JPS6318607A - Magnetic recording medium - Google Patents

Abstract

PURPOSE:To obtain a magnetic recording medium of good abrasion resistance and heat resistance by vapor-depositing a magnetic film of a metal of the Co- Ni-B-(Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W) system containing O and/or N on a heat-resistant plastic film. CONSTITUTION:If, on a heat-resistant plastic tape, a magnetic film composed of 10-30wt.% of Ni, 0.02-1.5wt.% of B, 0.02-5wt.% of Ti and the remainder being Co is vapor-deposited, the abrasion resistance of the deposited film improves due to Ni, and the borides of Ti, Zr,... disperse into the film improving the corrosion and abrasion resistances of the deposited film of the Co-Ni system. Futher, a film of 10-30% of Ni, 0.02-1.5% of B, 0.2-3% of O, 0.2-5% of Ti and the remainder being Co, or a film of 10-30% of Ni, 0.02-1.5% of B, 0.02-2% of N, 0.02-5% of Ti and the remainder being Co, or a film of 10-30% of Ni, 0.02-1.5% of B, 0.2-3% of O, 0.02-2% of N, 0.02-5% of Ti and the remainder being Co is deposited, the abrasion and heat resistances further improve. The film thicnkness may be 0.1-0.2mum.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention generally relates to magnetic recording media,
In particular, the present invention relates to a magnetic recording medium in which a deposition source material is evaporated to form a magnetic deposited film on a support by a deposition method such as a vacuum deposition method or an ion blating method, and a method for producing the same.

In recent years, it has been desired to increase the amount of recorded information in, for example, video tapes and various other fields, and in order to meet this demand, various high-density magnetic recording media have been proposed.

Currently, as such high-density magnetic recording media, magnetic recording media in which a deposition source material is evaporated to form a magnetic deposited film on a support using a deposition method such as a vacuum deposition method or an ion blating method are particularly effective. For example, in JP-A No. 57-198614, Co-Ni is coated on a tape base material.
- A magnetic recording tape on which a magnetic vapor deposited film having a composition containing oxygen in a B-based metal is formed is also disclosed in Japanese Patent Application Laid-Open No. 59-74606.
In this issue, a magnetic recording tape was proposed in which a magnetic vapor deposited film having a composition containing oxygen and at least one element among Mo, Ta, and W was formed on a Co-Cr metal or a Co-Ni-Cr metal. ing.

Such magnetic recording tapes are particularly made of Co-Ni-B
A magnetic recording tape on which a magnetic vapor-deposited film having a metallic composition is formed is extremely preferable because the magnetic film has excellent magnetic properties, corrosion resistance, and abrasion resistance. However, with recent advances in video tape recorders, the frequency of use of tape has increased significantly, and the manner in which it is used has also become more complex.In particular, it is often used in still (still IF image) mode, and tape Since the head may be rubbed many times, it is desired to further improve the wear resistance.

The present inventors conducted many research experiments in order to improve the magnetic recording medium on which a magnetic vapor deposited film was formed, and found that it had a composition basically consisting of Co-Ni-B metal, and in addition, Ti. , Zr, Hf, V, Nb, Ta, Cr, Mo, W, more preferably oxygen (0) and/or
It has also been found that the abrasion resistance of the magnetic deposited film can be dramatically improved by containing nitrogen (N).

The present invention is based on this new knowledge.

Therefore, an object of the present invention is to improve the corrosion resistance and abrasion resistance of a magnetic deposited film having a composition basically consisting of Co-Ni-B metal, and to improve the corrosion resistance and wear resistance. An object of the present invention is to provide a magnetic recording medium having a magnetic deposited film with good abrasion resistance.

- The above-mentioned object of the present invention is achieved by the magnetic recording medium according to the present invention. In summary, the present invention provides Ni (10-30
weight%), B (0.02 to 1.5 weight%), Ti, Zr
, Hf, V, Nb, Ta, Cr, Mo, W (7)
According to a preferred embodiment of the present invention, the magnetic recording medium is characterized by forming a magnetic deposited film having a composition consisting of at least one element (0.02 to 5.0% by weight) and Co (the balance). , Ni is 15-20% by weight, B is 0.4-1
．． 5% by weight, Ti, Zr, Hf, V, Nb, Ta, Cr
, Mo, and W (7) have a temperature of 1°O to 4.0°C. O
i amount%, the balance is Co, and the support is #thermal plastic film.

More preferably, the magnetic deposited film is doped with 0 and/or N. To explain in more detail, Ni(
10-30% by weight), B (0.02-1.5% by weight),
0 (0.2-3.0%), Ti, Zr, Hf, V,
It is possible to form a magnetic deposited film having a composition consisting of one or more elements (0.02 to 5.0% by weight) of Nb, Ta, Cr, rvto, W (7), and Co (balance). I can,
In this case, more preferably Ni is 15 to 20% by weight, B
is 0.4 to 1.5% by weight, O is 2.0 to 2.5% by weight,
The content of one or more elements among Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W is 1.0 to 4.0% by weight, and the balance is C.
o. According to another aspect of the present invention, Ni (10 to 30% by weight) and B (0.02 to 1.5% by weight) are coated on the support.
weight%), N (0.02 to 2.0 weight%), Ti, Zr
, Hf, V, Nb, Ta, Cr, Mo, Wc7) (0.02-5.0% by weight), C.

In this case, Nt is more preferably 15 to 20.
Weight %, B is 0.4 to 1.5 weight %, N is 0.2 to 1.
7% by weight, Ti, Zr, Hf, V, Nb, Ta, Cr,
One or more elements among Mo and W are 1.0 to 4.0% by weight
, the remainder is Co. Furthermore, according to another aspect of the present invention, Ni (10 to 30% by weight), B(
0゜02-1.5% by weight), 0(0.2-3.0% by weight
), N (0.02-2.0% by weight), Ti, Zr, Hf
, V, Nb, Ta, Cr, Mo, W (0.02-5.0% by weight).

A magnetic recording medium is obtained in which a magnetic deposited film having a composition of Co (the remainder) is formed. At this time, more preferably N
i is 15-20% by weight, B is 0.4-1.5% by weight, 0
ji2, O~2, 5 weight 4%, N 0.2~1.
7% by weight, Ti, Zr, Hf, V, Nb, Ta, Cr,
The content of one or more elements in Mo and W (7) is 1.0 to 4.0% by weight, and the balance is Co.

Hereinafter, the present invention will be explained in more detail with reference to drawings and examples.

Referring to FIG. 1, an example of a vacuum evaporation apparatus for producing a magnetic recording medium according to the present invention is illustrated. In this apparatus, a cylindrical cooling can 2 is located in a vacuum (reduced pressure) tank l as shown by the arrow. It is rotatably supported in the direction. The vacuum +61 is normally 10-' to 10-6T or
It is evacuated to r. Also, the base material of the magnetic recording medium,
That is, the support S is a tape-shaped plastic film in this embodiment, and is fed from the supply roll 4 to the cooling can 2.
is wound around the outer periphery of the generally lower portion of , and is wound onto a winding roll 6. The moving speed of the support S is usually 100 cm/
As a plastic film, use any film that has appropriate flexibility and tensile strength, and is also heat resistant enough to withstand the high temperatures during vapor deposition.
However, films made of polyester resin, acetate resin, polycarbonate resin, etc., which are commonly used as base materials for magnetic tapes, are suitable.

An evaporation source 8 is disposed, preferably at a position diagonally below the cooling can 2, and is configured to perform diagonal loading. Therefore, in order to make the oblique evaporation effective, the support S wound around the outer periphery directly below the cooling can 2 is covered by the mask 10 over a predetermined range. The high-temperature source 8 contains the above-mentioned Co-Ni-B-(Ti, Zr
, Hf, V, Nb, Ta, Cr, Mo, W) based alloy is prepared and heated with any heating device such as resistance heating means, high frequency induction heating means or electron beam heating means, for example,
It is evaporated at a deposition rate of nm/sec. Evaporated Co-Ni-B-(Ti, Zr, Hf, V,
Nb, Ta, Cr.

The Mo, W) based alloy rises in the direction of the cooling can 2 disposed above, and is deposited on the supporting body S which is wound around the outer periphery of the cooling can 2 and moves.

The water device contains Co-Nt-B-(Ti, Zr, Hf, V
, Nb, Ta, Cr, Mo, W) system alloy vapor adheres to the support S through a nozzle 1 for selectively supplying oxygen or nitrogen, or a mixed gas of eI#, element and nitrogen
2 is arranged. The oxygen and nitrogen can be supplied from oxygen and nitrogen supply sources (not shown), respectively, but when oxygen and nitrogen are supplied at the same time, dry air from which moisture has been removed can also be supplied. Oxygen and nitrogen are
Pressure 1 kg/cm2, flow rate 0, l l / se
In the case of a mixed gas, the ratio of oxygen and nitrogen is 1:4 under standard conditions, and the pressure is 1 kg /
c ~ 2, supplied at a flow rate of 0.1 sentences/sec. In addition, when supplying dry air, the pressure is 1 kg/
c ~ 2, support S at flow rate 0.1 sentence/sec
It is supplied to the notebook area.

With the above configuration, the support S is transported by the cooling can 2 while Co-Ni-B-(Ti, Zr, H
, f, V, Nb, Ta, Cr, Mo, W) based alloy vapor and selectively oxygen or nitrogen or oxygen and nitrogen are supplied and deposited.

That is, according to the present invention, Ni (10-30% by weight) and B (0.02-1.
5% by weight), Ti, Zr, Hf,
A magnetic film formed with a magnetic method-deposited film containing AIIK# consisting of one or more elements (0.02 to 5.0% by weight) among V, Nb, Ta, Cr, Mo, and W and Co (the balance) Recording medium: Ni (10-30% by weight), B (0,
02-1.5% by weight), O (0.2-3゜0% by weight)
, Ti, Zr, Hf, V, Nb, Ta, Cr1M0. W
One or more elements (0°02 to 5.0% by weight), C
A magnetic recording medium in which a magnetic deposited film having a composition consisting of o (remainder) is formed; Ni (10 to 30% by weight) on a support
B (0°02~1.5% by weight), N (0.02~2.0% by weight)
weight%), Ti, Zr, Hf, V, Nb, Ta, Cr
, Mo, Wty) (0,02-5.
0% by weight) and Co (balance);
0-30% by weight), B (0.02-1.5% of wages), 0
(0.2-3.0% by weight), N (0.02-2.0% by weight), Ti, Zr, H! , V, Nb, Ta, Cr, Mo
, one or more elements in W (0.02 to 5.0% by weight)
, Co (the remainder) is obtained.

To explain further, in the present invention, Ni is contained in a proportion of 10 to 30% by weight, and is less than 10% or 30gEi%, which acts to improve the wear resistance of the Co-based magnetic deposited film. It has been found that when the value exceeds this value, the magnetic properties deteriorate. Therefore, preferably Ni is 15 to 20
% by weight.

According to the invention, in particular B and Ti, Zr, Hf, V,
One or more elements among N b, Ta, Cr, Mo, and W (7) react with each other to form Ti, Zr, Hf, V, N b, T
a, Cr, Mo, Wt7) By forming a boride and dispersing the boride in the magnetic deposited film, it works to improve the tactility and wear resistance of the magnetic deposited film of Co-Ni metal. I found out something. It was also found that when B is less than 0.02% by weight, the effect is not significant, and when it exceeds 1.5% by weight, the magnetic properties are deteriorated.

Particularly preferably, B is 0.4 to 1.5% by weight.

At this time, Ti, Zr, Hf, V, Nb, Ta, Cr,
It is important that the content of Mo and W is 0.02 to 5.0% by weight; outside this range, the tactility and abrasion resistance of the magnetic deposited film are not significantly improved.

Moreover, the magnetic properties tend to deteriorate.

Oxygen (0) and nitrogen (
N) is the above quaternary alloy, Co-Ni-B-(Ti, Zr
, Hf, V, Nb, Ta, Cr.

It is thought that when the Mo, W) based metal is vapor deposited on the support, it is combined with the metal to form oxides and nitrides. According to the research conducted by the present inventors, it is thought that oxygen (0) exists as cobal oxide (Coo) and nitrogen (N) is contained in the film as boron nitride (BN).
It has been found that the wear resistance of the magnetic deposited film is further improved when oxygen and/or nitrogen is contained in the magnetic film.

In the present invention, the thickness of the magnetic vapor deposited film can be arbitrarily designed depending on the application, but is preferably 0.1 to 0.2 gm.
According to research by the present inventors, if it is less than 0°1 gm, sufficient records cannot be obtained, and at the same time, sufficient wear resistance cannot be obtained.
It has also been found that when it exceeds 0.2 pm, although 1iIP1 wear resistance can be obtained, the flexibility of the support S tends to decrease and the recording density also tends to decrease. Therefore, the thickness of the magnetic deposited film is particularly preferably 0.15 μm.

The composition and film thickness of the magnetic vapor deposited film vary depending on the composition of the quaternary alloy of the evaporation source, the flow rate of oxygen and nitrogen gas supplied, the supply pressure, the moving speed of the support S, the reduced pressure state of the vacuum chamber L, etc. It will be adjusted accordingly.

Next, the present invention will be explained with reference to examples.

A quaternary alloy having the composition shown in Table 1 was prepared in an electron beam irradiation heated vacuum melting furnace and used as a tea source material.

A manufacturing apparatus as shown in FIG. 1 was used for vacuum deposition, and the vacuum chamber 1 was evacuated to 2.3×10' Torr. As the support S, a polyester film having a thickness of 28 JLm was used, which was wound around a cooling can having a diameter of 50 cm and moved at a speed of 100 cm/Sec.

The evaporation source material is irradiated with an electron beam to melt and evaporate, and is deposited on the support S at a rate of 50 nm/sec to form a magnetic deposited film with a thickness of 0.1 m on the support S. did.

The composition of the magnetic deposited film thus produced.

The magnetic properties and surface hardness were as shown in Tables 1 and 6. The surface hardness is Vickers hardness (Hv) measured using a microhardness meter (10 g load).

11-15~28 Quaternary alloys having the compositions shown in Table 2 were prepared in an electron beam irradiation heated vacuum melting furnace and used as evaporation source materials.

A manufacturing apparatus as shown in FIG. 1 was used for vacuum deposition, and the vacuum chamber 1 was evacuated to 2.3×10 −6 Torr. As the support S, a polyester film having a thickness of 28 ALm was used, which was wound around a cooling can having a diameter of 50 cm and moved at a speed of 100 cm/sec.

The evaporation source material is irradiated with an electron beam to melt and evaporate, and is deposited on the support S at a rate of 50 nm/sec to form a thin magnetic film with a thickness of 0.1 lm on the support S. did. still,
Oxygen is applied to the vapor deposition surface of the support S from the nozzle 12 at 0 and 11
/ sec at a pressure of 1 kg/cm 2 . As a result, the vacuum inside the vacuum chamber 1 is 1.4X10-
'Torr, and the vacuum state was maintained.

The composition, magnetic properties, and surface hardness of the magnetic 7Pi deposited film thus prepared were as shown in Tables 2 and 6. 0 Surface hardness is Vickers hardness measured using a microhardness tester (10g load). (Hv).

Knees 29-42 Magnetic vapor deposited films were produced on the support S under the same vapor deposition conditions as in Examples 15 to 28, except that nitrogen was sprayed onto the vapor deposition surface of the support S from the nozzle 12 instead of oxygen. The composition of the quaternary alloy of the evaporation source is as shown in Table 3.

The composition, magnetic properties, and surface hardness of the magnetic deposited film thus prepared were as shown in Tables 3 and 6. 0 surface hardness is the Vickers hardness (10 g load) measured using a microhardness meter (10 g load). Hv).

=-43 to 56 Example 1 except that dry air (SI element: nitrogen = 1:4) was sprayed from the nozzle 12 onto the deposition surface of the support S instead of oxygen.
A magnetic vapor deposited film was produced on the support S under the same vapor deposition conditions as in Examples 5 to 28. The composition of the quaternary alloy of the evaporation source is as shown in Table 4.

The composition, magnetic properties, and surface hardness of the magnetic deposited film thus prepared were as shown in Tables 4 and 6. 0 surface hardness is the Vickers hardness (10 g load) measured using a microhardness meter (10 g load). Hv).

] Mortar I"22A Evaporation source materials having the compositions shown in Table 5 were prepared, and Examples 1 to 1 were prepared.
A magnetic vapor deposited film was produced on the support S in the same manner as in Example 14.

The composition, magnetic properties, and surface hardness of the magnetic deposited film thus prepared were as shown in Tables 5 and 7.6 The surface hardness was the Vickers hardness (10 g load) measured using a microhardness tester (10 g load). Hv).

Example 15 An evaporation source material having the composition shown in Table 5 was prepared.
A magnetic vapor deposited film was produced on the support S in the same manner as in 28.

The composition, magnetic properties, and surface hardness of the magnetic deposited film thus prepared were as shown in Tables 5 and 7. 0 surface hardness is the Vickers hardness measured using a microhardness meter (Log load) Hv).

9-12 Evaporation source materials having the compositions shown in Table 5 were prepared, and Example 29
A magnetic vapor deposited film was produced on the support S in the same manner as in 42.

The composition, magnetic properties, and surface hardness of the magnetic deposited film thus prepared were as shown in Tables 5 and 7. 0 surface hardness is the Vickers hardness measured using a microhardness meter (Log load) Hv).

13-16 Evaporation source materials having the compositions shown in Table 5 were prepared, and Example 43
A magnetic vapor deposited film was produced on the support S in the same manner as in 56.

The composition of the magnetic deposited film thus produced.

The magnetic properties and surface hardness were as shown in Table 51 and Table 7. 0 Surface hardness is Vickers hardness (Hv) measured using a microhardness meter (10 g load).

Table 6 Table 7 Also, "L-3"J As can be understood from Tables 6 and 7, the magnetic recording medium according to the present invention basically has C magnetism and a deposited film.

-Ni -B -(Ti, Zr, Hf, ■, Nb, Ta
, Cr, Mo, W) based metals, and may further contain oxygen and/or nitrogen, thereby providing magnetic 4. ￥
The magnetic evaporated R film has the advantage that its corrosion resistance and Plu resistance are significantly improved without impairing its properties.

[Brief explanation of the drawing]

FIG. 1 shows one embodiment of a manufacturing bag that can suitably manufacture the magnetic recording medium according to the present invention. 1. Vacuum chamber 2. Cooling can 4. Support supply roll 6: Support winding reroll 8: /A source 12: Nozzle

Claims (1)

[Claims] 1) Ni (10 to 30% by weight), B (0.0% by weight) on the support
2-1.5% by weight), Ti, Zr, Hf, V, Nb, T
one or more elements among a, Cr, Mo, and W (0.02~
2) Ni is 15 to 20 weight % and B is 0.4 to 1.5 weight %. %, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo,
2. The magnetic recording medium according to claim 1, wherein the content of one or more elements in W is 1.0 to 4.0% by weight, and the balance is Co. 3) The magnetic recording medium according to claim 1 or 2, wherein the support is a heat-resistant plastic film. 4) The magnetic recording medium according to claim 3, wherein the support is tape-shaped. 5) Ni (10-30% by weight), B (0.0% by weight) on the support
2-1.5% by weight), O (0.2-3.0% by weight), T
i, Zr, Hf, V, Nb, Ta, Cr, Mo, one or more elements among W (0.02 to 5.0% by weight), Co(
1. A magnetic recording medium comprising a magnetic deposited film having a composition consisting of the remainder). 6) Ni is 15-20% by weight, B is 0.4-1.5% by weight, O is 2.0-2.5% by weight, Ti, Zr, Hf, V
6. The magnetic recording medium according to claim 5, wherein at least one element among Nb, Ta, Cr, Mo, and W is contained in an amount of 1.0 to 4.0% by weight, and the balance is Co. 7) The magnetic recording medium according to claim 5 or 6, wherein the support is a heat-resistant plastic film. 8) The magnetic recording medium according to claim 7, wherein the support is tape-shaped. 9) Ni (10-30% by weight), B (0.0% by weight) on the support
2-1.5% by weight), N (0.02-2.0% by weight),
One or more elements among Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W (0.02 to 5.0% by weight), Co
1. A magnetic recording medium comprising a magnetic vapor deposited film having a composition consisting of (the remainder). 10) Ni is 15-20% by weight, B is 0.4-1.5% by weight, N is 0.2-1.7% by weight, Ti, Zr, Hf,
10. The magnetic recording medium according to claim 9, wherein the content of one or more elements among V, Nb, Ta, Cr, Mo, and W is 1.0 to 4.0% by weight, and the balance is Co. 11) The magnetic recording medium according to claim 9 or 10, wherein the support is a heat-resistant plastic film. 12) Claim 11, wherein the support is tape-shaped.
Magnetic recording medium described in Section 1. 13) Ni (10-30% by weight), B (0.
02-1.5% by weight), O (0.2-3.0% by weight),
N (0.02-2.0% by weight), Ti, Zr, Hf, V
, Nb, Ta, Cr, Mo, and one or more elements among W (
1. A magnetic recording medium comprising a magnetic deposited film having a composition of 0.02 to 5.0% by weight) and Co (the balance). 14) Ni is 15-20% by weight, B is 0.4-1.5% by weight, O is 2.0-2.5% by weight, N is 0.2-1.7% by weight.
Weight%, Ti, Zr, Hf, V, Nb, Ta, Cr, M
o, one or more elements in W are 1.0 to 4.0% by weight,
14. The magnetic recording medium according to claim 13, wherein the remainder is Co. 15) The magnetic recording medium according to claim 13 or 14, wherein the support is a heat-resistant plastic film. 16) Claim 15, wherein the support is tape-shaped.
Magnetic recording medium described in Section 1.