Magnetic Recording Members

This invention relates to improved magnetic recording media of the type are known as discs and is particularly advantageous when embodied in those flexible disc products known as floppy discs.

In reading the following discussion of the background of the invention, it must be remembered that the discussion has been prepared with a full knowledge of the invention. It cannot be, and is not intended to be, a view of the existing art as apparent to one or ordinary skill in the art at a time preceding the invention.

The magnetic recording members, subject of this invention, comprise a coating of magnetic particles in a matrix such as an organic polymer matrix. There are two general kinds of such members. A first kind is typified by the most common type of magnetic tape. This kind of product moves in a longitudinal direction in relationship to a recording or reading head because information is recorded sequentially along the length of the medium. The other kind of product is a disc which rotates while the reading head is positioned radially or helically, much in the relationship of a needle on a phongraph disc. These products are very well recognized in the art and have each been in extensive commercial use for some time. There has been a great deal of effort expended over the last thirty years or so to improve the magnetic recording characteristics of such products. One such procedure has been the orientation of the magnetic particles within their matrix. A discussion of such orientation is presented in The Physics of Magnetic Recording by C. D. Mee; 1968; North-Holland Publishing Company - Amsterdam. Both longitudinal and vertical orientation is discussed. Longitudinal orientation is orientation along the direction of travel of the recording member, e.g. along a tape. Vertical orientation would be the same particles "standing up" on end, i.e. normal to the tape surface. Mee points out that use of orienting techniques is not indicated for applications such as magnetic discs "which require tape to be magnetized in different directions". Among additional publications disclosed various orientation techniques and procedures are U.S. Pat. Nos. 3,052,567 to Gabor et al; 3,185,755; 2,796,359; 3,256,112; 3,117,065; 2,711,901; 3,261,706; 3,065,105 and 3,627,680. U.S. Pat. Nos. 3,117,065; 3,052,567 and 3,185,775 discuss vertical orientation of magnetic particles. There is somewhat related art, typified by Patent 3,001,891, wherein an AC orienting field is used to allow a "free" orientation of particles in response to other fields.

In some known art, discs have included oriented particles. This is especially true of inadvertent radial orientation of rigid (as opposed to floppy) spin-coated magnetic discs. Also, U.S. Pat. Nos. 3,256,112 and 3,001,891 disclose the use of an orienting procedure and state that discs may be oriented. In such a procedure, the particles have always been oriented in a circular direction, i.e. in a direction directly analogous to the longitudinal direction in tapes. It is believed that not even this type of procedure has been sufficiently advantageous to be commercially adopted in disc manufacture.

The flexible articles known as floppy discs are formed on a coating apparatus exactly like magnetic tape, then cut into circular discs. Such discs carry unoriented particles and cannot take advantage of any high magnetic squareness attributes of said particles. One example of such a disc format is described in "IBM Diskette, Original Equipment Manufacturers' Information" Product Reference Literature Number GA21-9190-1, File GENL-19 available from IBM Corporation.

In still another area of the magnetic recording art, there has been a great deal of attention being paid to the development of superior magnetic particles. Usually such particles are cobalt-based metal particles like those disclosed in U.S. Pat. No. 3,909,240 to Deffeyes et al; U.S. Pat. No. 3,574,685 to Haines et al and U.S. Pat. No. 3,607,218 to Akashi et al. Such particles can be utilized in providing much superior magnetic recording members than are possible using the traditional iron oxide particles. However, it is difficult to form magnetic recording members which fully exploit the potential of the improved metallic particles on commercial mixing coating equipment operated at acceptable output rates.

A major problem, in this respect, is the adequate dispersal of such powders. A number of inventors have provided improved means for dispersing such particles more efficiently. For example, U.S. Pat. No. 3,026,215 suggests the lengthwise and breadthwise orientation of such particles. Manly, in U.S. Pat. No. 3,172,776 discloses a process wherein chains of metal particles are formed to facilitate their being adapted more readily to an orienting procedure. A somewhat similar suggestion is made in U.S. Pat. No. 3,228,882 to Harle et al. Akashi et al, in U.S. Pat. No. 3,740,266 suggests still another method for overcoming problems inherent in orienting the more acicular of said particles.

While the problem of coating defects has slowed down the commercial application of such metal powders in magnetic tape, it has been a particular barrier to using the powders in floppy discs wherein a defect in the coating will necessarily cause a large area of processed tape to be discarded.

In the disclosure set forth below, the inventors will describe an improved magnetic disc and process for making the same. The novel disc product embodies attributes substantially overcoming the limitations of the disc products described above. Applicants, in solving the problem associated with such discs, have discovered a general solution to the roping problems heretofore associated with both acicular particles and small metallic particles, a solution useful in both disc and tape products. Also of interest in the prior art are polymodal materials are disclosed in copending and commonly owned U.S. Patent Application Ser. No. 411,253 filed Oct. 31, 1973 by Deffeyes.

That application, and Belgian Patent 823,013, incorporated by reference herein, disclose a system based on the use of a magnetic identifiction medium formed of at least two distinct populations of ferromagnetic powders, wherein a first population is selected so that it can magnetically switched, i.e. recorded upon, by a magnetic field at which a second population will not be switched. Each population is also responsive to differing stimuli, say differing magnetic fields or temperatures, for erasing information therefrom; that is magnetic information can be retained by one population as magnetic information is erased from another population. In general, it is desirable to have populations in a bimodal system characterized by coercivity values have a difference of at least 200. In practice, bimodal systems may be selected to have differences of 1000 or greater. If additional functionality is built into a ferromagnetic system by adding different modes, the higher and lower coerivities will usually differ by at least a factor of 200 (X-1) wherein X is the number of modes and it will be advantageous to keep the coercive force difference between the different populations at 200 oersteds or more.

The discovery that certain combinations of powders can be utilized in achieving such distinctly polymodal ferromagnetic systems was unexpected in view of the performance of mixtures formed of the ferromagnetic powders generally used in the art. For example, a mixture formed of a first iron oxide, a second ion oxide and cobalt-based metal powders having coercivities of 180, 320 and 1000, respectively, yielded a lowcoercivity peak which was not distinct although there were distinct peaks between the low coercivity materials and the high coercivity material.

The above result may be partly understood in view of the teaching that the peaks should be about 200 oersteds apart. However, the two low coercivity powders interact more than would be expected on the sole basis of the insufficient difference in coercivities.

In general, it appears that the metal powders, i.e. those of Bm values exceeding about 8000 gauss are the most advantageous for use in forming bimodal systems, in that they can be used successfully in combination with oxides and other metal powders.

Some typical Bm values are 3400 for gamma Fe.sub.2 O.sub.3, 4000 black Fe.sub.3 O.sub.4, about 16,000 for the cobalt metal powder of Example 1 below and about 13,000 for the low-coercive force metal powder of Examples 2 and 3.

In general, the peaks visible on a non-integrated dM/dt curve of an advantageous polymodal system can usually be recognized in two ways:

1. As one raises the field on a BH meter the lower-coercivity curves will be substantially complete before the appearance of the next higher curve.

2. The valleys between adjacent peaks are advantageously of a depth equal to at least one half of the average height of the adjacent peaks over a base line.

It is an object of the present invention to provide improved magnetic recording members which exhibit an improved utilization of potential properties of magnetic particles.

Another object of the invention is to provide improved magnetic discs, especially improved floppy discs.

Another object of the invention is to provide improved bimodal magnetic recording media.

Further objects of the invention are to provide novel processes by which the aforesaid discs and other recording media are made.

Still another object of the invention is to provide improved magnetic recording members using metallic powders, especially high cobalt-alloy powder of excellent squareness.

Other objects of the invention will be obvious to those skilled in the art on their reading of this disclosure.

The above objects have been substantially achieved by the construction of an improved recording member using vertical orientation in the manufacture of discs or using vertical orientation in the manufacture of recording media using metallic particles.

Particular advantage is achieved when such orientation is used in conjunction with metallic particles of the type which tend to align and "rope" when subjected to magnetic orientation procedures.

The invention allows the manufacture of floppy discs which have an increased output signal over present media of up to about 3 decibels with iron oxide and an increase from about 5 up to about 12 decibels with the best metal particles. Like improvements can be achieved using such known magnetic fillers as cobalt-doped iron oxide, and chromium dioxide.

Moreover, for the first time, it is possible to approximate in a practical magnetic recording media, the performance which is believed to be ultimately possible with metallic particles, especially those particles comprising 50% or more by mass of iron or cobalt, and to do so while utilizing a relatively small quantity of such particles. This is apparently possible because the magnetic-particle-bearing coating in a vertically-oriented member can be limited to a coating so thin, e.g. about 100 microinches thick, that roping is found to be effectively prevented. In the most efficient utilization of the invention, the coating will be from 30 to 70 microinches in thickness.

In disc applications, there is another important processing advantage which is found to favor the use of vertically-oriented magnetic particles: There is often a single head for reading and recording. In such cases, the gap required for reading controls the single head design. Thus, a relatively short head gap is already used in such applications and vertically-oriented coatings are found to be particularly advantageous.

Moreover, the most such applications utilize rather short wave lengths: those best utilized with a thin, vertically oriented coating.

FIGS. 1 and 2 are schematic diagrams illustrative of the vertical-orienting rationale helpful in understanding the present inventions.

FIG. 1 shows a magnetic field configuration near the write head gap.

FIG. 2 illustrates the same head as shown in FIG. 1 with a magnetic coating moving from left to right with respect to the head.

FIG. 3 is a schematic fragment of a bimodal floppy disc prepared according to the invention.

FIG. 4 is a schematic diagram of a process line wherein a magnetic-recording web is being vertically oriented.

FIG. 1 illustrates write head 10 having a gap 12. The magnetic field of heat 10 is illustrated, in its normal condition, by a series of lines 14 which generally approximate the strength of the field at varying distances from gap 12. On each line 14 is a numerical designation of the field strength as a fraction (decimal equivalent) of the strength of the field in the gap, i.e. the so-called "deep-gap field". A magnetic coating 16 is shown in relationship to the gap and has, roughly, a depth equal to the gap width itself, i.e. about 100 microinches or 0.1 mil.

FIG. 2 illustrates the same apparatus shown in FIG. 1 except the recording member 16 is moving from left to right across the recording gap 12. The deep-gap field, for demonstration purposes, is taken so that recording is taking place between field limits of 0.3 and 0.375. It will be noted that the field portions represented in this range are primarily vertical near the head but primarily horizontal in volumes of the coating which are deeper than about 70-80 microinches from the head in the magnetic coating. A resultant field 20, i.e. the field formed by the horizontal and vertical components of the field, is also illustrated in FIG. 2.

When one is primarily interested in short-wave-length parts of the magnetic-recording spectrum, as is the case when one is recording digital information, substantially all of the information-storing-and-retrieval processes can be carried out in the surface region (near the head) of the magnetic coating. For digital signals which are fairly high in density, one will achieve better resolution, high output, and higher bit densities with the higher-squareness, vertically oriented particles as is described herein.

In a particularly favorable embodiment of the invention, one can utilize a polymodal embodiment, i.e. an embodiment using at least one additional magnetic-particle population in a layer adjacent to, or intermixed with, the vertically aligned population. These added populations may or may not themselves be vertically aligned. Such polymodal embodiments wherein particulate magnetic powders are used, should preferably have powders selected so that there is a difference in coercivity of about 200 oersteds or more and one of the powders should preferably be metallic, exhibiting a Bm value of 8000 gauss or more. Thus, a metal such as iron, cobalt and the like; e.g. the cobalt-iron-nickel alloy sold for mgnetic tapes by Cobaloy Co., a division of Grahm Magnetics Incorporated, can be advantageously combined with gamma iron oxide or chromium dioxide. In floppy discs used in storage of digital information, the space taken up by such ancillary information as required for addressing and indexing of the "hard data" is up to two-thirds of the available disc area. When this ancillary information space can be increased substantially. This advantage can be improved several times again because of the use of vertically-oriented particles. Moreover, the orientation procedure itself helps to achieve an improved functional separation of the different recording modes.

In manufacture of vertically-oriented discs, particles having a squareness value of 0.65 may be used advantageously. However, the particles which will exhibit squareness values of from 0.72 to 0.9 or higher, are preferred.

In making a bimodal disc of the general type being described, a number of possible choices exist. For example, the different magnetic particles can be coated together in one layer or segregated into two layers. If two layers are used, either material may be on top.

In practice, single-layer, poly-modal coatings are most economical. This is particularly true when one wishes to take advantage of the relatively thin coatings which are useful with the process of the invention. Indeed, the combination of a thin coating and vertical orientation, made possible by the process of the invention, results in a superior bimodal product. In a most advantageous embodiment of the invention, say where digital information is carried on a disc, the "address" information is preferably carried on the high coercivity material nearer the surface of the disc substrate. The temporary information would be carried on the lower coercivity material nearer the top of the disc. FIG. 2 shows schematically high coercivity particles and low coercivity particles dispersed in the same media. It is to be understood that most of the recording will occur in the vertically oriented section of the cooling.

In this application and accompanying drawings, there is shown and described a preferred embodiment of the invention and suggested various alternatives and modifications thereof, but it is to be understood that these are not intended to be exhaustive and that other changes and modifications can be made within the scope of the invention. These suggestions herein are selected and included for purposes of illustration in order that others skilled in the art will more fully understand the invention and the principles thereof and will be able to modify it and embody it in a variety of forms, each as may be best suited in the condition of a particular case.

Metal powders may be advantageously incorporated into magnetic tape utilizing many different polymer systems. One such system would comprise 77 parts by weight of the metal powder product which is acicular metal powder having an average particle size of about 0.5 micron by about 0.15 micron. It is formed of 18 parts nickel, 18 parts iron and 64 parts cobalt. Such a powder may be obtained from The Cobaloy Company, a division of Graham Magnetics Incorporated. Such a powder is typically characterized by a squareness value of 0.84, a coercive force of 659 oersteds, and a specific magnetic moment of about 138 emu per gram. Also included are parts soya lecithin, 19 pounds of the pre-polymerized polyurethane resin sold under the trade designation Estane 5707 by B. V. Goodrich Co., and as described in U.S. Pat. No. 2,871,128 to Schollenberger. Other additives would normally be added. These additives are known to those generally skilled in the art, and include fungicides, and the like. Two parts by weight of butoxyethyl stearate and 0.1 part by weight of diphenyl mercury would be suitable adjuvants for the formulation given above. The formulation when adequately mixed would be coated along a substrate such as a polyethylene terephthalate polymer film substrate at a wet thickness selected to yield an 80-microinch (dry) coating of magnetic coating composition on the film after the composition is dried.

After coating, but before drying, the coating is subjected to a magnetic field which is everywhere normal to the surfce of the web. FIG. 4 indicates, schematically, one such system which results in such a field but other systems can be used. For example, the field is about three times the coercive force of the metal particles used in the tape. The field may be continuously applied, pulsed, alternating, or a combination of these. If a combintion, one component might be of a lower value, e.g. 1.5 times the coercive force of the particle than that given above.

After the vertical orienting is accomplished, the web is dired. Part of the dired web is cut into "vertically-oriented" circular floppy discs, and then packaged in the maner usual for such products. A part of the web is also slit into continuous ribbons to form "vertically oriented" magnetic tape.

The above example is repeated using gamma iron oxide of the type sold under the trade designation HR280 by Hercules Corporation as the particle.

Example 2 is repeated using magnetic chromium oxide of the type sold by E.I. DuPont. A particle size of about 1 micron is selected and the volume of filler is maintained at the same level as for iron oxide in Example 2.

Example 1 is repeated using, instead of the magnetic fillers in Example 1, a substitute filler sufficient to equal the same volume % loading in the coting composition of the magnetic as the filler of Claim 1. This substitute filler itself comprised 40% by weight of the iron oxide of Example 2 and 60% by weight of the cobalt alloy of Example 1.

The resulting magnetic coating composition was coated onto the substrate in a coating selected to yield a 110-microinch (dry) coating.

The resultant tape is bimodal medium suitable, for example, for use in a procedure wherein basic information is maintained in the high-coercivity cobalt-alloy mode and wherein different, independently-erasable, inforamtion, or an interference pattern, is carried by the iron oxide mode.

FIG. 3 illustrates a fragment of a floppy disc 30 which comprises a polymeric film base sheet 32 and a magnetic coating 34. This coating comprises vertically oriented particles of cobalt alloy magnetic powder 36 near the surface of the disc.

FIG. 4 illustrates the manufacture of a tape web according to the invention showing movement of the web 44 from a coating device 40, through magnetic orienting magnets 42, through a drier 44 onto a take up roll 46.

It is to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described and all statements of the scope of the invention which might be said to fall therebetween.