JPH05311301A - Vapor deposition material - Google Patents

Abstract

(57) [Summary] [Objective] When depositing a Co-Ni alloy on a base film in the manufacture of VTR tapes, etc., a vapor deposition material that is excellent in workability and toughness is used as a wire rod so that stable vapor deposition conditions can be obtained. provide. [Composition] Substantially 80 wt% of Co and 20 wt% of Ni
%, The balance is a Co-Ni alloy wire with unavoidable impurities, the wire diameter is 1.5 mm or more and 10 mm or less, the wire diameter is 1000 times or more, and the tensile strength is 50 kg /
mm ² or more, at 150 kg / mm ² or less, aperture, 5%
As described above, it has a mechanical property of elongation of 5% or more (gage length 100 mm).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Co-Ni based alloy vapor deposition material used in a process for producing a vapor deposition VTR tape or the like.

[0002]

2. Description of the Related Art Recent VTR tapes are required to have higher image quality and higher sound quality, and in order to meet these demands, Co-Ni capable of achieving higher magnetic density than conventional ferrite or metal coated tapes. Vapor deposition tape is being used. C
By increasing the magnetic density, the o-Ni vapor deposition tape is
Higher image quality and higher sound quality are possible, and further demands are expected to increase in the future, such as long-term recording and high-definition broadcasting.

The vapor deposition process of such a tape will be described with reference to FIG. This figure is a schematic view of a vapor deposition apparatus. In the vacuum chamber 11, a delivery shaft 13 for the base film 12 is provided.
A crucible 1 for storing a winding shaft 14, a vapor deposition material 15
6, an electron gun 17 for heating, melting and evaporating the vapor deposition material by an electron beam, and a supply device 18 for supplying the vapor deposition material 15 are arranged. In such an apparatus, the inside of the vacuum chamber 11 is evacuated to about 10 ⁻⁵ to 10 ⁻⁶ Torr, and the vapor deposition material 15 is heated to 2000 ° C. by an electron beam.
Heat to a certain degree, melt and evaporate. Evaporated material 15
Reaches the base film 2 and a thin film is formed by vapor deposition.

Here, the vapor deposition material 14 must be replenished for the amount of vaporization, and the supply thereof is performed by dropping the pellet material (10φ × 15 to 25 mm) from the feeding device 19 or the bar material (30φ × 1 m). Etc. are used.

[0005]

However, in the case of the above-mentioned feeding method, the deposition conditions are unsatisfactory such as the melt surface of the vapor deposition material being disturbed, the molten metal being scattered, and the temperature distribution in the molten metal being non-uniform when the pellets fall. Be stable. Since these destabilize the evaporation direction and the evaporation amount of the material, there is a problem that a tape of stable quality cannot be manufactured.

On the other hand, as a measure against such a problem, it is considered that a long wire rod is used as the evaporation material, and this is continuously supplied into the crucible to stabilize the vapor deposition condition to manufacture a highly reliable tape. .. In this case, since there is also an advantage that continuous vapor deposition work can be performed for a long time, there has been a demand for a wire material of a Co-Ni alloy. Actually, even with the vapor deposition material, Al
For products that can be easily made longer, such as wire rods, continuous supply by wire is also used.

However, it is extremely difficult to process a Co-Ni alloy into a wire rod. That is, since it is a difficult-to-work material, it is difficult to lengthen it by cold working, and even if it can be lengthened by hot working, it is difficult to round the cross section of the wire rod, and unevenness occurs on the wire surface, There is also the problem of breakage during supply.

There is also a method of improving the workability and toughness of a wire by adding Fe to a Co-Ni alloy as disclosed in JP-A-59-64734. However, such a technique causes another problem such as deterioration of excellent magnetic properties of the Co—Ni alloy.

The present invention has been made under such a technical background, and in order to obtain stable vapor deposition conditions, C
It is an object of the present invention to provide a vapor deposition material for a wire which is an o-Ni alloy and is excellent in workability and toughness.

[0010]

In order to achieve the above object, the vapor deposition material of the present invention contains substantially 80 wt% Co,
20% by weight of Ni, the balance being Co-Ni which is an unavoidable impurity
An alloy wire having a wire diameter of 1.5 mm or more and 10 mm or less (preferably 3 mm or more and 5 mm or less) and having a wire diameter of 1
It has a length of 000 times or more and a tensile strength of 50 kg / m.
m ² or more and 150 kg / mm ² or less (preferably 70 k
g / mm ² or more, 100 kg / mm ² or less), diaphragm: 5% or more, elongation: 5% or more (gage length 100 m
It is characterized by having the mechanical properties of m).

In such a vapor deposition material, the surface roughness of the wire is 50 μm or less, the diameter deviation difference is 0.1 mm or less, and the waviness in the length direction is 0.2 mm per 1 mm in length.
It is characterized by the following.

As described above, the Co--Ni alloy containing no additional element is used in order to prevent the magnetic characteristics from deteriorating. The processing conditions will be described below. First, a certain amount of Co
And Ni are melted and cast to produce an ingot. This is hot cast to produce a bar, which is further heated and then a rolled wire is obtained. In the processing of the Co-Ni alloy after the rolling processing, the processing temperature has a great influence on its workability and wire rod characteristics. Generally, it is easy to work at a temperature of 800 ° C. or higher. Also, in the temperature range of 400 to 800 ° C, the diameter becomes smaller,
It is especially effective for wire drawing and has a great effect on material properties.

Co-Ni alloys are considered as difficult-to-work materials because they are extremely difficult to work, especially at room temperature. Therefore, in order to obtain the target shape and characteristics, it is very effective to perform only warm working or to combine it with cold working. For example, wire drawing at 400 to 600 ° C. can also be strongly worked (repeated area reduction rate of 20%), and the greater the degree of working, the better the elongation and drawing. When processed at room temperature, strong processing is impossible, but low processing (area reduction of 10% or less) is possible, drawing speed can be increased, and tensile strength can be improved.

When work hardening is large, 1000 ° C.
By annealing below, the wire characteristics can be improved. Here, if the annealing temperature is set to 1100 ° C. or higher, the characteristics are remarkably deteriorated, so it is necessary to avoid it.

The warm working has problems such as low productivity, but it is effective for obtaining a long wire without breaking and is particularly effective for thinning (strong working). Is. Also, the mechanical properties required when supplying the wire rod to the crucible of the vapor deposition apparatus can be improved.

As described above, when the diameter reduction (high area reduction rate) is not required in the warm working and the final wire drawing step,
By combining this with cold working, it is possible to obtain a wire rod having characteristics suitable for the purpose.

The characteristics of the wire will be described below. First, regarding the wire diameter, operability (ease of handling), supply speed, etc. are taken into consideration. That is, if it exceeds 10 mm, the handling of the wire is difficult, and the diameter of the winding coil is as large as 1 m or more, and the supply device itself is also large. As a result, a large space is required, especially when the supply device is provided in the vacuum chamber.

On the other hand, if it is less than 1.5 mm, it is easy to handle, but high speed feeding is required. For example, compared with a wire rod having a diameter of 10 mm, a supply speed of about 45 times or more is required, and a mass production machine requires a speed of 100 m / min or more.
As a result of such high speed feeding, it is difficult to feed the crucible at a fixed position, and problems such as disorder of the molten metal surface easily occur.

In order to carry out continuous operation, a length of 1000 times or more the diameter of the wire is required.

Next, regarding the mechanical characteristics, this also similarly takes into consideration supplyability and operability. If the tensile strength is less than 50 kg / mm ² , the strength will be insufficient, and problems such as breakage will occur, making supply difficult. On the other hand, 150 kg
If it exceeds / mm ² , it will be hard and difficult to handle. or,
If the elongation and the reduction are less than 5%, the material is weak in bending and the supply becomes difficult.

Further, in such a wire rod, the surface roughness and the like are limited in consideration of the degree of vacuum in the chamber when the wire rod is supplied. That is, when the wire rod is installed outside the vacuum chamber, the wire rod is supplied into the crucible via a vacuum sealing mechanism such as an O-ring. In this case, if the surface roughness of the wire and the difference in diameter deviation are small and the undulation is gentle,
The O-ring can follow the wire and remain in contact.
However, if it is large, on the other hand, it cannot be done, and the atmosphere is easily trapped in the chamber. Therefore, there arises a problem that the degree of vacuum in the chamber required for vapor deposition is lowered.
Here, if the surface roughness and the like are limited as described above,
Such a problem can be solved.

The processing for adjusting the surface roughness and the like within a certain range is performed by pickling the wire or mechanically grinding (peeling off) such as peeling. Incidentally, in order to form a vapor-deposited film of good quality, it is necessary to remove impurities on the surface of the wire, but this peeling or pickling also enables removal of impurities. Furthermore, it is more effective to wash with an organic solvent and a neutral detergent as needed.

[0023]

EXAMPLES Examples of the present invention will be described below. The vapor deposition apparatus is almost the same as that shown in FIG. 2 as shown in FIG. 1, and in the vacuum chamber 1 having a volume of 600 l, the delivery shaft 3 and the take-up shaft 4 of the base film 2, the crucible 6 for storing the vapor deposition material 5, An electron gun 7 for heating, melting and evaporating the vapor deposition material 5 with an electron beam is provided. The difference lies in the method of replenishing the vapor deposition material. In this example, the linear vapor deposition material is supplied from the outside of the vacuum chamber through the vacuum seal mechanism 9 using an O-ring.

First, in a vacuum of 10 ^-5 Torr, 80%
Co and 20% Ni were melted and cast to manufacture a 100 kg ingot. This is hot forged, about 70φ x 3
m after manufacturing the bar material and further heating it to 1100 ° C.,
Rolled wire rods having various sizes of 15φ to 5.5φ were obtained.

(Wire diameter) These rolled wire rods were thinned by warm working and cold working as described above, and when work hardening was large, they were annealed at 1000 ° C or lower. Wires having diameters of 15, 10, 8, 5, 3, 1.5 and 0.8 mm were manufactured by these processes, and a supply test to the vapor deposition apparatus was conducted. 1
If it is 5 mm, it is too thick and workability is extremely poor.
The m-sized one also lacked strength and had a problem in workability such as bending at an unexpected position. The one having a thickness of 1.5 to 10 mm is good in this respect, and the one having a diameter of 3 to 5 mm is suitable for both the workability and the supply speed and is suitable for the actual vapor deposition work.

(Mechanical properties) Next, in order to test the mechanical properties, the material strength was set to 30, 5 by working degree and annealing.
Wire rods of 0, 80, 110, 150 and 170 kg / mm ² were manufactured. The same supply test was conducted on these materials, and those of 30 kg / mm ² had insufficient strength and problems such as breakage and disconnection occurred. Also, 170 kg / mm
No. ² was too hard to handle. Meanwhile, 5
0 to 150 kg / mm ² , especially 70 to 100 kg
/ Mm ² was good in both handling and supply. Also, if the elongation and the drawing are each not less than 5%,
It was confirmed that problems such as easy breakage occurred during supply.

(Surface Roughness) Next, the relationship between the surface roughness of the wire and the degree of vacuum was tested. As described above, in order to melt the vapor deposition material with the electron beam, a certain degree of vacuum must be maintained, and entrapment of air from the sealing mechanism must be extremely small. The allowable entrainment amount is determined by the exhaust amount of the vacuum pump, the chamber volume, and the like. The basic conditions for supplying the wire rod are the vacuum pump displacement of 200 l / se.
c, the linear velocity was 5 m / min, the wire diameter was 5.5 mm, and a supply test was performed using a wire material having a different surface roughness. The results are shown below.

Surface roughness (μm) Degree of vacuum (Torr) 30 3 × 10 ⁻⁶ 50 2 × 10 ⁻⁵ 70 7 × 10 ⁻⁵ 90 1 × 10 ⁻⁴ (waviness of wire rod: 0.05 mm / mm)

As described above, in order to maintain the vacuum degree of 5 × 10 ^-5 Torr or more which can be dissolved by the electron beam, the surface roughness needs to be 50 μm or less.

(Waviness) Further, the relationship between the undulation of the wire and the degree of vacuum was tested in the same manner as in the case of the surface roughness. Here, the waviness will be described a little. The meandering state (amplitude) of the wire rod at a constant length is shown in FIG.
It shows the swell per 1 mm in length. In the case of Al or the like which has been conventionally supplied by a wire rod, since the wire rod itself is soft, undulation does not become a problem. But C
Since the o-Ni alloy is hard, air may be trapped in the chamber depending on the waviness, which is a problem to be considered. The test results are shown below. The surface roughness of the wire used was 50 μm, and the waviness was 1 mm in length.
It shows the hit.

Waviness (mm) Degree of vacuum (Torr) 0.05 5 × 10 ⁻⁶ 0.08 5 × 10 ⁻⁶ 0.1 5 × 10 ⁻⁶ 0.12 7 × 10 ⁻⁶ 0.18 4 × 10 ^-5 0.2 5 x 10 ^-5 0.25 8 x 10 ^-5

As described above, in order to maintain the degree of vacuum, it is necessary that the waviness is 0.2 mm or less per 1 mm.
Furthermore, undulations of 0.1 and 0.2 mm, wire diameter of 5.5 m
Although the m wire rod was supplied at a linear velocity of 1 to 10 m / min, the degree of vacuum was maintained at 1 × 10 ⁻⁵ Torr. On the other hand, a waviness of 0.3 mm was supplied under the same conditions, but the linear velocity was 1
The vacuum degree of 1 × 10 ⁻⁵ Torr could be maintained only up to ˜2 m / min.

(Difference in Radius) Further, the relationship between the difference in radius and the degree of vacuum was also investigated. Since it is difficult to select the eccentricity difference arbitrarily,
The difference in eccentricity when the degree of vacuum decreased was measured. The basic conditions during supply are the same as those in the surface roughness test. The test results are shown below.

Diameter deviation (mm) Surface roughness (μm) Vacuum degree (Torr) Rating 0.8 70 6 × 10 ⁻⁵ × 0.2 30 7 × 10 ⁻⁵ × 1.3 403 9 × 10 ^{− 5} x 1.0 50 5 x 10 ^-5 ○

Thus, the difference in eccentricity is 1.0 mm or less,
In addition, it is necessary that the surface roughness be 50 μm or less.

(Surface Impurity) Further, the residual degree of surface impurities adhered when the wire rod was processed was examined. 10.6 mmφ
The rolled wire rod was wire-drawn with a skinning hole die, and the peeled wire rod was analyzed for residual surface impurities by SEM. As a result, all the impurities attached during rolling were removed. However, the lubricant such as Ca remained.
When this was steam washed with an organic solvent, no impurities were recognized. Similarly, no impurities were found in the drawn wire material which was similarly peeled and then washed with a skinning hole die.

[0037]

As described above, according to the vapor deposition material of the present invention, it is possible to continuously supply a Co—Ni alloy wire. As a result, the deposition conditions, which had been a problem in the past, can be stabilized, high-quality deposition films can be formed, and long-term continuous operation is possible. In particular, it is expected to be effectively used in the field of manufacturing VTR tapes and the like.

[Brief description of drawings]

FIG. 1 is a schematic view of a vapor deposition apparatus showing a supply state of a vapor deposition material of the present invention.

FIG. 2 is a schematic diagram of a vapor deposition device showing a state where a vapor deposition material is replenished by dropping pellets.

FIG. 3 is an explanatory diagram showing undulations of a wire rod.

[Explanation of symbols]

 1,11 Vacuum chamber 2,12 Base film 3,13 Delivery shaft 4,14 Winding shaft 5,15 Deposition material 6,16 Crucible 7,17 Electron gun 8 Sealing mechanism 18 Supply device

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[Procedure amendment]

[Submission date] May 26, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction content]

[0034]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

As described above, the difference in eccentricity is 0.1 mm or less,
In addition, it is necessary that the surface roughness be 50 μm or less.

Claims (2)

[Claims] 1. Substantially 80 wt% of Co and 20 of Ni
wt%, the balance being an inevitable impurity Co-Ni alloy wire having a wire diameter of 1.5 mm or more and 10 mm or less,
It has a length of 00 times or more and a tensile strength of 50 kg / mm ² or more, 150 kg / mm
^A material for vapor deposition having a mechanical property of ² or less, a diaphragm of 5% or more and an elongation of 5% or more (a gauge length is 100 mm). 2. A wire rod having a surface roughness of 50 μm or less, a diameter deviation difference of 0.1 mm or less, and a lengthwise undulation of a length of 1
It is 0.2 mm or less per mm, The vapor deposition material of Claim 1 characterized by the above-mentioned.