This invention relates to a process and apparatus for coating a substrate with polytetrafluoroethylene (PTFE), and to PTFE-coated products.

PTFE is extraordinarily resistant to chemical attack, and the surface free energy of solid PTFE is very low. This means that liquids do not readily wet the solid, and other solids do not adhere strongly. These properties render PTFE very valuable for forming protective surface coatings, in a wide range of applications from non-stick cookware to surgical sutures. However, the very properties which make PTFE so useful in such applications also make it very difficult to form PTFE coatings which are sufficiently adherent to their substrates. In practice, - PTFE coatings formed hitherto have relied on mechanical keying for their adherence to their substrates. For example, one common method of forming PTFE coatings is to coat the intended substrate first with a primer and then to implant solid PTFE particles in the primer layer, while the latter is still tacky, so that it can trap the PTFE particles in a mechanical matrix. These PTFE particles then form anchor points for subsequent layers of PTFE particles which are attached thereto by sintering at temperatures of between 350 and 400°C, depending on the type of PTFE used. In an alternative method for forming PTFE coatings, an extruded or skived PTFE sheet is fibrillated by subjecting it to substantial mechanical. stresses. The voids created in the PTFE allow adhesives or other materials to penetrate the PTFE sheet and form a mechanical bond therewith.

A still further method employed for coating with PTFE telomers is to spray, brush or otherwise spread onto

the substrate a dispersion of low molecular weight solids of PTFE suspended in a suitable liquid such as Freon or water, and then to evaporate the solvent. Such coatings are sometimes sintered or even buffed in order to increase the uniformity of the coating. However, coatings formed by this method are only poorly adherent and usually intended for single applications such as in mould release applications or as release layers for decalcomanias.

The present invention provides an entirely new method of depositing PTFE films. The method is applicable to forming PTFE coatings on a wide range of substrates, and produces a type of PTFE coating which is believed to be unique.

The present invention is based on the unexpected discovery that PTFE can be made to form films of un¬ precedented adherence merely by rubbing minute particles of PTFE with sufficient force across the surface of a substrate. It is believed that the bond obtained between the PTFE coating and the material of the substrate when the method of the invention is used is not merely the result of mechanical keying between the PTFE and micro¬ scopic rugosities on the surface of the substrate, because friction coatings of the latter type are known to be only very weakly adherent. For example, a method which has been used in the study of friction wearing of

PTFE has been to cause a solid rod of PTFE having a pointed end bearing perpendicularly onto a plate of glass to traverse back and forth over the same track until a layer of the desired magnitude is deposited. Coatings formed in this way can be lifted from the surface of the glass merely by immersion in water containing a surfactant.

The difference between the PTFE coating of the present invention and the PTFE friction coating just described is believed to be due to the high energies which

are involved in forming the coatings of the invention. While the exact mechanism of coating is not known, it is thought that at sufficiently high energies, the PTFE particles serve to decontaminate the surface of the substrate, the surface thus being activated in. some way so as to be highly receptive to any molecule with which it might come into contact. When a sufficient number of PTFE particles are rubbed across the surface at a sufficient rate, fresh PTFE particles are presented to the decontaminated surface, and thus bond therewith, before recontamination by other molecules can occur. A possible alternative mechanism is that under the very high energy conditions which obtain at the interface between the PTFE particle and the substrate, an intimate molecular mixture or complex is formed between the PTFE and the material of the substrate, analogous to a.metallic alloy, that the two materials would not normally form an alloy with each other.

Quite apart from its adherence, the PTFE coating of the present invention has a number of characteristics which are not found, at least in combination, in con¬ ventional PTFE coatings. Firstly, they are very thin, being less than 3 microns in thickness. More usually, they are substantially thinner than this, very often being less than 500 nm thick and often less than 200 n thick. Typical film thicknesses are from 10 to 100 nm thick, for example from 20. to 50 nm thick. A most unusual characteristic of the process of the invention is that the PTFE coatings produced thereby are effectively self-limiting in thickness, in the sense that the coating, once formed, will generally not increase in thickness even when more PTFE powder is rubbed over the surface.

Another characteristic of the PTFE films formed by the process of the invention is that they are substantially

non-porous. This is highly unexpected in such a thin

PTFE coating.

Yet a further characteristic of the coatings formed by the method of the invention is that they are sub- stantially free of voids. Even sintered PTFE coatings include a sufficient number of voids to bring the bulk

3 density of the coating down to 1.5 g/cm or even less.

In contrast, the coatings formed by the method of the present invention have a bulk density which is at least 1.70 g/cm 3, most usually greater than 1.80 g/cm3 and

3 often greater than 1.90 g/cm . Typical coatings according to the invention have a bulk density of

2.0 g/cm 3S or greater, for example from 2.1 g/cm3 to

2.25 g/cm" Accordingly, the present invention provides a method of coating a substrate with PTFE, comprising causing discrete, substantially dry particles of PTFE to move - across the surface of the substrate with sufficient ^' force and at sufficient speed relative to the surface to cause PTFE to become deposited on the surface of the substrate in an adherent film.

Viewed from a different aspect, the present invention provides a method of forming a PTFE coating on a substrate, comprising rubbing discrete, sub- stantially dry particles of PTFE across the surface of the substrate with sufficient force and at sufficient speed relative to the surface of the substrate to cause a PTFE coating of self-limiting thickness to be deposited on the substrate Also provided by the present invention is an apparatus for coating a substrate using the method, said apparatus comprising a support for the substrate, a rotary

applicator arranged to bear against a substrate supported on said support, means for delivering a supply of substantially dry particles of PTFE to the surface of the applicator, or of the substrate, or both, and means for rotating the rotary applicator to cause the surface thereof to rub said particles against the substrate, whereby to coat the substrate with the coating material. Further provided by the invention is a substrate having deposited thereon an adherent substantially non-microporous PTFE film which is less than 3 microns thick.

The application of PTFE to the substrate with the requisite rate of energy input may be achieved by bombarding the intended substrate with particles of PTFE carried on the surface of larger particles of the same or different resilient material such as cork. The carrier particles may be projected at the surface to be treated by entrainment in a cold or heated high velocity jet of gas. Alternatively, the carrier particles may be caused to vibrate acoustically (ultra-sonically) , magnetically or mechanically against a substrate.

Preferably, however, the PTFE particles are rubbed across the surface of the substrate by means of an applicator having a resilient surface which is in sliding contact with the substrate. The applicator may be, for example, a rotary applicator such as a roller or wheel.

A particularly preferred applicator for use in the method of the invention is a jeweller's buffing wheel. Suitable buffing wheels include those available from W. Canning Materials Limited, Great Hampton Street, Birmingham, England. These buffing wheels generally comprise a plurality of fabric discs clamped together in a way which allowsthe density of fabric at the periphery of the wheel to be adjusted,or are made of felt.

The term "PTFE" as used herein is intended to embrace both PTFE homopolymers and polymers formed by copolymerising tetrafluoroethylene with other monomers. Polymers of fluoroethylene-containing other halogens are also included, as are mixtures of polymers of different composition. Polymers may be of different chain lengths (molecular weights), molecular weight distribution and crystalunity. Oligomers and telomers of tetrafluoroethylene are also included. If desired, other particles, such as mineral particles of a pigmentary character, may be included with PTFE particles.

The PTFE particles are preferably less than 100 microns in diameter, and more preferably less than 50 microns in diameter. Particularly preferred are PTFE particles having a maximum diameter less than 30 microns.

The PTFE particles may be delivered to the surface of the applicator in the dry state, but it has been found to be more convenient to ^" deliver the PTFE particles to the surface of the applicator in the form of a liquid dispersion. Preferably, the dispersing solvent is sufficiently volatile to evaporate almost instantly, leaving the particles in a substantially dry state, A suitable dispersing solvent is trichlorotrifluoroethane, though other low-boiling halogenated hydrocarbons can also be used.

The method of the invention can be used for coating virtually any substrate, but it is of particular utility in the formation of thin PTFE films on plastics sheets, foils, tapes and films. Remarkably, the process may also be used to great advantage for coating paper and woven and nonwoven fabrics (whether of natural fibres such as cellulosic fibres, or synthetic fibres such as

polyesters, polyolefins, polya ides and substituted celluloses) and other materials of a soft nature.

When the substrate has an uneven surface, such as the surface of a nonwoven fabric, the coating may be macroscopically discontinuous, in that only the high points of the substrate are coated with a thin, adherent, substantially nonmicroporous film. However, when such substrates are coated by the method of the invention, it is found that both the micro and macro interstices between and within the fibres are filled with loosely compacted sub-particulate materials which are thought to be micro platelets and it is thought that these platelets are formed when the PTFE particle is violently scraped across the protruding fibres on the surface of the substrate. It will be understood that the PTFE deposited on the highlights does not require sintering to ensure an effective and adherent film. Depending on the end use for which the coated substrate is intended, however, it may be desirable to increase the coherence and adherence of the micro platelets which accumulate in the depressions between the highlights. This can be achieved by subjecting the coated substrate to a flash sintering operation. This flash sintering involves the passing of a coated substrate through a nip where at least one roller is heated, for example to a surface temperature of above 350°C, e.g. 410°C. The coated substrate has to pass through rapidly so as not to cause scorching or other structural damage. The thicker the platelet deposits, the longer is the dwell time necessary in the heated nip. Therefore there is a natural restriction on the thickness of sintered coatings which may be formed on substrates which are liable to thermal damage.

In certain cases, the above-described method of flash sintering will not be appropriate. For example, if a PTFE-coated bank note is flash sintered using heated rollers, the elevated temperature and pressure at the nip of the heated sintering roller cause ink at the raised images produced by the Intaglio process to soften and flatten. Consequently it is appropriate in this instance to use a non-contact heat source such as high intensity radiation. In cases where the PTFE coating of the invention is deposited on a relatively uneven surface, the thin film which is formed on the high points of the substrate constitutes an anchor to which further PTFE layers may be bonded by conventional sintering processes. It will be appreciated that the nature of the present invention is such as to preclude precise enumeration of the appropriate process conditions for forming a PTFE film on a given substrate. This is because coatings can be formed using a wide range of process conditions, which are all dependent on each other. Thus, for example, when a buffing wheel is used to rub the PTFE particles across the substrate, the pressure applied by the wheel, the area of contact between the wheel and the substrate, the peripheral speed of the wheel, and the relative speed between the surface of the wheel and the substrate may all be varied.

However, alteration of any one of these parameters may require that one or more of the other parameters be adjusted in order to compensate. Moreover, the conditions necessary for forming a PTFE coating according to the invention will depend greatly on the physical and chemical nature of both the PTFE and the substrate. In all cases, however, the appropriate process conditions will be readily determinable by the person skilled in the art,

particularly having regard to the guidelines and specific examples set out below.

Generally, we have found that the more delicate the substrate, the lower the pressure with which the PTFE particles should be pressed against the substrate, in order to avoid damage thereto. Thus, for example, a very lightweight nonwoven farbic may be coated using a 30 cm diameter soft fabric buffing wheel, by training the fabric round the buffing wheel, and applying only a slight tension (e.g. from 10 to 100 grams/cm width of fabric, depending on the strength of the fabric). With this arrangement, the pressure with which the wheel bears against the fabric is very low indeed, for example from less than 1 g/cm 2 to a few grams/cm2. However, such low pressures are compensated for by the fact that individual PTFE particles are drawn over a very sub¬ stantial length of the nonwoven abric, such as from one quarter to three quarters of the circumference of the wheel. In the example first described, the roller can conveniently be rotated at 2000 rpm, while the nonwoven fabric web is drawn through at about 10 metres/ minute.

When the substrate is rather more robust, such as a paper of weight 100 g/m , a convenient coating technique is to feed the substrate into the nip between a buffing wheel and a retaining roller. In this case, the distance for which individual PTFE particles are in contact with the substrate is very much smaller (generally from 1 to 20 mm, e.g. from 2 to 10 mm), and substantially larger pressures are therefore appropriate. Conveniently, the. static pressure of the roller on the substrate will be at least 100 ^" g/cm , preferably at""""" least 200 g/cm , and more preferably from 300 g/cm ² to

10 kg/cm 2, e.g. from '

Generally the harder the intended substrate, the harder the applicator which may be used. For example, we have coated a 50 micron thick polyester sheet using a soft fabric buffing wheel (see Example 2 below), but it was preferred to use a hard felt polishing wheel ( 20 cm x 2.5 cm, 1700 rpm, 3kg/cm estimated dynamic nip pressure) for coating aluminium.

Although the factors which determine the appropriate operating conditions for different substrates are imperfectly understood, it will be apparent that identifying the appropriate conditions for a given substrate is merely a matter of trial ^' and error. The operator need only choose a coating technique which is appropriate to the strength and flexibility of the substrate in question, and then increase the applicator pressure and/or applicator speed until a desired coating is formed.

The method of the invention can be used for coating six enormous range of products. Particular examples include the- coating of magnetic recording media, such as video recorder tapes, audio recording tapes, computer tapes, computer floppy discs and computer hard discs. The PTFE coating services to protect both the recording medium itself and the information stored in it against dirt, liquids and other materials which might interfere with proper recording and reading of stored information. Because the process of the invention results in the formation of a very thin film of PTFE. the recording and reading heads which are used for storing and retrieving

information from magnetic recording media can be placed in their normal very close relationship to the surface of the recording medium.

Another area of application for the method of the invention is in the coating of medical products, such as bandages, wound dressings, burns dressings, personal hygiene products, surgical needles, staples, sutures, catheters, surgical drapes and surgical gowns. Wound dressings which are PTFE coated in accordance with the invention are dirt-repellant, and therefore more hygienic, and also non-adherent to wounds. PTFE-coated fabrics in accordance with the invention may be used to form water-repellant, but air-permeable gowns and drapes. Needles and staples may be given a low-friction coating to decrease the discomfort caused to the patient by their use, and PTFE-coated sutures according to the invention are more easily removed.

Yet further applications of the invention are in forming anti-soiling coatings for security paper, bank notes, stamps, maps, charts, paper bags, envelopes, food wrappings, cookware, fabrics for curtains, wallpaper, yarns such as carpet yarns, threads and ropes. Still further applications include the formation of low-friction coatings for nip rollers, calenders, process machinery, missile and aircraft skin coatings, helicopter and air¬ craft blades, impellers and propellors, boat and ship hulls, low speed bearings, razor blades and conveyor tube coatings. Further applications include the formation of water-repellant coatings for tent fabrics, clothing fabrics, and incontinence products including diapers, and the formation of release coatings for pressure sensitive adhesive tape backings, dry print foils, mould release papers and foils, heat transfers and decalcomanias.

Still further examples of the applications of the present invention are set out in our earlier British Patent Application No. 8401838, filed 24th January 1984.

A number of embodiments of the invention will now be particularly described with reference to the accompanying drawings in which:-

Figure 1 illustrates diagrammatically a rotary applicator for carrying out the method of this invention; and

Figure 2 shows diagrammatically the applicator in the context of apparatus for use in carrying out the method of this invention. The apparatus shown in Figure 2 will be carried within a metal frame of such mass and proportions so as to withstand the loadings and stresses imposed upon it by the operation. A rotary motive power unit, in this case an electric motor (not shown), capable of delivering rotational speeds at the torque necessary for the operation, is mounted to drive the apparatus. Within this description we shall consider only the coating of . a moving web of approximately 20 cm width. The apparatus therefore also requires the means of conveying the web through the apparatus.

At theheart of the apparatus of the present example are two rollers 10, 11 forming a nip 12 through which the substrate 13 must pass. One of these rollers 10 is the applicator and the other is the retainer 11. The retainer roller rotates in the same direction as the web is travel¬ ling. The applicator roller is driven and rotates so that its surface in the region of the nip moves in the same direction as the web, but at a different speed, or in the opposite direction, all as indicated by arrows in Figure 2.

The two rollers 10, 11 are mounted within the frame in such a way that the centre lines of their axis may be moved relative to each other and possess the necessary facility to be firmly fixed in the desired position after the correct nip pressure has been set.

Apart from the small segment of its circumference at the nip and the aperture required through which the coating material is conveyed or any surplus which may be extracted via a flexible duct 14A, the applicator is contained in an enclosure 14.

The coating material may be applied to the applicator by any means so long as the particulate material is in a dry form when it reaches the nip and it is uniformly deposited over the face of the applicator.

In the present example an airless spray 15 is used to convey the PTFE particles at a nozzle pressure of 480 P.S.I. Although in the above-mentioned airless spray the PTFE particles are dispersed in a solvent, which being FREON (Registered- Trade Mark) TF is highly volatile and is thought to "flash off" almost completely before the PTFE particles hit the surface of the applicator, the preferred method .is to apply the coating material uniformly in a dry particulate state. One benefit of using the dry particulate state is to avoid using solvents which are unattractive for commercial and environmental reasons.

The airless spray is equipped with a switch mechanism (not shown) which is operated by a cam which is rotating at 38 RPM and has lifting knobs having an effective operating dwell of 3° arc on the cam. The number of lifting knobs used is determined by the surface roughness of the substrate and or the quantity of particulate material that is desirable to be deposited on the substrate.

The spray nozzle is adjusted to produce a fan-shaped spray pattern 15 in which the particles are evenly dis¬ tributed when they contact the applicator roller 10. The applicator roller 10 and the spray cam (not shown) are linked through gearing in such a way that with each squirt

of the nozzle approximately one quarter of the applicator's surface areaalong its circumference receives a deposit of the coating material and 40 revolutions later the appli¬ cator receives a second squirt of material which should land on the second quadrant and so forth.

The applicator is made from sheets of cotton fabric 17 cut in 10 cm diameter discs withahole in the centre of each disc of 2. 5 cm diameter. These cotton discs are then pulled onto a threaded steel shaft 18 of 2.5 cm diameter and are retained by 6 mm thick steel washers 19 of 8.9 cm diameter to form an applicator 30 cm wide. The washers in turn are retained by suitable nuts. The cotton discs: are compacted by tightening the retaining nuts to produce a density at the perimeter face of the compacted cotton mass appropriate to the material to be coated. We ave found that delicate substrates require softer rollers than resilient substrates. When using polyester films and other delicate materials the applicator is considered to be of sufficient density for use on a polyester film when it cannot be compressed by more than 6 mm when reasonable thumb pressure is applied.

When a softer applicator is desired intermediate nuts 18 and washers 20 may be used on the shaft at say every 1 to 2 cm along the length of the applicator. Alter- natively, the nuts may be tightened further in order to compact the cotton sheets into a more solid mass.

Once the correct applicator density is achieved it is then ground in by running it at high speed against the retaining roller, the surface of which is closely covered with a sheet or coarse abrasive material such as emery cloth and running in a counter direction to the rotation of the applicator for 1 or 2 hours or until such time as a smooth enough surface corresponding to the con¬ tours of the retainer roller is produced. Following this operation the coarse abrasive material is removed and the

the deposition process is ready to commence.

In general, we have found that the rate of energy input required for the best operation of the invention increases with the molecular weight and/or the crystallinity of the PTFE.

The invention is now further illustrated by the following examples:-

EXAMPLE 1 To coat a common grade of paper we have used the following formulation:-

Fluon LI68 (PTFE) 150 gm

Freon TF (trichlorotri- fluoroethane) , as dispersant 2,750 gm

2,900 gm

Fluon is a Trade Mark of ICI, and Freon is a Trade Mark of Du Pont.

In this particular example the paper used was a stencil based paper manufactured by Tullis Russell. It was an uncoated, unsized paper of 105 gm per metre.

The pressure applied by the applicator roller was 0.77 kgs/Sq.cm. The substrate (paper) web moved at 27 metres per minute. The speed of rotation of the appli¬ cator roller was 1550 rpm but the retainer roller rotated at only 92 rpm.

EXAMPLE 2 The same apparatus as in Example 1 was used to coat a polyester film of 50 microns thickness (Melinex S grade polyester sold by ICI) . The applicator roller applied pressure was 0.5 kgs/Sq.cm. which was reduced to this level because the substrate is in this case a relatively smooth surface material. It was also found best to use a softer roller for this type of substrate than was used for coating paper. Also the best results on this type of

substrate occurred when a low molecular weight PTFE was used with a formulation of the following proportions:

Vydax AR (20% solid in Freon) 600 gms Freon TF 2,900 gms

3,500 gms

Vydax fluorotelomers are dispersions of a white, waxy comparatively short-chain telomer of tetrafluoro¬ ethylene in Freon TF.

EXAMPLE 3 Stainless steel surgical wire was coated with PTFE by rubbing with a felt buffing wheel (20 cm diameter x 2.5 cm) rotating at 3000 rpm, to which the PTFE dispersion described in Example 1 was continuously applied. By way of comparison, a sample of the same wire was coated by the method currently recommended for coating surgical staples. This method is to dip the wire into a dispersion of Vydax AR and Freon, and to allow to dry. The coating is then sintered at 350°C until it develops a glossy appearance. When the wire coated with the conventional method was contacted with acidic ferric chloride solution, it was attacked and etched within seconds. By contrast, when the wire coated with the method of the present invention was contacted with the same ferric chloride solution, it showed no sign of attack even after days.

In order to test the friction properties of wire coated by the two methods, the conventionally coated wire was inserted into a fabric which is commercially referred to as mole-skin, left in place for 30 minutes at 25°C, and then pulled through by an Instron instrument. It showed an initial resistance of 50 gms and a dynamic resistance of 20 gms. When a wire coated with the method

of the invention was subjected to the same test, the corresponding values were 26 gms and 9 gms.

The applicator roller pressures mentioned in the above examples were estimated on the basis of the degree of deformation of the surface of the roller, when station¬ ary. It is believed, however, that very substantially larger pressures (e.g. from 10 to 50 times the values given above) are developed when the roller rotates against the substrate at the high rotational speeds used for coating, which will typically involve peripheral speeds of from 2 to 200 m/sec, more usually from 5 to 100 m/sec, e.g. from 10 to 50 m/sec.

It will be understood that the present invention has been described above purely by way of example, and modi- fications of detail may be made without departing from the scope of the invention.