A spray wax concentrate adapted to be applied in a highly diluted state in an aqueous spray to a surface, such as a vehicle surface, in the hot sun comprising about 2 to 10 wt. % of a fine polishing powder, of about 10 to about 40 wt. % of mineral spirits, of about 0.5 to about 3 wt. % of a dimethyl silicone fluid polymer, from about 0.5 to about 1.75 wt. % of an alkanolamide surface-active agent; from about 1 to about 1.75 wt. % of a higher alkyl amino functional group substituted dimethyl silicone polymer wax, and the balance, water, to obtain a total of 100 wt. %. The spray wax concentrate is preferably applied as pressurized, turbulent aqueous spray containing about 1 part by volume of the spray wax concentrate and about 40 to about 100 parts by volume of water.

A wax/polish for automobiles, other vehicles, windows, and like surfaces, and methods of applying the wax/polish.
Waxes and polishes have been used for at least several hundred years for waxing and polishing surfaces such as floors, windows, furniture, and vehicle surfaces. Originally, most waxes were paste waxes which required that the surface first be cleaned of all dirt and oxidation. The wax is then applied by hand or with a buffering-like device to rub the wax into the surface. The rubbing or buffing can cause swirling on the surface. The wax is allowed to dry and then it is rubbed or buffed off the surface. Preferably, the waxing is done on a clean, cool surface and not in direct sunlight. This application process is still used to some extent and is very labor-intensive and requires physical strength either to rub the wax on and buff it off, either by hand or with a mechanical buffing machine.
In the 1950""s, liquid waxes became available. Liquid waxes are easier to apply than paste wax since they can be poured onto an applicator, such as a cloth, sponge, reinforced paper, or other type of applicator, and then rubbed or buffed onto the surface. The rubbing can leave swirling on the surface. The wax is allowed to dry and then it is rubbed or buffed off. Liquid waxes are similarly applied. The liquid waxes are preferably applied to a clean, cool surface and the waxing is not done in direct sunlight. In the 1970""s, spray devices became available and waxes and polishes were developed that could be sprayed onto the surface. One type of device was the finger trigger sprayer commonly used for household cleaners and the like. The sprayer has a pump actuated by the finger which draws fluid up from a reservoir and sprays the fluid out of a nozzle. Waxes and polishes applied by this method have many of the characteristics of liquid wax and polish. These types of applicators have not been very popular because the sprayers only spray a limited amount of fluid for each finger pull of the sprayer and accordingly, it takes time to spray large surface areas such as a car, airplane, or other large vehicle. In addition, it is very tiring and can be painful to actuate the finger trigger sprayer for long periods of time. The wax or polish is preferably applied to a clean, cool surface and not in direct sunlight. Once the wax is sprayed on the surface, it is rubbed onto the surface to cover the surface and allowed to dry. The rubbing can leave swirls on the surface. After it is dried, it is rubbed off or buffed off, as with paste wax and liquid wax. Polishes normally do not have to be buffed.
A recent variation of the liquid wax is the wipe-on and hose-off wax. This wax is sprayed on the surface and rubbed in, or poured onto an applicator or directly onto the surface and rubbed into the surface. The rubbing can leave swirls on the surface. Once the wax is dry, it is hosed off with a water spray from a garden hose. Following removal of the wax with the hose spray, the vehicle has to be dried off. With this method of waxing, the hosing-off step does not guarantee that all the wax residue will be removed from the vehicle. It has been found that the user of the wax normally has to go back over the vehicle with a water spray after drying it to remove residual wax and then dry the surface again.
When applied to a hot surface, wax normally forms a hard coating or scum that adheres to the surface. Frequently, this coating or scum cannot be removed by rubbing or buffing. Frequently, these areas have to be removed by re-waxing, letting the application of fresh wax dry, then rubbing or buffing off the applied wax. It is for this reason that waxing, such as an automobile or other vehicle surface, is not done on a hot surface or under the sun.
The demarcation between a wax and polish is not a bright line. For purposes of this invention, the term xe2x80x9cwaxxe2x80x9d will include both wax and polish.
The wax composition of the present invention has been termed a xe2x80x9cspray wax concentratexe2x80x9d and is sometimes referred to as a spray wax and comprises a water base or carrier incorporating a surfactant, wax, silicone fluid, mineral spirits, and a mild inorganic polishing agent.
The spray wax of the present invention, when applied to a surface, such as a vehicle surface or glass surface, does not bead. The spray was forms a sheet or film of liquid which separates into an organic phase and an aqueous phase. The bulk of active organic ingredients report to the organic phase which adheres to the surface, whether the surface is horizontal or vertical. The fine polishing powder reports to both phases. The aqueous phase runs off the surface as a sheet leaving the organic phase adhering to the surface as a relatively continuous film. The organic phase, almost immediately upon application and clearly after separation of the aqueous phase, forms a white haze. The formation of the white haze appears to be independent of the drying of the organic phase. The white haze becomes more pronounced as the organic phase dries. Surprisingly, the hazy organic phase may be wiped off a minute or two after application and before it has dried. In fact, the surface should be fully wiped while still xe2x80x9cwetxe2x80x9d to ensure that the entire surface has been contacted or treated with the organic phase. Then the surface, which may or may not be dry to the touch, is wiped clean of the hazy film. When the hazy film has been wiped off the surface, the waxing is complete. Since the applied wax is not rubbed in, no swirl marks are created on the surface. On the average, the entire operation, from the step of wetting the surface with water to completion of the wiping-off step, for a vehicle, takes about ten minutes; however, it can take as little as two and one-half minutes.
The spay wax can be applied to windows as an aqueous spray to clean the windows. The finish on the windows so treated is superior to that of windows cleaned, polished and/or waxed with conventional window and glass cleaning, polishing, and/or waxing compositions. The spray wax will not smear the windows.
The spray wax can be applied on a hot surface, in the sun, on a wet surface, in the rain, on a cool day, or at night. Preferably, the spray wax is applied as an aqueous spray prepared from the spray wax concentrate and water on a hot or warm surface in the sun.
The spray wax concentrate of the present invention comprises a percent by weight (wt. %) from about 2 to 10 wt. % of a fine polishing powder; from about 10 to about 40 wt. % of mineral spirits; from about 0.5 to 3.0 wt. % of dimethyl silicone fluid polymer; 0.5 to 1.25 wt. % of alkanolamide surface-active agent; 1.0 to 1.75 wt. % of a higher alkyl amino functional group substituted dimethyl silicone polymer; and the balance water to obtain a total of 100 wt. %. Optionally, the spray wax can contain preservatives, colorant and/or fragrances.
The spray wax applied as an aqueous spray will not harm rubber, vinyl and other plastics and polymers.
In the preferred embodiment of the present invention, the spray wax concentrate, comprises about 4 wt. % anhydrous aluminum silicate; about 24 wt. % of mineral spirits; about 1.25 wt. % of a dimethyl silicone fluid polymer having a viscosity of about 350 c.s. (centistokes); about 0.8 wt. % of a non-ionic alkanolamide surfactant agent; about 1.3 wt. % of a higher alkyl-substituted amino functional group substituted dimethyl silicone; 0.005 wt. % of a preservative and about 68.6 wt. % water.
The spray wax concentrate can be applied with or without water. However, in the preferred embodiment of the invention, the spray wax is applied with water as an aqueous spray. The wax can be mixed with water in a bucket and applied with a rag. Preferably, the wax is applied with a venturi-type sprayer (also called an aspiration-type sprayer) using water as the transportation medium to draw the wax from a reservoir into a venturi tube and into the water stream to form an emulsion, i.e., the aqueous spray.
Venturi-type sprayers have been around ever since the advent of the garden hose. These sprayers use the Bernoulli principle to draw a composition through a straw from a reservoir and then inject it into a water stream to be sprayed out. They have been used commonly as garden sprayers for spraying insecticides, nutrients and the like. The sprayer is normally comprised of a reservoir containing a venturi draw tube going to the bottom of the reservoir. The spray element or nozzle increases the velocity of the water stream over a venturi hole in which the venturi exits. The increased velocity of the water stream places a partial vacuum at the venturi hole drawing up fluid from the reservoir and through the venturi straw. The fluid exits the venturi hole and enters the water stream where it is intimately mixed in the highly agitated, highly turbulent water stream. Some venturi-type sprayers have a closed system wherein the water is passed through a constriction at the area where the venturi hose is located. Other venturi-type sprayers eject the water as a spray over the venturi hole from a nozzle. A short downstream from the nozzle, the spray crosses over the venturi hole to create the partial vacuum and draw the composition from the reservoir. The venturi-type sprayers are preferred because they keep the mixing ratio of the spray wax concentrate and water, in the water stream, relatively constant.
The spray wax concentrate is intimately mixed in the turbulent water stream or spray of the sprayer to form a fine emulsion of an aqueous phase and organic phase, which coats the surface when the spray from the sprayer hits the surface. The dimethyl silicone fluid polymer, alkanolamide surface-active agent, and the higher alkyl and amino functional groups substituted dimethyl silicone polymer, and mineral spirits report primarily to the organic phase, where the mineral spirits function as a carrier. The fine polishing powder, e.g., anhydrous aluminum silicate powder, is distributed to both the aqueous phase and the non-aqueous phase. On application to the surface, the water phase separates from the non-aqueous or organic phase which contains the dimethyl silicone fluid polymer, a portion of the anhydrous aluminum silicate powder, mineral spirits, and the higher alkyl-substituted amino functional group dimethyl silicone polymer. The bulk of the water sheets off the surface leaving the non-aqueous or organic phase containing the fine polishing powder on the surface. The remaining material on the surface is allowed to either fully dry or (preferably) partially dry and then is wiped to leave a high gloss wax finish on the surface. The wiping acts as a polishing step, as well as a cleaning step.
Preferably, the surface is cleaned prior to the application of the spray wax. The cleaned surface can be wet when the wax is applied. The surface can optionally be prewetted with water. The prewetting with a water spray moistens and removes some of the dirt and dust on the surface and makes the adhering dirt more amenable to being removed with the components of the spray wax from the surface. Unexpectedly, the wax can be sprayed on a surface in the rain and the wax composition adheres to the surface, even vertical surfaces.
Using a water stream as the transportation medium for the spray wax onto a surface, such as a car surface, has several benefits. The wax can be quickly applied. The water flowing through a venturi-type sprayer is adjusted to between 3 to 5 gallons per minute although a lower or higher water flow rate can be used. Spray wax is drawn from the reservoir into the water stream at a ratio of about 20 to 200 parts by volume water to about 1 part by volume spray wax, preferably about 45 to 60 parts by volume water to about 1 part by volume spray wax. The application of the spray wax with the venturi-type sprayer has been found to remove dust and dirt from the surface. This saves a considerable amount of time.
The spray wax can also be applied by mixing the spray wax with water in a bucket and applying the mixture to the surface using an applicator, such as a sponge, chamois, towel, or the like. The spray wax is a two-phase system comprising an aqueous phase and an organic phase. The anhydrous aluminum silicate powder constitutes a solid phase. However, when the spray wax concentrate and water are sufficiently agitated, the anhydrous aluminum silicate powder is easily dispersed between the organic phase and the aqueous phase.
The phases separate with time. This phase separation is even faster when the spray wax is diluted with water. It has been found that when the spray wax is to be applied by hand from a spray wax-water mixture in a bucket, the ratio of spray wax to water be not less than 7 parts water by volume to 1 part spray wax by volume (also called xe2x80x9cspray wax concentratexe2x80x9d). This dilution does not prevent separation but it slows its rate. When applying the spray wax in a water mixture by such application, the mixture of water and spray wax must be frequently agitated to disperse the organic phase throughout the water. The applicator will absorb some of the organic phase and some of the aqueous phase. Application of the wet applicator onto the surface re-mixes the organic phase into the aqueous phase to give a relatively uniform application of the spray wax to the surface. This method of application provides that the dirt and dust on the surface are rubbed and scrubbed away. The alkanolamide surface-active agent and the mineral spirits greatly aid in the cleaning of the surface while simultaneously waxing the surface.
Using the venturi-type sprayer to apply the spray wax in the water stream to the surface is the preferred method of application. The high-speed, turbulent water stream picks up the small amount of spray wax (20 to 200 parts by volume water to 1 part by volume spray wax), draws it into the stream from the venturi to break up the organic phase into very small droplets which are relatively evenly distributed through the water stream. Because the wax stream or spray hits the surface in a relatively short period of time (less than a second), uniform distribution of the organic phase in the aqueous phase remains intact. Once the aqueous phase and wax phase come in contact with the surface at a relatively high velocity, the aqueous phase and organic phase coat the surface with the organic phase displacing the aqueous phase and coating the surface, permitting the aqueous phase to coalesce and sheet off the car, leaving the organic phase coating the surface of the car.
The spray wax is specifically formulated to be thin enough, i.e., have a low enough viscosity, to be drawn through the venturi straw or tube from the reservoir of the venturi-type sprayer and to be drawn into the water stream. The viscosity is also adjusted so that the organic phase is easily dispersed into fine droplets of organic phase in the water stream. This ensures that the surface of the car is evenly coated with fine droplets of the organic phase which carry the wax, mineral spirits and the like.
Preferably, the spray wax is applied upon a warm surface, even a hot surface, and in the sun. The heat of a warm or hot surface and the heat from the sun dry the spray wax on the surface quickly and permit the surface to be wiped or rubbed down shortly after application, shortening the entire waxing and cleaning process. For some reason, the hot surface and/or the heat of the sun does not cause the spray wax to form a coating or cake on the surface, as it does with conventional waxes, which is very difficult, if not sometimes almost impossible, to remove without using a polishing or rubbing compound or more conventional wax.
The spray wax concentrate can be applied directly to the surface of a car to remove dust, dirt, and scum. In this application, the spray wax concentrate is applied directly to an applicator or sprayed onto the surface with a sprayer, such as a finger trigger-type sprayer. The spray wax is particularly effective in this mode for removing organic scum on the cars, such as tar deposits, oil deposits and the like. The wax is applied directly to the organic scum and then wiped off after a few seconds. For more difficult removal of dirt and scum, the spray wax can be allowed to remain on the scum or dirt for up to a minute before wiping off. It is believed that the mineral spirits in the concentrate soften the organic scum or dirt, permitting the aqueous phase of the spray wax concentrate with the surface-active agent to function as a detergent or soap to remove the organic scum and dirt deposit from the surface.
The present invention is also directed to a method of waxing a car by spraying an emulsion of an organic phase and aqueous phase onto a warm surface and allowing the applied emulsion to at least partially dry, and then wiping off the applied emulsion to yield a waxed surface, the emulsion formed by combining 1 part of a spray wax concentrate by volume with about 20 to about 200 parts by volume water. Lower ratios can be used but to no advantage. Higher ratios may be operational but have not been tested.
In the preferred embodiment of the above method, the surface is prewetted with a water spray to rinse off dust and dirt from the surface. Optionally, the surface may be washed with an aqueous soap or detergent solution and rinsed off with water prior to application of the emulsion.
In another embodiment of the present invention, a spray for waxing a surface is created which comprises an organic phase and an aqueous phase, the spray emulsion is created by drawing the spray wax concentrate into a spray of water by a venturi action at a rate of about 1 part by volume spray wax concentrate to 20 to 200 parts by volume of water, by formulation of the concentrate as described herein.
In an alternative embodiment of the present invention, a spray for waxing a surface comprising an emulsion of an organic phase and aqueous phase is created by drawing a spray wax concentrate by venturi action into a stream of water to form the emulsion of the organic phase and aqueous phase, propelling the emulsion through a nozzle to form a spray for waxing, comprising the organic phase and aqueous phase. The spray wax concentrate is of the formulation as described herein.
The spray wax or spray wax concentrate comprises a surface-active agent, a fine polishing powder, mineral spirits, a dimethyl silicone fluid polymer, an alkanolamide surface-active agent, a higher alkyl-substituted amine functional group substituted dimethyl silicone polymer and water. The spray wax concentrate comprises between about 2-10 wt. % of fine polishing powder, preferably about 4 wt. %. The fine polishing powder is ground to a powder which promotes good suspension in most liquid systems and provides easy passage through venturi tubes. This powder is compatible with amine-functional group substituted silicones. The powder is inert, insoluble, and nonhydrosopic. This powder will not deteriorate in an aqueous or organic phase. In the composition, the powder performs several functions. The powder is finely ground and has an equivalent spherical diameter in microns, so that 100% of the fine polishing powder is less than 3 microns. The particle-size distribution, based on equivalent spherical diameter in microns, is such that 80% of the powder is less than 1.2 microns. 50% of the powder is less than 0.6 microns, and 20% is less than 0.3 microns. This distribution can vary but it is preferred that all the powder be less than 4 microns in size, and at least 80% of the powder be less than 1.2 microns in size. Aluminum silicate, aluminum oxide, silica, microcrystal silica, talc and Cabosil brand silica can be used in the spray wax. Anhydrous aluminum silicate powder is preferred. Any anhydrous aluminum silicate fine powder meeting the above criteria can be used in the present invention. Applicant has found that Kaopolite(copyright) SF anhydrous aluminum silicate is well-adapted for the present invention. Kaopolite(copyright) SF is supplied by Kaopolite Inc., 2444 Morris Avenue, Union City, N.J. 07083.
The fine polishing powder performs a number of functions in the composition. The powder functions as a pigment giving the spray wax, when applied to a surface, before and after drying, a white haze or white sheen which is easy for the operator to see when wiping off or rubbing off the wax after its application and/or after it is dried. The fine polishing powder also appears to enhance the amount of wax that adheres to the surface. The anhydrous aluminum silicate also appears to speed up the drying process, possibly by increasing the surface area of the applied spray wax. The sheeting off of water after application of the spray wax is an important advantage of the present spray wax. The fine polishing powder is crucial for the organic phase to cover the surface as a sheet or film. If the powder is omitted, the organic phase clumps or beads. The fine polishing powder also appears to minimize water spotting.
The sheeting off of the aqueous phase after application of the wax appears to enhance application of the spray wax to the surface. The increased surface area caused by the fine polishing powder increases sheeting of the water which allows the wax or organic phase to stick to the surface before running off the side of the surface with the aqueous phase. The fine polishing powder also acts as a mild abrasive or polish to help smooth the surface that is being waxed and it aids in removing any water spotting that might occur while using the product, which will be explained below.
It is believed that the wax in the organic phase first adheres to the surface upon application of the spray wax, and then the fine polishing powder adheres to the initial wax coating, and then additional wax in the organic phase adheres to the fine polishing powder building up the wax layer. Once the powder adheres to the wax, it increases the surface area, which provides additional surface for the wax to adhere to. Since a large quantity of water is used to transport and distribute a small quantity of spray wax concentrate onto the surface, it is preferable to have as much of the organic phase of the spray wax adhere to the surface directly or to the fine polishing powder before it runs off the surface with the transporting water medium.
The spray wax can be applied in dry, cool, hot, rainy, foggy or even freezing weather. The viscosity of the spray wax is thinned by the mineral spirits so that it can be drawn up through a venturi tube of a venturi tube type sprayer. It is believed that the mineral spirits also speed up the drying time of the spray wax after its application to the surface. The mineral spirits thin the organic phase and allow it to be more evenly distributed, both in the water spray stream and onto the surface where the spray wax is applied. Water spots often result after the drying of the spray wax on the surface. The mineral spirits seem to aid in minimizing water spots and making the water spots easily removed by a single swipe of a dry towel. The omission of the mineral spirits makes the concentrate thick and prevents its use in a venturi-type sprayer.
Almost all water coming from a hose contains mineral values, typically salts of sodium, potassium, calcium, magnesium with a carbonate, sulfate, silicate, and/or phosphate cation. If straight water is sprayed on a car or windows, and the car or window is allowed to dry, water spots will result. It is very difficult to remove such spots. Normally, the surface has to be washed again and/or a mild abrasive wax or polishing compound has to be used to remove the spots.
When the spray wax of the present invention is applied to a black or dark color surface with a venturi-type sprayer, the surface can be left to dry. Some water spots may appear but they are easily wiped off with a towel.
The spray wax composition also comprises from about 0.5 to about 3.0 wt. % of a dimethyl silicone fluid polymer having a nominal viscosity between about 10 to about 60,000 c.s., preferably about 350 c.s. Preferably about 1.25 wt. % of the dimethyl silicone polymer is used. Dimethyl silicone fluid polymers are well known and supplied by many manufacturers, such as Dow Corning, General Electric Corporation, Union Carbide Corporation, and Rhodia. L-45 dimethyl silicone fluid having a viscosity of 350 c.s. manufactured by Witco Corporation, One American Lane, Greenwich, Conn. 06831, has been found satisfactory.
Dimethyl silicone fluid polymers are used primarily as mechanical lubricants or as lubricants for plastic and rubber parts. They are especially effective in plastic or metal lubrication. They are also used as release agents for molding rubber, glass, plastic parts, or for shell and core molds. The dimethyl silicone fluid polymers of the present invention impart easy rub-out to the applied spray wax to resist oxidation of the surface and thus provide protection to the surface from oxidation and they give the waxed surface a deep gloss. The dimethyl silicone fluids are water insoluble and report to the organic phase and are soluble in the mineral spirits. The dimethyl silicone fluid polymer also gives the surface a high-gloss finish, after the wipe-off or rub-off, and a waxed or smooth touch. The silicone fluid appears to minimize water spotting. The silicone fluid also aids in uniform distribution of the organic phase of the spray wax to the surface after application. Since the silicone fluid does not quickly evaporate off the surface after application of the spray wax, it is believed that during the wiping-off, excess higher alkyl substituted amino functional group substituted dimethyl silicone polymer, the alkanolaminde surface active agent and any residual mineral spirits remain with the silicone fluid and are spread across the surface during the wiping. Thus, it appears that the silicone fluid aids in the even spreading of the organic phase on the surface.
The composition also contains from about 0.5 to about 1.25 wt. % of nonionic alkanolamide surface-active agent, preferably about 0.8 wt. %. It has been found that Witcamide(copyright) 511 surfactant, manufactured by Witco Corporation, is particularly useful in the present invention. Witcamide(copyright) 511 is an alkanolamide made by reacting an amine with a fatty acid, alkyl methyl ester or triglycerides in ratios which produce 1:1 or 2:1 amides. Witcamide(copyright) is a fatty acid alkanolamide which is liquid at room temperature, has a free amine content of 6.0 wt. %, and a free fatty acid content of about 1.3%. It is a known invert emulsifier for polishes and waxes, as well as hydraulic fluids. In the present invention, the alkanolamide performs a number of functions. It aids in emulsifying the organic phase and the aqueous phase during the application of the spray wax by a venturi-type sprayer. It permits the spray wax to be finely and evenly distributed into the water stream and spray from the sprayer so that a uniform application of the spray wax is applied to the surface. The alkanolamide also appears to function as a detergent and cleans the surface so that the wax, more correctly, the organic phase, will adhere to the surface. When no alkanolamide is utilized in the present invention, very little of the organic phase adheres to the surface and most of the organic phase, and thus most of the wax, runs off with the water from the surface. In addition, little, if any, haze is formed. It is believed that its omission results in most of the wax draining off the surface with the water leaving beads of aqueous phase containing some of the organic phase. If too much fatty acid alkanolamide is utilized, a smudge forms on the surface after application of the wax spray that makes it more difficult to wipe off the wax. Surprisingly, in order to apply the spray wax using a venturi-type sprayer, it has been found that the alkanolamide is absolutely essential to the composition.
The composition also comprises a higher alkyl-substituted amino functional group substituted dimethyl silicone polymer. This is deemed the wax component of the spray wax. The dimethyl silicone fluid imparts a sheen to a surface in conjunction with the wax component. In the spray wax concentrate, about 0.5 to about 3.0 wt. % of the higher alkyl-substituted amino functional group substituted dimethyl silicone wax is employed in the composition, preferably about 1.25 wt. %. The wax is a substituted dimethyl silicone fluid where the silicone backbone has been modified with higher alkyl organic substituents and amino functional groups. The waxes are also called amino functional dimethyl siloxanes polymers. By higher alkyl organic substituents, it is meant alkyl substituents having a molecular weight greater than methyl, such as ethylene, ethyl, propylene, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, and the like. In addition, the backbone may be substituted with aromatic groups such as benzene, toluene, xylene, and the like. Such substituents combine the unique attributes of the dimethyl silicone portion with those of the substituted substituent, primarily greater water resistance and more hydrocarbon and wax-like properties. Applicant has found that AFL-5, manufactured by Witco Corporation, is a suitable substituted dimethyl silicone wax which can be employed in the present invention. The material has been used in polishes. The material has low surface energy, has good lubricity, low surface tension, a viscosity-shear relationship which is stable over a wide range of temperatures, has excellent thermal stability and can be used over a wide temperature range without the formation of undesired scum and deposits, and proved orientation of amino derivatives on the backbone. The wax is resistant to detergents and the weather. It has reactive amino functional groups. The amino functional chemical groups adhere to the surface, whether it is a painted surface, metal surface, vinyl surface, plastic surface, rubber surface or the like. In addition, the wax has a high refractive index and gives a very high gloss. Lastly, the wax has an ultra-high molecular weight which gives superior durability to the wax. The wax is employed in the composition for the above reasons; it gives the waxed surface a high gloss; and it gives it a protective coat against weathering and washing with detergents or soaps.
The balance of the spray wax concentrate is water which ranges from 88.3 to about 63 wt. %. Any good quality water can be utilized. Hard water is to be avoided. Distilled water can be used. Deionized water can be used. The water is to be free of suspended matter, have a neutral pH or near neutral pH (5.5 to 8.5 pH), and have a low to moderate hardness, i.e., a hardness of less than 50 ppm.
The above constituents can be added together in any order. Preferably, however, the constituents are formed into two pre-concentrates. Pre-concentrate A comprising anhydrous aluminum silicate powder and water, and optionally a preservative, such as Dowicil 75. The second pre-concentrate, pre-concentrate B, comprises the mineral spirits, the surface-active agent, the dimethyl silicone fluid, the higher alkyl-substituted amino functional group substituted dimethyl silicone polymer, and optionally a dye soluble in the mineral spirits and fragrances. The dye, fragrances and preservative are optional and are not required for practice of the invention. After the pre-concentrates A and B are prepared, they are mixed together to form the spray wax concentrate which has good stability. The pre-concentrates A and B must be mechanically mixed at least thirty minutes and preferably for an hour. The mixture is conveniently made in large amounts, over 100 gallons at a time, and constantly stirred while bottled which can take up to six (6) hours. The mixing is crucial. Mixing 300 gallons of concentrate with a propeller mixer at 300 to 1,000 rpm for one (1) hour has been found to be sufficient. The unbottled concentrate is stirred, however, during the filling operation until all 300 gallons have been bottled. This normally takes five (5) to six (6) hours. Spray wax concentrate that is insufficiently mixed does not spread evenly over a surface on which it is sprayed. Spray wax concentrate that is too energetically mixed, such as in a homogenizer, can form a thick mixture that cannot be sprayed. After appropriate mixing, the concentrate will separate into two phases over time. Accordingly before use, the concentrate is shaken to form an emulsion which has stability for several minutes before separation becomes apparent. At present, we are making the spray wax concentrate in 3,000 gallon batches with constant stirring during bottling (5 to 6 hours to bottle).
One of the most critical steps in formulating, i.e., forming, the wax spray concentrate, is the mixing of the components. The reason for this is not definitely known. However, it is believed that mixing further reduces the particle size, and possibly smoothes the particle surfaces, of the fine polishing powder and permits the organic and surface active ingredients to be absorbed and adsorbed in the particles and on the particle surface.
If the mixing agitation of the components is not energetic enough and/or long enough, the phase separates and sheeting of the aqueous phase is far less pronounced upon application if the spray wax concentrate is an aqueous spray.
Preferably, the mixture is stored or mixed for at least one-half (xc2xd) hour, preferably at least one (1) hour, with a propeller mixer at 300 to 1200 rpm. The spray wax concentrate is made in bulk and preferably is stirred or mixed continuously until the bulk mixture is bottled. The spray wax concentrates of the first bottles are mixed for one-half (xc2xd) to one (1) hour, and the unbottled spray wax concentrate is mixed continually for five (5) to six (6) hours until all is bottled. The difference in performance, i.e., phase separation and aqueous phase sheeting, between the first bottles and last bottles is relatively small if the spray wax concentrate is adequately stirred at the beginning.
If the spray wax concentrate mixture is mixed too energetically, the spray wax concentrate forms into a thick composition that cannot be applied with a venturi-type sprayer. For example, if the spray wax mixture is mixed in a homogenizer at 10,000 rpm, the resulting spray wax concentrate mixture can be so thick that it cannot be drawn up the straw in a venturi sprayer.
The spray wax is preferably applied as an aqueous spray prepared from the spray wax concentrate and water. The spray wax concentrate is highly diluted in the water. About 20 to about 200 parts by volume water are used for each part by volume of spray wax concentrate. This highly dilutes the organic phase. About nine (9) fluid ounces of spray wax concentrate are required to wax a full-size car. Assuming a ratio of 1 part concentrate to 60 parts water, the concentrations of the organic constituents in the aqueous spray are approximately as follows:
Spray wax is preferably applied using a venturi-type sprayer powered by the water from a garden hose. Normally, water pressure from 30 to 100 lbs. psi is sufficient to power the sprayer. The sprayer has a reservoir that will hold at least a half-pint of the concentrate. The water volume through the sprayer is preferably adjusted from 3 to 5 gallons per minute with a draw through the venturi so that the applicator spray from the venturi-type sprayer has a ratio of about 20 to 200 parts per water per 1 part spray wax by volume, preferably 45 to 60 parts water per 1 part spray wax concentrate by volume. The venturi-type sprayer is one of the oldest sprayer devices known and uses the Bernoulli principle for drawing up the spray wax from the sprayer reservoir into the water stream. The venturi sprayer can be an open system or a closed system. In the closed system, the water stream goes through a constriction which has the opening for the venturi straw under the reservoir. In an open system, a water spray exits a nozzle and the stream of water spray before it expands too greatly passes over the venturi hole for the venturi straw and draws up the spray wax. In both systems, the water has a high velocity and is highly agitated so that the spray wax drawn into the stream is immediately and rapidly broken up and evenly distributed throughout the water stream for application to the surface.
Preferably, the surface to be waxed is first cleaned. The surface can be left wet. The surface can also be prewetted with water. This wets the dirt and dust on the surface for a more effective cleaning of the surface by the spray wax. However, cleaning and/or prewetting is not required.
The spray wax is quickly applied to the surface. For a typical automobile surface, using 9 ounces of spray wax, the surface is quickly sprayed with the wax in 1 to 3 minutes. This has been found to be an optimum time to apply sufficient wax to provide a good wax application to surface of the vehicle. Shorter times can be used but it is very inconvenient for the operator to move around the entire vehicle surface to get an even application of wax in less than 45 seconds. Longer times can also be utilized but without advantage. It has been found that most vehicles can be quickly and evenly sprayed with the aqueous spray in one minute. It has also been found that all automobiles, including utility vans and trucks, can be waxed using 9 ounces of the spray wax concentrate. Naturally, large commercial trucks, often referred to as eighteen-wheelers, which include ten-wheelers and fourteen-wheelers, buses, and large motor homes, will require more than 9 ounces of spray wax concentrate. Airplanes and boats may require more or less concentrate, depending upon the size of the airplane or boat.
Preferably, the surface to be waxed is warm, if not hot. Preferably the surface is in the sun, utilizing the heat of the sun. The spray of water and spray wax will cool off the surface to some extent from the application of the cold water from the hose. However, when the surface is waxed in 3 minutes or less, the cooling is de minimis and the surface retains enough heat to help dry off the applied spray wax. When the spray wax is applied with the venturi-type sprayer, especially on the dark surfaces, a whitish haze immediately appears on the surface while the water sheets off the surface, whether it is a vertical surface or a horizontal surface. With the air temperature above 60xc2x0 F., and the surface at least as warm and exposed to the sun, the applied spray wax will dry or at least partially dry within two minutes. Although the surface can be wiped off when it is fully dry, normally the surface is rubbed off when it is partially dry, using dry, soft towels. For a typical automobile surface, three or four towels measuring 24 inchesxc3x9718 inches normally suffice to wipe down the entire car to dry the surface, leaving a high gloss sheen. The spray wax not only waxes the cars; it also cleans the car. It will remove most grime and dust from the vehicle surface. If the surface is particularly dirty because it has been exposed to mud and the like, most of the mud and heavy debris should be first washed off prior to applying the wax.
As mentioned earlier, the spray wax can also be applied by the old-fashioned bucket method. However, application with a venturi-type sprayer is preferred and is much easier and quicker The bucket is filled with a gallon to a half-gallon of water and 9 ounces of spray wax concentrate is added to the bucket. This mixture is stirred and a towel or other applicator is wetted with the fluid and applied directly to the surface. With each fresh application of composition from the bucket, the composition must be agitated to form an emulsion of the organic phase and aqueous phase. After application of the bucket composition to the surface, the surface is allowed to dry in the same manner as when the spray wax is applied with a venturi-type sprayer.
When the surface has oily deposits or tar-like deposits, the concentrate can be applied directly to such deposits prior to waxing to remove the deposits. As explained above, the mineral spirits appear to wet and soften the tar-like deposits and the oily deposits, permitting the aqueous phase with the emulsifier to break the adhesion of the oil deposits and tar-like deposits from the surfaces.
Not only can the spray wax be applied to painted surfaces, it can also be applied directly to metal surfaces, glass surfaces, and plastic surfaces.


The present invention is related to scoring or cutting balloon catheters carrying at least on a portion of their surface at least one oxidation-insensitive drug or oxidation-insensitive polymer-free drug preparation and at least one lipophilic antioxidant at a ratio of 3-100% by weight of the at least one lipophilic antioxidant in relation to 100% by weight of the drug, wherein the at least one oxidation-insensitive drug is selected of taxanes, thalidomide, statins, corticoids and lipophilic derivatives of corticoids, and the at least one lipophilic antioxidant is selected of nordihydroguaiaretic acid, resveratrol and propyl gallate.

1. Field of the Invention
The invention relates to the transfer of a drug loosely adhering to the surface of a scoring or cutting balloon catheter to a site inside the body, usually in a diseased blood vessel. The preferred application is local drug therapy during percutaneous transluminal angioplasty (PTA) or percutaneous transluminal coronary angioplasty (PTCA). The interventions are performed to restore blood flow in stenotic or occluded blood vessels, usually into arteries. A catheter is introduced in a major artery. At the distal end the catheter carries a cylindrical balloon in folded state with very small diameter and additional tools or structures which scratch or cut the luminal surface of the treated blood vessel or tissue. In the folded state the balloon can enter or pass the stenotic or occluded segment of e.g. a blood vessel. Once positioned in the narrowed segment, the balloon is inflated to enlarge the lumen of the blood vessel to its original diameter. Simultaneously, a drug may be transferred to the vessel wall to prevent early and late re-narrowing due to hyperproliferation of the injured vessel wall.
Medical devices may contain drugs either to improve the tolerance, efficacy or in vivo life-time of the device or the device serves as carrier for the drug. In any case the dose density (e.g. mg drug/mg device or mg drug/mm device surface), chemical stability, adherence, release rate, and total amount released are important and frequently critical features of the drug formulation. These properties are the more critical the more the requirements during production and application of the device vary or may even be contradictory. Drug-coated angioplasty catheters are typical examples: the drug coating must adhere firmly to tolerate mechanical stress during production including folding of balloons, crimping of stents, packaging, transportation to customers, and during final application, which involves the passage through a narrow hemostatic valve, an introductory sheath or guiding catheter and a variable distance through possibly tortuous and narrow blood vessels. When the balloon is inflated the drug should be released within a minute or less as rapidly and as completely as possible. The problem was demonstrated by Cremers et at (Cremers B, Biedermann M, Mahnkopf D, Bdhm M, Scheller B. Comparison of two different paclitaxel-coated balloon catheters in the porcine coronary restenosis model. Clin Res Cardiol 2009; 98:325-330) who retrieved as much as 50% of the dose from balloons after expansion for one minute in coronary arteries of pigs, whereas other catheters coated with the same drug and dose but in a different formulation released more than 95%. Almost perfect results (i.e., loss of only 10% of dose and residual drug on the balloon after expansion in an artery of about 10%) were achieved with a rigid prototype balloon (Scheller B, Speck U, Abramjuk C, Bernhardt U, Bohm M, Nickenig G. Paclitaxel balloon coating—a novel method for prevention and therapy of restenosis. Circulation 2004; 110: 810-814). The application of the same coating composition to more flexible modem balloon catheters resulted in problems, i.e., larger premature loss of the drug. The coating of scoring or cutting balloons with drugs in a reliable way with a dose which is sufficient to be efficacious imposes additional problems because of the more complex structure of the device and the more complex production process.
2. Prior Art
Protection from premature drug release. Premature release of a drug from a balloon is a major problem which has been addressed by a variety of methods. Some of them are mechanical, e.g. the use of protection tubes, sleeves, envelops. Examples are U.S. Pat. No. 5,370,614, U.S. Pat. No. 6,306,166, and U.S. Pat. No. 6,616,650 disclosing various protective sheaths which are retracted before the balloon is inflated, or U.S. Pat. No. 6,419,692 proposing a cover which bursts during balloon expansion. A different approach is taken in U.S. Pat. No. 5,893,840 disclosing structured balloon membranes with tiny cavities, WO 94/23787 with roughened balloon membranes to enhance the adherence of coating, or more recently U.S. Pat. No. 7,108,684 proposing a pouch which protects the drug-containing layer on the balloon and WO 2009/066330 disclosing methods placing the drug selectively under the folds of a folded balloon. Although efficacious these methods have the disadvantage of increasing the complexity and cost of production or make handling of the devices more difficult or add to the diameter of the devices (which must be kept as small as possible to facilitate passage through stenotic lesions) lesions). In some embodiments the protective membranes or perforated membranes interfere with the scoring components of the balloons or prevent a homogeneous transfer of the drug to the tissue or even put the patient at risk. None of these methods has been applied to scoring or cutting balloons and nothing is known about problems which will arise from the increasing complexity and mechanical problems or from a disturbance of the protecting envelops by the scoring or cutting structures and vice versa vice versa.
Other approaches use either physical or chemical methods to control the release of drugs from a balloon surface, e.g. U.S. Pat. No. 5,304,121 describes a hydrogel which releases the drug only after exposure to a triggering agent; U.S. Pat. No. 5,199,951 relies on thermal activation; according to U.S. Pat. No. 7,445,792 a lipophilic "hydration inhibitor" protects water-soluble drugs from premature release; and according to U.S. Pat. No. 5,370,614 a viscous matrix protects the drug from premature release, however, the viscous matrix must be protected by a sheath during the passage to the stenotic vessel segment. None of the methods has been tested in practice and proven to fulfill the requirements for fast, reliable and complete drug transfer to the target tissue. None of the methods has been designed to be used with scoring or cutting balloons.
Numerous methods of sustained drug release are known and successfully used in practice but are not applicable to medical devices which are in contact with the target tissue for only a few seconds or minutes. Sustained drug release is usually achieved by embedding the drug in a polymer which restricts the diffusion rate to the surface and in this way controls the transfer into the adjacent tissue.
Therefore, a need remains for a method or formulation which protects the coating from premature losses during production, handling, and on the way to the lesion and still allows the immediate and complete release of the active ingredient at a location and point in time determined by the user. During the production process this problem is even more severe for scoring and cutting balloons because of the more complex structure of the product. Scoring and cutting balloons have merits in the treatment of certain lesions, e.g. if the conventional smooth balloons tend to dislocate during inflation or if a controlled and predetermined injury of the vessel wall is preferred to an uncontrolled dissection during balloon inflation. Nevertheless, the problem of renarrowing of the vessel lumen due to excessive neointimal proliferation as a reaction to the unavoidable injury during dilatation is the same as with conventional balloon catheters.
An advantageous way to control adherence and release of a drug from a medical device, e.g., an angioplasty balloon, is the selection of a suitable formulation and coating which do not require mechanical protection, or additional physical or chemical interaction with the coating except the usual operation of the device e.g. inflation of a folded balloon to induce the release of the drug. Although desirable and frequently tried, the conflicting objectives of perfect adherence during production and before use and immediate release at the site of action make it a difficult task. A large variety of patent applications vaguely disclose measures, compositions and devices to solve this problem for conventional balloon catheters either by the selection of drugs, the choice of specific coating processes or formulations containing various additives. Long lists of compounds have been copied from textbooks of chemistry, pharmacology, or pharmacy but even with extensive experimentation disclosures are not sufficiently clear to allow a person familiar with the subject and skilled in the art to come to a satisfactory solution without an inventive step. Examples of prior art are US 2008/0118544 reciting an excessive number of substances and substance classes or U.S. Pat. No. 7,445,795 which discloses the use of "hydration inhibitors" not applicable to the preferred class of very lipophilic drugs which require "hydration enhancers" or "dispersion and dissolution enhancers" as, e.g., disclosed in WO 2004/028582. Although the hydrophilic additives (which may be regarded as "hydration enhancers") work quite well on certain conventional balloon membranes (Scheller B, Speck U, Abramjuk C, Bernhardt U, Bohm M, Nickenig G. Paclitaxel balloon coating—a novel method for prevention and therapy of restenosis. Circulation 2004; 110: 810-814) the adherence to various modem conventional or scoring PTA or PTCA balloons is either too weak or too tight resulting in premature loss of a major proportion of the drug or incomplete release at the target site. None of the known compositions has been tried on scoring or cutting balloon catheters.
Antioxidants.
In theory, antioxidants address an almost universal feature of diseased tissue, namely the "reactive oxygen species", and should have widespread medical applications. In practice, only very few controlled clinical trials have shown beneficial effects of antioxidants (Suzuki K. Antioxidants for therapeutic use: Why are only a few drugs in clinical use? Advanced Drug Delivery Reviews 2009; 61:287-289). Antioxidants are mentioned as potentially useful drugs for the treatment of focal vascular disease such as stenosis, restenosis, atherosclerotic plaques, and vulnerable plaques in US 2009/0136560 with no additive, in U.S. Pat. No. 5,571,523 as agents inducing apoptosis in vascular smooth muscle cells, in WO 2004/022124 either as active drugs or as "hydration inhibitors". In US 2008/0241215 probucol, a drug approved for the treatment of hyperlipidemia, a known risk factor for atheriosclerosis, is proposed as the active ingredient in stent coating, either alone or combined with rapamycin or another anti-restenotic agent in a slow-release formulation. U.S. Pat. No. 6,211,247 claims pharmaceutical compositions containing an effective dose of resveratrol for preventing or treating various vascular pathologies following coronary interventions. Similarly, US 2007/0037739 discloses local delivery systems comprising various bioactive agents including resveratrol which either alone or in the specified combinations are suitable for treating or preventing abnormal luminal cell proliferation. None of the above-mentioned documents contains data encouraging the use as additives to a lipophilic drug to delay the release rate of the drug and no specific compositions are disclosed which address the above-mentioned problems of adhesion of a drug before the target lesion is reached and immediate release when required.
Small proportions of antioxidants are commonly used to protect drugs or nutrients from decomposition by oxygen or oxidation, an application which has also been proposed for drugs coated on implantable medical devices such as stents (US 2007/0020380, US 2009/0246253) or balloon catheters (US 2005/003 7048, US 2009/0246252, especially paragraph [105]). However, antioxidants are commonly used in proportions of less than 1% by weight in relation to 100% by weight of the drug. Normally it is intended to use as less antioxidant as possible, i.e., less than 0.1% by weight in relation to 100% by weight of the drug (Voigt R. Lehrbuch der pharmazeutischen Technologie. 5. Edition, Verlag Chemie, Weinheim-Deerfield Beach, Florida—Basel, 1984). US 2005/0037048 discloses a specific example which refers to a selected drug in a polymeric matrix requiring an unusually high proportion of antioxidant.
Again, none of the above mentioned documents provides any hint to an advantage in using antioxidants in combination with stable (i.e. oxidation-resistant drugs) and/or at dose levels which provide no therapeutic or prophylactic action.
Present Invention.
The problem underlying the present invention was the provision of a scoring or cutting balloon catheter with an improved adherence of the drug without negative effect on the release of the drug at the target site.
The problem was solved by a scoring or cutting balloon catheter according to claim 1. In other words, the problem was solved by a scoring or cutting balloon catheter carrying at least on a portion of its surface at least one oxidation-insensitive drug or oxidation-insensitive polymer-free drug preparation and at least one lipophilic antioxidant at a ratio of 3-100% by weight of the at least one lipophilic antioxidant in relation to 100% by weight of the drug, wherein the at least one oxidation-insensitive drug is selected of taxanes, thalidomide, statins, corticoids and lipophilic derivatives of corticoids, and the at least one lipophilic antioxidant is selected of nordihydroguaiaretic acid, resveratrol and propyl gallate. "Polymer-free" means that no additional polymer is part of the coating. Preferred embodiments are disclosed in the dependant claims. Usually, antioxidants are used to stabilize oxidation-sensitive drugs against degradation by oxygen. They are considered useless in this regard if the drug is stable against oxidative degradation, i.e. if the drug is oxidation-insensitive. Below, the terms "oxidation-insensitive drug", "active drug" and "drug" are used interchangeable all meaning an oxidation-insensitive drug if the invention is concerned.
During testing of a large variety of coating methods, additives and drug combinations the surprising discovery was made that certain lipophilic antioxidants added to less or even more lipophilic and more or less water soluble drugs, which are oxidation-insensitive, in a defined mass ratio significantly increase the adherence of the drug to scoring and cutting balloons during handling and on the way to the target lesion even if the target lesion is located far away from the site where the device first enters a blood-filled introductory sheath, guiding catheter or vessel containing During testing of a large variety of coating methods, additives and drug combinations the rapidly flowing blood. This was also tested with scoring balloons. In spite of the additional mechanical stress (as compared to conventional balloons) imposed on the coating due the movement of the scoring wires surrounding the folded balloons the loss of the drug during the passage through a narrow hemostatic valve and a curved guiding catheter was very low. Thus, at least one lipophilic antioxidant in an amount of 3-100% by weight is used as an adherence improver for drugs coated on a scoring or cutting balloon catheter during this initial step of introducing the medical device into the vasculature. The wording "at least one lipophilic antioxidant" means that single antioxidants but also mixtures of different antioxidants are included. Other substances or pharmaceutical compounds may be added to further adjust the properties of the product to the demand in respect of stability or other pharmaceutical requirements and tolerance etc.
Examples of active drugs are inhibitors of cell proliferation, preferably taxanes such as paclitaxel, docetaxel and protaxel. Alternatively, specific inhibitors of neovascularization such as thalidomide, statins like atorvastatin, cerivastatin, fluvastatin or anti-inflammatory drugs like corticoids or even more preferred lipophilic derivatives of corticoids such as betamethasone diproprionate or dexa-methasone-21-palmitate are examples of oxidation-insensitive drugs. Various drugs may be applied or combined if different pharmacological actions are required or efficacy or tolerance is to be improved. Thus, the wording "at least one drug or drug preparation" means that single drugs but also mixtures of different drugs are included. Preferred drugs are either lipophilic (partition coefficient between n-butanol and water >10, or display very poor water solubility (<1 mg/ml. 20° C.)). Preferred are those drugs which in dry state are chemically stable during long-term storage without the addition of an antioxidant, e.g., paclitaxel and other taxanes, statins, thalidomide, corticosteroids and lipophilic derivatives of corticoids. Thereof, the preferred ones are paclitaxel, protaxel and docetaxel with paclitaxel being the most preferred drug. Drugs must be used in a dose range providing the desired effect without compromising the technical features of the coated balloon (balloon catheter) such as flexibility. A preferred dose range is between 1 and 10 pg/mm2 balloon surface, most preferred up to 6 g/mm2.
The lipophilic antioxidants are antioxidants which are solid at temperatures up to 40° C. Preferred are nordihydroguaiaretic acid, propyl gallate and resveratrol, more preferred nordihydroguaiaretic acid and resveratrol, most preferred only resveratrol. Probucol is not a preferred additive.
Combinations of these antioxidants with the above-mentioned drugs showed an improved adherence. Different combinations, especially with other oxidation-insensitive drugs, did not how a significantly improved adherence or required very high amounts of the antioxidant which impairs the mechanical features of the balloons (much more than 100% by weight in relation to 100% by weight of the drug).
Lipophilic antioxidant means that the partition coefficient of the antioxidant between n-butanol and water is >1, more preferred >10, and even more preferred >100.
Preferably, the drug is more lipophilic than the antioxidant, i.e., the partition coefficient between n-butanol and water of the drug is higher than the partition coefficient between n-butanol and water of the antioxidant. If, however, an excipient prevents premature loss of the drug from the medical device and/or enhances the fast and complete transfer to the tissue it shall not be excluded because of its physicochemical properties.
At the dose density used the chosen antioxidants do not display relevant therapeutic or prophylactic effects in respect of the disease which is treated by the coated medical device nor is the relative amount of the antioxidant chosen to protect the drug from oxidative decomposition. This means that a non-bioactive dose of the antioxidant is preferred. The dose density and the mass relation of the antioxidant to the drug are solely optimized in respect of adherence of the drug to and release from the medical device surface. The antioxidant dose on the medical device is too low to provide the desired pharmacological effect, i.e., it is ineffective on its own. The antioxidant on the medical device is not required to protect the active drug (e.g., the antiproliferative drug) from oxidative decomposition during production, sterilization and storage; at least it is not required at the dose or concentration applied according to this invention. "Not required" means that the active drug is stable enough without the antioxidant or at an antioxidant dose or dose density or ratio to the active drug below the dose according to the present invention. "Sufficient stability" means that less than 5% of the active drug is lost due to oxidative decomposition between the coating of the device and the use in patients one year after production if stored at ambient temperature (drug or drug preparation stable against oxidative decomposition, air-oxygen exposure not excluded). In conclusion the invention relates to a combination of an antioxidant with a drug which needs no protection from oxidative decomposition or at least a dose of the antioxidant which surpasses the amount of antioxidant required protecting the drug from oxidation by its antioxidant action. The antioxidant serves as additive or excipient not functioning as a stabilizer for an oxidation-sensitive biologically active ingredient (drug) nor displaying a therapeutic or prophylactic effect on its own at the selected dose.
The dose of the antioxidant on the surface of a medical device may be defined in respect of the therapeutic drug. Preferred relationships (weight/weight) are 3-100% antioxidant of the weight of the drug. For example, if the dose density of the drug is 5 g/mm2 device surface, the amount of antioxidant is 0.15-5.0 g/mm2. Higher proportions of the antioxidant may be selected if either the drug is applied at a dose below 3 pg/mm2 device surface or the adherence of the drug to the device surface is further improved. The antioxidant load of the device may reach 10 g/mm2. A higher load is possible. Other preferred ranges for the relationship of antioxidant to drug on a weight/weight basis are 5-100%, more preferred 10-100%, and even more preferred 20-100% and most preferred 50-100% in relation to 100% of the drug. Especially the range of 50-100% on a weight/weight basis enhances the adherence significantly (see Example 3). The relationship may also be defined in respect of moles: in a preferred embodiment the antioxidant is present from 10 mole % relative to the drug to 200 mole %.
Higher amounts of the antioxidant may be useful; they may be only excluded if they display on their own significant pharmacological prophylactic or therapeutic effects in respect of the disease to be treated.
If more than one drug is used the total weight of the drugs or the total moles of the drugs serve as basis for the calculation of the amount of the antioxidant. If more than one antioxidant is used the total weight of the antioxidants or the total moles of the antioxidants serve as basis for the calculation of the amount of the antioxidants.
Other well tolerated and approved additives and/or excipients may be applied to further improve the mechanical or pharmaceutical properties of the coating. Polymer-free coating compositions are preferred. It is a special advantage of the present compositions that they do not require the use of polymers to prevent premature release of the drug. Nevertheless, small amounts of pharmaceutically acceptable polymers such as polyacrylic acids may be added, e.g., to improve the distribution of the drug on the balloon or adherence of the dry coating during handling. Small amounts mean about 1-20% by weight in relation to 100% by weight of the drug(s). If polymers are used substances with low to moderate molecular weight, i.e., 2000 to 50,000 D are preferred.
Usually, drugs and mixtures of drugs with additives are coated on medical devices as liquid formulations in volatile solvents, according to the current invention preferably without addition of a polymer, i.e. polymer-free. The choice of solvent is important for the distribution of the drug on the device, especially if the device is coated at an advanced stage of production. An advanced stage of production of a scoring or cutting balloon may include the scoring or cutting elements of the device, the structures required to fix these elements and an already folded balloon. The solvents further determine the structure of the coating in dry state and the adherence and release of the drug from the surface. Preferred organic solvents are acetone, tetrahydrofuran, and various alcohols such as methanol and ethanol. Usually, 1 to 30% (volume/volume) water is added. The drug or drugs and the antioxidents may be applied at the same time dissolved in the same solvent or mixture of solvents. Alternatively, they may be separately dissolved in the same or different solvents and sequentially applied. The solution(s) is/are polymer-free in either case. In a preferred embodiment, the scoring or cutting balloon catheter has been polymer-free coated with at least one oxidation-insensitive drug and at least one antioxidant both together dissolved in tetrahydrofuran or a mixture of solvents containing more than 25% (v/v) tetrahydrofuran or each separately dissolved optionally selecting a different solvent for the at least one lipophilic antioxidant. Another preferred embodiment is based on a scoring or cutting balloon catheter, which has been polymer-free coated with at least one oxidation-insensitive drug and at least one antioxidant both together dissolved in acetone or a mixture of solvents containing more than 25% (v/v) acetone or each separately dissolved optionally selecting a different solvent for the at least one lipophilic antioxidant. Coating with dry particles such as micro- or nano-particles, crystals, capsules etc. or particles suspended in a liquid preparation is possible. Coating with particles may be facilitated by a roughened or sticky surface of the medical device.
A variety of coating procedures providing more or less uniform layers on medical devices are known from the literature and are disclosed in patent applications. These include simple dipping, spraying, and methods providing precise doses and homogeneous distributions (e.g., WO 2009/018816). Coating may be applied stepwise, either as multiple layers of the same composition or as layers with different compositions e.g. the drug first and the antioxidant second or in the opposite order. All these methods may be applied to the formulations of the current invention. The sequential coating with, e.g., (a) the drug first and (b) second the antioxidant dissolved in a solvent in which the drug is poorly soluble by, e.g., spraying results in substantially separate layers. This is completely different from the application of antioxidants for chemical protection of oxidation sensitive drugs which requires a homogeneous mixing of the antioxidant with the drug.
Thus, a preferred embodiment of the present invention is a scoring or cutting balloon catheter, which has been polymer-free sequentially coated with at least one oxidation-insensitive drug and at least one lipophilic antioxidant in a way that the oxidation-insensitive drug and the antioxidant are not homogeneously mixed.
Furthermore, coated scoring or cutting balloon catheter may be dried under different conditions such as temperature, air flow, gas composition, and pressure at different stages of the production process. They may be stored in water-vapor-tight seals with a separately packed water absorbing-agent within the seal.
Subject of the current invention are scoring or cutting balloon catheters, e.g., catheters for angioplasty or coronary angioplasty. Preferred are scoring or cutting balloon catheters for short-lasting use during an interventional image guided therapy. Short lasting use means that the device is not implanted but eliminated from the body when the procedure is finished, usually within less than 10 minutes, but never later than a few, preferably 5, hours after the end of the procedure. Catheters may contain balloon membranes made from various polymers and copolymers, polyamides (nylon 12, pebax), polyethylenes, polyurethanes, various polyvinyls and the like. Independently of the type of material, the adherence and release properties of drugs are improved by the addition of lipophilic antioxidants. Furthermore, catheters comprise elements which are aimed at scoring or cutting the surfaces in direct contact with the inflated balloons, e.g. wires with various profiles, or protrusions of the balloon surface.
The scoring or cutting balloon catheter carries the at least one drug or drug preparation and the at least one lipophilic antioxidant at least on a portion of its surface which is aimed at coming into close contact with the tissue to be treated, e.g., the balloon at the distal portion of a catheter shaft. This means that at least 5%, preferably more than 50%, most preferably more than 90% of the surface is coated. The balloon of a scoring or cutting balloon catheter has a central cylindrical part and two opposite conical ends. If less than 100% of the balloon catheter's surface is coated, it is preferred that the cylindrical part is coated and that at least parts of or the complete conical ends remain uncoated.
Another embodiment is a scoring or cutting balloon catheter carrying at least on a portion of its surface polymer-free at least one Limus drug or Limus drug preparation and at least one lipophilic antioxidant, which is nordihvdroguaiaretic acid or resveratrol, preferably resveratrol, at a ratio of 3-100% by weight of the at least one lipophilic antioxidant in relation to 100% by weight of the drug.
Preferably, the Limus drug is an mTOR inhibitor, more preferably selected from sirolimus, everolimus, zotarolimus, biolimus and temsirolimus, most preferred sirolimus. Concerning preferred ways of carrying out this embodiment, the same applies as described above with respect to the combination of oxidation-insensitive drugs/drug preparations and lipophilic antioxidants.
Below, the invention is described by means of Examples.

This patent is subject to a terminal disclaimer.

Coating formulations for scoring or cutting balloon catheters


A clip applying apparatus is described for applying clips seriatim to tissue. The apparatus includes a lockout member for limiting distal movement of the camming member after the proximal-most clip has been applied to tissue. In one embodiment, the apparatus includes a jaw locking member for preventing approximation of the jaw members of the apparatus. In one embodiment, a latch assembly is provided to releasably engage a clip pusher of the apparatus to the camming member of the apparatus.

1. Technical Field
This present disclosure relates generally to an apparatus for applying surgical clips to tissue. More specifically, the present disclosure relates to an apparatus for applying a series of clips to tissue seriatim.
2. Background of Related Art
Surgical procedures frequently require ligation of blood vessels, severed tissues and/or other organs to control or stop bleeding. Clip applying apparatus for quickly applying a surgical clip about tissue are well known. Such clip applying apparatus include single clip applicators and multiple clip applicators. In single clip applicators, a new clip is loaded into the apparatus after application of each clip. Multiple clip applicators include a series of clips which can be sequentially applied to tissue during the course of a surgical procedure. Because surgical procedures usually require the use of a multiplicity of surgical clips, multiple clip applicators are generally preferred.
Typically, clip applying apparatus include a handle mechanism, an elongated body portion, and a clip crimping assembly, e.g., a jaw or pair of jaws. Such clip applying apparatus are configured for endoscopic or open surgical procedures. Although known clip applying apparatus for sequentially advancing individual clips have provided good results, a continuing need exists for a clip applying apparatus which is less complex and provides effective hemostasis.


A device for honing blind bores in parts, a blind bore including a cylindrical bore open at one end and closed adjacent to the opposite end including a honing mandrel for mounting on a honing machine that produces rotation thereof, the mandrel having a cylindrical honing portion adjacent one end which portion and the adjacent portion of the mandrel have spaced axially extending slot therethrough to enable the honing portion of the mandrel to expand and contract in size, the honing portion having a portion adjacent to the end thereof which is somewhat larger than the rest of the honing portion when the honing portion is expanded for honing in the blind hole, the end portions of the mandrel between the spaced slots being elastically expandable from a retracted position which is less than the diameter of the surface to be honed to enable insertion therein to a more expanded condition wherein the diameter of the honing portion at the largest point is the diameter at which the mandrel will hone the blind hole. The present invention also includes a method for programming the operation of the device to produce the desired honing operations when honing blind holes.

The present invention relates to a honing tool which is specifically constructed and used to accurately hone blind bores or holes located in workpieces. A blind bore is a bore that does not go all the way through the workpiece and because of this the tool and method of using the tool must be modified from the more conventional honing tool which rotates and expands as it is stroked and moves back and forth in the workpiece. In the more conventional honing tool, the honing mandrel is expanded by pushing a wedge shaped member against the member or members on which the abrasives are located to move them radially outwardly into engagement with the work surface while also maintaining them in a cylindrical condition. This is not possible with blind holes because with a blind bore the tool cannot reciprocate in the ordinary manner and usually must be retracted to enter the bore before the honing operation commences and the expansion of the honing member or mandrel is reversed from the usual method so as to enable a portion of one end of the honing portion to expand outwardly more than the other positions thereof to enable the mandrel to hone a cylindrical surface to the desired diameter and to do so over the entire length of the blind hole.
Since a blind bore does not go all the way through the part or workpiece, the honing or finishing of a blind bore is usually relatively difficult because the honing tool cannot pass all the way through the bore or hole and beyond and therefore stroking in the usual way is difficult or impossible. Typically, the obstructed end of the workpiece usually has some type of relief or undercut area. The size and length of the relief area is usually not necessarily critical but the length of the undercut can be important because the length determines the amount of over stroke which can be accomplished when attempting to finish a blind bore to the same final size along the full length and with minimum taper. In the past, the honing of blind holes often used a single stroke procedure, but even this would produce some inaccuracy and would often require that the bore be rehoned by a second, third or more stroking without producing a taper of some kind. When honing with a tool that strokes back and forth, the stroking of the tool beyond the end of the workpiece bore into the relief area is usually required if the operation is to be successful and accurate. If there is not adequate relief for a long enough over stroke at the closed end of the bore, a barrel shaped bore often occurs in the surface being honed and this will produce a bore that is not cylindrical along its full length.
When using a single stroke honing tool, the tool is generally tapered for removing the material. The nature of this type of tool typically makes the final size of the bore smaller at the bottom or closed end as compared to the rest of the bore length. This is true because the size of the relief is usually not large enough to allow the bottom or closed end of the workpiece bore to be properly honed to its desired final size.
The present invention is directed to a honing tool and method of use specifically designed to hone blind bores to the same desired final size or diameter along the entire length of the bore surface. In this case, the tool is designed so as to be operated in a reverse manner as compared to a typical honing tool. More specifically, the present tool is designed so as to be positioned within the blind bore to be honed in its retracted condition, that is, at a dimension that is less than the dimension of the bore, and is then expanded while at or near the bottom or closed end of the blind bore to a particular size and pulled or drawn out of the blind bore while rotating at a controlled feed rate to achieve the final diameter which is uniform along the length of the bore. Depending upon the amount of material to be removed in this manner, this honing operation can be accomplished with a single pass or with multiple passes as will be described later.
The present tool includes an elongated substantially tubular member having an opening or passageway extending the entire length thereof and adaptable for insertably receiving an elongated expander member or wedge positioned for axial movement therein. The tubular member includes inner and outer surfaces, at least a portion of the outer surface at one end including an abrasive material thereon for accomplishing the honing operation, while the inner surface of at least that portion of the tool that corresponds to the outer abrasive portion is conically tapered over substantially the entire length of the abrasive portion as will be explained later and shown in the drawings. In contrast with the conventional honing devices the expander member or wedge assembly in the present construction has an outer surface which is conically tapered over at least a portion of its length at or near the same taper rate as the conical taper associated with that portion of the inner surface of the tubular honing member where the outer abrasive surface is located. This means that when the expander member is positioned within the tubular member, the tapered outer surface of the expander member can move into surface-to-surface contact with the tapered inner surface of the tubular honing member.
The tubular honing member also includes one or more slots extending from the end thereof along and beyond the abrasive portion of said member to permit expanding and contracting the abrasive portion of the honing member when the wedge is advanced or retracted axially therein. The present tool also includes means associated with one end portion thereof for mounting the tool to a rotatable member or spindle on a honing machine so that the tool can be rotated about its axis of rotation during a honing operation. In similar manner, the expander member or wedge assembly engages and is axially moved by means on the honing machine which are operable to move the wedge axially to change the diameter of the outer surface of the abrasive portion of the honing member. The abrasive portion of the present tool can have any desired pattern or configuration and, importantly, includes at least one lead-in or cutting taper near the lead end which is designed to remove most of the material during a particular honing stroke. The present honing tool is constructed to be retracted before insertion into the blind bore, and thereafter is expanded and pulled back through the hole while rotating. The cutting taper is usually slight and located at or near the free end of the abrasive portion of the tool. In other words, the cutting taper is such that the largest diameter is at or adjacent the free end of the abrasive portion of the tool as is shown in the accompanying drawings. This is different from conventional honing tools where the honing portion is cylindrical over its entire length.
The present tool may include a plurality of lead-in tapers such as first and second tapers, the second taper being positioned and located immediately following the first taper and being of a taper rate which is less than the taper rate of the first taper. The second or later taper portion can be followed by a substantially cylindrical abrasive portion, and the cylindrical abrasive portion can be followed by a reverse taper portion if desired. Any combination of tapers and cylindrical honing sections can be utilized in a particular tool depending upon the particular application.
Furthermore, if there are a plurality of slots associated with the present honing tool, this enables it to more uniformly expand and contract and the slots may take several different forms including being of straight or helical configurations. The same is true of the honing surfaces which may take helical, straight or other shapes that extend around the outer surface of the honing portion of the tool. The use of nonlinear grooves or flutes in the abrasive portions of the honing member also provide means for the circulation of honing oil or coolant during the honing operation which often times is an advantage. The tool needs to be formed of a relatively elastic material so that it can retract when the wedge is withdrawn and can expand when the wedge is advanced.
The method for using the subject tool is also new and enables the machine operator to manually or otherwise program the honing of blind bores by positioning the mandrel in its retracted condition so that it can enter the unhoned bore without touching or rubbing on the wall of the bore during entry. The tool is then moved to adjacent to the bottom or closed end of the bore and once properly positioned, the tool is expanded and rotated at a controlled rate. The amount of time that the tool remains in the bottom or closed end position before moving can be used to allow the material at the closed end of the bore to be removed by the tool before vertical or axial movement of the tool begins. The expanded rotating tool is then pulled out of the workpiece at an appropriate rate which will ensure that the workpiece bore is honed to the same size over its entire length. If the amount of material removed during a single pass of the tool through the bore is less than the total amount of material which must be removed from the bore to reach the desired size this process can be repeated with the tool expanded out further for each succeeding pass until the desired final dimension is reached. The entire sequence can be programmed so as to allow the operator to move the tool to any desired position in the bore at different rates and different numbers of times in order to bring the workpiece surface up to the desired size. The expanding and contracting of the tool can take place at different rates and the speed of rotation of the tool can also be varied depending upon the nature of the abrasive material used and the material of the surface being honed. Typical abrasives include plated diamond and borozon particles and various metal bonded abrasives. In a computer operated machine, the starting and final diameters can be preprogrammed as well as the other operating conditions such as the length of the bore, the material from which the workpiece is made, and the type of abrasive material that is being used and other parameters as will be described. The present method will size and finish the blind bores to precise tolerances without the tolerance levels degrading the even wear of the tool. This then is a honing method that does not fail because of uneven wear of the tool.
It is a principal object of the present invention to provide means to enable a honing machine to be used to accurately hone blind bores.
Another object of the present invention is to enable existing honing machines to be programmed to hone blind bores.
Another object is to enable existing honing machines to be modified to enable them to hone in blind bores.
Another object is to enable accurately honing blind bores by inserting a retracted honing mandrel into the bore being honed and expanding it when fully inserted so that when it is drawn out of the bore while rotating, it will hone the surface to the same dimension over its full length.
Another object is to teach a novel method for honing blind bores which can make use of some existing technology.
These and other objects and advantages of the present invention will become apparent after considering the following detailed description of the present invention in connection with the accompanying drawings.
The present invention relates to a novel apparatus which can be used to accurately hone blind bores which are bores that are open at one end but blocked at or adjacent to the opposite end. The present invention also relates to the method of programming and using the same apparatus for honing blind bores.

Method for honing blind bores in workpieces