JP6020704B2 - Method for producing vapor deposition film using vacuum vapor deposition apparatus - Google Patents

Description

  The present invention relates to a method for producing a vapor deposition film using a vacuum vapor deposition apparatus, and more particularly to a method for producing a vapor deposition film using a vacuum vapor deposition apparatus for forming a mixed film composed of different elements on a film.

  Conventionally, as a device for forming a mixed film by simultaneously depositing a plurality of materials on a film traveling in a vacuum chamber, for example, Patent Document 1 discloses a plurality of crucibles 8 containing a plurality of deposition materials 10 as shown in FIG. As shown in FIG. 2, there is described an apparatus arranged so as to be mixed on the same line in a direction intersecting with a traveling direction of a traveling film. This apparatus has an advantage that a uniform mixed film can be formed in the thickness direction of the vapor deposition film because a time difference hardly occurs until each material evaporated from a plurality of vapor deposition materials (mainly metal) adheres to the traveling film.

  However, in this apparatus, since the width of the side wall portion of the crucible between the adjacent different vapor deposition materials becomes an unevaporated region, the total thickness of the actual vapor deposition film formed in the width direction of the running film is equal to the side wall portion. There is a problem in that the vapor deposition rate is reduced in a substantially upper portion of the film, resulting in non-uniformity.

  As an apparatus for improving this problem, for example, in Patent Document 2, in order to hold different kinds of vapor deposition materials in a vacuum vapor deposition apparatus capable of forming a mixed film made of different elements on a film running in a vacuum chamber, The apparatus provided with the partition part which sorts the vapor deposition material of this is described. In this apparatus, a plurality of different vapor deposition materials are divided not by the thick crucible side wall but by a thin partition plate, so that an unevaporated region between different vapor deposition materials can be reduced. For example, an electron gun is used as a heating means. In this case, since the electron beam can be irradiated to the vicinity of the boundary between the adjacent vapor deposition materials, there is an advantage that the vapor deposition rate in the vicinity of the upper part of the partition plate is difficult to decrease.

  However, in this apparatus, since the heat insulating properties of the partition plates are not sufficient, there is a problem that if the temperature set for each is different, the heat is likely to move through the partition portion, so that the temperature is difficult to stabilize. Therefore, improvement is still necessary to control the temperature of the different vapor deposition materials across the partition plate to the optimum temperature, and the apparatus is insufficient to control the evaporation rate of each vapor deposition material.

Japanese Patent Laid-Open No. 6-235061 JP 2000-239832 A

  As described above, in the conventional technology, it is difficult to control a mixed film having a predetermined composition and film thickness in the width direction and the running direction of the film continuously and stably for a long time.

  Therefore, the object of the present invention is to eliminate the above-mentioned problems of the prior art, and to provide a continuous film at a high level for a long time with a mixed film having a predetermined composition and film thickness on the long film surface. Furthermore, it is providing the manufacturing method of the vapor deposition film using the vacuum vapor deposition apparatus which can be formed stably. In the present invention, the “film” is a generic term for materials having a thin shape with respect to width and length, and is used as a concept including not only the original film but also a sheet-like material.

  The above object can be achieved by the invention described in the claims. That is, the apparatus includes a material holding means that holds at least two kinds of different vapor deposition materials in a vacuum chamber and includes a partition unit that sorts these vapor deposition materials, and a heating means that heats and vaporizes the vapor deposition materials. In the method for producing a vapor deposition film using a vacuum vapor deposition apparatus capable of forming an inorganic thin film on the film running in the vacuum chamber, the thermal conductivity in the direction perpendicular to the partition direction of the partition portion is changed to the thermal conductivity in the partition direction. On the other hand, the present invention is characterized in that a method for producing a vapor deposition film using a vacuum vapor deposition apparatus that is twice or more is used.

In this case, it is preferable that the thermal conductivity in the partition direction of the partition portion is 10 W / m · K or less.
Moreover, it is preferable that the bending strength of the said partition part is 100 Mpa or more.
And it is preferable that the said partition part is a long fiber fabric type carbon fiber reinforced carbon material.
Furthermore, it is preferable that the partition portion is composed of two or more plate materials and a space is provided between at least two plate materials.
Furthermore, it is preferable that the material holding means has a mechanism for horizontally moving in the film running direction.
Moreover, it is preferable that the partition part is installed so that the longitudinal direction of the partition part may be parallel to the film running direction.

  According to this configuration, a plurality of different vapor deposition materials are divided not by the side wall of the thick crucible but by a thin partition, so that an unevaporated region between the different vapor deposition materials can be reduced. For example, an electron gun can be used as a heating means. When used, it is possible to irradiate the electron beam up to the vicinity of the boundary between adjacent vapor deposition materials. Therefore, the fall of the vapor deposition rate in the upper vicinity of a partition part is suppressed. And since the heat insulation of a partition part is enough, it is possible to control the temperature of the different vapor deposition material which separated the partition part to each optimal temperature.

  As a result, the composition in the width direction and the uniformity of the film thickness of the mixed film formed on the film are improved, and are composed of at least two kinds of materials over the width direction and the length direction of the long film surface, It is possible to provide a method for producing a vapor deposition film using a vacuum vapor deposition apparatus capable of continuously and uniformly forming a mixed film having a composition and a film thickness at a high level required today.

It is a figure explaining the schematic whole structure of one Embodiment of the vacuum evaporation system used by this invention method. It is a figure explaining the structure of the crucible of the vacuum evaporation system used by this invention method. It is a figure explaining the structure of the partition part of the vacuum evaporation system used by this invention method. It is a graph explaining the evaporation characteristic and thickness distribution at the time of using the crucible of this embodiment. It is a graph explaining the evaporation characteristic at the time of using the conventional crucible and thickness distribution. It is a figure which shows the crucible used for the conventional vacuum evaporation system, and its arrangement | positioning.

  A film to which the method for producing a vapor deposition film using the vacuum vapor deposition apparatus of the present invention can be applied, for example, a polymer film is not particularly limited, but polyester, polypropylene, polyethylene, polyamide 6, polyamide 66, polyamide 12, polyamide 4, Examples include films made of polyvinyl chloride, polyvinylidene chloride, and the like.

The partition part as used in the field of this invention means the part which has the function to classify | divide so that each vapor deposition material may not be mixed in the means to hold | maintain at least 2 types of vapor deposition material.
Moreover, the partition direction used by this invention is a direction which goes to the adjacent material from a certain vapor deposition material, and when it partitions with a board, it becomes the thickness direction of a board.
Further, the direction perpendicular to the partition direction is the direction along the surface of the plate when partitioned by the plate.
In the present invention, the vapor deposition material is filled adjacent to the partition portion. The material evaporates from the upper surface, and in the vertical direction, the direction parallel to the depth direction of the vapor deposition material is the depth direction, and the direction perpendicular to the depth direction is the length direction.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  FIG. 1 shows a schematic overall structure of a vacuum deposition apparatus used in the present embodiment. In this vacuum vapor deposition apparatus, the film 11 set on the unwinding roll 1 in the vacuum chamber 6 runs on the cooling roll 3, passes through the tension roll 5, and is wound on the winding roll 2. The degree of vacuum in the vacuum chamber 6 is maintained at a predetermined degree of vacuum by an exhaust device 9 including an oil diffusion pump (not shown). A crucible 8, which is an example of a material holding means arranged at the bottom of the vacuum chamber 6, moves horizontally at a low speed while maintaining parallel to the vapor deposition surface of the film 11 in the axial direction of the electron gun 4 which is an example of a heating means. . The electron gun 4 irradiates the electron beam 12 onto the vapor deposition material 10 stored in the crucible 8. A part of the material heated and evaporated by the electron beam 12 is deposited on the surface of the film 11 running on the cooling roll 3. Reference numeral 7 denotes a shielding plate for forming a uniform and good vapor deposition film on the film 11, and reference numeral 15 denotes a cooling pipe through which cold water or the like is circulated in order to cool the crucible 8.

  When the material holding means is movable relative to the electron beam 12 irradiated from the electron gun 4, the heating position by the electron gun 4 is not changed, and the material holding means moves horizontally to cause evaporation. The reduced deposition material 10 is supplied. For this reason, the irradiation conditions of the electron beam 12 for irradiating the vapor deposition material 10 accommodated in the material holding means, for example, the distance between the electron gun 4 and the vapor deposition material 10 can be made as constant as possible. Evaporation can be performed uniformly and for a long time in the width direction of the material.

  As shown in FIG. 2, the partition portion 13 is disposed in the crucible 8. It is preferable that the partition portion 13 is disposed to be inclined at substantially the same angle as the incident angle of the electron beam 12 irradiated from the electron gun 4.

  When configured in this way, not only can it withstand continuous use for a long time, but it can irradiate the electron beam 12 to the very vicinity of each adjacent vapor deposition material 10 without disturbing the incidence of the electron beam 12, Even when the vapor deposition material 10 is used to evaporate and the height of the material surface is lowered, the influence of the partition portion 13 can be reduced. It is convenient that the thickness of the deposited film can be more uniformly stabilized.

  Reference numeral 16 in FIG. 2 denotes a holding portion that adjusts and holds the angle and interval of each partition portion 13. A pair of parallel holding portions 16 and 16 and a plurality of partition portions 13 form a lattice. Is placed inside. And the box 17 which accommodates the vapor deposition material 10 by the adjacent partition part 13 is formed. The partition 13 on the center side faces the vertical direction, and the angle formed by the partition 13 and the vertical line increases toward the end, and the electron beam 12 irradiated from the electron gun 4 is the partition 13. The vapor deposition material 10 in each box 17 can be heated by preventing the shielding as much as possible. In addition, when there are two kinds of vapor deposition materials 10, the vapor deposition material (for example, A) and the vapor deposition material (for example, B) are alternately loaded into the box 17 so as to be A, B, A, B. To do.

In the present invention, the ratio between the thermal conductivity in the vertical direction and the thermal conductivity in the partition direction of the partition portion 13 needs to be 2 or more, preferably 3 or more, and more preferably 4 or more.
The thermal conductivity in the partition direction of the partition portion 13 is preferably 10 W / m · K or less, and more preferably 0.5 to 10 W / m · K. If the thermal conductivity in the partition direction is 10 W / m · K or less, good heat insulating properties of the partition portion 13 can be obtained. Therefore, the temperatures of the different vapor deposition materials 10 across the partition portion 13 are controlled to respective optimum temperatures. It becomes possible.

  On the other hand, the thermal conductivity in the direction perpendicular to the partition direction of the partition portion 13 is preferably 20 W / m · K or more, and more preferably 20 to 50 W / m · K. When the thermal conductivity is larger in the length direction than in the partition direction, the heat escapes in the length direction or depth direction, and finally the heat is released to the crucible 8 which is water-cooled. Damage can be prevented. If the thermal conductivity in the vertical direction becomes too high, the temperature of the partition 13 is extremely lowered, and evaporation is prevented.

  The partition portion may have a mode of penetrating the holding portion 16 as indicated by reference numeral 13 in FIG. 2, or may be another mode of being fitted into a groove provided in the holding portion 16.

  According to the configuration of the present invention, the plurality of different vapor deposition materials 10 are divided not by the thick crucible side walls but by the thin partition portion 13, so that the undeposited regions between the different vapor deposition materials 10 can be reduced. 2-10 mm is preferable and, as for the thickness of the partition part 13, it is still more preferable that it is around 5 mm. The thinner the partition portion 13 is, the better. However, if the thickness is less than 2 mm, it is not preferable because the usable time is shortened due to the consumption by heating from the heating means, and the cost is increased.

  The partition portion 13 has a certain degree of mechanical strength, and preferably has a bending strength of 100 MPa or more, which makes it possible to reduce the thickness of the partition portion 13, and prevent evaporation between different vapor deposition materials 10. Since the area can be reduced, it can further contribute to stabilization of vapor deposition and improvement of uniformity.

It is preferable that the thermal expansion coefficient of the partition part 13 in the direction perpendicular to the partition direction at 0 to 800 ° C. is 0.1 × 10 ^{−6 to} 1.0 × 10 ⁻⁶ / ° C. If the thermal expansion coefficient of the partition part 13 is in this range, the partition part 13 will not be cracked or chipped due to contact with the crucible 8 in the heat vapor deposition, and it will be highly durable. Moreover, even if the process of high temperature to evaporate the material in the crucible 8 and cooling after completion is repeated, damage such as cracking and chipping is unlikely to occur, so that the deposition can be repeated several tens of times. Will be cheaper.

  Furthermore, it is preferable that the space | interval of the adjacent partition parts 13 shall be 10-120 mm. This is convenient because the composition ratio of the deposited film can be made uniform in the width direction. When the interval between the partitioning portions 13 is less than 10 mm, the volume of the partitioning portions 13 is relatively larger than the volume of the box 17 in which the deposition material 10 is loaded, and the replenishment frequency of the deposition material 10 is increased. The efficiency is lowered, which is not preferable. Moreover, when the space | interval of the partition parts 13 exceeds 120 mm, it becomes difficult to evaporate the different vapor deposition material 10 uniformly in the width direction of a vapor deposition material, and is unpreferable.

  It is preferable to use a material containing carbon as a main component for the partition portion 13. This is because, in vacuum, the carbon material can withstand the highest temperature and has excellent dimensional stability. The carbon material is more preferably a carbon-based composite material such as a carbon fiber reinforced carbon material. This is because the carbon fiber reinforced carbon material is not easily damaged by irradiation with an electron beam and has a high heat resistance, so that cooling of this portion is not necessarily required.

In the present invention, in order to make the ratio of the thermal conductivity in the direction perpendicular to the partition direction of the partition portion 13 and the thermal conductivity in the partition direction more than double, the long fiber webs stacked in the thickness direction are hardened and carbonized. It is preferable to use a long-fiber woven carbon fiber-reinforced carbon material that is made into a plate shape. For example, after a prepreg obtained by impregnating a polyacrylonitrile-based carbon long fiber fabric with a phenol resin is laminated, hot pressing is performed to produce a phenol resin molded product (CFRP) using a plate-like carbon fiber as a reinforcing material, and vacuum It baked at 1000-2300 degreeC in inside, and the part of a phenol resin is carbonized. By repeating the impregnation of the phenol resin and the calcination carbonization, a long fiber woven carbon fiber reinforced carbon material in which the carbon fiber is surrounded by carbon can be obtained.

  In the present invention, the partition portion 13 may be configured only by a single long-fiber woven carbon fiber-reinforced carbon material plate (FIG. 3-A), and the two carbon plates are arranged in parallel at intervals of several mm. You may comprise what was installed in the one partition part 13 (FIG. 3-B).

  The characteristics of the partition part 13 were evaluated using the following method.

(1) Thermal conductivity The value measured at 100 ° C. according to JIS-A-1412.

(2) Bending strength The value measured according to JIS-R-7212.

  As the film 11, a polyethylene terephthalate (PET) film roll (Toyobo Ester (registered trademark) film manufactured by Toyobo Co., Ltd., E5102, thickness 12 μm) was used.

As the vapor deposition source, particulate aluminum oxide (Al ₂ O ₃ , purity 99.5%) having a size of about 3 to 5 mm and silicon oxide (SiO ₂ , purity 99.9%) were used, as shown in FIG. Vapor deposition was performed with an apparatus. The outer frame of the crucible 8 holding the vapor deposition material 10 was made of copper, and the partition portion 13 was placed in the crucible 8. A cooling water cooling tube 15 having an outer diameter of 20 mmφ was provided at the bottom of the crucible 8. The flow rate of the cooling water is about 4 m3. As will be described later, the partition portion 13 is disposed so as to be inclined at an angle substantially equal to the angle at which the electron beam 12 irradiated from the electron gun 4 is incident on each vapor deposition material 10. This is because the electron beam 12 can be irradiated to the very vicinity between the adjacent vapor deposition materials 10 without disturbing the incidence of the electron beam 12. A long-fiber woven carbon fiber reinforced carbon material having a thickness of 10 mm was used as the partition portion 13. In addition, the thermal conductivity of the partition part was 5.7 W / m · K in the partition direction, and 27 W / m · K in the direction perpendicular to the partition part. Moreover, the bending strength in the direction perpendicular to the partition was 160 MPa. The two types of vapor deposition materials 10 were alternately and uniformly accommodated in each box 17 secured by the partition portion 13. In FIG. 2, the schematic structure of the crucible 8 used for the present Example is shown. The thickness of the partition part 13 was 5 mm, and the pitch of the partition part 13 was about 100 mm pitch. The inclination angle of the partition portion 13 was adjusted to the incident angle of the electron beam, and the crucible 8 was moved at a speed of about 2 mm / min in a direction approaching the incident side of the electron beam 12. Polymer films deposited with aluminum oxide and silicon oxide can be widely used as packaging materials and gas barrier materials that require airtightness such as foods, medical products, and electronic parts.

The electron gun 4 having an output of 250 kW was disposed so as to face the crucible 8 disposed in parallel with the film width direction. The electron gun 4 is configured to deposit the vapor deposition material 10 in a total of 9 boxes of 4 boxes of silicon oxide and 5 boxes of aluminum oxide alternately arranged in the crucible 8. In this embodiment, one electron gun 4 is used. However, when the total amount of energy to be charged into the crucible 8 cannot be secured by one unit, or when a wide polymer film is deposited, a plurality of electron guns 4 are used. The method of dividing the vapor deposition region may be employed, and the number of electron guns installed is not particularly limited. In this case, this can be dealt with by increasing the crucible width and increasing the number of partitions 13. Moreover, it is preferable to install the partition part 13 corresponding to the incident angle of the electron beam from a plurality of electron guns.

The pressure in the vacuum chamber 6 during vapor deposition was an exhaust system that could always maintain 4 × 10 ⁻² Pa or less. Specifically, the oil diffusion pump of 50,000 L / sec was directly connected to the bottom of the vacuum chamber. In addition, although the measuring method of the thickness of the vapor-deposited mixed film layer is not particularly limited, an on-line thickness measuring device (not shown) disposed almost directly above the tension roll 5 and in the center in the width direction of the polymer film 11 is used. It is preferable that continuous measurement is performed because continuous data is obtained and convenience is increased.

  As shown in FIGS. 4A and 4B, the distribution of the gas evaporated from the vapor deposition material 10 divided by each partitioning portion 13 shows a distribution in which the top is strongest and the strength decreases as it spreads sideways. The intensity distribution and shape mainly depend on the intensity of the electron beam 12, the angle at which the electron beam 12 is incident, the distance between the electron gun 4 and the crucible 8, the evaporation area, and the like. Therefore, in order to form a film having the same composition ratio in the width direction and the running direction of the film forming the thin film and having a uniform total thickness, the arrangement of the vapor deposition material 10 is the most important. The arrangement method of the vapor deposition material 10 implemented this time is shown in FIGS.

  A comparative example is shown in FIG. FIG. 6 shows individual materials placed side by side in a crucible as in the prior art.

  FIG. 4 shows the measurement results of the evaporation characteristics and film thickness distribution according to the example, and FIG. 5 shows the measurement results of the evaporation characteristics and film thickness distribution according to the comparative example. 4 and 5, a is the film thickness distribution of aluminum oxide, b is the film thickness distribution of silicon oxide, and c is the thickness distribution of the mixed film in the width direction. 4 and 5, the vertical axis represents the film thickness of the mixed vapor deposition film (the film thickness at each position divided by the maximum film thickness, which is x100), and the horizontal axis represents the film position.

  It can be seen that the vacuum deposition apparatus according to the present embodiment is uniformly deposited in the film width direction.

[Another embodiment]
(1) In the above embodiment, the crucible 8 made of copper is shown as the container for the vapor deposition material holding means. However, the invention is not limited to this, and the material is not easily damaged by the heating means such as the electron beam 12. Other materials may be used. The container may have a basket-like shape as long as it can hold the vapor deposition material 10.

(2) In the above embodiment, an example in which a so-called one-chamber system is used as a vacuum tank has been shown. However, the vacuum chamber is set to a vacuum state in which a chamber for traveling a deposition material such as a film and a chamber for heating the deposition material 10 are differently reduced. The present invention can also be applied to a so-called two-chamber apparatus that performs vapor deposition.

(3) In the said embodiment, although the example which has arrange | positioned the unwinding roll 1 and the winding roll 2 of a to-be-deposited material in the vacuum tank was shown, it was outside the vacuum tank which vapor-deposits the unwinding roll 1 and the winding roll 2 It can also be applied to a continuous system in which the vapor deposition is performed in a high vacuum chamber.

(4) In the above embodiment, a polymer film is taken as an example of the film-form deposition material. However, the deposition material may be paper, cloth, or the like. In addition to the above-described aluminum oxide and silicon oxide, various elements and compounds can be used as the vapor deposition material 10, and a mixture composed of two or more elements or components using two or more vapor deposition materials 10. A film may be formed.

Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments, and various improvements and modifications can be made within the technical concept described in the specification.

  The vacuum deposition apparatus of the present invention is a mixed film having a predetermined composition and film thickness, in which the thermal conductivity in the direction perpendicular to the partition direction of the partition portion in the crucible is at least twice the thermal conductivity in the partition direction, It is preferable as an apparatus for forming a high level continuously and stably for a long time.

DESCRIPTION OF SYMBOLS 1 Unwinding roll 2 Winding roll 3 Cooling roll 4 Electron gun 5 Tension roll 6 Vacuum tank 7 Shield plate 8 Crucible 9 Exhaust device 10 Deposition material 11 Film 12 Electron beam 13 Partition part 14 Crucible side wall part 15 Cooling pipe 16 Holding part 17 boxes

Claims (7)

  A material holding means for holding at least two kinds of different vapor deposition materials in a vacuum chamber and having a partition part for sorting these vapor deposition materials; and a heating means for heating and evaporating the vapor deposition materials, In a method for producing a vapor deposition film using a vacuum vapor deposition apparatus capable of forming an inorganic thin film on a film running in a vacuum chamber, the thermal conductivity in the direction perpendicular to the partition direction of the partition portion is relative to the thermal conductivity in the partition direction. The manufacturing method of the vapor deposition film using the vacuum vapor deposition apparatus which is 2 times or more.   The manufacturing method of the vapor deposition film of Claim 1 whose heat conductivity of the partition direction of the said partition part in the said vacuum evaporation system is 10 W / m * K or less.   The manufacturing method of the vapor deposition film of Claim 1 or 2 whose bending strength of the said partition part in the said vacuum evaporation system is 100 Mpa or more.   The method for producing a vapor deposition film according to any one of claims 1 to 3, wherein the partition portion in the vacuum vapor deposition apparatus is a long fiber woven carbon fiber reinforced carbon material.   The method for producing a vapor-deposited film according to claim 1, wherein the partition portion in the vacuum vapor deposition apparatus is configured by two or more plate materials, and a space is provided between at least two plate materials.   The manufacturing method of the vapor deposition film in any one of Claims 1-5 which has the mechanism in which the said material holding means in the said vacuum vapor deposition apparatus moves horizontally in a film running direction.   The manufacturing method of the vapor deposition film in any one of Claims 1-6 in which the partition part is installed so that the elongate direction of the said partition part in the said vacuum evaporation system may become parallel to a film running direction.