vicinity of the peeling point 32 and the winding point 33 on the sheet guide surface 3, the sheet peeling roller is set so that the distance that the sheet 1 is conveyed in the air is shortened. 21 and a sheet feeding roller 22 are preferably provided. The sheet peeling roller 21 and the sheet feeding roller 22 are installed in the vicinity of the sheet guide surface 3 and have an effect of suppressing fluctuations in the positions of the peeling point 32 and the winding point 33. In order to exhibit this effect more effectively. The length in the sheet traveling direction in which the sheet 1 is conveyed in the air between the sheet peeling roller 21 and the sheet guiding surface 1 and between the sheet feeding roller 22 and the sheet guiding surface 1 is within 200 [mm]. It is preferable to do. If it is larger than 200 [mm], even when the peeling point 32 is shifted to the downstream side, the change in the peeling angle of the sheet 1 with respect to the sheet guiding surface 3 is small and the tension of the sheet is difficult to be transmitted. It may be easy to wind around. Further, the sheet peeling roller 21 and the sheet feeding roller 22
It is preferable that the wrapping angle of the sheet 1 is 45 [°] or more. The winding angle is 45 [
If the angle is smaller than [°], the sheet 1 slides on the sheet peeling roller 21 and the sheet feeding roller 22, and the sheet 1 may be wrinkled. In addition, it is preferable that the sheet peeling roller 21 and the sheet feeding roller 22 are electrically insulated so that no adhesion force acts between the sheet 1 and the sheet 1 so as not to be wound. In addition, as a countermeasure for preventing the sheet 1 from being wound around the sheet guide surface 3, it is preferable to provide drive rolls that can adjust the tension of the sheet 1 on the upstream side and the downstream side of the sheet guide surface 3. It is preferable that the tension of the sheet 1 on the upstream side of the winding point 33 or the downstream side of the peeling point 32 is appropriately adjusted by this driving roll so that the sheet 1 does not wind around the sheet guide surface 3.

Further, when the sheet is adhered or peeled while a voltage is applied between the sheet guide surface 3 and the first thin film 13, the winding point 33 or the peeling point 32 particularly when the sheet 1 is flexible. In some cases, the sheet flutters. During the fluttering, a steep current change occurs in the electric circuit that applies a voltage between the sheet guide surface 3 and the first thin film 13, and the fluttering of the sheet 1 is reduced by limiting the current change. There are cases where it is possible. In FIG. 1A, a current limiting resistor 16 is inserted in series with the DC power source 15 between the first thin film 13 and the sheet guide surface 3. According to the knowledge of the present inventors, the current flowing in this circuit is 50 [mA] or less, more preferably 10 mA.
[MA] Selecting the resistance value of the current limiting resistor 16 so as to limit the current to less than or equal to mA was effective in suppressing fluttering of the sheet 1.

Further, heat loss, which is a subject of the present invention, refers to a phenomenon in which the sheet 1 such as a plastic film is melted or deformed by a thermal load during vapor deposition, and the sheet 1 is particularly hot on the sheet guide surface 3. It refers to deformation that expands and contracts under load and wrinkles that accompany the deformation.
In order to suppress the occurrence of this heat loss, when the sheet 1 is subjected to a thermal load, the sheet 1 is brought into close contact with the sheet guide surface 3, thereby cooling the sheet 1 and sliding the sheet 1 on the sheet guide surface 3. The most effective measure is to suppress the movement to try.

For this purpose, the adhesion between the sheet 1 and the sheet guide surface 3 is a sufficient adhesion that does not cause the sheet 1 to lose heat due to a thermal load, and at the same time, when the sheet 1 is peeled off from the sheet guide surface 3, A range that is not too strong is not necessary. Although this adhesion force depends on the volume resistance of the insulator layer 20 and the applied voltage, the flexible sheet 1 and the sheet guiding surface can be formed in a relatively wide contact area like the cylindrical sheet guiding surface 3 of the present invention. When the sheet 1 is conveyed while being in close contact, if there is uneven adhesion on the sheet guide surface 3, the position of the separation point 32 is shifted in the width direction when the sheet 1 is separated from the sheet guide surface 3. There is a concern that 1 flutters and the sheet 1 is wrinkled. Since the voltage applied to the first thin film 13 and the sheet guide surface is uniform, the adhesion force mainly depends on the volume resistance of the insulator layer 20. If there is a difference that the volume resistance is larger than twice in the circumferential direction or width direction of the sheet guide surface, the contact force may change by about twice, which may cause fluttering or wrinkling of the sheet. When the volume resistances at two arbitrary points in the region in contact with the sheet 1 of the insulator layer 20 covering the peripheral surface of the guide surface 3 are R1 and R2 (R1 ≦ R2), it is preferable to satisfy the following formula.

          1 ≦ R2 / R1 ≦ 2 (2)

FIG. 5 shows an outline of a method for measuring the volume resistance at an arbitrary point of the insulator layer 20. As shown in FIG. 5, a conductive measuring electrode 61 is brought into contact with a portion of the surface of the insulator layer 20 to be measured, and a voltage is applied by a resistance measuring DC power source 62 to thereby measure the measuring electrode 61 and the sheet guide surface 3. Is measured by a microammeter 63. This flowing current is I [A], the voltage applied between the measurement electrode and the sheet guide surface is V [V], the contact area between the measurement electrode and the insulator layer is S [cm ² ], and the insulator layer The volume resistance R is obtained by the following formula (3) where t is [cm].

          R = (V / I) × (S / t) [Ωcm] (3)

In addition, it is necessary to cool the sheet 1 when the sheet 1 receives a heat load.
In general, a cooling medium is circulated inside the sheet guide surface 3, and the cooling capacity of the sheet 1 is adjusted by controlling the medium to a desired temperature. If the heat transfer in the insulator layer 20 is insufficient, the sheet 1 may easily lose heat. there,
The heat conductivity of the material used for the insulator layer 20 should be as high as possible, and the thickness of the insulator layer 20 should be as thin as possible. The thermal conductivity of the insulator layer 20 is preferably 2 [W / m · K] or more. Moreover, it is preferable that the thickness of the insulator layer 20 is in the range of 40 to 200 [μm]. When the thickness is less than 40 [μm], the unevenness of thickness becomes conspicuous, and the above-described unevenness of resistance may occur. Alternatively, when a voltage is applied, dielectric breakdown may occur in the insulator layer 20 and a hole may be formed in the insulator layer 20. When the thickness of the insulator layer 20 is thicker than 200 [μm],
Insufficient heat transfer may cause the sheet 1 to lose heat.

The material of the insulator layer 20 is preferably alumina (aluminum oxide) or zirconia (zirconium oxide) from the viewpoint of heat conductivity inherent to the material and workability for uniform coating film thickness. In particular, it is preferable to form alumina by a thermal spraying method because the insulator layer 20 that satisfies the above characteristics can be obtained at a relatively low cost. However, alumina has a volume resistance of 10
^{12 ~10 14 [Ωcm]} next, ¹⁰ 8 ^{~10 11 [Ωcm]} volume resistivity in the range of, more preferably it is difficult to obtain a volume resistivity ranging from ¹⁰ 8 ^{~10 10 [Ωcm]} of the present invention. Therefore, the insulator layer 20 is made of a material containing alumina as a main component and a mixture of at least one selected from magnesia (magnesium oxide), silica (silicon oxide), chromia (chromium oxide), and calcium oxide having a relatively low volume resistance. It is preferable to configure. Further, since titania (titanium oxide) having a relatively low volume resistance is a material that exhibits semiconductivity when sprayed, a coating obtained by spraying a material obtained by granulating alumina and titania has a volume resistance of 10 ⁸ to 10.
It is a suitable material that can be easily adjusted within the range of ¹¹ [Ωcm]. For example, the insulating layer 20 is formed on the peripheral surface of the sheet guide surface 3 made of a metal roll by spraying the material mixed or granulated in this way.
Thus, the volume resistance insulator layer 20 of the present invention can be formed on the peripheral surface of the sheet guide surface 3 with the uniformity expressed by the equation (2).

Further, the material of the first thin film 13 to be deposited is conductive or semiconductive in order to use an adhesion force between the first thin film 13 and the sheet guide surface 3 that acts by applying a voltage. The material which shows property is preferable, and the metal compound represented by metal materials, such as aluminum and copper, aluminum oxide, etc. is suitable as illustrated previously. The aluminum oxide referred to here refers to a compound thin film in which oxygen and aluminum are synthesized at an arbitrary degree of oxidation, unlike alumina exemplified as the material for the insulator layer. In order to utilize the adhesion force between the first thin film 13 and the sheet guide surface 3 by applying a voltage from the DC power supply 15 and acting on the both, the surface resistance of the first thin film 13 is 10 ⁵ [Ω. / □] The following range is preferable. In particular, in the prior art, the surface resistance, which is more difficult to adhere to the sheet guide surface 3 than the metal thin film, is 10 ¹ to 1.
Even in the semiconductive first thin film 13 within the range of 0 ⁵ [Ω / □], the above-mentioned Janssen-Rahbek force exerts an effect of applying an adhesion force to such a semiconductive object. By providing the insulator layer 20 of the present invention, an adhesive force stronger than that of the prior art acts between the sheet guide surface 3 and the first thin film 13. Therefore, this is particularly effective when such a semiconductive material is deposited on both sides. When the surface resistance of the first thin film 13 is greater than 10 ⁵ [Ω / □], the adhesion is weakened, the tension acting on the sheet and the stress in the sheet acting by thermal deformation prevail, and the sheet becomes the sheet. There are cases where it is difficult to carry the sheet while being in close contact with the guide surface.

As such a semiconductive material, a process in which oxygen is introduced into a metal vapor atmosphere and the second thin film 14 and the first thin film 13 of the metal oxide are provided on both surfaces of the sheet 1 has a relatively high film formation rate. Since it is a high process and easily loses heat due to the heat load during vapor deposition, it is suitable as an application to which the present invention is applied for the purpose of speeding up. In particular, in the case where the metal oxide is aluminum oxide, industrially high-speed vapor deposition technology has been established, which is a suitable subject of the present invention. When the aluminum oxide thin film is deposited, the surface resistance is 1 on one surface of the undeposited sheet.
When the first aluminum oxide thin film in the range of 0 ¹ to 10 ⁵ [Ω / □] is deposited,
In the prior art, the film forming rate could be 600 [nm / second] or more. However, when the second aluminum oxide thin film 14 is further formed on the other surface of the sheet, it has been difficult for the conventional technique to cause heat loss in the conventional technique. Using the sheet guide surface 3 coated with the insulator layer 20 of the invention, the sheet guide surface 3 and the first
By applying a voltage between the thin film 13 and the thin film 13, an adhesive force acts on the sheet 1 and the sheet guide surface 3, and heat loss hardly occurs even at a film formation rate of 600 [nm / sec] or more.

In addition, as a parameter for the rate at which the thin film is deposited, a parameter called a dynamic rate [nm · m / min] obtained by multiplying the sheet conveyance speed [m / min] and the film thickness [nm] may be used. When an aluminum oxide thin film is formed, a film deposition condition suitable for the present invention is 12000 [nm · m / min] or more at this dynamic rate.

Note that the voltage applied between the sheet guide surface 3 and the first thin film 13 is 100 [V] or more, 4
00 [V] or less is preferable. If the applied voltage is less than 100 [V], the adhesion may be insufficient, and if it is greater than 400 [V], the sheet guide surface 3 to which a voltage is applied is applied.
In addition, abnormal discharge such as spark discharge or glow discharge may occur around the intermediate roller (winding side) 5 and the first thin film 13. In addition, abnormal discharge may occur between the sheet guide surface 3 and the first thin film 13 in the vicinity of the peeling point 32. When the abnormal discharge occurs, the applied voltage temporarily decreases, the adhesion force becomes insufficient, and partial heat loss may occur. for that reason,
The applied voltage is preferably 400 [V] or less, more preferably 300 [V] or less in order to keep the sheet 1 and the sheet guide surface 3 that are continuously conveyed in close contact with each other. Further, in the case where the thickness of the insulator layer 20 is smaller than 100 [μm], when a voltage higher than 400 [V] is applied between the sheet guiding surface 3 and the first thin film 13, the insulation sandwiched between the two is provided. The body layer 20 may cause a dielectric breakdown, and a hole may be formed in a part of the insulator layer 20. When a hole is formed in the insulator layer 20, a current flows locally between the first thin film 13 and the sheet guide surface 3 that are in contact with the insulating layer 20, and the thin film 1
3 may still have damage such as electric discharge scratches. In order to avoid such problems, the applied voltage when the thickness of the insulator layer 20 is less than 100 [μm] is 10 mm.
The applied voltage per 0 μm is 400 V / 100 μm or less, more preferably 300 V /
100 μm or less is preferable. For example, when the thickness of the insulator layer 20 is 50 [μm], the applied voltage is 200 [V] or less, more preferably 150 [V] or less.

It is preferable that the cylindrical roll which comprises the conveying means mentioned above is provided with the following insulator layers 20. That is, the insulator layer 20 is a mixture of alumina (aluminum oxide) and titania (titanium oxide), has a volume resistance of 10 ⁸ to 10 ¹¹ Ωcm, and a thickness of 40 to 200.
μm and the titanium element concentration is 2.2 to 4.0 at%. As described above, when the titanium element concentration is 2.2 to 4.0 at%, the titanium element can be relatively uniformly dispersed as described later.

The material of the insulator layer 20 in which alumina and titania are mixed is formed from granulated powder obtained by agglomerating an arbitrary powder into particles having an appropriate size and firing. Since it forms from such granulated powder, compared with the mixed powder which mixed the powder of a different material, a material disperse | distributes uniformly and becomes advantageous to a dielectric breakdown. Such an insulator layer 20 is performed by the following plasma spraying method. That is, after a blasting process is performed on the processing range (cylindrical metal roll body), it is applied by a plasma spraying method. In order to withstand a voltage of several hundred volts with a thin film thickness, it is necessary to perform thermal spraying with a uniform film pressure without any unevenness. For this purpose, the cylindrical metal roll is rotated at a certain rotation speed (for example, 20 RPM) using a turntable, and the spray gun is attached at a position where the angle is orthogonal to the cylindrical metal roll body, and the cylindrical metal roll is mounted. Traverse in the axial direction of the roll at a constant speed (for example, 1.5 mm / sec). Moreover, a gravity drop type hopper is used so that the powder supply amount becomes constant.

After the spraying step, cylindrical grinding is performed in order to make the film thickness a predetermined film thickness and smooth the surface. As the grindstone, a hard abrasive grain having a particle diameter of 1 mm or less is hardened with a bond to form a disk, which is rotated and brought into contact with the workpiece surface for grinding. In the grinding of the cylindrical roll of the present invention, the cylindrical roll is fixed at the axis, and the cylindrical roll and the grindstone are rotated and brought into contact with each other. The surface roughness after processing can be reduced by setting the remarkably fast speed and setting the cutting allowance as small as about several μm.

Moreover, it is preferable that the dielectric breakdown voltage per 100 micrometers of film thickness of the insulator layer 20 is 500 V / 100 micrometers or more. Thereby, in a stable applied voltage condition that does not cause dielectric breakdown,
The above-mentioned Janssen-Rahbek force can be satisfactorily exhibited.

Further, the cylindrical roll has a standard deviation of the titanium element concentration in each region divided by a square lattice with 10 μm as one side in an arbitrary cross section of the insulator layer 20 perpendicular to its circumferential direction. % And the coefficient of variation is preferably less than 2.0. Thereby, the titanium element can be dispersed relatively uniformly in the insulator layer 20, the dielectric breakdown voltage can be made higher than the above-mentioned numerical value, and the sheet 1 can be cooled well.

Furthermore, it is preferable to apply a mirror finish to the surface of the insulator layer 20 or the surface of the metal roll,
The surface roughness Ra of the surface of the insulator layer 20 is preferably 0.01 to 0.1 μm, and the surface roughness Ra of the surface of the metal roll before thermal spraying is preferably in the range of 1 to 3 μm. Processing costs are required to perform cylindrical grinding with the surface roughness Ra of the surface of the insulator layer 20 being smaller than 0.01 μm. On the other hand, if it is larger than 0.1 μm, a sufficient contact area with the sheet 1 cannot be secured, and local heat loss may occur. The surface roughness Ra of the metal roll surface before spraying is 3 μm.
When it is larger than m, the thickness unevenness of the sprayed coating becomes large, and local dielectric breakdown is likely to occur. On the other hand, when the thickness is smaller than 1 μm, the adhesive strength between the thermal spray coating and the metal roll becomes weak, and the film may peel off.

Further, FIG. 6 shows a schematic cross-sectional view of one embodiment of a winding type double-sided vapor deposition apparatus including a sheet guide surface coated with the insulator layer of the present invention. In FIG. 6, only the main part is shown, and the vacuum chamber and the intermediate roll for housing the structure are omitted. In addition, the same number is attached | subjected to the component which has the same or equivalent function as FIG. 1-1, and detailed description is abbreviate | omitted. 6 includes a sheet guide surface 3 that conveys the sheet 1 while being in contact with the sheet 1, and a crucible 7 that evaporates metal vapor toward the sheet 1 on the sheet guide surface 3 (evaporation). Two sources are provided. In such an apparatus, a sheet 1 that has not yet been deposited is a raw roll 2
The metal vapor 10 and the oxygen nozzle 17 evaporated from the crucible 7 are conveyed while being wound around the sheet guide surface 3 which is a metal surface not provided with an insulator layer.
The first metal oxide thin film 13 is formed on the surface of the sheet 1 due to oxygen introduced from. Thereafter, the intermediate sheet is conveyed to the second sheet guide surface 3 whose surface is covered with the insulator layer 20, and the second metal oxide thin film 14 is formed on the other surface of the sheet 1. The sheet 1 on which the first thin film 13 and the second thin film 14 are vapor-deposited is wound around the winding roll body 6. Such a double-sided vapor deposition device has the advantage that it can be vapor-deposited on both sides in one process,
In the prior art, the second is particularly the case when the sheet 1 is thin or the second thin film 14 is thick.
Since heat loss is likely to occur during the deposition of the thin film, the deposition is performed at such a low rate that heat loss does not occur during the deposition of the second thin film. Therefore, the manufacturing apparatus of FIG. 6 in which the sheet guide surface 3 having the peripheral surface coated with the insulator layer 20 of the present invention is applied to the deposition of the second thin film may take advantage of the double-sided vapor deposition apparatus.

Further, by applying the sheet guide surface 3 coated with the insulator layer 20 of the present invention described above to the metal oxide thin film formation on both surfaces of the sheet 1, it can be used for a base film for magnetic tape, for example. A sheet having strength and dimensional stability can be obtained.

  The measurement method and detection method of heat loss used in this example are shown below.

(1) Thickness of thin film Cross-sectional observation was performed under the following conditions, and the average value of the thicknesses 9 nm in total obtained was calculated as the thickness [nm] of the metal oxide thin film.
Measuring device: Transmission electron microscope (TEM) H-7100FA type Hitachi measurement conditions: Acceleration voltage 100 [kV]
Measurement magnification: 200,000 times Sample preparation: Observation surface of ultrathin film section method: TD-ZD cross-section measurement count: 3 points per field and 3 fields were measured.

(2) Surface resistance value of thin film Since the measurable apparatus differs depending on the range of the surface resistance value, first, measurement is performed by the method of i), and the sample of the surface resistance value which is too low to be measured is the method of ii) Measured with The average value of the five measurement results was defined as the surface resistance value in the present invention.
i) High resistivity measurement Measured using the following measuring device in accordance with JIS-C2151 (1990).
Measuring device: Digital ultrahigh resistance / microammeter R8340 Advantest Co., Ltd. Applied voltage: 100 [V]
Application time: 10 seconds Measurement unit: Ω
Measurement environment: Temperature 23 ° C Humidity 65% RH
Number of measurements: Measure 5 times.
ii) Low resistivity measurement Measured using the following measuring device in accordance with JIS-K7194 (1994).
Measuring device: Lorester EP MCP-T360 Mitsubishi Chemical Measuring Environment: Temperature 23 ° C Humidity 65% RH
Number of measurements: Measure 5 times.

(3) Total light transmittance of sheet with thin film A sample was set in a “haze computer HZ-1” apparatus manufactured by Suga Test Instruments Co., Ltd., and the total light transmittance was measured. The measurement was performed 5 times, and the average value was defined as the total light transmittance in the present invention.

(4) Volume Resistance of Insulator Layer on Sheet Guide Surface By the method shown in FIG. 5, the conditions of the measurement electrode 61 and the measurement DC power source 62 are set under the following conditions. The volume resistance distribution was measured at a total of 50 points including 10 points in the circumferential direction and 5 points in the axial direction. An electrometer 6517A manufactured by KEITHLEY was used for the DC power source 62 for measurement and the minute ammeter 63.
Measurement electrode: An aluminum foil having a thickness of 15 [μm] was cut into a 3 [cm] × 3 [cm] square and fixed with vinyl tape so as to be in close contact with the peripheral surface of the insulator layer.
-Applied voltage: 500 V (If the dielectric breakdown phenomenon described later in (8) is observed at 500 V, the volume resistance is measured by reducing the voltage to a point where dielectric breakdown does not occur.)

(5) Covering thickness of the insulator layer on the sheet guide surface With the outside micrometer, the diameter of the sheet guide surface before covering the insulator layer is 2 in the circumferential direction and 3 in the axial direction. Measure. After coating the insulator layer, the same position 6
The diameter of each part was measured, and the coating thickness of the insulating layer was determined from the average of the diameter increments before and after coating.

In the examples and comparative examples described below, the winding type vacuum vapor deposition apparatus shown in FIGS. 3 and 9 is used to coat and deposit the insulator layer of the present invention on the surface of the sheet guide surface. Example 1
To Example 4), when vapor-deposited without covering the insulator layer (Comparative Example 1), when vapor-deposited while covering the insulator layer of the prior art (Comparative Example 2), the insulator layer is a powder of alumina and titania When the volume resistance, titanium element concentration, and variation coefficient of titanium element concentration of the insulator layer deviate from the scope of the present application (Comparative Example 3), the volume of the insulator layer is formed. When the resistance, the titanium element concentration, the standard deviation of the titanium element concentration, and the variation coefficient deviate from the scope of the present application (Comparative Example 4), the case where the second aluminum oxide thin film is deposited is compared.

(6) Heat Loss Detection Method The sheet color after vapor deposition is run at a speed of several [m / min] so that it passes in front of the planar light source, and the color of the sheet is observed while observing the light of the planar light source passing through the sheet Observe unevenness and wrinkles visually. The sheet is observed for a length of 100 [m]. A portion having a deep color (low transmittance) or a thin portion (high transmittance) is cut out locally. The cut sheet piece is gently placed on a desk, and if there is a wrinkled sheet deformation starting from a dark or light part, it is determined that the heat is lost.

(7) Measurement of dispersion of titanium element in insulator layer, etc. SEM-EDX method (scanning electron microscope-energy dispersive X-ray spectroscopy) is used to analyze the cross section of the sprayed coating and extract only the titanium element distribution. A cross-sectional photograph was taken. As the sample, a sample coated with a thermal spray coating is cut into an appropriate size with a wet cutting machine, embedded in a resin with an epoxy resin, and then wet-polished so that the observation surface becomes a mirror surface. JSM5600V made by JEOL Ltd. was used for SEM, and INCAEnergy made by Oxford Instruments was used for EDX. In this photo, the titanium element portion appears white and the other elements appear dark. From this photograph, an image of the insulator layer region in the circumferential direction of 250 μm was extracted and stored in a gray scale mode. In this case, the circumferential direction of 250 μm corresponds to 220 images. This image is read by image processing software Matrox Inspector Ver.2.2, and this image is converted into two gradations to obtain a monochrome image (see FIGS. 11 and 12, FIG. 11 is [Example 2], and FIG. 12 is [Comparative Example 3]). ). At this time, the threshold value for the two gradations is set so that the ratio of the white portion (titanium element) of the image after the two gradations becomes the same as the titanium element ratio detected by the previous EDX method. An area of 10 μm × 10 μm was extracted from the edge of this image, and the ratio of the white image area was calculated in the same manner. This operation was performed over the entire insulator layer image. The average [%], the standard deviation [%], and the coefficient of variation obtained by dividing the standard deviation by the average value were calculated. This standard deviation and coefficient of variation are parameters indicating the degree of dispersion of the titanium element present in the insulator layer. When this value is small, it is indicated that the titanium element is present relatively uniformly in the insulator layer. means.

(8) Dielectric breakdown voltage of the insulator layer By the method shown in FIG. 5, the measurement electrode 61 is fixed under the following conditions, the conditions of the measurement DC power supply 62 are set, the circumferential direction of the insulator layer is 10 points, and the axial direction is 5 The current flowing through the insulator layer at a total of 50 points was measured. As the DC current 62 for measurement and the minute ammeter 63, an electrometer 6517A manufactured by KEITHLEY was used. When the voltage is increased by 100 V at each measurement location and the current measurement display flows 1 mA or more, or when “Overflow” is displayed, the insulation is not maintained at that location and the insulation breaks down. It was judged.
Measurement electrode: An aluminum foil having a thickness of 15 [μm] was cut into a square of 3 [cm] × 3 [cm] and fixed with vinyl tape so as to be in close contact with the peripheral surface of the insulator layer.
・ Applied voltage: 100V to 500V (Increase in increments of 100V)
・ Measurement locations: 4 locations in the circumferential direction and 5 locations in the axial direction for a total of 20 locations

(9) Surface roughness of metal roll before thermal spraying and cylindrical roll after thermal spraying Using a contact-type surface roughness meter, blasting was performed with a reference length and an evaluation length specified in JIS B0633 (2001). The surface roughness of the metal roll before subsequent thermal spraying and the surface roughness of the cylindrical roll after thermal spraying and cylindrical grinding were measured. As a measuring instrument, a small surface roughness shape measuring machine Surfcom 130A manufactured by Tokyo Seimitsu Co., Ltd. was used, and a total of 12 locations were measured, 4 in the circumferential direction of the cylindrical roll and 3 in the axial direction.

[Example 1]
As a sheet, a polyethylene terephthalate film having a thickness of 5 [μm] and a width of 1100 [mm] (“Lumirror” manufactured by Toray Industries, Inc.) is used, and a winding type vacuum deposition apparatus shown in FIG. 9 is used. An aluminum oxide thin film was vapor-deposited, and then an aluminum oxide thin film was vapor-deposited on the other surface under the vapor deposition conditions shown below using a winding vacuum vapor deposition apparatus shown in FIG. FIG. 9 shows a metal sheet guide surface and a first thin film 13 that do not cover the insulator layer of the prior art.
It is the schematic which showed the vapor deposition method which applies a voltage between.

(First aluminum oxide thin film)
・ Thin film material: Aluminum oxide film ・ Film thickness: 60 [nm]
-Light transmittance: 25 [%]
・ Surface resistance: 2.3 × 10 ³ [Ω / □]

(Deposition conditions for the second aluminum oxide thin film)
Evaporation source container: Alumina crucible Evaporation source heating method: Heating with an electron gun Evaporation material: Aluminum Shortest distance between the evaporation source crucible and the sheet guide surface: 450 [mm]
-Mask opening length in the film transport direction: 350 [mm]
-Mask opening length in the film width direction: 1000 [mm]
Oxygen nozzle: nozzles in which holes of Φ2 [mm] are arranged at equal intervals of 20 [mm] pitches in the sheet width direction at the positions shown in FIG. 1
A formula was set up.

(Sheet guide surface conditions)
As shown in FIG. 3, a cylindrical sheet guide surface was used. 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.
-Diameter of cylindrical sheet guide surface: 1000 [mm]
・ Temperature of medium flowing inside the sheet guide surface: -20 [℃]
-Applied voltage between the sheet guide surface and the thin film: 200 [V]
・ Current limiting resistance between the sheet guide surface and the thin film: 100 [kΩ]

(Insulator layer conditions)
An insulating layer having the following conditions was coated on the peripheral surface of the sheet guide surface by a plasma spraying method.
・ Insulator layer material: Alumina and chromia mixture ・ Coating thickness: 102 [μm]
Volume resistance: 2.6 × 10 ^{9 to} 3.3 × 10 ⁹ [Ωcm]

(Formation of metal oxide thin film)
A film roll on which the first aluminum oxide thin film has already been deposited on one surface is set on the raw roll body 2 in FIG. The film end was pasted and set on the roll 6. The apparatus has an alumina crucible 7 having a volume of 150 [mm] in the sheet conveying direction and 1500 [mm] in the sheet width direction.
Are arranged so that the longitudinal direction of the crucible 7 is the same as the film width direction, and the metal material 8
As an aluminum, 20 kg was set. Then, the winding chamber 41a and the film forming chamber 41b of the vapor deposition machine were depressurized, and the vacuum pressure in the film forming chamber 41b was exhausted to 5 × 10 ⁻³ [Pa]. Thereafter, the aluminum in the crucible 7 was melted by the electron gun heating method with the shutter member 51 closed. The electric power input was 75 [kW]. After confirming that all the aluminum material was melted, the electric power of the electron gun was finely adjusted to about 65 [kW]. The tension of the raw roll body 2 is set to 140 [N], the tension of the take-up roll body 6 is set to 140 [N], and the speed of the sheet guide surface 3 and the intermediate rollers 4 and 5 is set to 150 [m / min]. The conveyance of the film was started at a speed. Thereafter, aluminum was deposited by opening the shutter member 51. In this state, the film formation chamber 41
The pressure of b was 2.0 × 10 ⁻² [Pa]. Thereafter, the amount of oxygen introduced from the upstream and downstream oxygen nozzles 17 in the crucible sheet conveyance direction was increased to 28 [l / min].
As the oxygen was introduced, the pressure in the film forming chamber 41b became 2.5 × 10 ⁻² [Pa]. In this state, film winding and conveyance for 11000 [m] was performed at a conveyance speed of 150 [m / min] to form a second aluminum oxide thin film. Thereafter, the shutter member 51 was closed to stop the introduction of oxygen, and the power supply to the electron gun for heating the evaporation source was cut off. And the conveyance speed was lowered to 5 [m / min], and the pressure release of the winding chamber 41a and the film-forming chamber 41b was performed.

The average film thickness in the sheet width direction of the second aluminum oxide thin film thus formed is 95 [nm.
The surface resistance value was 2.7 × 10 ³ [Ω / □]. Further, no wrinkled heat loss was observed in the film after film formation. If the film formation rate at this time is calculated from the above-mentioned conditions, 6
80 [nm / sec].

[Example 2]
As a sheet, a polyethylene terephthalate film having a thickness of 5 [μm] and a width of 1100 [mm] (“Lumirror” manufactured by Toray Industries, Inc.) is used, and a winding type vacuum deposition apparatus shown in FIG. 9 is used. An aluminum oxide thin film was vapor-deposited, and then an aluminum oxide thin film was vapor-deposited on the other surface under the vapor deposition conditions shown below using a winding vacuum vapor deposition apparatus shown in FIG. FIG. 9 shows a metal sheet guide surface and a first thin film 13 that do not cover the insulator layer of the prior art.
It is the schematic which showed the vapor deposition method which applies a voltage between.

(First aluminum oxide thin film)
・ Thin film material: Aluminum oxide film ・ Film thickness: 60 [nm]
-Light transmittance: 25 [%]
・ Surface resistance: 2.3 × 10 ³ [Ω / □]

(Deposition conditions for the second aluminum oxide thin film)
Evaporation source container: Alumina crucible Evaporation source heating method: Heating with an electron gun Evaporation material: Aluminum Shortest distance between the evaporation source crucible and the sheet guide surface: 450 [mm]
-Mask opening length in the film transport direction: 350 [mm]
-Mask opening length in the film width direction: 1000 [mm]
Oxygen nozzle: nozzles in which holes of Φ2 [mm] are arranged at equal intervals of 20 [mm] pitches in the sheet width direction at the positions shown in FIG. 1
A formula was set up.

(Sheet guide surface conditions)
As shown in FIG. 3, a cylindrical sheet guide surface was used. 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.
-Diameter of cylindrical sheet guide surface: 1000 [mm]
・ Temperature of medium flowing inside the sheet guide surface: -20 [℃]
-Applied voltage between the sheet guide surface and the thin film: 200 [V]
・ Current limiting resistance between the sheet guide surface and the thin film: 100 [kΩ]

(Insulator layer conditions)
An insulating layer having the following conditions was coated on the peripheral surface of the sheet guide surface by a plasma spraying method.
-Insulator layer material: Granulated powder material of alumina and titania (ratio of titania: 10.1 wt%
)
・ Coating thickness: 102 [μm]
Volume resistance: 2.8 × 10 ^{9 to} 3.6 × 10 ⁹ [Ωcm]
・ Titanium element concentration (SEM-EDX method): 3.6 at%
Standard deviation of titanium element concentration (see FIG. 10): 6.5
-Coefficient of variation of titanium element concentration: 1.8
・ Dielectric breakdown voltage: 500 V or more ・ Surface roughness (Ra): 0.07 μm
-Metal roll surface roughness (Ra) before spraying: 2.3 μm

(Formation of metal oxide thin film)
A film roll on which the first aluminum oxide thin film has already been deposited on one surface is set on the raw roll body 2 in FIG. The film end was pasted and set on the roll 6. The apparatus has an alumina crucible 7 having a volume of 150 [mm] in the sheet conveying direction and 1500 [mm] in the sheet width direction.
Are arranged so that the longitudinal direction of the crucible 7 is the same as the film width direction, and the metal material 8
As an aluminum, 20 kg was set. Then, the winding chamber 41a and the film forming chamber 41b of the vapor deposition machine were depressurized, and the vacuum pressure in the film forming chamber 41b was exhausted to 5 × 10 ⁻³ [Pa]. Thereafter, the aluminum in the crucible 7 was melted by the electron gun heating method with the shutter member 51 closed. The electric power input was 75 [kW]. After confirming that all the aluminum material was melted, the electric power of the electron gun was finely adjusted to about 65 [kW]. The tension of the raw roll body 2 is set to 140 [N], the tension of the take-up roll body 6 is set to 140 [N], and the speed of the sheet guide surface 3 and the intermediate rollers 4 and 5 is set to 150 [m / min]. The conveyance of the film was started at a speed. Thereafter, aluminum was deposited by opening the shutter member 51. In this state, the film formation chamber 41
The pressure of b was 2.0 × 10 ⁻² [Pa]. Thereafter, the amount of oxygen introduced from the upstream and downstream oxygen nozzles 17 in the crucible sheet conveyance direction was increased to 28 [l / min].
As the oxygen was introduced, the pressure in the film forming chamber 41b became 2.5 × 10 ⁻² [Pa]. In this state, film winding and conveyance for 11000 [m] was performed at a conveyance speed of 150 [m / min] to form a second aluminum oxide thin film. Thereafter, the shutter member 51 was closed to stop the introduction of oxygen, and the power supply to the electron gun for heating the evaporation source was cut off. And the conveyance speed was lowered to 5 [m / min], and the pressure release of the winding chamber 41a and the film-forming chamber 41b was performed.
The average film thickness in the sheet width direction of the second aluminum oxide thin film thus formed is 93 [nm].
The surface resistance value was 2.4 × 10 ³ [Ω / □]. Further, no wrinkled heat loss was observed in the film after film formation. If the film formation rate at this time is calculated from the above-mentioned conditions, 66
4 [nm / sec].

[Example 3]
As a sheet, a polyethylene terephthalate film having a thickness of 5 [μm] and a width of 1100 [mm] (“Lumirror” manufactured by Toray Industries, Inc.) is used, and a winding type vacuum deposition apparatus shown in FIG. 9 is used. An aluminum oxide thin film was vapor-deposited, and then an aluminum oxide thin film was vapor-deposited on the other surface under the vapor deposition conditions shown below using a winding vacuum vapor deposition apparatus shown in FIG. FIG. 9 shows a metal sheet guide surface and a first thin film 13 that do not cover the insulator layer of the prior art.
It is the schematic which showed the vapor deposition method which applies a voltage between.

(First aluminum oxide thin film)
・ Thin film material: Aluminum oxide film ・ Film thickness: 60 [nm]
-Light transmittance: 25 [%]
・ Surface resistance: 2.3 × 10 ³ [Ω / □]

(Deposition conditions for the second aluminum oxide thin film)
Evaporation source container: Alumina crucible Evaporation source heating method: Heating with an electron gun Evaporation material: Aluminum Shortest distance between the evaporation source crucible and the sheet guide surface: 450 [mm]
-Mask opening length in the film transport direction: 350 [mm]
-Mask opening length in the film width direction: 1000 [mm]
Oxygen nozzle: nozzles in which holes of Φ2 [mm] are arranged at equal intervals of 20 [mm] pitches in the sheet width direction at the positions shown in FIG. 1
A formula was set up.

(Sheet guide surface conditions)
As shown in FIG. 3, a cylindrical sheet guide surface was used. 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.
-Diameter of cylindrical sheet guide surface: 1000 [mm]
・ Temperature of medium flowing inside the sheet guide surface: -20 [℃]
-Applied voltage between the sheet guide surface and the thin film: 200 [V]
・ Current limiting resistance between the sheet guide surface and the thin film: 100 [kΩ]

(Insulator layer conditions)
An insulating layer having the following conditions was coated on the peripheral surface of the sheet guide surface by a plasma spraying method.
-Insulator layer material: Granulated powder material of alumina and titania (ratio of titania: 8.7 wt%)
・ Coating thickness: 48 [μm]
Volume resistance: 6.8 × 10 ^{10 to} 9.5 × 10 ¹⁰ [Ωcm]
・ Titanium element concentration (SEM-EDX method): 2.5 at%
Standard deviation of titanium element concentration (see FIG. 11): 4.4
-Coefficient of variation of titanium element concentration: 1.8
・ Dielectric breakdown voltage: 500 V or more ・ Surface roughness (Ra): 0.07 μm
-Metal roll surface roughness (Ra) before spraying: 2.5 μm

(Formation of metal oxide thin film)
A film roll on which the first aluminum oxide thin film has already been deposited on one surface is set on the raw roll body 2 in FIG. The film end was pasted and set on the roll 6. The apparatus has an alumina crucible 7 having a volume of 150 [mm] in the sheet conveying direction and 1500 [mm] in the sheet width direction.
Are arranged so that the longitudinal direction of the crucible 7 is the same as the film width direction, and the metal material 8
As an aluminum, 20 kg was set. Then, the winding chamber 41a and the film forming chamber 41b of the vapor deposition machine were depressurized, and the vacuum pressure in the film forming chamber 41b was exhausted to 5 × 10 ⁻³ [Pa]. Thereafter, the aluminum in the crucible 7 was melted by the electron gun heating method with the shutter member 51 closed. The electric power input was 75 [kW]. After confirming that all the aluminum material was melted, the electric power of the electron gun was finely adjusted to about 65 [kW]. The tension of the raw roll body 2 is set to 140 [N], the tension of the take-up roll body 6 is set to 140 [N], and the speed of the sheet guide surface 3 and the intermediate rollers 4 and 5 is set to 150 [m / min]. The conveyance of the film was started at a speed. Thereafter, aluminum was deposited by opening the shutter member 51. In this state, the film formation chamber 41
The pressure of b was 2.0 × 10 ⁻² [Pa]. Thereafter, the amount of oxygen introduced from the upstream and downstream oxygen nozzles 17 in the crucible sheet conveyance direction was increased to 28 [l / min].
As the oxygen was introduced, the pressure in the film forming chamber 41b became 2.5 × 10 ⁻² [Pa]. In this state, film winding and conveyance for 11000 [m] was performed at a conveyance speed of 150 [m / min] to form a second aluminum oxide thin film. Thereafter, the shutter member 51 was closed to stop the introduction of oxygen, and the power supply to the electron gun for heating the evaporation source was cut off. And the conveyance speed was lowered to 5 [m / min], and the pressure release of the winding chamber 41a and the film-forming chamber 41b was performed. The average film thickness in the sheet width direction of the second aluminum oxide thin film thus formed is 97 [nm], and the surface resistance value is 2.7 × 10 ³ [Ω.
/ □]. Further, no wrinkled heat loss was observed in the film after film formation. Note that the film formation rate at this time is 693 [nm / sec] when calculated from the above-described conditions.

[Example 4]
As a sheet, a polyethylene terephthalate film having a thickness of 5 [μm] and a width of 1100 [mm] (“Lumirror” manufactured by Toray Industries, Inc.) is used, and a winding type vacuum deposition apparatus shown in FIG. 9 is used. An aluminum oxide thin film was vapor-deposited, and then an aluminum oxide thin film was vapor-deposited on the other surface under the vapor deposition conditions shown below using a winding vacuum vapor deposition apparatus shown in FIG. FIG. 9 shows a metal sheet guide surface and a first thin film 13 that do not cover the insulator layer of the prior art.
It is the schematic which showed the vapor deposition method which applies a voltage between.

(First aluminum oxide thin film)
・ Thin film material: Aluminum oxide film ・ Film thickness: 60 [nm]
-Light transmittance: 25 [%]
・ Surface resistance: 2.3 × 10 ³ [Ω / □]

(Deposition conditions for the second aluminum oxide thin film)
Evaporation source container: Alumina crucible Evaporation source heating method: Heating with an electron gun Evaporation material: Aluminum Shortest distance between the evaporation source crucible and the sheet guide surface: 450 [mm]
-Mask opening length in the film transport direction: 350 [mm]
-Mask opening length in the film width direction: 1000 [mm]
Oxygen nozzle: nozzles in which holes of Φ2 [mm] are arranged at equal intervals of 20 [mm] pitches in the sheet width direction at the positions shown in FIG. 1
A formula was set up.

(Sheet guide surface conditions)
As shown in FIG. 3, a cylindrical sheet guide surface was used. 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.
-Diameter of cylindrical sheet guide surface: 1000 [mm]
・ Temperature of medium flowing inside the sheet guide surface: -20 [℃]
-Applied voltage between the sheet guide surface and the thin film: 200 [V]
・ Current limiting resistance between the sheet guide surface and the thin film: 100 [kΩ]

(Insulator layer conditions)
An insulating layer having the following conditions was coated on the peripheral surface of the sheet guide surface by a plasma spraying method.
-Insulator layer material: Granulated powder material of alumina and titania (ratio of titania: 14.0 wt%
)
・ Coating thickness: 178 [μm]
Volume resistance: 3.8 × 10 ^{8 to} 7.1 × 10 ⁸ [Ωcm]
・ Titanium element concentration (SEM-EDX method): 3.9 at%
Standard deviation of titanium element concentration (see FIG. 12): 5.3
-Coefficient of variation of titanium element concentration: 1.4
・ Dielectric breakdown voltage: 500 V or more ・ Surface roughness (Ra): 0.07 μm
-Metal roll surface roughness (Ra) before spraying: 2.6 μm

(Formation of metal oxide thin film)
A film roll on which the first aluminum oxide thin film has already been deposited on one surface is set on the raw roll body 2 in FIG. The film end was pasted and set on the roll 6. The apparatus has an alumina crucible 7 having a volume of 150 [mm] in the sheet conveying direction and 1500 [mm] in the sheet width direction.
Are arranged so that the longitudinal direction of the crucible 7 is the same as the film width direction, and the metal material 8
As an aluminum, 20 kg was set. Then, the winding chamber 41a and the film forming chamber 41b of the vapor deposition machine were depressurized, and the vacuum pressure in the film forming chamber 41b was exhausted to 5 × 10 ⁻³ [Pa]. Thereafter, the aluminum in the crucible 7 was melted by the electron gun heating method with the shutter member 51 closed. The electric power input was 75 [kW]. After confirming that all the aluminum material was melted, the electric power of the electron gun was finely adjusted to about 65 [kW]. The tension of the raw roll body 2 is set to 140 [N], the tension of the take-up roll body 6 is set to 140 [N], and the speed of the sheet guide surface 3 and the intermediate rollers 4 and 5 is set to 150 [m / min]. The conveyance of the film was started at a speed. Thereafter, aluminum was deposited by opening the shutter member 51. In this state, the film formation chamber 41
The pressure of b was 2.0 × 10 ⁻² [Pa]. Thereafter, the amount of oxygen introduced from the upstream and downstream oxygen nozzles 17 in the crucible sheet conveyance direction was increased to 28 [l / min].
As the oxygen was introduced, the pressure in the film forming chamber 41b became 2.5 × 10 ⁻² [Pa]. In this state, film winding and conveyance for 11000 [m] was performed at a conveyance speed of 150 [m / min] to form a second aluminum oxide thin film. Thereafter, the shutter member 51 was closed to stop the introduction of oxygen, and the power supply to the electron gun for heating the evaporation source was cut off. And the conveyance speed was lowered to 5 [m / min], and the pressure release of the winding chamber 41a and the film-forming chamber 41b was performed. The average film thickness in the sheet width direction of the second aluminum oxide thin film thus formed was 92 [nm], and the surface resistance value was 2.2 × 10 ³ [Ω.
/ □]. Further, no wrinkled heat loss was observed in the film after film formation. If the film formation rate at this time is calculated from the above-mentioned conditions, it becomes 657 [nm / sec].

[Comparative Example 1]
As a sheet, a polyethylene terephthalate film having a thickness of 5 [μm] and a width of 1100 [mm] (“Lumirror” manufactured by Toray Industries, Inc.) is used, and a winding type vacuum deposition apparatus shown in FIG. 9 is used. The 1st aluminum oxide thin film was vapor-deposited, and the 2nd aluminum oxide thin film was vapor-deposited also on the other surface on the other surface using the winding type vacuum vapor deposition apparatus similarly shown in FIG.

(First aluminum oxide thin film)
・ Thin film material: Aluminum oxide film ・ Film thickness: 60 [nm]
-Light transmittance: 25 [%]
・ Surface resistance: 2.3 × 10 ³ [Ω / □]

(Deposition conditions for the second aluminum oxide thin film)
Evaporation source container: Alumina crucible Evaporation source heating method: Heating with an electron gun Evaporation material: Aluminum Shortest distance between the evaporation source crucible and the sheet guide surface: 450 [mm]
-Mask opening length in the film transport direction: 350 [mm]
-Mask opening length in the film width direction: 1000 [mm]
Oxygen nozzle: nozzles in which holes of Φ2 [mm] are arranged at equal intervals of 20 [mm] pitches in the sheet width direction at the positions shown in FIG. 1
A formula was set up.

(Sheet guide surface conditions)
As shown in FIG. 3, a cylindrical sheet guide surface was used. 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.
-Diameter of cylindrical sheet guide surface: 1000 [mm]
・ Temperature of medium flowing inside the sheet guide surface: -20 [℃]
-Hard chrome plating on the surface-Applied voltage between sheet guide surface and thin film: 200 [V]
・ Current limiting resistance between the sheet guide surface and the thin film: 100 [kΩ]

(Formation of metal oxide thin film)
A film roll on which the first aluminum oxide thin film has already been deposited on one surface is set on the raw roll body 2 in FIG. The film end was pasted and set on the roll 6. The apparatus has an alumina crucible 7 having a volume of 150 [mm] in the sheet conveying direction and 1500 [mm] in the sheet width direction.
Are arranged so that the longitudinal direction of the crucible 7 is the same as the film width direction, and the metal material 8
As an aluminum, 20 kg was set. Then, the winding chamber 41a and the film forming chamber 41b of the vapor deposition machine were depressurized, and the vacuum pressure in the film forming chamber 41b was exhausted to 5 × 10 ⁻³ [Pa]. Thereafter, the aluminum in the crucible 7 was melted by the electron gun heating method with the shutter member 51 closed. The electric power input was 75 [kW]. After confirming that all the aluminum material was melted, the electric power of the electron gun was finely adjusted to about 65 [kW]. The tension of the raw roll body 2 is set to 140 [N], the tension of the take-up roll body 6 is set to 140 [N], and the speed of the sheet guide surface 3 and the intermediate rollers 4 and 5 is set to 150 [m / min]. The conveyance of the film was started at a speed. Thereafter, aluminum was deposited by opening the shutter member 51. In this state, the film formation chamber 41
The pressure of b was 2.0 × 10 ⁻² [Pa]. Thereafter, the amount of oxygen introduced from the upstream and downstream oxygen nozzles 17 in the crucible sheet conveyance direction was increased to 28 [l / min].
As the oxygen was introduced, the pressure in the film forming chamber 41b became 2.5 × 10 ⁻² [Pa]. In this state, when the film transport state after vapor deposition was observed with a viewing window (not shown), remarkable wrinkle-like heat loss was observed in the entire width of the film, so that the vapor deposition was temporarily terminated with the shutter member 51 closed. Thereafter, the amount of electric power of the electron gun was adjusted to about 45 [kW], the sheet conveyance speed was set to 70 [m / min], and then the shutter member 51 was opened again to perform aluminum deposition. In this state, the pressure in the film forming chamber 41b was 2.0 × 10 ⁻² [Pa]. Thereafter, the amount of oxygen introduced from the upstream and downstream oxygen nozzles 17 in the crucible sheet conveyance direction was increased to 8 [l / min]. The pressure in the film forming chamber 41b is 2.2 × 1 as oxygen is introduced.
0 ⁻² [Pa]. Film winding conveyance for 10000 [m], conveyance speed 70 [m /
Minutes] to form a second aluminum oxide thin film. Thereafter, the shutter member 51 was closed to stop the introduction of oxygen, and the power supply to the electron gun for heating the evaporation source was cut off. And the conveyance speed was lowered to 5 [m / min], and the pressure release of the winding chamber 41a and the film-forming chamber 41b was performed.

The average film thickness in the sheet width direction of the second aluminum oxide thin film thus formed is 75 [nm.
The surface resistance value was 3.3 × 10 ³ [Ω / □]. Moreover, the film after film-forming showed weak wrinkle-like heat loss. Note that when the film formation rate at this time is calculated from the above-mentioned conditions,
180 [nm / sec].

[Comparative Example 2]
As a sheet, a polyethylene terephthalate film having a thickness of 5 [μm] and a width of 1100 [mm] (“Lumirror” manufactured by Toray Industries, Inc.) is used, and a winding type vacuum deposition apparatus shown in FIG. 9 is used. The 1st aluminum oxide thin film was vapor-deposited, and the 2nd aluminum oxide thin film was vapor-deposited on the other surface on the other surface using the winding type vacuum vapor deposition apparatus shown in FIG.

(First aluminum oxide thin film)
・ Thin film material: Aluminum oxide film ・ Film thickness: 60 [nm]
-Light transmittance: 25 [%]
・ Surface resistance: 2.3 × 10 ³ [Ω / □]

(Deposition conditions for the second aluminum oxide thin film)
Evaporation source container: Alumina crucible Evaporation source heating method: Heating with an electron gun Evaporation material: Aluminum Shortest distance between the evaporation source crucible and the sheet guide surface: 450 [mm]
-Mask opening length in the film transport direction: 350 [mm]
-Mask opening length in the film width direction: 1000 [mm]
Oxygen nozzle: nozzles in which holes of Φ2 [mm] are arranged at equal intervals of 20 [mm] pitches in the sheet width direction at the positions shown in FIG. 1
A formula was set up.

(Sheet guide surface conditions)
As shown in FIG. 3, a cylindrical sheet guide surface was used. 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.
-Diameter of cylindrical sheet guide surface: 1000 [mm]
・ Temperature of medium flowing inside the sheet guide surface: -20 [℃]
-Applied voltage between sheet guide surface and thin film: 400 [V]

(Insulator layer conditions)
An insulating layer having the following conditions was coated on the peripheral surface of the sheet guide surface by a plasma spraying method.
Insulator layer material: Alumina Coating thickness: 110 [μm]
Volume resistance: 5.9 × 10 ^{12 to} 2.1 × 10 ¹³ [Ωcm]
・ Dielectric breakdown voltage: 500 V or more ・ Surface roughness (Ra): 0.09 μm
-Metal roll surface roughness (Ra) before thermal spraying: 5.4 μm

(Formation of metal oxide thin film)
A film roll on which the first aluminum oxide thin film has already been deposited on one surface is set on the raw roll body 2 in FIG. The film end was pasted and set on the roll 6. The apparatus has an alumina crucible 7 having a volume of 150 [mm] in the sheet conveying direction and 1500 [mm] in the sheet width direction.
Are arranged so that the longitudinal direction of the crucible 7 is the same as the film width direction, and the metal material 8
As an aluminum, 20 kg was set. Then, the winding chamber 41a and the film forming chamber 41b of the vapor deposition machine were depressurized, and the vacuum pressure in the film forming chamber 41b was exhausted to 5 × 10 ⁻³ [Pa]. Thereafter, the aluminum in the crucible 7 was melted by the electron gun heating method with the shutter member 51 closed. The electric power input was 75 [kW]. After confirming that all the aluminum material was melted, the electric power of the electron gun was finely adjusted to about 65 [kW]. The tension of the raw roll body 2 is set to 140 [N], the tension of the take-up roll body 6 is set to 140 [N], and the speed of the sheet guide surface 3 and the intermediate rollers 4 and 5 is set to 150 [m / min]. The conveyance of the film was started at a speed. Thereafter, aluminum was deposited by opening the shutter member 51. In this state, the film formation chamber 41
The pressure of b was 2.0 × 10 ⁻² [Pa]. Thereafter, the amount of oxygen introduced from the upstream and downstream oxygen nozzles 17 in the crucible sheet conveyance direction was increased to 28 [l / min].
As the oxygen was introduced, the pressure in the film forming chamber 41b became 2.5 × 10 ⁻² [Pa]. In this state, the film after vapor deposition was slightly weak but wrinkled heat loss was observed. Therefore, the electric energy of the electron gun was adjusted to about 53 [kW] while the shutter member 51 was left open, and the sheet was conveyed. When the speed was set to 110 [m / min] and the oxygen introduction amount was set to 18 [l / min], no heat loss was observed. In this state, the pressure in the film forming chamber 41b was 2.3 × 10 ⁻² [Pa].
In this state, film winding and conveyance for 10,000 [m] was performed at a conveyance speed of 100 [m / min] to form a second aluminum oxide thin film.

The average film thickness in the sheet width direction of the second aluminum oxide thin film thus formed is 75 [nm.
The surface resistance value was 4.0 × 10 ³ [Ω / □]. Further, in the longitudinal direction of the film after film formation, heat loss was partially observed at the same period as the circumference of the sheet guide surface. Note that the film formation rate at this time is 360 [nm / sec] when calculated from the above-described conditions.

[Comparative Example 3]
As a sheet, a polyethylene terephthalate film having a thickness of 5 [μm] and a width of 1100 [mm] (“Lumirror” manufactured by Toray Industries, Inc.) is used, and a winding type vacuum deposition apparatus shown in FIG. 9 is used. An aluminum oxide thin film was vapor-deposited, and then an aluminum oxide thin film was vapor-deposited on the other surface under the vapor deposition conditions shown below using a winding vacuum vapor deposition apparatus shown in FIG.

(First aluminum oxide thin film)
・ Thin film material: Aluminum oxide film ・ Film thickness: 60 [nm]
-Light transmittance: 25 [%]
・ Surface resistance: 2.3 × 10 ³ [Ω / □]

(Deposition conditions for the second aluminum oxide thin film)
Evaporation source container: Alumina crucible Evaporation source heating method: Heating with an electron gun Evaporation material: Aluminum Shortest distance between the evaporation source crucible and the sheet guide surface: 450 [mm]
-Mask opening length in the film transport direction: 350 [mm]
-Mask opening length in the film width direction: 1000 [mm]
Oxygen nozzle: nozzles in which holes of Φ2 [mm] are arranged at equal intervals of 20 [mm] pitches in the sheet width direction at the positions shown in FIG. 1
A formula was set up.

(Sheet guide surface conditions)
As shown in FIG. 3, a cylindrical sheet guide surface was used. 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.
-Diameter of cylindrical sheet guide surface: 1000 [mm]
・ Temperature of medium flowing inside the sheet guide surface: -20 [℃]
-Applied voltage between the sheet guide surface and the thin film: 200 [V]
・ Current limiting resistance between the sheet guide surface and the thin film: 100 [kΩ]

(Insulator layer conditions)
An insulating layer having the following conditions was coated on the peripheral surface of the sheet guide surface by a plasma spraying method.
-Insulator layer material: Mixed powder material of alumina and titania (ratio of titania: 5.2 wt%)
・ Coating thickness: 105 [μm]
Volume resistance: 8.5 × 10 ^{11 to} 2.5 × 10 ¹² [Ωcm]
・ Titanium element concentration (SEM-EDX method): 2.1 at%
Standard deviation of titanium element concentration (see FIG. 13): 5.2
-Coefficient of variation of titanium element concentration: 2.5
・ Dielectric breakdown voltage: 200 V or less ・ Surface roughness (Ra): 0.07 μm
-Metal roll surface roughness (Ra) before spraying: 2.6 μm

(Formation of metal oxide thin film)
Since dielectric breakdown was observed at 200 V or lower, formation of a metal oxide thin film was not achieved.

[Comparative Example 4]
As a sheet, a polyethylene terephthalate film having a thickness of 5 [μm] and a width of 1100 [mm] (“Lumirror” manufactured by Toray Industries, Inc.) is used, and a winding type vacuum deposition apparatus shown in FIG. 9 is used. An aluminum oxide thin film was vapor-deposited, and then an aluminum oxide thin film was vapor-deposited on the other surface under the vapor deposition conditions shown below using a winding vacuum vapor deposition apparatus shown in FIG.

(First aluminum oxide thin film)
・ Thin film material: Aluminum oxide film ・ Film thickness: 60 [nm]
-Light transmittance: 25 [%]
・ Surface resistance: 2.3 × 10 ³ [Ω / □]

(Deposition conditions for the second aluminum oxide thin film)
Evaporation source container: Alumina crucible Evaporation source heating method: Heating with an electron gun Evaporation material: Aluminum Shortest distance between the evaporation source crucible and the sheet guide surface: 450 [mm]
-Mask opening length in the film transport direction: 350 [mm]
-Mask opening length in the film width direction: 1000 [mm]
Oxygen nozzle: nozzles in which holes of Φ2 [mm] are arranged at equal intervals of 20 [mm] pitches in the sheet width direction at the positions shown in FIG. 1
A formula was set up.

(Sheet guide surface conditions)
As shown in FIG. 3, a cylindrical sheet guide surface was used. 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.
-Diameter of cylindrical sheet guide surface: 1000 [mm]
・ Temperature of medium flowing inside the sheet guide surface: -20 [℃]
-Applied voltage between the sheet guide surface and the thin film: 200 [V]
・ Current limiting resistance between the sheet guide surface and the thin film: 100 [kΩ]

(Insulator layer conditions)
An insulating layer having the following conditions was coated on the peripheral surface of the sheet guide surface by a plasma spraying method.
・ Insulator layer material: Granulated powder material of alumina and titania (ratio of titania: 16 wt%)
・ Coating thickness: 210 [μm]
Volume resistance: 2.5 × 10 ^{7 to} 4.9 × 10 ⁷ [Ωcm]
・ Titanium element concentration (SEM-EDX method): 4.2 at%
Standard deviation of titanium element concentration (see FIG. 14): 9.6
-Coefficient of variation of titanium element concentration: 2.3
・ Dielectric breakdown voltage: 200 V or less ・ Surface roughness (Ra): 0.07 μm
-Metal roll surface roughness (Ra) before spraying: 1.5 μm

(Formation of metal oxide thin film)
Since dielectric breakdown was observed at 100 V or lower, formation of a metal oxide thin film was not achieved.

As described above, in the vapor deposition for forming the second aluminum oxide thin film having a film thickness of 75 to 95 [nm], in Example 1, the film was partially lost even at the conveyance speed of 150 [m / min]. It was possible to deposit without generating. On the other hand, in Comparative Example 1, since wrinkle-like heat loss occurred, the speed was reduced to 70 [m / min], but still a weak wrinkle-like heat loss occurred. Comparative Example 2
Then, although vapor deposition was possible at a conveyance speed of 100 [m / min], partial heat loss occurred in the film after film formation.

In addition, as a result of Examples 2 to 4 and Comparative Examples 3 to 4, in the sprayed coating in which alumina and titania are mixed, by the optimization of the concentration of the sprayed material (selection of granulated powder) and titania, dielectric breakdown does not occur, We have found the conditions for full adhesion.

The present invention is very suitable for vacuum deposition in which a thin film is formed on both sides of a plastic film, but it can also be applied to vacuum deposition of webs such as paper and metal foil, and its application range is not limited to these. Absent.

DESCRIPTION OF SYMBOLS 1 Sheet | seat 2 Original fabric roll body 3 Sheet | seat guide surface 4 Intermediate | middle roller (unwinding side)
5 Intermediate roller (winding side)
6 Winding roll body 7 Crucible (evaporation source)
DESCRIPTION OF SYMBOLS 8 Vapor deposition material 10 Vapor 11a Width direction mask 11b Travel direction mask 12 Opening part 13 1st thin film 14 2nd thin film 15 DC power supply 16 Current limiting resistance 17 Oxygen nozzle 18 Oxygen supply piping 20 Insulator layer 21 Sheet peeling roller 22 Sheet Feed roller 24 Partition 25 Sheet conveying direction 26 Sheet deposition region 30 Deposition start point 31 Deposition end point 32 Separation point 33 Winding point 41 Decompression chamber 41a Winding chamber 41b Film forming chamber 42 Vacuum pump 42a For winding chamber Vacuum pump 42b Vacuum pump for film formation chamber 43 Valve 44 Gas cylinder 45 Pressure reducing valve 46 Gas flow regulator 51 Shutter member 61 Measuring electrode 62 DC power source for resistance measurement 63 Microammeter

Claims (16)

In a reduced-pressure atmosphere, the sheet on which the first thin film is formed on one surface is brought into contact with the surface of the cylindrical roll, and on the other surface of the sheet being conveyed along with the rotational movement of the cylindrical roll A method for producing a sheet with a thin film, in which metal vapor is blown toward the sheet from an evaporation source in which an evaporation material is melted, and a second thin film is continuously formed on the sheet, the cylindrical roll as der range of volume resistivity is 10 ⁸ to 10 ¹¹ [Omega] cm the circumferential surface of the cylindrical metal body part is, the aluminum oxide as a main component, magnesium oxide, silicon oxide, chromium oxide, calcium oxide, selected from zirconium oxide It used after coating the configured insulator layer of a material obtained by mixing at least one that is, 100 between the first surface on which the thin film is formed between the cylindrical roll By applying a voltage in the range of 400V, the method of manufacturing the thin film with a sheet and forming a second thin film on the other surface of the sheet.   2. The production of a sheet with a thin film according to claim 1, wherein a thickness of the insulator layer coated on a surface of the cylindrical roll is in a range of 40 to 200 μm as the cylindrical roll. Method.   The method for producing a sheet with a thin film according to claim 1 or 2, wherein the thickness of the sheet is 10 µm or less, and the conveyance speed of the sheet is 100 m / min or more. The first thin film is a metal compound thin film, and the surface resistance of the metal compound thin film is in the range of 10 ¹ to 10 ⁵ Ω / □. Manufacturing method of sheet with thin film.   The method for producing a sheet with a thin film according to claim 4, wherein the metal compound thin film is aluminum oxide and a film forming rate is 600 nm / second or more. A decompression chamber, a cylindrical roll that conveys the sheet while being in contact with the sheet in the decompression chamber, a conveyance unit that conveys the sheet in accordance with a rotational movement of the cylindrical roll, and the cylindrical roll An evaporation source for scattering metal vapor toward the sheet and a potential difference generating means for generating a potential difference between the sheet and the cylindrical roll, and continuously forming a thin film on the conveyed sheet An apparatus for manufacturing a sheet with a thin film, wherein the cylindrical roll is configured by coating an insulating layer on a peripheral surface of a cylindrical metal body, and the insulating layer is mainly made of aluminum oxide. The composition is made of a material in which at least one selected from magnesium oxide, silicon oxide, chromium oxide, calcium oxide, and zirconium oxide is mixed, and the volume resistance is 10 ⁸ to 10 ^11. An apparatus for producing a sheet with a thin film, characterized by being in the range of Ωcm. The sheet with thin film according to claim 6, wherein the volume resistivity at any two points in a region in contact with the sheet of the insulator layer is R1, R2 (R1 ≦ R2), and the following formula is satisfied Manufacturing equipment.
1 ≦ R2 / R1 ≦ 2   The thickness of the said insulator layer exists in the range of 40-200 micrometers, The manufacturing apparatus of the sheet | seat with a thin film of Claim 6 or Claim 7 characterized by the above-mentioned.   The sheet conveyance distance between the guide roll immediately before and after the cylindrical roll and the cylindrical roll is within 200 mm, and the surface of the sheet in contact with the guide roll is the cylindrical roll. The apparatus for producing a sheet with a thin film according to any one of claims 6 to 8, wherein the apparatus is a surface opposite to the surface in contact with the thin film.   The thin film according to any one of claims 6 to 9, wherein the potential difference generating means includes a current suppression circuit that limits a current flowing between the sheet and the cylindrical roll to 50 mA or less. Equipment for manufacturing attached sheets. The surface of a cylindrical metal roll with a structure that circulates the medium inside is provided with an insulator layer in which aluminum oxide and titanium oxide are mixed, and a rotational movement is made while a long sheet is in contact with the surface of the insulator layer. A cylindrical roll to be conveyed along with
The insulator layer has a volume resistance of 10 ⁸ -10 ¹¹ A cylindrical roll characterized by Ωcm, a thickness of 40 to 200 μm, and a titanium element concentration of 2.2 to 4.0 at%. The cylindrical roll according to claim 11, wherein a dielectric breakdown voltage per 100 μm thickness of the insulator layer at an arbitrary position on the surface is 500 V / 100 μm or more. In any cross section of the insulator layer perpendicular to its circumferential direction, the standard deviation of the titanium element concentration in each region divided by a square lattice with 10 μm as one side is less than 7.5% and fluctuates The cylindrical roll according to claim 11 or 12, wherein the coefficient is less than 2.0. 14. The surface roughness Ra of the insulator layer surface is 0.01 to 0.1 [mu] m, and the surface roughness Ra of the metal roll surface is within a range of 1 to 3 [mu] m. A cylindrical roll according to any one of the above. A decompression chamber, a cylindrical roll that conveys the sheet while being in contact with the sheet in the decompression chamber, a conveyance unit that conveys the sheet in accordance with a rotational movement of the cylindrical roll, and the cylindrical roll An evaporation source for scattering metal vapor toward the sheet and a potential difference generating means for generating a potential difference between the sheet and the cylindrical roll, and continuously forming a thin film on the conveyed sheet It is a manufacturing apparatus of a sheet | seat with a thin film, Comprising: The said cylindrical roll is a cylindrical roll in any one of Claims 11-14, The manufacturing apparatus of the sheet | seat with a thin film characterized by the above-mentioned. In a reduced-pressure atmosphere, the sheet on which the first thin film is formed on one surface is brought into contact with the surface of the cylindrical roll, and on the other surface of the sheet being conveyed along with the rotational movement of the cylindrical roll A method for producing a sheet with a thin film, in which metal vapor is blown toward the sheet from an evaporation source in which an evaporation material is melted, and a second thin film is continuously formed on the sheet, the cylindrical roll The cylindrical roll in any one of Claims 11-14 is used, and the voltage within the range of 100-400V is applied between the surface in which the said 1st thin film is formed, and the said cylindrical roll. A method for producing a sheet with a thin film, comprising forming a second thin film on the other surface of the sheet.