JP2003129229A - Method and apparatus for producing film with metal oxide film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film-winding-type vapor deposition method for obtaining a metal oxide film by melting and vaporizing a vapor-depositable metal and introducing oxygen in the mid course, more particularly, for forming a thick metal oxide film on a film by fully oxidizing the metal, to provide a method for increasing the strength of a film as thin as 2-6 μm, especially, for increasing the strength of a film for a magnetic recording medium, and to provide a magnetic recording medium support desirable for producing magnetic recording media, especially DVC-LP tapes, having few DOs and excellent running performances. SOLUTION: The method is a film forming method comprising disposing a cooling can over a vapor source prepared by melting a metal, conveying an undeposited film delivered from an unwinding means along the can to expose it to the formed vapor and to thereby form a metal oxide, and winding the deposited film by means of a winding means, wherein the metal vapor is passed from an opening situated at a height equal to (0.6-0.9)×h (wherein (h) is the shortest distance between the surface of the molten metal in the vapor source and the undeposited film), enclosing the perpendicular part of the surface of the molten metal, and being larger by at least 1.5 times than the area of the molten metal, and oxygen is introduced from the space between the opening and the can.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film with a metal oxide film, which uses a film winding-type vapor deposition method to melt and evaporate a vapor-deposited metal and introduce oxygen in the process to obtain a metal oxide film. Manufacturing method and manufacturing apparatus. In particular, the present invention relates to a method and an apparatus for producing a film with a metal oxide film, which is capable of providing a thick metal oxide film on a thin film. Further, the present invention relates to a method for producing a film with a metal oxide film and a production apparatus for obtaining a metal oxide film by sufficiently oxidizing a metal. Further, the film with a metal oxide film obtained by the present invention is used in applications where its insulating property and transparency are required.

The present invention also relates to a method and an apparatus for producing a film with a metal oxide film for reinforcing the strength of a thin film having a thickness of 2 to 6 μm. Further, the present invention relates to a method and an apparatus for producing a film with a metal oxide film, which reinforces the strength of the film for a magnetic recording medium. In particular, the present invention relates to a method and an apparatus for producing a film with a metal oxide film, which is suitable as a film for a digital recording type magnetic recording medium. Further, a method and an apparatus for producing a film with a metal oxide film, which is suitable for a magnetic recording medium in which a large amount of data such as image data is digitally recorded by a helical scan method such as VTR of a DVC system. Regarding Further, the present invention relates to a method and an apparatus for producing a film with a metal oxide film, which provides a metal oxide film on the side opposite to the surface having a ferromagnetic material.

[0003]

2. Description of the Related Art Hitherto, as a film with a metal oxide film, a film with a film of aluminum oxide or silicon oxide has been proposed in the field of a packaging film having an excellent gas barrier property. Aluminum oxide film and silicon oxide film in this field are made by directly heating and evaporating aluminum oxide and silicon oxide ceramics into a thin film.In the case of aluminum oxide, the film forming method is to melt metal aluminum and There is a method of forming an oxide film by introducing oxygen. For such a packaging film with a metal oxide film, a method of forming a metal oxide film having a thickness of about 5 to 30 nm on a plastic film is usually proposed. If aiming at gas barrier properties, the film thickness is 5 to 30 n.
Sufficient function can be exhibited at about m.

Further, in a method of obtaining a metal oxide of a material containing CoNi or Fe as a main component of a ferromagnetic material used for a magnetic recording material, it is partially oxidized in the film thickness direction in order to improve magnetic characteristics. Or a method for obtaining a semi-metal oxide is disclosed in Japanese Patent Laid-Open No.
Although it is disclosed in Japanese Patent Application Laid-Open No. 2-275316, it is not used in this field for the purpose of completely oxidizing a metal to obtain an insulating or transparent film.

As a conventional method for obtaining aluminum oxide, Japanese Patent Laid-Open No. 63-222849 has an oxidation nozzle between an evaporation source and a cooling can, and oxygen is introduced from both the upstream side and the downstream side of the evaporation source. A method of obtaining a metal oxide is disclosed. When an attempt is made to form a metal oxide film having a thickness of 2 to 6 μm on a film having a thickness of more than 50 nm, the film loses heat due to a very large heat load due to the metal vapor and the reaction heat in the oxidation, and the sewing machine is broken. It caused heat-wrinkling like eyes. Actually, when the method described in this conventional example was melted by the high frequency induction heating method without any modification, and oxygen was introduced in the middle to obtain an aluminum oxide film of about 60 nm, it was found that the heat load was sudden. The film was broken and a film with a metal oxide film could not be obtained.

Further, the oxidation nozzle is disclosed in Japanese Patent Laid-Open No. 62-2753.
There is one in which the position of the oxidation nozzle is specified in Japanese Patent Laid-Open No. 16 but this example is an example in which the vaporized vapor in the oblique incident portion is used instead of the vaporized vapor in the vertical portion of the evaporation source. The heat load caused by steam and the radiant heat load from the evaporation source material are relatively small. Nevertheless, when oxygen was introduced at the specified position, the position of oxygen introduction was too close to the film, and the film lost heat due to the sudden heat of oxidation reaction. Further, in the case of this conventional example, instead of completely oxidizing the metal to obtain an insulating or transparent film, a ferromagnetic material of a Co--Ni alloy in the film thickness direction is provided in order to improve the magnetic characteristics. It is used as a method of partially oxidizing a metal or obtaining a semi-metal oxide. Therefore, it does not specify the position of the oxidation nozzle as a condition for sufficient oxidation.

Further, in Japanese Patent Laid-Open No. 5-339718,
Although there is a disclosure regarding the shape of the oxidation nozzle, when blown out in this shape, the diffusion state of oxygen introduced into the vacuum is not sufficient, and a sudden metal vapor is generated against the oxygen that is blown out with a certain degree of viscosity. When the oxygen introduction amount was increased until an attempt was made to obtain sufficient oxidation, the film lost heat.

Further, in Japanese Patent Laid-Open No. 6-17238,
Although a mechanism for cooling the mask between the cooling can and the evaporation source is shown, an example adopted for the purpose of improving vapor deposition efficiency rather than preventing deformation of the nozzle is disclosed.

In any case, when an attempt is made to form a metal oxide film having a thickness of 50 to 500 nm on a thin film by a process in which a metal is used as an evaporation source to oxidize in the middle, the film loses heat and metal oxidation occurs. A film with a physical film could not be manufactured. Further, even if it was possible to some extent, sufficient and uniform oxidation could not be obtained.

Further, there were the following situations regarding the magnetic recording medium.

A consumer digital video tape which was put into practical use in 1995 has a metal magnetic thin film of Co provided on a polyester base film having a thickness of 6 to 7 μm by vacuum deposition, and a diamond-like carbon film is coated on the surface thereof. In the case of a camera-integrated video using a DV mini cassette tape, the basic specification (SD specification) has a recording time of 1 hour.

This digital video cassette (DVC)
Is the world's first digital video cassette for home use, a. It can record huge amount of information in spite of its small body. B. Image quality and sound quality do not deteriorate even after years because the signal does not deteriorate. C. Enjoy high image quality and high sound quality because it is not disturbed by noise. D. The market has a high reputation because it has the advantage that the image does not deteriorate even after repeated dubbing.

In 1998, one hour and 20 hours for SD specifications
DV mini-cassette tape (DVC-
LP tape) has been put to practical use, and the base film uses a polyethylene-2,6-naphthalate film having a thickness of 4 to 5 μm or an aromatic polyamide film. This tape also has a long recording time. , The market is highly evaluated.

These base films have a particle size of 10 to 3
It contains fine particles of 00 nm and has a height of 5
A fine film having a fine surface protrusion of ˜90 nm and a discontinuous coating mainly composed of a polar polymer having a thickness of 50 nm or less, which is adhered to at least one side of the film, and the height of the fine surface protrusion Is higher than the height of the discontinuous coating (for example, Japanese Patent Publication No. 6-
No. 51401), Young's modulus is 600 kg in the longitudinal direction.
/ Mm ² or more, and a thickness of 7 μm or less of polyethylene-2,6-
Naphthalate film (for example, JP-A-5-185507)
Publication), digital data storage (DDS-2,
3, 4) Aromatic polyamide film for tape (for example, JP-A-10-162349, JP-A-10-114038)
No. gazette) is used.

Since these DVC tapes are very popular,
The demand for increasing the production amount is increasing more and more, and in order to increase the productivity of DVC tape, the winding length of the base film roll is lengthened to 15000 m or more (conventional 10000 m or less), and the vacuum deposition process is performed. It is considered to increase the production amount per batch.

With a polyethylene terephthalate film having a thickness of 6 to 7 μm, a base film roll having a length of 15000 m or more can be stably produced in a large amount, but a polyethylene-2,6-naphthalate having a thickness of 4 to 5 μm can be produced. It is difficult for a film because the film is easily broken during manufacturing. The aromatic polyamide film is 15,000
Not only products with a thickness of m or more, the amount currently on the market is significantly smaller than conventional polyester films, and DVC-
There are major restrictions on the quantitative expansion of LP tapes.

As a means for solving these restrictions of quantitative expansion, in JP-A No. 11-48434, there is a filler surface having particles and a mat surface having a coating containing particles and an organic compound, and the thickness is 2 to 2. A 5.5 μm polyester film having a Young's modulus in the longitudinal direction of 6000 MPa or less and a Young's modulus in the width direction of 8000 MPa or more was used, and metal, semimetals and alloys and their oxides and composites were used on both sides of this film. Forming a reinforced film made of a selected metal material to form a magnetic recording medium support, and further forming a ferromagnetic metal thin film on the matte side of the support to form a magnetic recording medium. Is proposed.

[0018]

The present inventor has arrived at the present invention described below as a result of extensive studies to solve the above problems. Even if it is a thin film,
A method for producing a film with a metal oxide film, which can form a metal oxide film having a thickness of 500 nm on a film, and the metal oxide film can be sufficiently oxidized to have functions such as insulation and transparency. And to provide a manufacturing apparatus. In addition, digital video cassette (DV
In a support for a digital recording medium which has been put into practical use as a film for C), rigidity which cannot be realized by a raw base film of polyethylene terephthalate or polyethylene-2,6-naphthalate can be obtained with a thin film. It is an object of the present invention to provide a manufacturing method and a manufacturing apparatus of a film with a metal oxide film, which is capable of increasing the number of windings, and is suitable for a magnetic recording film that has good head touch properties and does not have running defects or a significant reduction in output.

Regarding the magnetic recording medium, Japanese Patent Application Laid-Open No. HEI-1
It has become clear that the DVC-LP tape disclosed in JP-A-1-48434 tends to have variations in image quality and running durability, and is not always satisfactory as an industrial product. That is, when the image quality of the DVC-LP tape is poor, that is, there are many dropouts (DO), or when the DVC-LP tape is repeatedly run, the tape extends in the longitudinal direction and the magnetic layer on the support partly peels off. It has become clear that there may be many dropouts that occur.

Therefore, an object of the present invention is to provide a magnetic recording medium using a highly productive polyester film as a support, which has a small amount of DO, has a good image quality, and has good running durability even after repeated running, and DO. Less occurrence of DV
PROBLEM TO BE SOLVED: To provide a method and an apparatus for producing a film with a metal oxide film suitable for use as a support for a magnetic recording medium capable of producing a magnetic recording medium suitable for digital recording by a helical scan method such as C-LP tape. It is to be.

[0021]

The method and apparatus for producing a film with a metal oxide film of the present invention comprises the following method, structure and apparatus for solving the above problems.

(1) After a cooling can is arranged above the evaporation source in which the metal is melted, the film to be vapor-deposited is conveyed from the unwinding means along the cooling can and exposed to the evaporation vapor to form a metal oxide. A thin film forming method of winding by a winding means, wherein a height of 0.6 to 0.9 × h from the molten metal surface with respect to the shortest distance h between the molten metal surface of the evaporation source and the vapor deposition film The metal vapor is allowed to pass through an opening including the vertical portion of the molten metal surface and having a size 1.5 times or more the size of the molten metal surface portion, and oxygen is introduced between the opening and the cooling can. A method for producing a film with a metal oxide film.

(2) The film with a metal oxide film as described in (1) above, wherein the opening is formed by a partition plate, and the partition plate is cooled by a refrigerant at 50 ° C. or less. Production method.

(3) The metal oxide as described in (1) or (2) above, wherein the oxygen is introduced through a plurality of oxygen blowing holes provided in the width direction of the film to be vapor-deposited. A method for producing a film with a physical film.

(4) The introduction of oxygen is performed in a range from a horizontal position toward the opening to a vertical position toward the cooling can.
~ The method for producing a film with a metal oxide film according to any one of (3).

(5) The introduction of oxygen is ± 30 with a straight line connecting the shortest distance between the hole and the apex of the cooling can as the center.
The method for producing a film with a metal oxide film as described in (3) or (4) above, wherein the film is introduced toward a range of degrees.

(6) Any of the above (3) to (5), wherein the hole described in any of the above (3) to (5) has a diameter of 0.1 to 1.5 mm. A method for producing a film with a metal oxide film according to claim 1.

(7) The introduction of oxygen is introduced from the unwinding side and / or the winding side of the film transport, and the introduction pressure and the flow rate are independently adjusted for each of the above (1) to (1). The method for producing a film with a metal oxide film according to any one of (6).

(8) Production of the film with a metal oxide film as described in (7) above, wherein the introduced amount on the unwinding side described in (7) is larger than the introduced amount on the winding side. Method.

(9) Any of the above (1) to (8), wherein the introduction of oxygen is started after the molten state of the metal of the evaporation source is stabilized and the amount of oxygen introduced is gradually increased. The method for producing a film with a metal oxide film according to.

(10) The metal oxide film as described in (9) above, wherein the rate of increase in the oxygen introduction amount described in (9) above is controlled so as not to exceed (10 ml / min) / sec. Method for producing a coated film.

(11) The metal oxidation described in the above (9) or (10) is characterized in that the introduction of oxygen described in the above (9) is performed on the unwinding side before the introduction on the winding side. A method for producing a film with a physical film.

(12) The amount of oxygen introduced is monitored by a vacuum gauge installed between the main body of the vapor deposition machine and the vacuum pump,
The method for producing a film with a metal oxide film as described in any one of (1) to (11) above, wherein the introduction amount is such that the pressure starts to rise.

(13) The amount of oxygen introduced is adjusted so that the difference between the pressure after the oxygen is introduced and the pressure before the oxygen is introduced is 3 × 10 ^-2 Pa or less. The manufacturing method of the film with a metal oxide film as described in any of 1).

(14) The thickness of the metal oxide film is 50 to
The thickness is set to 500 nm, and the above (1) to (1
The method for producing a film with a metal oxide film according to any one of 3).

(15) The surface resistance value of the metal oxide film is 10 ⁷ Ω / sq or more, (1)
~ The method for producing a film with a metal oxide film according to any one of (14).

(16) The metal as described in any one of (1) to (15) above, wherein the difference in total light transmittance between the film with metal oxide and the non-deposited film is within 5%. A method for producing a film with an oxide film.

(17) The transmittance of the film with a metal oxide is measured, and based on the transmittance, the energy and / or oxygen introduction amount of the evaporation source is adjusted so that the transmittance becomes substantially constant. The method for producing a film with a metal oxide film according to any one of (1) to (16) above, which comprises controlling the adjustment.

(18) The metal to be evaporated is aluminum and / or
Alternatively, the method for producing a film with a metal oxide film according to any one of (1) to (17) above, which is a material mainly containing copper.

(19) The vapor-deposited film has a thickness of 2 to
It is 6 micrometers, The manufacturing method of the film with a metal oxide film in any one of said (1)-(18) characterized by the above-mentioned.

(20) The Young's modulus in the longitudinal direction and the width direction of the film with the metal oxide film is 5500, respectively.
MPa or more, and 7500 MPa or more, The manufacturing method of the film with a metal oxide film in any one of said (1)-(19) characterized by the above-mentioned.

(21) A film for a magnetic recording medium in which the Ra value of the surface A on one side of the vapor-deposited film is 1 to 5 nm, and a strength reinforcing film is formed on the surface B (back surface) of the film. The method for producing a film with a metal oxide film according to any one of (1) to (20), which is characterized.

(22) The vapor-deposited film comprises a polyester film of polyethylene terephthalate or polyethylene-2,6-naphthalate, or a polyamide film.
The method for producing a film with a metal oxide film according to any one of (21).

(23) The method for producing a film with a metal oxide film as described in (21) or (22), wherein a ferromagnetic thin film is provided on the surface A described in (21).

(24) The film with a metal oxide film according to any one of the above (1) to (23), which is used for a magnetic recording medium of a digital recording system. Production method.

(25) A means for decompressing the inside of the vapor deposition machine and a means for heating and evaporating metal are provided, a cooling can is arranged above the evaporation source, and the film is conveyed from the unwinding means along the cooling can. A device for producing a film with a metal oxide film, which is wound up by a winding means after forming a metal oxide by exposing it to evaporating vapor, wherein the shortest distance h between the molten metal surface of the evaporation surface and the vapor deposition film, 0.6 to 0.9 from the surface
The partition member has a partition member that forms an opening at a height of × h, and the opening includes a vertical portion of the molten metal surface portion and is 1.5 times or more the size of the molten metal surface portion. An apparatus for producing a film with a metal oxide film, comprising means for introducing oxygen between the cooling can member and the cooling can member.

(26) The metal oxide film according to claim 25, wherein the partitioning member for forming the opening is provided with a means for joining a cooling pipe and flowing a refrigerant through the cooling pipe. Film manufacturing equipment.

(27) An oxygen introducing nozzle having a plurality of holes in the width direction of the film to be vapor-deposited is arranged between the partition member and the cooling can member, and a substantially constant amount of oxygen is supplied to the oxygen introducing nozzle. The apparatus for producing a film with a metal oxide film as described in (25) or (26) above, which is provided with a means for introducing.

(28) The hole of the oxygen introducing nozzle is installed so as to open in a range from a horizontal plane toward the center of the vaporized vapor opening to a vertical plane toward the cooling can. 27) An apparatus for producing a film with a metal oxide film as described in 27).

(29) The hole portion of the oxygen introducing nozzle is installed so as to open in a range extending toward a range of ± 30 degrees around a straight line connecting the shortest distance between the hole portion and the apex of the cooling can. The apparatus for producing a film with a metal oxide film as described in (27) or (28) above.

(30) In the above (27) to (29), the hole described in any of (27) to (29) has a diameter of 0.1 to 1.5 mm. An apparatus for producing a film with a metal oxide film according to any one of claims.

(31) The oxygen introduction nozzle is arranged on the unwinding side and / or the winding side of the film transport, and has means capable of independently controlling the respective introducing pressure and flow rate. An apparatus for producing a film with a metal oxide film according to any one of (27) to (30).

(32) The metal oxide as described in any of (25) to (31) above, wherein a vacuum gauge for monitoring the pressure inside the vapor deposition machine is arranged between the vapor deposition machine main body and the vacuum pump. A film manufacturing device.

(33) A plurality of optical monitors are arranged in the width direction of the film to be vapor-deposited between the portion exposed to the vaporized vapor and the winding means, and the optical monitor has a means for monitoring the transmittance. The manufacturing apparatus for a film with a metal oxide film according to any one of (25) to (32) above.

(34) In the above (33), there is provided means for receiving a signal from the optical monitor and adjusting and controlling the amount of oxygen introduced or the energy of the evaporation source so that the transmittance becomes substantially constant. Manufacturing equipment for film with metal oxide film.

[0056]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, a cooling can is arranged above an evaporation source in which a metal is melted, and a film to be vapor-deposited is conveyed from the unwinding means along the cooling can and exposed to evaporation vapor. After forming the film, the film is formed by a winding means and is wound up by a winding means, and the shortest distance h between the surface of the evaporation source and the film to be vapor-deposited is 0.6 to 0.9 × h from the surface of the surface.
At a height of 0.5 mm or more, including the vertical portion of the molten metal surface, through which the metal vapor passes, and oxygen is introduced from between the opening and the cooling can. It is a manufacturing method of a film with a metal oxide film.

A method of manufacturing the device will be described with reference to the drawings showing an example of the device showing the characteristics of the present invention. FIG. 2 shows a vertical cross-sectional view of an example of a vacuum vapor deposition machine for carrying out the present invention, and FIG. 1 shows an example particularly showing the features of the present invention.

In FIG. 2, the vacuum chamber is roughly divided into an upper chamber 11 for winding and unwinding a film and a lower chamber 12 for vapor deposition, and the pressure is reduced by the upper chamber pump 9 and the lower chamber pump 8, respectively. . The vacuum pump often uses a roughing pump and a high vacuum pump to reach a high vacuum. In ordinary vacuum deposition, the pressure in the lower chamber is set to be lower by one digit than that in the upper chamber. In the case of aluminum vapor deposition, the upper chamber is 10 ^-1 to 1
The level is set to 0 ^-2 Pa and the lower chamber is set to 10 ^-3 to 10 ^-4 Pa. Set the roll-shaped film 3a on the unwinding means 1,
The film 3b is placed along the guide rolls 5a, 5b, 5c, 5d, the film 3c is placed further along the cooling can 4, the film is made to face the evaporation source 7, and then the film is placed on the guide rolls 6a, 6b, 6c, 6d. Along 3d,
The film is wound by the winding means 2 and the film is set so as to be the roll-shaped film 3e. The guide means 5a to 5d and 6a to 6d are adapted to give appropriate tension to the film 3. In this system, after the film is set, the metal material is set in the evaporation source 7, the pressure is reduced, the evaporation source 7 is heated to evaporate, and the film is conveyed at a certain speed to obtain an evaporated film.

Examples of the method for melting the metal include a high frequency induction heating method under reduced pressure, a resistance heating method, an electron beam method, and a laser ablation method. To increase the thickness of the metal oxide film, a high frequency induction heating method and an electron beam method are preferably used, and a high melting point material, for example, a melting point material of 1500 ° C. or higher is preferably used. Also,
The cooling can 4 is often cooled to about −20 ° C. by using a refrigerant such as ethylene glycol. More specifically, the arrangement is shown in FIG.

FIG. 1 is a vertical cross-sectional view for enlarging the region where the metal vapor is flying and for easily explaining the positional relationship such as the arrangement of the present invention. Metal material 2 in crucible 22
1 is put and heated by a heating method not shown to bring the metal material 21 into a molten state. For example, when the metal is heated by the high frequency induction heating method, the metal gradually starts to emit light, and when it is further heated, it becomes in a molten state and the light emitting state becomes stable. When further heated, the molten metal surface 28 starts to flap. The point at which the flapping of the molten metal surface 28 begins is also the point of stable evaporation. Thus, the metal is melted and evaporated.

Assuming that the shortest distance (vertical) of the film 3c along the cooling can 4 from the molten metal surface 28 is h, the partition plates 24a, 2 are positioned at 0.6 to 0.9 × h.
4b is arranged, and the oxygen nozzles 26a and 26b are arranged between the partition plates 24a and 24b and the cooling can 4. By arranging the partition plates 24a, 24b at this position, the metal vapor 30 can be efficiently distinguished by being distinguished from the oxygen introduction region shown below without giving a heat load due to melting of the metal to the film to be vapor-deposited more than necessary. It can react with oxygen. If the position of the partition plates 24a, 24b is larger than the position of 0.9 × h from the position of the molten metal surface 28, the region for sending oxygen for converting metal oxide with high energy into metal oxide is too small, If it is attempted to be sufficiently oxidized, the heat of reaction is directly applied to the film and the film loses heat, causing wrinkles. If sufficient oxidation is not required, the amount of oxygen introduced may be appropriately reduced, and if the target film thickness is as thin as 50 nm or less, the heating power of the evaporation source can be set to a small value. This means to make it smaller, but it is possible to carry out oxidation vapor deposition without a large heat load. However, in order to perform sufficient oxidation to obtain a thick metal oxide film with a large amount of evaporation, the partition plates 24a, 24
If the position b is larger than the position 0.9 × h from the molten metal surface 28, the film is damaged by the abrupt reaction heat. Further, if the positions of the partition plates 24a and 24b are smaller than the position of 0.6 × h from the molten metal surface 28, the area of the oxygen atmosphere is too large, and the oxygen molecules are sufficiently obstructed to evaporate the metal vapor. Metal atoms do not reach the film. This is a problem that the oxygen partial pressure becomes large and the mean free path becomes small. Further, if the partition plates 24a and 24b are closer to the evaporation source 21, deformation is likely to occur even if the partition plates 24a and 24b are cooled by the heat load of the evaporation source 21, and the rapidly cooled metal vapor condenses, resulting in poor evaporation efficiency.
Therefore, the height position of the partition plate is from 0.6
The position is 0.9 × h, and 0.7 to
The position of 0.8 × h is preferable.

Further partition plates 23a and 23b may be arranged to use only the effective vaporized vapor portion to form a region which is filled with an oxygen atmosphere to some extent as shown in FIG. The partition plates 24a, 24b prevent the oxygen nozzle from being deformed by the heat load of the high-temperature steam, and further, in order to prevent the deformation of the partition plates 24a, 24b, the refrigerant pipes 25a, 25 of 50 ° C. or less are used.
It is preferable to cool b by welding b to the partition plates 24a and 24b. If the temperature of the refrigerant exceeds 50 ° C., it is not preferable because it impedes the heat load on the film. Often, there is an example of an oxygen nozzle without a cooling structure, but according to the findings of the present inventors, an oxygen nozzle without a cooling mechanism is deformed and is not able to blow oxygen sufficiently evenly. The opening of the partition plate that determines the area where the vapor deposition film is exposed to the vaporized vapor 30 is 1.5 times as large as the size of the molten metal 21 in the crucible 22 including the vertical surface of the molten metal 28. It is preferable to have an opening in the film transport direction. That is,
When the size of the molten metal surface in the film transport direction is W, the size W of the opening between the partition plates 24a and 24b is W.
1 is preferably W1> 1.5 × W. By doing so, vaporization of the vaporized vapor of the molten metal is performed in a region including vaporized atoms or the like having a vaporized particle density of sufficiently large kinetic energy and dense.

In the case of a magnetic recording film or the like, the molten metal 21 is intentionally set so as to be positively obliquely deposited.
Avoiding the vertical part of the molten metal surface 22, the film quality depends on the deposition state,
That is, a method of maintaining the magnetic recording characteristics is disclosed, but in this case, since the densely evaporated portion of the evaporated vapor is not used, it is very inefficient, and in the example of the present invention, it is very thick. Since it is a method that can obtain the film thickness at once,
No such example is used. In other words, this is a method that uses evaporated molecules and the like with the highest efficiency and large kinetic energy. The evaporative vapor can be efficiently used by including the most active particles in the vertical portion of the molten metal surface and further including the region of 1.5 times or more of the molten metal surface. If the size of the molten metal is less than 1.5 times the size of the molten metal surface, the efficiency is very poor, and the deposits deposited on the partition plate fall into the molten metal.

A method which positively utilizes this is described in Japanese Patent Laid-Open No.
Although it is disclosed in Japanese Patent Publication No. 17238, it is not preferable to use it in the present invention in the sense of contamination of materials with impurities. The direction of introduction of oxygen is horizontal toward the opening, for example, from the dotted line 31 to the oxygen nozzle 26a in FIG. 1 to vertical toward the cooling can 4, for example, from the dotted line 32 to the oxygen nozzle 26a in FIG. Introduced into the range, more preferably, for example, in the case of the oxygen blowing hole 29a of the oxygen nozzle 26a, introduced toward the range of ± 30 degrees around the straight line 33 connecting the shortest distance to the apex 34 of the cooling can 4. Preferably. If the holes 29a and 29b are directly introduced into the film, in this case, the same as when the holes 29a and 29b for blowing out oxygen are directly below the can, and the rapid heat of oxidation reaction is transmitted to the film, which is not preferable. Therefore, as the positions of the partition plates 24a and 24b are closer to the height of 0.6 × h from the molten metal level 28, the holes 29 are formed.
The directions of a and 29b may be oriented in the vertical direction, but it is not preferable to direct them in the direction of the openings and the partition plates 24a and 24b.
Is closer to the height of 0.9 × h from the molten metal level 28, it is preferable to orient the holes 29a and 29b toward the opening, but not to the vertical direction. become.

Further, as shown in FIG. 3, it is preferable that oxygen is introduced from a plurality of holes 43 in the width direction of the film to be vapor-deposited and uniformly and evenly introduced into the oxygen nozzle 42 in the width direction.
For example, in order to uniformly form an oxide film in the width direction on a film having a width of 1 m, it is preferable to use holes 43 having a width larger than 1 m in the width direction of the film, for example, every 10 mm. Furthermore, the hole diameter of 43 is 0.1
By setting the thickness to 1.5 mm, it is possible to introduce sufficiently diffused oxygen molecules and the like. If it is smaller than 0.1 mm, the workability is poor, and the holes are often blocked by wraparound adhesion of the vapor deposition material. If it exceeds 1.5 mm, the introduced oxygen remains undiffused, that is, a viscous flow state. Since it is introduced into a vacuum, a non-uniform oxidation or a rapid oxidation reaction occurs, the heat load increases, and eventually the film loses heat, which is not preferable.

Further, as shown in FIG. 2, the introduction of oxygen is carried out by the film feeding side 26a and / or winding side 26b.
It is preferable to adjust the introduction pressure and flow rate independently of each other. The pressure is adjusted from the oxygen gas cylinder 14 outside the vapor deposition machine 13 via the regulator 16, the pipe 15 is branched into two pipes 17a and 17b, and then the pressure is individually adjusted by the regulators 18a and 18b, and then the mass flow controller. The flow rate is adjusted through 19a and 19b, and is introduced through the pipes 20a and 20b.

When the pipe is provided on only one side, unevenness of oxidation occurs in the transport direction of the film to be vapor-deposited, that is, when the degree of oxidation is measured in the thickness direction of the film, unevenness of oxidation appears in the thickness direction. For example, when a so-called depth profile is taken, which analyzes the strength characteristics of metal and oxygen or metal oxide in the depth direction by Auger electron spectroscopy, the unevenness can be analyzed in the depth direction.

The amount of oxygen introduced on the unwinding side is preferably larger than the amount of oxygen introduced on the winding side. This is because the oxide film in the process of being oxidized is brought into the portion where the density of the metal vapor is high due to the transportation of the film, and the oxidation is efficiently promoted. This is because the oxygen introduction amount on the unwinding side and the oxygen introduction amount on the winding side are, for example, 7: 3, that is, as an example, the oxygen introduction amount on the unwinding side is 2800 ml / min by the mass flow controller and 1200 ml on the winding side. When a film with a metal oxide film was obtained by introducing 1 / min, the metal oxide film could form a transparent and sufficiently oxidized film, but conversely, it was unwound to introduce oxygen at a ratio of 3: 7. After introducing oxygen to the side of 1200 ml / min,
When oxygen was introduced to the winding side at 2000 ml / min, the heat load on the film became large and heat loss occurred. Therefore, at this time, the increase of oxygen introduction amount was stopped, and a metal oxide film was obtained under this condition.

In this case, the difference can be clearly understood by the analysis by Auger spectroscopy. That is, the strength of the metal element is observed. This phenomenon is due to the fact that, for example, when aluminum is used as the metal, the degree of transparency of the film varies depending on the degree of oxidation of aluminum oxide. The difference in the degree of oxidation can also be determined by the difference in

Further, it is preferable that the introduction of oxygen is started after the molten state of the metal of the evaporation source is stabilized, and the amount of introduction of oxygen is gradually increased. Here, the stabilization of the molten state of the metal of the evaporation source means the following contents. That is, when the metal is placed in a crucible and heated, the metal gradually begins to emit light and becomes reddish. After that, energy is converted into heat energy according to the heat capacity, and the metal gradually becomes liquid near the melting point. After that, since it is placed under reduced pressure, it becomes a gas when it reaches the boiling point at its vapor pressure, but it is heated to as close to the boiling point as possible at the temperature between the point when this molten state is created and the boiling point in that atmosphere. A stable state is a state in which the surface of the water is shaken to the extent that it does not shake. The reason why the oxygen introduction amount is gradually increased is that if the target oxygen introduction amount is increased all at once, the film loses heat due to a rapid oxidation reaction. There is also a method to reduce the heat load by increasing the transport speed of the vapor-deposited film sufficiently, but even if it is transported at a speed of about 5 times the film transport speed under the target conditions, the film may break due to heat loss. did. Therefore, it is preferable to gradually increase the introduction amount, and as a result of various studies, it is preferable to control the increase rate of the oxygen introduction amount so as not to exceed (10 ml / min) / sec. If it exceeds (10 ml / min) / sec, the heat load is large and the film is greatly damaged by heat.

As for the order of introducing oxygen, it is preferable to introduce oxygen on the unwinding side before on the winding side. When oxygen is introduced from the winding side, a heat load due to a rapid oxidation reaction is applied to the film at the moment of introduction, and the film is likely to lose heat, which is not preferable. The management of the optimum point of the oxygen introduction amount is preferably monitored by a vacuum gauge installed between the vapor deposition machine main body and the vacuum pump, and the oxygen introduction amount is preferably introduced up to the introduction amount. When the amount of oxygen introduced is gradually introduced, the degree of vacuum is consumed in the reaction with the metal.Therefore, depending on how to increase the amount of introduced oxygen, if the amount of increase is large, the pressure rises temporarily, and the amount of oxygen introduced then reacts. When it contributes to, it returns to the original pressure again. If the amount of increase is small, the pressure changes little. When the amount of metal vapor flying is sufficiently oxidized, the original vacuum pressure (attainment pressure) begins to be exceeded. This point can be regarded as the pressure at which the necessary and sufficient metal vapor reacts.
This can be regarded as an almost appropriate point, though there is a balance of capacity with the vacuum pump. Vacuum pump 8 and vapor deposition machine 1
The vacuum pressure is monitored by a vacuum gauge 10 installed between the pressure gauge 3 and the pressure gauge 3 and the difference between the pressure after oxygen introduction and the pressure before oxygen introduction is 3
A sufficient metal oxide film can be maintained by adjusting the amount of oxygen introduced so as to be 10 ⁻² Pa or less.

The thickness of the metal oxide film obtained by the present invention is 50 to 50 when it is thicker than the thickness of 50 nm or less used in packaging vapor deposition and the like.
The effect is demonstrated when it is set to 0 nm. Ie 5
In the case of a film thickness of 0 nm or less, for example, the example described in JP-A-63-222849, it can withstand a heat load, but if it exceeds this film thickness, it becomes very difficult in terms of heat load to the film. In addition, this phenomenon causes a larger heat load as the thickness increases. According to our results, this method is 500n
If the thickness is more than m, the film will be thin, especially if it is less than 4 μm, and heat will be lost.

Further, the surface resistance value of the metal oxide film is 10 ⁷
It can be suitably used when it is Ω / sq or more. If it is less than 10 ⁷ , a sufficient metal oxide film is not formed, and in a sense, it is in a semi-oxidized state. In the case of such a film, the load of heat of oxidation reaction is small. Therefore, the case where the effect of the present invention is most exerted is 10 ⁷ or more, which is preferably used.

Further, it is preferably used when the difference in total light transmittance between the film with a metal oxide film and the undeposited film is within 5%. If the oxidation of the metal vapor is insufficient, the total light transmittance will decrease. If oxidation is sufficient, transparency will increase. This is a particularly suitable method in the case of forming a thick film, that is, a film having a thickness of 50 nm to 500 nm while maintaining transparency and insulating property. Further, it is preferable to measure the transmittance of the film with a metal oxide and adjust and control the energy and / or oxygen introduction amount of the evaporation source based on the transmittance so that the transmittance becomes substantially constant. It is preferable to measure and maintain the transmittance in-line to maintain the quality of transparency. There is also a method of adjusting the amount of energy (electric power) applied to the evaporation source, but it is easier and easier to adjust the amount of oxygen introduced. However, when the quality of the film thickness is important, it is preferable to control the balance between the input power to the evaporation source and the amount of oxygen introduced.

The transmittance means the transmittance for C light or D65 light source or the transmittance at a certain wavelength defined by JIS, and the total light transmittance of the film means the transmittance for C light or D65 light source. , For example, the total light transmittance that can be measured by a "Haze Computer HZ-1" device manufactured by Suga Test Instruments Co., Ltd. The transmittance monitored in-line may be the total light transmittance or the transmittance of light of a certain specific wavelength, but the light intensity is high in relation to the measurement accuracy and the resolution of the measuring device. 500
The transmittance of light having a specific wavelength of ˜600 nm may be used as a substitute. When receiving light of a specific wavelength, it can be realized by passing light of a specific wavelength using an interference filter or the like and receiving the light.

Optical monitor (transmittance measuring device) 51 here
For the sensor, a sensor using a photomultiplier or a silicon photodiode is preferably used, and specifically, UL
"FADM-2" manufactured by VAC is commercially available and used. In the case of this product, a halogen lamp is used as a light source, and a light of 565 nm is received by using a bandpass filter of 565 ± 5 nm as a light receiving part wavelength.

The metal 21 used in the present invention is not particularly limited so long as the desired characteristics can be obtained, but a material mainly composed of aluminum and / or copper has a low melting point and is an inexpensive material, and thus is suitable. Used. In addition, the aluminum oxide film and the copper oxide film are preferably used because of their excellent gas barrier properties, rigidity, thermal expansion properties and the like. Other materials include Zn, Sn, Ni, Ag, Co, Fe, Mn, and M.
Metals such as g and In are also included. Among these materials, there are materials such as Sn, Mg, In, etc. in which the oxide has the performance of semiconductor, or alloy materials thereof, but these materials are selected in the application requiring conductivity.

It is preferably used when the thickness of the vapor-deposited film is 2 to 6 μm. If the film thickness is thick, it may be possible to do without losing heat even if there is a heat load due to its heat capacity, but in the case of a thin film of 2 to 6 μm, it is easy to tear due to the heat load, and if tearing occurs, it also accompanies breakage However, it becomes necessary to release the pressure of the vacuum container, which not only takes a very long time to restore, but also deteriorates productivity. Further, even if the film is as thin as 2 to 6 μm, by setting the thickness of the metal oxide film to 50 to 500 nm, as a result, the Young's modulus in the longitudinal direction and the width direction of the film is 5500, respectively.
A film with a metal oxide film having a pressure of at least 7500 MPa can be produced.

Further, a film for magnetic recording medium having a surface roughness Ra value of 1 to 5 nm on the surface A on one side of the vapor-deposited film, which is formed as a strength reinforcing film on the surface B (back surface) of the film. , A thin film having a thickness of 2 to 6 μm can be used as a magnetic recording film, and the number of windings can be increased even in the same cassette, and the memory can be increased, which is very preferable. Since the film to be vapor-deposited is polyester, polyethylene terephthalate or polyethylene-2,6-naphthalate, or is a polyamide film, it is used as a DVC film currently used, so it can be linked to commercialization. preferable. By providing a ferromagnetic thin film on the surface A, the performance as a magnetic recording film can be exhibited. A film with a metal oxide film is preferably used for a magnetic recording medium of digital recording type.

The polyester used in the present invention may be any polyester which can form a high-strength film by molecular orientation, but polyethylene terephthalate, polyethylene-
2,6-naphthalate is preferred. That is, 80% or more of the constituent components are polyethylene terephthalate and polyethylene-2,6-naphthalate, which are ethylene terephthalate and ethylene naphthalate. Examples of the polyester copolymer component other than ethylene terephthalate and ethylene naphthalate include diethylene glycol and
Propylene glycol, neopentyl glycol, polyethylene glycol, p-xylylene glycol, 1,
A diol component such as 4-cyclohexanedimethanol,
Adipic acid, sebacic acid, phthalic acid, isophthalic acid, 5
-Dicarboxylic acid components such as sodium sulfoisophthalic acid, polyfunctional dicarboxylic acid components such as trimellitic acid and pyromellitic acid, and p-oxyethoxybenzoic acid.

Further, in addition to the above polyester,
At least one of an alkali metal salt derivative of sulfonic acid which is non-reactive with polyester and polyalkylene glycol which is substantially insoluble in polyester may be mixed in an amount not exceeding 5% by weight.

The surface roughness Ra value of the surface A on one side of the support of the present invention is to minimize abrasion of the ferromagnetic metal thin film formed on the surface A by vacuum deposition by the video head during recording and reproduction. , 5 nm, preferably 2 to 4 nm in order to keep the output characteristics of the DVC tape good. If the Ra value is less than 1 nm, the ferromagnetic metal thin film layer formed by vacuum deposition on the surface A is too smooth,
The ferromagnetic metal thin film of the video tape is worn by the video head when recording and reproducing with a digital video tape recorder. If the SRa value exceeds 5 nm, the ferromagnetic metal thin film layer becomes too rough and the output characteristics of the DVC tape deteriorate.

In order to bring the surface roughness Ra value of the surface A to the above-mentioned level, the average particle size is 5 to 30 n on the film surface.
m, preferably 8 to 30 nm fine particles, 0.5 to 1
A coating layer made of an organic compound containing 2.0% by weight, preferably 0.6 to 10.0% by weight, is formed, and the surface of the coating layer is
The surface A is desirable. Fine particles of silica, calcium carbonate, alumina, polyacrylic acid spheres, polystyrene spheres, organic compounds of polyvinyl alcohol, tragacanth gum, casein, gelatin, cellulose derivatives, water-soluble polyester, polar polymers such as polyurethane, blends of these Can be used, but is not limited to these.

Next, a method for producing the film of the present invention will be illustrated.

As the polyester film used for the support of the present invention, polyester in which the contained particles are removed as much as possible is used as the A-side raw material, and the polyester film is manufactured by a usual plastic film manufacturing process including melting, molding, biaxial stretching and heat setting. ,
2.7 to 5.5 at 90 to 140 ° C in the vertical and horizontal directions, respectively
It can be manufactured by performing the following operation under the condition that the film is stretched twice, 3.5 to 7.0 times, and heat-set at a temperature of 190 to 220 ° C.

In order to adjust the Ra value of the surface A, fine particles having an average particle size of 5 to 30 nm, preferably 8 to 25 nm are added to the A surface side of a smooth polyester film after stretching in one direction of 0.5 to 0.5. 12.0% by weight, preferably 0.6 to 10.
A coating liquid consisting of 0% by weight of an organic compound is applied to form a coating layer on the surface A side, and fine surface protrusions are formed on the surface A. The coating layer may have a continuous film shape or a discontinuous film shape. Silicone, silane coupling agent, to improve its slipperiness and durability
A small amount of titanium coupling agent may be added.

When it is desired to further increase the durability of the magnetic layer of the DVC tape, the average particle size within the polyester layer forming the surface A is 30 to 90 nm, preferably 40 to 80 nm.
nm fine particles are 1.0% by weight or less, preferably 0.8
It is preferable that the surface protrusions are provided on the surface A by including it in an amount of not more than wt%. As the fine particles, silica, calcium carbonate, alumina, polyacrylic acid spheres, polystyrene spheres and the like can be used, but are not limited thereto.

The surface roughness Ra value of the surface A is as follows.
It can be adjusted by adjusting the type of fine particles in the polyester layer, the average particle size, and the addition amount.

A / B laminated film is melt-extruded into a film by a co-extrusion technique using the above-mentioned A-side raw material (for A layer) and the raw material positively containing larger fine particles (for B layer). You may. Further, a coating solution containing a lubricant may be applied to the surface (B side) opposite to the surface A side of the above-mentioned monolayer film made of the A side raw material, and the B side may be a surface subjected to easy slip treatment. . The type of fine particles contained in the B layer,
Ra value on the B side is 2 to 50n by adjusting the particle size and content.
It is preferable to adjust to m. It can also be adjusted by incorporating fine particles in a coating liquid containing a lubricant and adjusting the type, particle size and content of the fine particles. As the fine particles, silica, calcium carbonate, alumina, polyacrylic acid spheres, polystyrene spheres and the like can be used, but not limited to these.

The support for magnetic recording media obtained by the present invention comprises a polyester film, a reinforcing film formed on the surface B on one side of the film, that is, the metal oxide film of the present invention and, if necessary, the opposite. And a coating layer formed on the surface A on the side, and the thickness of this support is 2.0 to
The thickness is 6.0 μm, preferably 2.0 to 5.5 μm, and more preferably 3.0 to 5.0 μm. If the thickness exceeds 6.0 μm, the recording time of the DV mini cassette tape prepared from the support of the present invention is less than 80 minutes, which is not preferable. If the thickness is less than 2.0 μm, the rigidity of the support will be lowered too much, the contact between the DVC tape and the magnetic head in the video tape recorder will be weakened, and the electromagnetic conversion characteristics of the DVC tape, especially the output will be lowered.

The Young's modulus in the longitudinal and width directions of the support is
5500 MPa or more and 7500 MPa or more, respectively, preferably 6000 to 20000 MP
a, 8000 to 24000 MPa. If the Young's modulus in the longitudinal direction is less than 5500 MPa, repeated reproduction of the DVC tape will elongate and the DO during reproduction will increase. D when the Young's modulus in the width direction is less than 7500 MPa
When the VC tape is repeatedly reproduced, the edges of the DVC tape are deformed by the magnetic head and become wakame, which increases DO during reproduction. Young's modulus in the longitudinal direction and width direction of the support is 20000 MPa and 24000 MP, respectively.
In order to make it as high as more than a, the Young's modulus of the polyester film used is 11,000 MPa or more in the longitudinal direction,
It must be extremely high, such as 15000 MPa or more in the width direction, and for that purpose the stretching ratio of the polyester film must be made very large. Up,
This is extremely difficult and is not preferable.

By forming the reinforcing film, that is, the metal oxide film of the present invention on the surface B of the film, the Young's modulus and bending rigidity of the support are improved. The thickness of the reinforcing film is 5500 M in Young's modulus in the longitudinal direction and width direction of the support, respectively.
If it can be Pa or more and 7500 MPa or more,
There is no particular limitation, and it may be determined depending on the material of the reinforcing film material. The thickness of the metal oxide film is preferably 50 to 500 nm, and more preferably 50 to 200 nm. If it is less than 50 nm, it is difficult to achieve the purpose of strengthening.
When it exceeds 00 nm, the reinforcing film tends to peel off from the polyester film, which is not preferable.

The DVC tape prepared from the support of the reinforcing film, that is, the polyester film having a thickness of 2 to 6 μm, on which the metal oxide film of the present invention is not formed, is stretched by repeated reproduction and the DOC at the time of reproduction is increased. May increase, and the edges of the DVC tape may also be deformed by the magnetic head to become wakame, and the DO during reproduction may increase.

The reinforcing film, that is, the metal oxide film of the present invention is preferably provided on the surface B of the polyester film.
When the reinforcing film is provided on the surface A of the polyester film, the surface of the reinforcing film tends to have a large surface roughness, and the ferromagnetic metal thin film layer formed by vacuum deposition on the surface tends to become a rough surface. The output characteristics of are likely to deteriorate, which is not preferable. Of course, it is not limited to this as long as the film has fine crystal grains.

The surface electric resistance of the surface of the support of the present invention on the side where the reinforcing film is formed is preferably 10 ⁷ Ω / sq or more. This description is given below. In the vacuum deposition of Co on the magnetic recording surface A, a ferromagnetic film is formed by a vacuum deposition apparatus as shown in the example of FIG.

The Co vacuum deposition machine 113 shown in FIG.
Reference numeral 11 has substantially the same mechanism as that in FIG. 1, and the lower chamber 112 has a magnetic recording mechanism.

In FIG. 4, the vacuum chamber is roughly divided into an upper chamber 111 for winding and unwinding the film and a lower chamber 112 for vapor deposition. The upper chamber pump 9 and the lower chamber pump 8 are respectively separated.
Decompressed by. The vacuum pump often uses a roughing pump and a high vacuum pump to reach a high vacuum. In ordinary vacuum deposition, the pressure in the lower chamber is set to be lower by one digit than that in the upper chamber. For example, the upper chamber is set to 10 ^-1 to 10 ^-2 Pa and the lower chamber is set to 10 ^-3 to 10 ^-5 Pa. Unwinding means 10
1, the roll-shaped film 103a is set, the film is set along the guide rolls 105a, 105b, 105c, 105d, and the film 3c is further placed on the cooling can 104.
So that the film faces the evaporation source 7, and then the film is wound along the guide rolls 106a, 106b, 106c, and 106d, and the film is wound by the winding means 2 to form the roll-shaped film 103e. The film is set. Guide means 105a-105d,
106a to 106d are adapted to give appropriate tension to the film 103. After setting the film in this way, after setting, for example, Co as a metal material in the evaporation source 107, the pressure is reduced, and the evaporation source 1 is reduced by using the electron beam 136.
It is a system that obtains a vapor deposition film by heating and evaporating 07 and transporting the film at a certain speed.

The cooling can 104 is often cooled to about -20 ° C. by using a refrigerant such as ethylene glycol.

Further, in order to form a film having a good magnetic recording property, a mask is formed by using the deposition preventing plates 124a and 124b,
The opening of the evaporation portion is provided so that the evaporation particles are obliquely incident and precipitated from the evaporation source. Further, in order to oxidize the Co metal surface, oxygen can be introduced from the winding side using the oxygen introduction tube 126.

In the evaporation of a ferromagnetic material, an electron beam method is usually preferably used as an evaporation source. However, this is because the melting point of a ferromagnetic material such as Co is very high and the evaporation source is controlled. It is adopted from the point. This is done while the surface of the support on which the reinforcing film, that is, the metal oxide film of the present invention is formed, extends along the surface of the cooling can. In vapor deposition by such an electron beam method, reflected electrons and secondary electrons are generated by applying a material electron beam to be vaporized, and the electrons reach the vapor deposition target film side. The electrons serve to charge the film and strengthen the adhesion of the film to the cooling can. Alternatively, the film may be charged by another means to strengthen the close contact between the cooling can and the film. For example, the electron beam is directly applied to the vapor-deposited film to be negatively charged, or positive ions are positively charged to the vapor-deposited film by an ion gun or the like. As described above, the electrostatic adhesion effect of the film is used to enhance the adhesion of the film to the cooling can and increase the cooling efficiency, thereby reducing the heat load associated with the vapor deposition of the high melting point material such as Co. However, if the surface electrical resistance of the reinforcing film of the support, that is, the surface on the side where the metal oxide film of the present invention is formed is less than 10 ⁷ Ω / sq, the electrostatic adhesion force between the support surface and the cooling can is increased. Does not work, the adhesion between the surface of the support and the cooling can is reduced, and during the vacuum deposition of Co, the radiant heat due to the light emission generated by the melting of Co and the kinetic energy and latent heat of the vaporized vapor are transferred to the support,
It becomes difficult for the heat transferred to the film to escape to the cooling can, and the polyester film constituting the support is easily melted, so-called heat loss occurs and the vacuum deposition of Co cannot be performed.

To prepare a magnetic recording medium using the magnetic recording medium support of the present invention, vacuum deposition is performed on the surface A of the support (when the surface A is a coating layer, the surface of the coating layer). Although a known metal can be used for forming the ferromagnetic metal thin film layer, it is not particularly limited, but a metal made of a ferromagnetic material of iron, cobalt, nickel, or an alloy thereof is preferable. The thickness of the metal thin film layer is generally 100 to
It is 300 nm. It can be prepared by forming a diamond-like carbon film with a thickness of about 10 nm on this ferromagnetic thin film layer by coating, and further treating it with a lubricant such as perfluoroether.

In the magnetic recording medium of the present invention, the support surface B
May be used as it is as the running surface side of the magnetic tape,
In order to secure the running property and durability when traveling with various guides and pins in the DVC video tape recorder, a solution containing solid fine particles and a binder, and various additives as necessary, is applied on the surface B. By doing so, the back coat layer may be formed. The thickness of the back coat layer is about 0.5 to 1.5 μm. As the fine particles, carbon black, alumina, etc., as the lubricant, silicone, a fluorine compound, etc., as the binder, polyurethane,
Epoxy resins and the like are used, but not limited to these. The support for magnetic recording media of the present invention is suitable when used as a support for producing a DVC-LP tape, because excellent results can be obtained. Also, excellent results can be obtained when used as a support for data storage applications such as AIT systems.

A schematic view of the insulation resistance measuring device is shown in FIG.
KAWAGUHI ELECTRIC WORKS
The sample measuring part of "TERA OHM METER" by TOKYO and its measuring circuit are shown. Set the sample 60 as shown. That is, the metal oxide film 62 to be measured is on the lower side in the figure, and the base film 6 is on the upper side.
Set it to be 1. In this way, it is sandwiched between the electrodes and put in the volume box 63 for measurement. The measurement circuit is shown on the right side in the figure, but the measurement unit has a resistance of 65 and the insulation resistance meter unit has a resistance of 64.

[0104]

EXAMPLES The measurement methods used in this example are shown below.

(1) Ra Value The surface roughness Ra value of the surface A of the magnetic recording medium support in the present invention is determined by an atomic force microscope (scanning probe microscope).
Was measured using. Using a scanning probe microscope (SPI3800 series) manufactured by Seiko Instruments Inc., the surface of the film is 3 in dynamic force mode.
Atomic force microscope measurement scanning is performed in the range of 0 μm square, and from the surface profile curve obtained, JIS B0601
It was calculated from the arithmetic mean roughness corresponding to Ra. The magnification in the in-plane direction was 10,000 to 50,000 times, and the magnification in the height direction was about 1 million times.

(2) Young's modulus Longitudinal direction (MD) and width direction (TD) of the film of the present invention
The Young's modulus of AST is calculated from the rising slope of the start point in the stress-strain curve obtained by the tensile test measurement to AST.
It is measured according to M-D-882-67, and the unit is expressed in MPa. At this time, the sample width and effective length are 10 mm and 1
The pulling speed was 100 mm / min.

(3) Total light transmittance "Haze Computer HZ-" manufactured by Suga Test Instruments Co., Ltd.
The sample was set with a 1 "device and the total light transmittance was measured.

(3) Surface resistance value of the metal oxide film of the present invention KAWAGUCHI ELECTRIC WORKS
It was measured using "TERA OHM METER" manufactured by TOKYO. Figure 5 shows the sample measurement section and its measurement circuit.
Shown in. The measurement voltage was 10V.

(4) Characteristic evaluation of magnetic tape (DVC tape) Recorded in a quiet room using the LP mode of a commercially available camera-integrated digital video tape recorder, played for 1 minute, and appeared in block form on the screen. By counting the number of mosaics (dropout (DO) number) of D
The VC tape properties were evaluated. DO number is normal temperature (25 ℃)
First, the initial characteristics of the tape after manufacturing were examined. Next, measure the number of DOs after the tape has been run 100 times
The running durability of the C tape was evaluated.

(5) Evaluation of Film Thickness and Composition of Metal Oxide Film The depth direction analysis of Auger electron spectroscopy was performed. The device is
It was measured using "PH1670" manufactured by PERKIN ELMER. The measurement vacuum degree is 5 × 10 ⁻⁶ Pa to 1 × 10.
^It was measured at ^-7 Pa. The sample is fixed on the sample table, the acceleration voltage is 3 kV, the irradiation current is 10 nA, the sample tilt angle is 74 degrees,
The measurement was performed under the measurement conditions of a beam diameter of 200 nm or less. As ion etching conditions, ion species Ar + and acceleration voltage 3
It was measured at kV, an ion current of 2 μA, and a sample inclination angle of 30 degrees.

Next, the present invention will be described based on examples.

Example 1 (1) Film Formation Polyethylene terephthalate raw material A containing substantially no inert particles, and polyethylene terephthalate containing substantially no inert particles, and aluminum silicate having an average particle size of 220 nm. With a raw material B containing 0.48% by weight at a thickness ratio of 5: 1, coextruded through a die, closely adhered to a cooling drum to form a sheet, and longitudinally stretched at 110 ° C. to 3.4 times by a roll stretching method. did.

In the step after the longitudinal stretching, an aqueous solution having the following composition was applied to the outside of the layer A at a solid content concentration of 22 mg / m ² . Outside of layer A: Methyl cellulose 0.11% by weight Water-soluble polyester (70% by mole of terephthalic acid, 30% by mole of 5-sodium sulfoisophthalic acid and 1: 1 copolymer of ethylene glycol and ethylene glycol) 0.28% by weight Aminoethylsilane coupling agent 0.01% by weight Ultrafine silica having an average particle size of 11 nm 0.03% by weight After that, it was stretched in a transverse direction at 110 ° C by 4.0 times and heat treated at 210 ° C to obtain a thickness. A 4.5 μm thick polyester film was obtained. This film is slit into a width of 600 mm using a slitter, and the winding length is 20000.
m film roll.

The total light transmittance of one obtained film was calculated by
"Haze Computer HZ-" manufactured by Suga Test Instruments Co., Ltd.
It was 92.2% when measured with a 1 "device. (2) Formation of metal oxide film Using the film roll thus obtained, an aluminum oxide film was formed to a thickness of 150 nm as follows. The shortest distance between the evaporation source crucible and the cooling can was taken almost vertically at the apex of the cooling can, and the distance was 800 mm, and the position of the partition plate was the evaporation source crucible. It was placed at a position of 640 mm from the partition plate.
Cooled with water at 0 ° C. 20 openings in the film transport direction
It was set to 0 mm. The oxygen nozzle is attached at a position retracted 50 mm from the opening on both the unwinding side and the winding side,
For the outlet part, a nozzle having 0.5 mmφ holes at 10 mm intervals was used in a member having a structure in which both ends of a circular tube member having a width of 800 mm, a diameter of 12 mm and a thickness of 1 mm were closed. Three pipe members 41 are connected to the circular pipe member so that oxygen is supplied. The holes were oriented toward the top of the cooling can on both the unwinding side and the winding side. First, the obtained film roll was set in the unwinding means of FIG. 2, the film was set along the guiding means 5a to 5d, the cooling can, and the guiding means 6a to 6d, and the film end was attached to the winding means 2 and set. . The device is 100mmφ x 100m depth
Four carbon crucibles of m were lined up in the width direction of the film, and 800 g of metal aluminum and 3200 g of metal aluminum were set in each. Then, depressurize the vapor deposition machine 13,
The vacuum pressure in the upper chamber was evacuated to 1 × 10 ⁻¹ Pa and the vacuum pressure in the lower chamber 12 was evacuated to 1 × 10 ⁻² Pa. Then, with the shutter member 35 closed, aluminum was melted by a high frequency induction heating method. Power input is 32 kW in total for 4 crucibles
Met. The electric power supplied to the four crucibles was adjusted so that the four crucibles were evenly melted. After that, the state of the molten aluminum surface was observed, and the amount of electric power was finely adjusted to about 35 kW so that the fluttering of the molten aluminum surface due to boiling fluctuated. Adjust the tension of the unwinding means to 44.1N (4.5
kgf), the winding tension is set to 39.2 N (4.0 kgf), the cooling can 4 and the guide rollers 5a to 5d, 6a to.
By the speed setting of 6d, the deposition target film was started to be conveyed at a speed of 300 m / min. Then, the shutter member was opened and aluminum vapor deposition was performed. The optical monitor 51 was used to monitor whether the aluminum film was uniformly vapor-deposited in the width direction, and the input power to the four crucibles of the evaporation source was finely adjusted so that the transmittance was constant. The transmittance here is the total light transmittance converted into the light intensity distribution of the D65 light source defined by JIS using a halogen lamp as a light source. Four optical monitors were attached in the width direction of the film, and adjustment was made so that the variation in transmittance of these four was ± 1%. Vacuum gauge 10 in this state
The pressure was 2.5 × 10 ^-2 Pa. After that, the rising rate of the oxygen introduction amount from the unwinding side oxygen nozzle 26a is set to (10
ml / min) / sec.
Introduced up to 0 ml / min. Vacuum gauge 10 depending on oxygen introduction
The value of fluctuated and increased repeatedly and then returned to the original pressure. After that, the rate of increase of the amount of oxygen introduced from the oxygen nozzle 26b on the winding side was gradually increased so that it did not exceed (10 ml / min) / sec and the oxygen was introduced up to 1700 ml. The value of the vacuum gauge 10 fluctuated and increased in response to the introduction of oxygen, and then returned to the original pressure. In this state, the pressure of the vacuum gauge 10 was 5 × 10 ^-2 Pa. In this state, when the film was observed through the winding-side monitoring window 36, it looked almost transparent. The transmittance is 88.5% with the values of 4 optical monitors,
88.6%, 88.7%, and 88.4% were shown. After that, the film after vapor deposition was monitored through a monitoring window to confirm that the film did not lose heat, and the transport speed of the film was gradually reduced. At 120m / min, some perforation-like heat loss occurred, so 140m /
Speed up again to minutes. 16000m in this state
The film was wound and conveyed for a minute to form an aluminum oxide film.
Then, the shutter member 35 was closed to stop the introduction of oxygen, and the power supply to the evaporation source was cut off. And the transport speed is 1
The pressure was reduced to 0 m / min and the pressure of the vapor deposition machine 13 was released. The film thickness of this aluminum oxide film was 150 nm. The film thickness was analyzed by Auger electron spectroscopy. The analysis result is shown in FIG.
There is also a method of optically determining the thickness by inputting the refractive index of aluminum oxide using the spectral reflectance characteristic. The total light transmittance of the obtained film is "Suga Test Instruments Co., Ltd."
8 when measured with a haze computer HZ-1 "device
It was 8.5%. Surface resistance value is 1.5 × 10 ¹² Ω / s
It was q. Thus, a support having a thickness of 4.65 μm was prepared. The characteristics of this support are shown in Table 1.

Then, a cobalt-oxygen thin film having a thickness of 180 nm was formed on the surface A of this support by vacuum evaporation.
Next, a diamond-like carbon film having a thickness of 10 nm was formed on the cobalt-oxygen thin film layer by the CVD method. After that, the surface B side was brought into contact with a hot roller at 150 ° C. to run, and the curl was returned. Subsequently, a fluorine-containing fatty acid ester lubricant is applied to a thickness of 3 nm, and finally a back coat layer (thickness 400 nm) made of carbon black, polyurethane and silicone is applied on the film surface B by a solution application using a methyl ethyl ketone solution. And slit it to a width of 6.35 mm with a slitter.
A magnetic recording tape (DVC-LP tape, recording time 120 minutes in LP mode) was wound on a reel. The characteristics of the obtained DVC-LP tape are shown in Table 2.

Example 2 The metal was melted using an apparatus using an electron beam instead of the method of heating the evaporated metal by the high frequency induction heating method. 1 and 2, vapor deposition was performed using a vapor deposition machine having almost the same specifications except that the heating method of the evaporation source was an electron beam. The film used was exactly the same as in Example 1. The vapor deposition method was exactly the same as in Example 1. The input power of the electron gun was 50 kW (accelerating voltage: 20 kV, emission current: 2.5 A).
Scanning was performed in the film width direction by scanning so as to prevent unevenness in the film width direction. Tension of unwinding means is 4
4.1N (4.5kgf), winding tension 39.2N
(4.0 kgf), and the speed of the cooling can 4 and the guide rollers 5a to 5d and 6a to 6d is set to 300 m /
The transport of the vapor deposition film was started at a speed of minutes. Then, the shutter member was opened and aluminum vapor deposition was performed. Optical monitor 5 to check if aluminum film is evenly deposited in the width direction
The electric power input to the four crucibles of the evaporation source was finely adjusted so that the transmittance was constant, as monitored by No. 1. The transmittance here is
The total light transmittance converted into the light intensity distribution of the D65 light source defined by JIS using a halogen lamp as a light source. Four optical monitors were attached in the width direction of the film, and adjustment was made so that the variation in transmittance of these four was ± 1%.
In this state, the pressure of the vacuum gauge 10 was 2.0 × 10 ^-2 Pa. Then, the rate of increase of the amount of oxygen introduced from the unwinding side oxygen nozzle 26a was gradually increased so as not to exceed (10 ml / min) / sec and the oxygen was introduced up to 3000 ml / min. The value of the vacuum gauge 10 fluctuated and increased in response to the introduction of oxygen, and then returned to the original pressure. After that, the rate of increase in the amount of oxygen introduced from the oxygen nozzle 26b on the winding side was adjusted to 10 ml.
/ Min) / sec is gradually raised so as not to exceed 2500m
1 was introduced. The value of the vacuum gauge 10 fluctuated and increased in response to the introduction of oxygen, and then returned to the original pressure. In this state, the pressure of the vacuum gauge 10 was 4 × 10 ^-2 Pa. In this state, when the film was observed through the winding-side monitoring window 36, it looked almost transparent. The transmittances of the four optical monitors are 89.0%, 88.7%, 88.7%, 89.
It showed 1%. After that, the film after vapor deposition was monitored through a monitoring window to confirm that the film did not lose heat, and the transport speed of the film was gradually reduced. 80
At a speed of m / min, some perforation-like heat loss occurred, so the speed was increased again to 100 m / min. In this state, the film was wound and conveyed for 12000 m to form an aluminum oxide film. Then, the shutter member 35 was closed to stop the introduction of oxygen, and the power supply to the evaporation source was cut off.
Then, the transport speed was lowered to 10 m / min to release the pressure of the vapor deposition machine 13. The thickness of this aluminum oxide film was 200 nm. The film thickness was analyzed by Auger electron spectroscopy. The analysis result is shown in FIG. 7. There is also a method of optically determining the thickness by inputting the refractive index of aluminum oxide using the spectral reflectance characteristic. The total light transmittance of one obtained film was 89.0% when measured with a "Haze Computer HZ-1" apparatus manufactured by Suga Test Instruments Co., Ltd. Surface resistance is 8
It was × 10 ¹² Ω / sq. Thus the thickness 4.70 μm
The support was created. The characteristics of this support are shown in Table 1.

Then, a cobalt-oxygen thin film having a thickness of 180 nm was formed on the surface A of this support by vacuum evaporation.
Next, a diamond-like carbon film having a thickness of 10 nm was formed on the cobalt-oxygen thin film layer by the CVD method. After that, the surface B side was brought into contact with a hot roller at 150 ° C. to run, and the curl was returned. Subsequently, a fluorine-containing fatty acid ester lubricant is applied to a thickness of 3 nm, and finally a back coat layer (thickness 400 nm) made of carbon black, polyurethane and silicone is applied on the film surface B by a solution application using a methyl ethyl ketone solution. And slit it to a width of 6.35 mm with a slitter.
A magnetic recording tape (DVC-LP tape, recording time 120 minutes in LP mode) was wound on a reel. The characteristics of the obtained DVC-LP tape are shown in Table 2.

Example 3 An aluminum oxide film was formed by using the same film and apparatus as in Example 1 and under exactly the same conditions as in Example 1 except for the amount of oxygen introduced. The amount of oxygen introduced is the rate of increase of the amount of oxygen introduced from the unwinding side oxygen nozzle 26a (10 m
1 / min) / sec.
Introduced up to ml / min. The value of the vacuum gauge 10 fluctuated and increased in response to the introduction of oxygen, and then returned to the original pressure. After that, the rate of increase of the amount of oxygen introduced from the oxygen nozzle 26b on the winding side was gradually increased so that it did not exceed (10 ml / min) / sec, and the oxygen was introduced up to 2000 ml. The value of the vacuum gauge 10 fluctuated and increased in response to the introduction of oxygen, and then returned to the original pressure. When the film was observed through the monitoring window 36 on the winding side in this state, it appeared that a slightly brownish, almost transparent film was formed. The transmittance is 85.3%, 84.6%, 8 with the values of 4 optical monitors.
It showed 4.7% and 85.4%. The transmittance here is the total light transmittance converted into the light intensity distribution of the D65 light source defined by JIS using a halogen lamp as a light source. After that, the film after vapor deposition was monitored through a monitoring window to confirm that the film did not lose heat, and the transport speed of the film was gradually reduced. At 140m / min, some perforation-like heat loss occurred, so 1
The speed was increased again to 60 m / min. 16 in this state
The film was wound up and conveyed for 000 m to form an aluminum oxide film. Then, the shutter member 35 was closed to stop the introduction of oxygen, and the power supply to the evaporation source was cut off. Then, the transport speed was lowered to 10 m / min to release the pressure of the vapor deposition machine 13.
The film thickness of this aluminum oxide film was 105 nm. The film thickness was analyzed by Auger electron spectroscopy. Figure 8 shows the analysis result.
Shown in. There is also a method of optically determining the thickness by inputting the refractive index of aluminum oxide using the spectral reflectance characteristic. The total light transmittance of one obtained film was 84.8% as measured by "Haze Computer HZ-1" apparatus manufactured by Suga Test Instruments Co., Ltd. Surface resistance value is 2.5 × 10
It was ⁸ Ω / sq. Thus, a support having a thickness of 4.605 μm was prepared. The characteristics of this support are shown in Table 1.

Comparative Example 1 A polyester film having a thickness of 4.5 μm was produced in the same manner as in Example 1 except that the reinforcing film was not formed. Using this as a support, DVC-L was used.
A P-tape (120 minutes recording time in LP mode) was created. The characteristics of the obtained support (film) and DVC-LP tape are shown in Tables 1 and 2.

[0120]

[Table 1]

[0121]

[Table 2]

As is clear from the characteristics shown in Tables 1 and 2, the magnetic tape having the ferromagnetic metal thin film layer on one surface A of the support of the present invention has a small number of DOs and is excellent in running durability. It was a DVC-LP tape that can be recorded for a long time. On the other hand, a magnetic tape could not be processed from a support other than the present invention, or at least one of initial characteristics and running durability was inferior even if a magnetic tape could be prepared.

[0123]

According to the present invention, there is provided a film winding type vapor deposition method, in which a vapor-deposited metal is melted and vaporized, and oxygen is introduced during the vaporization to obtain a sufficiently oxidized metal oxide film. You can In particular, a thin metal oxide film having a thickness of 50 to 500 nm can be provided for a thin film having a thickness of 2 to 6 μm. Furthermore, it can be used in applications where insulation and transparency are required.

The present invention can also provide a method for reinforcing the strength of a thin film having a thickness of 2 to 6 μm, and is suitably used for a magnetic recording medium film, particularly a digital recording type magnetic recording medium film. be able to. Therefore, since a thin film has strength, a magnetic recording film having the same size and a large capacity can be obtained.

When the magnetic recording medium support according to the present invention is used, running durability is good even after repeated running, dropout (DO) is less likely to occur, and a helical recording medium such as a DVC-LP tape capable of recording for a long time. A magnetic recording medium suitable for digital recording by the scan method can be manufactured.

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of an apparatus for producing a film with a metal oxide film of the present invention.

FIG. 2 is an enlarged schematic view of an evaporation portion of FIG.

FIG. 3 is a schematic view showing an example of an oxidation nozzle of the present invention.

FIG. 4 is a schematic view showing an example of a manufacturing apparatus for depositing a magnetic substance by a conventional method.

FIG. 5 is a schematic diagram of a surface resistance measuring device.

FIG. 6 is a result of analysis in the depth direction of the aluminum oxide film of Example 1 by Auger electron spectroscopy.

FIG. 7 is a result of analysis in the depth direction of the aluminum oxide film of Example 2 by Auger electron spectroscopy.

FIG. 8 is a result of depthwise analysis of the aluminum oxide film of Example 3 by Auger electron spectroscopy.

[Explanation of symbols]

1: unwinding means 2: winding means 3a: film roll (before unwinding) 3b: film (unwinding means-cooling can) 3c: film (portion along vapor deposition section, cooling can) 3d: film (cooling Can-winding means) 3e: film roll (after winding) 4: cooling cans 5a, 5b, 5c, 5d: guide rolls 6a, 6b, 6c, 6d: guide roll 7: evaporation source 8: lower chamber vacuum pump 9: Vacuum pump for upper chamber 10: Vacuum gauge 11: Upper chamber of vacuum deposition machine 12: Lower chamber of vacuum deposition machine 13: Vacuum deposition machine 14: Oxygen cylinder 15: Pipe 16: Regulator 17a, 17b: Oxygen gas pipe 18a, 18b : Regulators 19a, 19b: Mass flow controllers 20a, 20b: Pipe 21: Metal 22: Crucibles 23a, 23b: Anti-stick plates 24a, 24b: Partition plates 25a, 25b: Cooling Structure (hatched portion) 26a, 26b: Oxygen nozzle 27: 28: Molten metal molten metal surface 29a, 29b: Oxygen nozzle hole for blowing out oxygen 30: Evaporated vapor 31: Horizontal straight line 32 of partition plate: Oxygen blowing Line 33 showing the vertical direction of the hole for cooling: a straight line connecting the hole for blowing oxygen and the lower apex of the cooling can 34: the lower apex 35 of the cooling can: shutter member 36: peep windows 26a, 26b: oxygen nozzle 41: Oxygen introduction pipe 42 to oxygen nozzle: Oxygen nozzle 43: Oxygen blowout hole portion 51 of the oxygen nozzle 51: Optical monitor 60: Sample 61: Base film 62: Metal oxide film 63: Volume box 64: Super insulation meter 65: Measurement part 66: Electrode plate 67: Electrode plate 101: Unwinding means 102: Winding means 103a: Film roll (before unwinding) 103b: Film (unwinding means-cooling can) 03e: Film roll (after winding) 104: Cooling cans 105a, 105b, 105c, 105d: Guide rolls 106a, 106b, 106c, 106d: Guide roll 107: Evaporation source 108: Lower chamber vacuum pump 109: Upper chamber vacuum Pump 110: Vacuum gauge 111: Vacuum vapor deposition machine upper chamber 112: Vacuum vapor deposition machine lower chamber 113: Vacuum vapor deposition machine 114: Oxygen cylinder 130: Evaporative vapor 116: Regulator 118: Regulator 119: Mass flow controllers 124a, 124b: Anti-adhesion plate 126 : Oxygen nozzle 136: electron beam

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4K029 AA11 AA25 BA43 BD11 CA02                       DA03 DA06 DB19 DB20 EA01                       KA01                 5D006 CB01 CB03 CB04 CB07 CB08                       EA03 FA00 FA02 FA05 FA09                 5D112 AA02 AA22 AA30 BA01 BA05                       BA09 FA02

Claims (34)

[Claims] 1. A cooling can is disposed above an evaporation source in which a metal is melted, and a film to be vapor-deposited is conveyed from the unwinding means along the cooling can to be exposed to evaporation vapor to form a metal oxide. A method of forming a thin film wound by a winding means, wherein a height of 0.6 to 0.9 × h from the molten metal surface with respect to the shortest distance h between the molten metal surface of the evaporation source and the vapor deposition film. ,
A metal including a vertical portion of the molten metal surface and allowing a metal vapor to pass through an opening having a size 1.5 times or more the size of the molten metal surface, and introducing oxygen from between the opening and the cooling can. A method for producing a film with an oxide film. 2. The method for producing a film with a metal oxide film according to claim 1, wherein the opening is formed by a partition plate, and the partition plate is cooled by a refrigerant at 50 ° C. or lower. . 3. The film with a metal oxide film according to claim 1, wherein the oxygen is introduced through a plurality of holes for oxygen blowing provided in the width direction of the film to be vapor-deposited. Manufacturing method. 4. The oxygen is introduced into a range from a horizontal position toward the opening to a vertical position toward the cooling can, according to any one of claims 1 to 3. A method for producing a film with a metal oxide film. 5. The oxygen is introduced toward a range of ± 30 degrees with a straight line connecting the shortest distance between the hole and the apex of the cooling can as a center. A method for producing a film with a metal oxide film. 6. The hole according to any one of claims 3 to 5,
The method for producing a film with a metal oxide film according to any one of claims 3 to 5, which has a diameter of 0.1 to 1.5 mm. 7. The introduction of oxygen is introduced from the unwinding side and / or the winding side of the film transport, and the introduction pressure and the flow rate are adjusted independently of each other.
7. The method for producing a film with a metal oxide film according to any of 6. 8. The method for producing a film with a metal oxide film according to claim 7, wherein the introduction amount on the unwinding side according to claim 7 is larger than the introduction amount on the winding side. 9. The metal according to claim 1, wherein the introduction of oxygen is started after the molten state of the metal of the evaporation source is stabilized, and the amount of oxygen introduced is gradually increased. A method for producing a film with an oxide film. 10. The film with a metal oxide film according to claim 9, wherein the increasing rate of the oxygen introduction amount according to claim 9 is controlled so as not to exceed (10 ml / min) / sec. Production method. 11. The film with a metal oxide film according to claim 9, wherein the introduction of oxygen according to claim 9 is performed on the unwinding side before the introduction on the winding side. Production method. 12. The oxygen introduction amount is monitored by a vacuum gauge mounted between the vapor deposition apparatus main body and a vacuum pump, and the oxygen introduction amount is introduced up to the introduction amount. The method for producing a film with a metal oxide film according to any one of claims. 13. The oxygen introduction amount is adjusted so that the difference between the pressure after the oxygen introduction and the pressure before the oxygen introduction is 3 × 10 ⁻² Pa or less. The method for producing a film with a metal oxide film according to. 14. The thickness of the metal oxide film is 50 to 500.
nm is set, The manufacturing method of the film with a metal oxide film in any one of Claims 1-13 characterized by the above-mentioned. 15. The surface resistance of the metal oxide film is 10 ⁷
Ω / sq or more, The method for producing a film with a metal oxide film according to claim 1, wherein the film has a metal oxide film. 16. The metal oxide film according to claim 1, wherein the difference in the total light transmittance between the film with the metal oxide and the undeposited film is within 5%. Film manufacturing method. 17. The transmittance of the film with a metal oxide is measured, and the energy and / or oxygen introduction amount of the evaporation source is adjusted based on the transmittance so that the transmittance becomes substantially constant. It controls, It is characterized by the above-mentioned.
7. The method for producing a film with a metal oxide film according to any of 6. 18. The metal to be evaporated is a material mainly containing aluminum and / or copper.
18. The method for producing a film with a metal oxide film according to any one of 17. 19. The vapor-deposited film has a thickness of 2 to 6 μm.
The method for producing a film with a metal oxide film according to any one of claims 1 to 18, wherein 20. The Young's modulus in the longitudinal direction and the width direction of the film with the metal oxide film is 5500 MPa, respectively.
20 or more, and 7500 MPa or more, The manufacturing method of the film with a metal oxide film in any one of Claims 1-19 characterized by the above-mentioned. 21. R on the surface A on one side of the vapor-deposited film
21. A film for a magnetic recording medium having an a value of 1 to 5 nm, wherein a strength-reinforcing film is formed on the front surface B (rear surface) of the film, the metal oxide according to claim 1. A method for producing a film with a physical film. 22. The metal oxide according to claim 1, wherein the vapor-deposited film is a polyester film made of polyethylene terephthalate or polyethylene-2,6-naphthalate, or a polyamide film. A method for producing a film with a film. 23. The method for producing a film with a metal oxide film according to claim 21 or 22, wherein a ferromagnetic thin film is provided on the surface A according to claim 21. 24. The method for producing a film with a metal oxide film according to claim 1, wherein the film with a metal oxide film is used for a magnetic recording medium of a digital recording system. 25. A vaporizer having means for decompressing the inside of a vapor deposition machine and means for heating and evaporating a metal, a cooling can is disposed above an evaporation source, and a film is conveyed from the unwinding means along the cooling can and vaporized. A device for producing a film with a metal oxide film, which is wound up by a winding means after forming a metal oxide by exposing to steam, and wherein the shortest distance h between the molten metal surface of the evaporation surface and the vapor deposition film is 0.6 to 0.9 xh from the surface
A partition member that forms an opening at the height of 1., and the opening includes the vertical of the molten metal surface portion and has a size of 1.
An apparatus for producing a film with a metal oxide film, which has a constitution of 5 times or more and has means for introducing oxygen between the partition member and the cooling can member. 26. The metal oxide film according to claim 25, wherein the partition member for forming the opening is provided with means for joining a cooling pipe and flowing a refrigerant through the cooling pipe. Film manufacturing equipment. 27. An oxygen introducing nozzle having a plurality of holes in the width direction of a film to be vapor-deposited is arranged between the partition member and the cooling can member, and a substantially constant amount of oxygen is introduced into the oxygen introducing nozzle. 27. The apparatus for producing a film with a metal oxide film according to claim 25 or 26, further comprising: 28. The hole portion of the oxygen introducing nozzle is installed so as to open in a range from a horizontal plane toward the center of the vaporized vapor opening to a vertical plane toward the cooling can. An apparatus for producing a film with a metal oxide film according to. 29. The hole portion of the oxygen introducing nozzle has a straight line connecting the shortest distance between the hole portion and the apex of the cooling can ±.
29. The apparatus for producing a film with a metal oxide film according to claim 27, wherein the apparatus is installed so as to open in a range toward a range of 30 degrees. 30. The metal oxide according to claim 27, wherein the hole portion according to any one of claims 27 to 29 has a diameter of 0.1 to 1.5 mm. Manufacturing equipment for film with material film. 31. The oxygen introducing nozzle is arranged on the unwinding side and / or the winding side of the film transport, and has means capable of independently controlling the respective introducing pressure and flow rate. 27. A manufacturing apparatus for a film with a metal oxide film according to any one of 27 to 30. 32. A film with a metal oxide film according to claim 25, wherein a vacuum gauge for monitoring the pressure inside the vapor deposition machine is arranged between the vapor deposition machine main body and the vacuum pump. Manufacturing equipment. 33. A means for arranging a plurality of optical monitors in the width direction of a film to be vapor-deposited between a portion exposed to vaporized vapor and a winding means, and means for monitoring the transmittance by the optical monitor. The manufacturing apparatus of the film with a metal oxide film according to any one of claims 25 to 32. 34. The metal according to claim 33, further comprising means for receiving and controlling the signal from the optical monitor and adjusting and controlling the amount of oxygen introduced or the energy of the evaporation source so that the transmittance becomes substantially constant. Manufacturing equipment for film with oxide film.