PROCESS FOR PRODUCING A MAGNETIC RECORDING MEDIUM

Abstract: A process for producing a magnetic recording medium comprises heating a crucible (11) containing a ferromagnetic material (17) in a high vacuum (2) corresponding to a pressure of 8 × 10⁻⁴ torr or lower thereby vaporizing the ferromagnetic material (17), impinging accelerated electrons from an elec­ tron radiation source (12) against the vapor particles to ionize them, and accelerating the resulting ionized vapor particles in an electric field (14) and impinging them against a substrate (5) composed of a non-magnetic material to form a fer­ romagnetic thin film thereon.

Description: DESCRI PTION PROCESS FOR PRODUCING A MAGNETIC RECORDING MEDIUM This invention relates to a process for producing magnetic recording media such as magnetic tapes, magnetic discs and magnetic drums by an ion plating method in a high vacuum. There have been widely used magnetic recording media obtained by coating a dispersion of a ferromagnetic powder such as a gamma-iron oxide powder, a chromium oxide powder or a ferromagnetic metal powder in a resinous binder on a non-magnetic substrate made of such a material as polyethylene terephthalate or aluminum. Various improvements have been suggested in recent years on this type of magnetic recording media in order to meet the requirement for high-density recording. However, there is a theoretical limit to the increasing of recording density in this type of magnetic recording media because the ferromagnetic material used is in the form of a powder and the reduction attainable of its particle diameter is limited. More recently, magnetic recording media having a magnetic layer composed solely of a ferromagnetic material in thin film form (vapor deposited type) have been energitically investigated and developed using such film-forming methods as wet plating, vacuum deposition, sputtering and ion plating in an attempt to obtain a striking increase in recording density, and some of such recording media have already gained commercial acceptance. In practice, however, these magnetic recording media have their own defects, and there is still room for further improvement. For example, because thin-film type magnetic recording media formed by wet plating or vacuum deposition have a very low adhesion strength between the magnetic layer and the substrate, they have the defect that the magnetic layer tends to be peeled, worn or otherwise damaged by mechanical friction (namely, by contact with the magnetic head) during recording and playback. Thin film-type magnetic recording media formed by sputtering and the conventional ion plating methods (for example, as disclosed in Japanese Laid-Open Patent Publications Nos. 33807/1975 and 99703/1975) have an improved adhesion strength between the magnetic layer and the substrate. Since, however, film formation by these methods relies on the utilization of glow discharge or plasma in a low vacuum corresponding to a pressure of 10 3 torr or higher, the inclusion of re- sidual gases and impurities adversely affects the crystallinity of the ferromagnetic film layer, and the resulting magnetic recording medium has defective magnetic characteristics typified by reduced aguareness ratios. Owing to the non-uniformity of a discharge condition, the magnetic recording media obtained by these methods vary in film quality and magnetic characteristics. Accordingly, they still have problems to be solved when they are intended for high-performance and high-density recording. It is an object of this invention therefore to provide a magnetic recording medium having a ferromagnetic film layer which has magnetic characteristics suitable for high-density recording (that is to say, having a high coercivity and a squareness ratio of near 1) and possesses good resistance to peeling or damage by contact with a magnetic head. The present inventors have now found that the above object of the invention can be achieved by a magnetic recording medium having a ferromagnetic film formed by an ion plating method in a high vacuum corres ponding to a pressure of 8 x 10 4 torr or lower without using glow discharge or plasma. Thus, according to this invention, there is provided a process for producing a magnetic recording medium, which comprises heating a crucible containing a ferromagnetic material in a high vacuum corresponding to a pressure of 8 x 10 4 torr or lower thereby vaporizing the ferromagnetic material, impinging accelerated electrons from an electron radiation source against the vapor particles to ionize then, and accelerating the resulting ionized vapor particles in an electric field and impinging them against a substrate composed of a non-magnetic material thereby forming a ferromagnetic thin film thereon. In the present invention, the ferromagnetic material for forming the magnetic layer (ferromagnetic thin film) is preferably composed of an element such as iron, cobalt or nickel, an alloy containing at least one such element, or a mixture of such an element with another element. Examples of iron alloys are alloys of iron with cobalt, nickel, manganese, chromium, copper, gold, titanium, etc. Example of cobalt alloys are alloys of cobalt with phosphorus, chromium, copper, nickel, manganese, gold, titanium, yttrium, samarium, bismuth, etc. Examples of nickel alloys are alloys of nickel with copper, zinc, manganese, etc. The other element mentioned above includes, for example, phosphorus, chromium, copper, zinc, gold, titanium, yttrium, samarium, and bismuth. The thickness of the magnetic layer, i.e. the ferromagnetic thin film, is preferably in the range of 200 i to 50,000 i, especially preferably in the range of 500 2 to 5,000 Examples of the non-magnetic material constituting the substrate used in this invention include polymeric materials such as polyvinyl chloride, polyvinyl fluoride, cellulose acetate, polyethylene terephthalate, polybutylene terephthalate, polyethylene, polypropylene, polycarbonate, polyimide, polyether sulfone and poly parabanic acid; non-magnetic metal materials such as copper and copper-zinc alloy, and ceramic materials such as sintered bodies, porcelains, ceramics and glass. The shape of the substrate composed of the aforesaid non-magne.ic material may be determined suit ably according to the ultimate use of the resulting magnetic recording medium. It is, for example, in the form of a tape, film, disc, or drum. According to the high-vacuum ion plating method of this invention, a ferromagnetic thin film is vapordeposited on the substrate by the following steps. (1) An open crucible containing a vapor source material capable of forming a ferromagnetic thin film is heated in a vacuum chamber evacuated to a high vacuum of 8 x 10 4 torr or lower by a heating means such as resistance heating, electron beam heating, electron bombardment heating or induction heating, thereby vaporizing the vapor source material. (2) Thereafter, electrons released from an electron radiation source are accelerated in an electric field and impinged against the vapor particles to ionize them. (3) Next, the ionized vapor particles are accelerated by a field effect to impart a high energy thereto, and then impinged against a substrate composed of a non-magnetic material at a desired incidence angle. One preferred embodiment of the present invention is described below in detail with reference to the accompanying drawing which is a diagram showing an example of an apparatus for performing the process of this invention. A vacuum chamber 2 in 2 vacuum vessel 1 is adapted to be evacuated to a high vacuum of up to 1 x 10-8 torr by means of an evacuating system (composed of an oil rotary pump, an oil diffusing pump, etc. but not shown) connected to an exhaust port 3. Within the vacuum chamber 2 are disposed an ion source 4 for deposition, a film-like substrate 5, a feed roll 6 for the film-like substrate, a wind-up roll 7 for the product (a roll driving device is not shown) and an ion accelerating electrode 8. The ion source 4 for deposition is constructed of a vapor generating section 9 and e vapor ionizing section 10. The vapor generating section 9 is comprised of an open crucible 11, a filament 12 for releasing hot electrons and a guard 13 for controlling the electric field. The vapor ionizing section 10 is comprised of a filament 14 for releasing hot electrons, a mesh electrode 15 for accelerating the released electrons in an electric field and a guard 16 for controlling the electric field The drawing further shows power supplies 21 to 25 for energizing the present apparatus and an electric circuit therefor outside of the vacuum vessel 1 The production of a magnetic recording medium in accordance with this invention using the abovedescribed apparatus is described specifically. First, as shown in the drawing, the nonmagnetic substrate 5 such as a polyethylene terephthalate film is set on the feed roll 6 so that it is wound up on the wind-up roll 7. A ferromagnetic material 17 capable of forming a ferromagnetic thin film is fed into the crucible 11 and the ion source 4 for deposition is set as shown in the drawing. Then, the vacuum chamber 2 is evacuated to a high vacuum of high vacuum of 8 x 10 4 torr to 1 x 10 -8 torr (usually from 1 x 10 -5 to 1 x 10 6 torr) by the evacuating system through the exhaust port 3. At this time, it is preferred to wind and unwind the film-like non-magnetic substrate 5 in order to remove the matter adsorbed to the surface of the substrate 5 and the air entrained in the feed roll 6. When the degree of vacuum of the vacuum chamber 2 has reached a definite value, the power supplies 21 to 25 are turned on. The crucible 11 is heated by passing a current through the filament 12 by the power supply 22 to heat it and release hot electrons, applying a negative DO voltage to the filament 12 and the guard 13 by means of the power supply 21, and grounding the crucible 11 thereby accelerating the released electrons in an electric field end bombarding the crucible 11. Preferably, the above "operation is performed so that the accelerated electrons are also impinged against the ferromagnetic meterj"l 17. The heated ferromagnetic material 17 voporj?eS at s vapor pressure corresponding to the heating tellperature, and the evaporated particles reach the vapor ionizing section 10. In the vapor ionizing section 10, the vapor particles are ionized by passing a current through the filament 14 from the power supply 23 to heat them and release hot electrons, applying a negative DO voltage to the filament 14 and the guard 16 by means of the power supply 24, and grounding the mesh electrode 15 to accelerate the released electrons in an electric field thereby impinging the accelerated electrons against the vapor particles. Usually, up to 50%, preferably 1 to 2¯/or o4 the vapor particles are ionized. Since the ionized vapor particles are in the positively charged state, they are accelerated by applying a negative DO voltage to -the ion eccelerating electrode 8 by tulle power supply 25, whereby a high kinetic energy is impiirted thereto. Thus, the electrically accelerated vapor particle ions of the ferromsgnetic material collide with tlie surface of the substrate 5 to form a thin film of the ferromagnetic material thereon. Those vapor partic ] es which have not been ionized (neutral particles) do not undergo acceleration by the electric field, and therefore, they are impinged against, and deposited on, the surface of the substrate 5 at the speed imparted during the evaporation. A ferromagnetic thin film having magnetic an isotro))Y in a specified direction can be formed if the accelerated vapor particle ions are impinged obliquely against. the substrate (namely, when they are impinged against the substrate in a direction angularly displaced with respect to the perpendicular to the..substrate) The oblique impingement may be performed by inclining the substrate (tape) toward the advancing direction with respect to the ion source 4 (the preferred incidence angle being 30 to 87 with respect to the per pendicular-WU the substrate), or by inclining the substrate (tape) in the widthwise direction with respect to the ion source 4 (the preferred incidence angle being at least 100 especially 40 to 750 with respect to the perpendicular to the substrate). The magnetic recording medium in accordance with this invention is produced as a result of the formation of such a ferromagnetic thin film on the substrate surface in the above manner. The magnetic recording medium so produced is then taken up on the wind-up roll 7. In order to obtain a magnetic recording medium having better mechanical properties and magnetic characteristics by the process described above, it is preferred to apply an electron current of at least 30 mA for ionization of vapor particles, maintain the ion current density by the ionized vapor particles at 1 iiA/cm2 or higher, and to adjust the incidence angle of the accelerated vapor particle ions to the substrate 5 to at least 300. In the production of the magnetic recording medium in accordance with this invention, sputtering of the material constituting the surface of the substrate, etching of the substrate surface and ion implantation including physical embedding of the sputtered substrate material particles and the vapor particles occur in the course of the impingement of accelerated ions against the substrate As a result, the adhesion strength between the resulting ferromagnetic thin film layer and the substrate increases, and a magnetic recording medium having excellent abrasion resistance and head crush resistance can be obtained Since the method of this invention is carried out in a high vacuum of 8 x 10 torr or lower, the present invention is free from the defects of the conventional ion plating method, that is, the inclusion of re usl gases and impurities and the poor crystallinity of the magnetic film which are attributed to the fact that application of glow discharge or plasma for ionization has to be effected in a low vacuum of 10-3 torr or higher. Accordingly, the method of this invention gives a magnetic recording medium having excellent magnetic characteristics, especially an improved squareness ratio. The non-limitative Example given below illustrates the present invention more specifically. Examples 1 and 2 Ten grams of cobalt lumps (purity 99.99to) were charged into crucible 11 made of high-purity carbon using the high-vacuum ion plating apparatus shown in the attached drawing. A 15 micron-thick polyethylene terephthalate film was used as non-magnetic substrate 5. The feed roll 6 and wind-up roll 7 were arranged as shown in the drawing. A ferromagnetic thin film of 2 ferromagnetic material was formed under the conditions shown in Table 1. Table 1 EMI9.1 <tb> <SEP> Example <SEP> 1 <SEP> Example <SEP> 2 <tb> <SEP> Initial <SEP> degree <SEP> of <SEP> 1 <SEP> x <SEP> 10 <SEP> 6 <SEP> 1 <SEP> x <SEP> 10 <tb> Vacuum <SEP> vacuum <SEP> (torr) <tb> conditions <tb> <SEP> Degree <SEP> of <SEP> vacuum <SEP> 1105 <SEP> 1 <SEP> 10 <tb> <SEP> during <SEP> deposition <SEP> (torr) <SEP> x <SEP> .5x <tb> <SEP> Current <SEP> pas#ed <SEP> through <tb> <SEP> the <SEP> filanent <SEP> (A; <SEP> Ac) <SEP> 28 <SEP> 25 <tb> Conditions <SEP> for <tb> heating <SEP> the <SEP> Electron <SEP> accelerating <SEP> 900 <SEP> 1,000 <tb> crucible <SEP> voltage <SEP> accelerting(V) <tb> crucible <SEP> voltsge <SEP> (V) <tb> <SEP> Electron <SEP> current <SEP> (mA) <SEP> 850 <SEP> 750 <tb> <SEP> Crucible <SEP> temperature <SEP> about <SEP> about <tb> <SEP> ( <SEP> 0) <SEP> 1,900 <SEP> 1,900 <tb> <SEP> Current <SEP> passed <SEP> through <SEP> 25 <SEP> 28 <tb> Conditions <SEP> for <SEP> the <SEP> filament <SEP> (A; <SEP> Ac) <tb> <SEP> ionization <SEP> Electron <SEP> accelerating <SEP> 400 <SEP> 600 <tb> <SEP> voltege <SEP> (V) <SEP> LcOO <SEP> 600 <tb> <SEP> Electron <SEP> current <SEP> (m) <SEP> 100 <SEP> 200 <tb> Conditions <SEP> for' <SEP> Acceleratin# <SEP> voltege <SEP> -2,500 <SEP> -1,000 <tb> ion <SEP> accele- <SEP> (v > <tb> ration <tb> <SEP> #on <SEP> currect <SEP> (#A) <SEP> 500 <SEP> 550 <tb> Roll <SEP> driving <SEP> peed <SEP> (nn/min.) <SEP> 10 <SEP> 10 <tb> Roll <SEP> drlving <SEP> epeed <SEP> (mm/min.) <SEP> 10 <SEP> 10 <tb> lncidence <SEP> angle <SEP> (degree) <SEP> about <SEP> 75 <SEP> about <SEP> 80 <tb> The thickness of each of the ferromagnetic films (magnetic layers) of the resulting magnetic record ing media, measured by a thickness gauge of the multiple 0 besm-interferometer type, was about 1,000 A. The basic magnetic characteristics of the magnetic recording media were measured by 2 DC magnetization measuring instrument (BHH-50, a product of Riken Denshi Co., Ltd.). Both showed very good magnetic characteristics as demonstrated by the results given in Table 2 below Table 2 EMI10.1 <tb> Magnetic <SEP> <tb> characteristics <SEP> <SEP> Example <SEP> 1 <SEP> Example <SEP> 2 <tb> Coercivity <SEP> (oersteds) <SEP> 540 <SEP> 800 <tb> Residual <SEP> magnetic <tb> flux <SEP> density# <SEP> (gauss) <SEP> 8,500 <SEP> 11,000 <tb> Squareness <SEP> <SEP> ratio <SEP> 0.92 <SEP> 0.95 <tb> The adhesion strength between the polyethylene terephthalate substrate and the ferromagnetic thin film in each of the resulting magnetic recording media was examined by a peel test using an adhesive cellophane tape. No peeling of the ferromagnetic thin film layer occurred in the test.

Claims: CLAIMS 1. A process for producing a magnetic recording medium by ion-plating a non-magnetic substrate (5) with a ferromagnetic material (17), characterised by heating a crucible (11) containing ferromagnetic material (17) in a high vacuum (2) corresponding to a pressure of 8 x 10 torr or lower thereby vaporizing the ferromagnetic material (17), impinging accelerated electrons from an electron radiation source (12) against the vapor particles to ionize them, and accelerating the resulting ionized vapor particles in an electric field and impinging them against a substrate (5) composed of a non-magnetic material to form a ferromagnetic thin film thereon. 2. A process according to claim 1 wherein the ferromagnetic material (17) comprises cobalt. 3. A process according to claim 1 or 2 wherein the ferromagnetic material (17) is vaporised by impinging accelerated electrons both against a crucible (11) having electric conductivity and against the ferromagnetic material (17). 4. A process according to claim 1, 2 or 3, wherein the vapor particles of the ferromagnetic material (17) are ionized by an electron current of at least 30 mA released from the electron radiation source (12). 5. A process according to claim 3 wherein the conductive crucible (11) is grounded. 6. A process according to any one of claims 1 to 5 wherein the accelerated ionized vapor particles are impinged against the substrate (5), at an angle of incidence of at least 300 with respect to the perpendicular to the substrate (5). 7. A process according to any one of claims 1 to 6 wherein the substrate (5) is a polyethylene terephthalate film.

Inventors: FUKAYA, KAZUHIRO, HOTTA, MASAHIRO, MIKAMI, YOICHI, NAKATA, SHINSAKU
Applicants: SEKISUI KAGAKU KOGYO KABUSHIKI KAISHA
Application year: 1981
Main classification: G11B5
IPC codes: H01F41, C23C14, G11B5