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Publication numberUS3577516 A
Publication typeGrant
Publication dateMay 4, 1971
Filing dateDec 2, 1969
Priority dateDec 2, 1969
Publication numberUS 3577516 A, US 3577516A, US-A-3577516, US3577516 A, US3577516A
InventorsFrancis E Gould, Thomas H Shepherd
Original AssigneeNat Patent Dev Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Preparation of spray on bandage
US 3577516 A
Images(1)
Previous page
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Description  (OCR text may contain errors)

1971 F. E. souu: E

PREPARATION or sun on BANDAGE Filed D60. 3, 1969 1 mvsm'oag mic/$56 0 04 p wwlgyh ATTORNEYS United States Patent 3,577,516 PREPARATION OF SPRAY 0N BANDAGE Francis E. Gould, Princeton, and Thomas H. Shepherd,

Hopewell, N.J., assignors to National Patent Development Corporation, New York, N.Y.

Continuation-impart of applications Ser. No. 567,856,

July 26, 1966, now Patent No. 3,520,949, Ser. No.

650,259, June 30, 1967, and Ser. No. 654,044, July 5,

1967. This application Dec. 2, 1969, Ser. No. 881,376

Int. Cl. A611 15/00 US. Cl. 424-46 17 Claims ABSTRACT OF THE DISCLOSURE A bandage is formed in situ on a wound by spraying on separately or simultaneously a hydrophilic water insoluble polymer and a high boiling plasticizer or solvent therefor. Preferably the polymer is a hydroxy lower alkyl acrylate or methacrylate. Medically active ingredients can be included in the composition.

The present application is a continuation-in-part of application Ser. No. 567,856 filed July 26, 1966 now Pat. 3,520,949 issued July 21, 1970; application Ser. No. 650,259, filed June 30, 1967 and now abandoned; and application Ser. No. 654,044, filed July 5, 1967.

The present application relates to spray-on bandages.

A spray-on bandage offers a convenient, easy method of protecting minor wounds, cuts and/or abrasions during the healing process, and avoids certain undesirable characteristics associated with the use of substrates coated with pressure sensitive adhesives and gauze pads; such as pain and peeling of hair during removal, disagreeable appearance, adhesion of the healing area to the gauze pad, etc. i

The requirements for a fully acceptable spray-on bandage include the following:

(1) It protects the wound from air borne bacteria and dirt.

(2) It has moisture vapor permeability sufiicient to prevent accumulation of aqueous fluid under the bandage.

(3) It must be non-toxic and non-irritating to the skin.

(4) It should not adhere to the wound area or permit infiltration by regenerating tissue.

(5) It should not cause a burning or stinging sensation when applied.

(6) It should not be water soluble or rendered tacky by contact with water to avoid dirt accumulation.

(7) It should be readily removeable when desired.

Prior art spray-on products suffer from a number of disadvantages with respect to the above criteria. Thus prior art materials having the desired moisture vapor permeability coupled with water resistance must be applied as a spray from alcohol or similar solvent solution which causes a strong burning sensation in the wound area.

It is an object of the present invention to develop a spray-on bandage having all seven of the above set forth desirable characteristics while avoiding the disadvantages of prior art spray-on bandages.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific Patented May 4, 1971 example, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

It has now been found that these objects can be attained and a film forming action can be caused by applying a mixture of a powder of certain water insoluble, hydrophilic polymers having a high moisture vapor permeability with high boiling non-toxic polar plasticizer solvents therefore to, in effect, create a room temperature gelling plastisol which has high moisture vapor permeability, is sufficiently adherent to the skin to remain in place for extended periods of time, and adequately protects wound areas from contamination. Films produced by this technique are readily removed by soaking the bandages area in water for a few minutes which loosens the bond between the plastisol film and the skin. The film can then be readily pulled from the skin surface without discomfort.

The invention can be used to form spray-on bandages not only for human wounds but also is useful in the field of veterinary medicine for wounds on the skins of animals such as dogs, cats, sheep, cattle (e.g. to protect cows having mastitis on their teats), goats, pigs and horses and zoological animals such as lions, tigers, deer, zebra, etc.

Furthermore there can be incorporated in the films of the invention medically active ingredients which will diffuse from the film to the wound area over extended periods of time and keep the wound area free from infection, or provide local anesthesia or analgesia properties.

The medically active ingredients can be incorporated in the film by either 1) having them impregnated in the polymer or (2) mixing the active ingredient with the polymer powder, or (3) dissolving or dispersing the active ingredient in the high boiling plasticizer-solvent.

Polymer powders useful in this invention include polymers of hydroxy lower alkyl acrylates and methacrylates alone or coplyrners with each other, e.g. copolymers of 1 to 99% of each. Such polymers include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxy propyl acrylate and hydroxypropyl methacrylates. The preferred polymers are hydroxy lower alkyl methacrylates, especially hydroxyethyl methacrylate polymers.

There are also be used copolymers of the hydroxyalkyl acrylates and methacrylates with up to weight percent of lower alkyl acrylates and methacrylates, e.g. methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate and butyl methacrylate, hydroxy lower alkoxy lower alkyl acrylates and methacrylates, e.g. diethylene glycol monoacrylate, diethylene glycol mono methacrylate, dipropylene glycol mono acrylate, dipropylene glycol mono methacrylate, acrylamide, methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N-ethyl acrylamide, Nethyl methacrylamide, N- propyl acrylamide, N-propyl methacrylamide, N-isopropyl acrylamide, N-isopropyl methacrylamide, lower alkoxy lower alkyl acrylates and methacrylates such as methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate and ethoxyethyl methacrylate, amine compounds, e.g. p-aminostyrene, 2-amino-4- vinyltoluene, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, piperidinoethyl acrylate, 2-vinyl pyridine, dimethylaminopropyl methacrylate, diacetone acrylamide, diacetone methacrylamide, N- vinyl pyrrolidone.

The copolymerizable material should not be used in such amount as to reduce the compatibility of the hydroxyalkyl acrylate or methacrylate with the solvent or plasticizer or render it either too soluble in water or reduce its hydrophilic properties too greatly.

Usually the hydroxyalkyl acrylate or methacrylate is at least 80% by weight of the total monomers.

Useful, but less preferable, copolymers are prepared from lower alkyl acrylates and methacrylates, e.g. having 1 to 3 carbon atoms in the alkyl group such as methyl acrylate, ethyl acrylate, isopropyl acrylate, methyl methacrylate, ethyl methacrylate and propyl methacrylate with 3080% of ethoxyethyl acrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, acrylamide, methacrylamide, n-alkyl substituted acrylamides and methacrylamides such as N-methyl acrylamide, N-propyl acrylamide, N-methyl methacrylamide and N-isopropyl methacrylamide and N-vinyl pyrrolidone. Also polymers of the alkyl acrylates and methacrylates with 30-50% of hydroxyethyl and hydroxy propyl acrylates and methacrylates are included in this less preferred category.

In addition to the monomer and monomer mixtures set forth above to prepare polymers there can be added to the monomer or monomer mixture up to 15% by weight of the total monomers of acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.

While in Shepherd patent 3,428,043 there is described the use of a bandage comprising a fabric having an infrequently cross-linked hydrophilic polymer combined therewith the polymers of the present invention unlike those set forth in the Shepherd patent are substantially devoid of cross-linking. Thus while the slight amount of crosslinking ethylene glycol dimethacrylate impurity (about 0.1 to 0.2% normally present in hydroxyethyl methacrylate can be tolerated any cross-linking agent present should not be sufiicient to interfere with compatibility of the hydrophilic polymer with the plasticizer-solvent so as to prevent plastisol formation or otherwise interfere with the formation of the bandage on the wound.

The presently most preferred polymer is Hydron S, a commercially available polymer of hydroxyethyl methacrylate. It is essentially a homopolymer except for the presence of a trace (about 0.1% by weight) of ethylene glycol dimethacrylates.

The main requirements of the polymers useful in the present invention are:

(1) Non-tackiness.

(2) Sufficient hydrophilic character to possess moisture vapor permeability of at least 200 grams/sq. meter/ 24 hours/mil, preferably at least 500 grams/sq. meter/24 hours/mil.

(3) Susceptibility to solvation (plastisol formation) by the useful polar plasticizer-solvents.

(4) Insolubility in water.

(5) Sufficient friability to be able to be prepared as a finely divided powder, e.g. less than 100 mesh and preferably less than 200 mesh (Tyler Screen series).

Plasticizer-solvents useful for film formation in combination with the polymer-powders include water soluble polar compounds including glycols such as propylene glycol, ethylene glycol, trimethylene glycol, butanediol-1,3, butanediol-l,4, hexanediol-2,5, 2-methyl-2,4-pentanediol, heptanediol-2,4, 2-ethyl-1,3-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycols and other polyethylene glycols having a molecular weight up to 800 (e.g. hydroxy terminated polymers of ethylene oxide having average molecular weights of 200 800), dipropylene glycol, tripropylene glycol and other polypropylene glycols having molecular weights up to 900, propylene glycol nionoethyl ether, mono acetin, trl(hydroxyethyl) citrate,

di(hydroxypropyl) oxalate, hydroxypropyl acetate, glyceryl triacetate, glyceryl tributyrate, liquid sorbitolethylene oxide adducts, liquid glycerine-ethylene oxide adducts, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol diacetate.

The ratio of the plasticizer-solvent to the polymer is not particularly critical and satisfactory results are obtained in the range of from %-20% polymer to 20%- 80% plasticizer-solvent, more preferably 3070% polymer to 70-30% plasticizer-solvent.

Unless otherwise indicated, all parts and percentages are by weight.

In practice, it has been found that a light application of the plasticizer-solvent to the skin followed by application of the polymer powder results in adherence of a sufficient quantity of the powder to the area wet with the plasticizer-solvent to result in a strong, tough, adherent film. The film can be built up to any desired thickness but is usually about 10 mils.

The spray-on bandage of this invention is most conveniently applied using aerosol spray techniques although a layer of liquid followed by a layer of polymer can be applied by brushing, dabbing, etc. The bandage may be applied by a Z-separate spray technique wherein the plasticizer-solvent is first applied, followed by application of the powder from a separate container. Alternatively, the powder and liquid may be applied simultaneously from separate aerosol cans and valves which have a common activating mechanism. In some cases the powder and liquid may be applied from the same can in which case, the presence of the propellant in the can prevents solvation and agglomeration of the powder by the plasticizer solvent.

Suitable propellants include those well known in the art. There can be used compressed gases such as carbon dioxide, nitrous oxide, nitrogen, liquified volatile hydrocarbons such as propane, n-butane, isobutane and 2-methyl butane, methylene chloride, vinyl chloride, fluorinated compounds including perhalogenated compounds and fluorinated hydrocarbons such as dichlorodifiuoromethane (Freon l2), trichlorofluoromethane, 1,2-dichlorotetrafluoroethane, octofiuorocyclobutane, chlorodifiuoromethane, 1,1-difluoroethane, vinyl fluoride, vinylidene fluoride, l-chloro-l,t-difluoroethane. The propellant should contain a substantial amount of volatile material boiling at not over 20 C., but there can also be present a significant amount of less volatile material boiling up to 50 C.

The invention will be understood best in connection with the drawings wherein:

FIG. 1 is a perspective view illustrating the spraying of the plasticizer-solvent according to the invention;

FIG. 2 is a perspective view showing the spraying of the polymer;

FIG. 3 is a view of the finishing bandage; and

FIG. 4 is a view of an alternative method according to the invention.

Referring more specifically to FIGS. 1 and 2 of the drawings there is shown a skin area 2, e.g. on the arm, having a cut 4 thereon. From aerosol can 6, there is directed a spray 8 of appropriate plasticizer-solvent, e.g. propylene glycol by means of propellant, e.g. dichlorodifluoromethane. After the spraying of the plasticizer-solvent is completed, there is then sprayed from aerosol can 10 powdered Hydron S 12 on top of the plasticizer solvent. The Hydron S merges with the plasticizer-solvent to form the completed bandage 14 as a plastisol as shown in FIG. 3.

In the form of the invention illustrated in FIG. 4 a single aerosol can 16 is provided with a chamber 18 for the Hydron S and a separate chamber 20 for the propylene glycol plasticizer-solvent. When valve 22 is operated in the direction of the arrow, it releases the polymer 18 and plasticizensolvent together with the propellant as shown to coat the wound 24 on skin 26 to provide a bandage.

Example 1 This example illustrates the use of a technique of forming a spray-on bandage which does not possess all of the advantages of the invention.

Into a 6 ounce aerosol can was charged 10 grams of a 10% solid solution of Hydron S in 45 grams of 95% ethanol and 20 grams of methylene chloride. The can was sealed with a valve and 25 cc. of Freon 12 were added as the propellant. The resulting spray placed a good film upon the skin surface but was objectionable because of inherent sting response when applied to the wound. Replacement of a portion of the ethanol with water did not appreciably decrease the sting.

POWDER SPRAYS Example 2 In this example a two can system was employed.

Component A was made by charging a six ounce aerosol can with 20 grams of propylene glycol, sealing with a dispensing valve and then additionally charging with 80 cc. of Freon 12.

Component B was made by charging a six ounce aerosol can with 10 grams of Hydron S powder (270 to 325 mesh, Tyler sieve), sealing with a powder valve and further charging with a mixture of 10 grams of methylene chloride and 20 cc. of Freon 12.

For use, a light coat of Component A (liquid) was sprayed upon skin, e.g. a hand having a cut therein, leaving a wet film. The wet film was then oversprayed with Component B (powder) until the skin area was white and slightly dusty. Within 10-30 seconds the powder and liquid coalesced to form a flexible protective skin coating which was readily removable after soaking the hand in water.

In Examples 3-6 a one can system was employed.

Example 3 A single, two chambered aerosol can assembly was utilized in conjunction with a conventional codispensing valve assembly. Filling was as follows:

A six ounce aerosol can was charged with 10 grams of Hydron S powder, 220 to 325 mesh, and sealed with a co-dispensing valve and bag assembly. The bag chamber was then charged with a mixture of 8 grams of propylene glycol and 32 grams of Freon 12. Depression of the valve button then codispersed powder and liquid which formed a skin covering over a wound, e.g. on the hand.

Example 4 To alter humectant, physical and adhesive properties of the final spray-on bandage other coalescent solvents can be used in combination with or in replacement of propylene glycol. Numerous solvents of this type are set forth above. Among the preferred solvents of this type are glycerine, polyethylene glycol, monoacetin and triacetin.

A six ounce aerosol can was charged with 10 grams of Hydron S powder, 270 to 325 mesh and sealed with a codispensing valve and bag assembly. The bag chamber was then charged with a mixture of 4 grams of glycerine, 4 grams of propylene glycol and 32 grams of Freon 12. The resulting bandage showed increased humectant properties and good adhesion to the skin surrounding a wound, eg on a leg.

Example 5 The procedure of Example 4 was repeated replacing the propylene glycol by 4 grams of polyethylene glycol 200 (polyethylene glycol having an average molecular weight of about 200) to obtain a bandage on the skin over and around the wound.

Example 6 The procedure of Example 4 was repeated replacing the propylene glycol by 4 grams of triacetin to obtain a satisfactory bandage over the wound.

Example 7 The procedure of Example 2 was repeated replacing the propylene glycol by polyethylene glycol 200 to obtain a satisfactory bandage.

Example 8 As previously pointed out in place of Hydron S other linear copolymers can be used. The term copolymers is intended to include polymers of two or more copolymerizable materials, i.e. it is generic to terpolymers, tetrapolymers, etc. These copolymers can be prepared as stated from combinations of hydroxyethyl methacrylate mono mer with the monomers of hydroxypropyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, butyl acrylate, t-butylaminoethyl methacrylate, diethylaminoethyl rnethacrylate, methacrylic acid, acrylic acid, itaconic acid, diacetone acrylamide, etc.

A copolymer prepared from 50% hydroxyethyl methacrylate and 50% methyl methacrylate was pulverized to 270 to 325 mesh, 10 grams of the powder charged into a six ounce aerosol can and sealed with a codispensing valve and bag assembly. The bag chamber was charged with a mixture of 4 grams of propylene glycol, 4 grams of triacetin and 32 grams of Freon 12. The resulting spray gave a skin coating around a wound similar to those set forth in Examples 2-7.

Example 8 was repeated using a terpolymer of 50% hydroxypropyl methacrylate, 10% methacrylic acid and 40% diacetone acrylamide with similar results.

Furthermore medicinally active ingredients such as germicides, fungicides, antibiotics, steroids, local anesthetics or the like may be utilized by having the medicinally active ingredient suspended or entrapped in the polymer, or if desired dissolved in the liquid phase of the system. Examples of such medicinally active ingredients include benzocaine, xylocaine, aspirin, sodium omadine (a derivative of 1-hydroxypyridine-Z-thione), hexachlorophene, bacitracin, cortisone, trimethyl benzyl ammonium chloride, cetyl pyridinium chloride, penicillin, Aureomycin (chlorotetracycline), chlorornycetin (chloromphenicol), merthiolate, sulfanilamide, sulfathiaozole, sulfaguanidine, sulfapyridine, salicylic acid, Griseofulvin, undecylenic acid, zinc undecylenate, tetracycline, hydroxytetracycline (Terramycin), dienestrol, ethynyl estradiol, diethyl stilbesterol, estradiol, myltestosterone, progesterone, ascorbic acid.

SUSPENSION OF MEDICALLY ACTIVE INGREDIENTS Example 9 To illustrate use of the invention with a fungicide, a six ounce aerosol can was charged with 9.98 grams of Hydron S powder, 270 to 325 mesh in which was dispersed 0.02 gram of sodium omadine. The can was sealed with a co-dispensing valve and bag assembly. The bag chamber was then charged with a mixture of 8 grams of polyethylene glycol 300 (polyethylene glycol having an average molecular weight of about 300) and 32 grams of Freon 12. The resulting film formed by spraying upon a colony of fungus (Aspergillus niger) showed marked depression of colony growth. The formulation was also sprayed on the skin around a wound to form a bandage.

Example 10 Example 9 was repeated using 9.7 grams of a 50-50 copolymer of hydroxypropyl methacrylate with methoxyethyl methacrylate and having 0.3 gram of hexachlorophene (a germicide) dispersed throughout the finely divided copolymer. The resulting film showed good suppression upon a colony of Salmonella typhosa. A spray on bandage was also prepared over a wound on the scalp.

Example 11 The procedure of Example 10 was repeated replacing the hexachlorophene by 0.3 gram of Bacitracin (or antiseptic). The film formed on spraying showed good suppression upon a colony growth of streptococci. A spray on bandage was also produced on skin on the cheek.

Example 12 The procedure of Example 10 was repeated replacing the hexachlorophene by 0.3 gram of cortisone. When the spray on bandage was formed on the skin good antiinflarnmatory effect upon the skin was noted.

Example 13 The procedure of Example 10 was repeated using 0.3 gram of Benzocaine (ethyl aminobenzoate, a local anesthetic) in place of the hexachlorophene. The resulting film showed good pain suppressing qualities upon abraded skin.

Example 14 Any medically active ingredient that is soluble in ethanol or an ethanol-water mixture can be put into solution with Hydron S or other hydroxyethyl or hydroxypropyl methacrylate polymers. Such solutions are then dried to a solid by any method known to the art, e.g. tray drying, roller drying, vacuum drying, spray drying, and then reduced to sprayable power form to produce an entrapped medically active ingredient.

For example, 9.0 grams of Hydron S plus 1 gram of Benzocaine were dissolved in 30 cc. of 95% ethanol. The solution was vacuum dried and the resulting polymer mix was pulverized to 270 to 325 mesh. This polymer mix was charged into an aerosol can as described in Examples l and 13. Upon spraying to form a bandage, the final film produced on the skin showed the same pain suppressing qualities as in Example 13 above.

Example 15 If the medically active ingredient is soluble in the liquid phase of the system, it can be dissolved in that phase with results similar to those described in Examples 9-14.

For example a six ounce aerosol can was charged with 9.7 grams of Hydron S, 220 to -325 mesh and sealed with a codispensing valve and bag assembly. The bag chamber was then charged with a solution of 8 grams of propylene glycol containing 0.3 gram of hexachlorophene and 32 grams of Freon 12. The sprayed film produced the same suppression of a Salmonella typosa colony as in Example 10. A satisfactory spray-on bandage was also produced on skin having a wound therein.

Obviously the medicinally active ingredient can be added to both the polymer and the plastisol forming solvent or plasticizer.

What is claimed is:

1. In a method of forming a powdery bandage in situ on skin having a wound therein which is readily removable therefrom after soaking, the improvement comprising the steps of (a) applying, as a powder, a hydrophilic water insoluble hydroxy or lower alkoxy lower alkyl acrylate or methacrylate polymer or a copolymer of 20 to 70% of a lower acrylate or methacrylate and 80 to 30% of acrylamide, methacrylamide, N-lower alkyl acrylamide or methacrylamide, or N-vinylpyrrolidone as a powder and (b) applying, simultaneously or in succession, a high boiling liquid plasticizer or solvent therefor which does not cause a burning or stinging sensation when applied on the skin and wound to form a plastisol film on the skin resulting from adherence of the powder to the wound area wet with the non-stinging plasticizer-solvent thereby covering said wound wherein the polymer powder and plasticizer are sprayed from separate containers in succession, or wherein the polymer powder and plasticizer are simultaneously sprayed from separate chambers in a single container, or wherein the polymer powder and plasticizer are sprayed simultaneously from the same chamber in a single container, the plasticizer and polymer powder being kept separate by the propellant which prevents solvation and agglomeration of the polymer powder by the plasticizer.

2. A method according to claim 1 wherein the polymer is in finely divided form substantially uncrosslinked and has a moisture vapor permeability of at least 200 grams/ sq. meter/24 hours/mil and the application is accomplished by spraying as an aerosol with the aid of a propellant.

3. A method according to claim 2 wherein the polymer has a moisture vapor permeability of at least 500 grams/ sq. meter/24 hours/mil.

4. A method according to claim 2 wherein there is included an effective amount of a medicinally active antiseptic germicide fungicide or antibiotic, local anaesthetic and/or anti-inflammatory steroid ingredient in at least one of said polymer and said plasticizer, said incorporated medically active ingredients diffusing from the film to the wound area over extended periods of time, thereby keeping the wound area free from infection, infiammation, or providing local anesthesia or analgesia.

5. A method according to claim 2 wherein the polymer powder and plasticizer are sprayed from separate containers in succession.

6. A method according to claim 2 wherein the polymer and plasticizer are simultaneously sprayed from separate chambers in a single container.

7. A method according to claim 2 wherein the polymer powder and plasticizer are sprayed simultaneously from the same chamber in a single container, the plasticizer and polymer powder being kept separate by the propellant which prevents solvation and agglomeration of the polymer powder by the plasticizer prior to spraying.

8. A method according to claim 2 wherein the polymer is selected from the group consisting of polymers of hydroxy lower alkyl acrylates, hydroxy lower alkyl methacrylates.

9. A method according to claim 8 wherein the lower alkyl group has 2 to 3 carbon atoms.

10. A method according to claim 9 wherein the polymer is essentially a homopolymer of hydroxyethyl methacrylate.

11. A method according to claim 9 wherein the polymer is a copolymer of the hydroxy lower alkyl acrylate or methacrylate with each other or with up to 50% of a lower alkyl acrylate or methacrylate, a hydroxy lower alkoxy lower alkyl acrylate or methacrylate, acrylamide, methacrylarnide, N-lower alkyl acrylamides and methacrylamides, lower alkoxy lower alkyl acrylates and methacrylates, diacetone acrylamide, diacetone methacrylamide, N-vinyl pyrrolidone or polymerizable amino substituted mono ethylenically unsaturated monomer.

12. A method according to claim 11 wherein the hydroxy lower alkyl acrylate or methacrylate is hydroxyethyl methacrylate.

13. A method according to claim 11 wherein there is also included in the polymerizable monomers an unsubstituted ethylenically unsaturated carboxylic acid in an amount up to 15%.

14. A method according to claim 9 wherein there is also included in the polymerizable monomers an ethylenically unsaturated carboxylic acid in an amount up to 15% 15. A method according to claim 14 wherein the acid is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid.

16. A method according to claim 2 wherein the polymer is a copolymer of 20 to 70% of a lower alkyl acrylate or methacrylate and to 30% of a lower alkoxy lower alkyl acrylate or methacrylate, acrylamide, methacrylamide, N-lower alkyl acrylamides and methacrylamides, or N-vinyl pyrrolidone.

17. A method according to claim 1 wherein the bandage has a thickness of about 10 mils.

References Cited UNITED STATES PATENTS Brown et a]. 424-81 Leader 424-81 Gallienne et al. 424-81 Wichterle et a] 18-58 Maeder 424-81 Wichterle et a1. 18-58 10 3,269,903 8/1966 Van Fieandt et a1. 424-81 3,400,890 9/1968 Gould 239-36 3,428,043 2/1969 Shepherd 128-268 3,483,870 12/1969 Coover et a1 128-334 5 SHEP K. ROSE, Primary Examiner US. Cl. X.R.

424-28, 32, 33, 45, 7s, 80, 81; 12s s2, 114, 155, 156, 172, 260, 265,268, 334, 335.5

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3855146 *Feb 29, 1972Dec 17, 1974Fuji Photo Film Co LtdProcess for preparing microscopic capsules containing hydrophobic oil droplets therein
US3856026 *Jan 16, 1974Dec 24, 1974Gaydos DApplication of flock to the body for cosmetic purposes
US3868447 *Feb 2, 1972Feb 25, 1975Nat Patent Dev CorpHema paste
US3880158 *Apr 4, 1974Apr 29, 1975Johnson & JohnsonSpray-spun bandage composition
US3888782 *May 8, 1972Jun 10, 1975Allergan PharmaSoft contact lens preserving solution
US3928556 *Feb 28, 1974Dec 23, 1975Novitas Nuprot SaNon-stinging wound dressing containing tertiary butyl alcohol
US3932602 *Dec 13, 1973Jan 13, 1976Novitas Nuprot SaSolvents, tetrachlorodifluoroethane
US3935303 *Nov 1, 1972Jan 27, 1976Gennady Lvovich KhromovAcrylamide-n-vinyl pyrrolidone-butyl acrylate terpolymer
US3935308 *Aug 8, 1974Jan 27, 1976The United States Of America As Represented By The Secretary Of The NavyWound covering and method of application
US3969498 *Sep 13, 1973Jul 13, 1976University Of The PacificDressing and method for treating a wound
US3978201 *Nov 12, 1975Aug 31, 1976Gennady Lvovich KhromovBase for ophthalmological medicinal preparation on opthalmological medicinal film
US3987000 *Aug 29, 1974Oct 19, 1976Beiersdorf AktiengesellschaftBandages, isobutene, acrylic esters, maleic acid monoalkyl ester
US4007258 *Sep 10, 1973Feb 8, 1977Union CorporationZein, hydrophilic polymer
US4021364 *Dec 4, 1973May 3, 1977Prof. Dr. Peter SpeiserMicrocapsules in the nanometric range and a method for their production
US4136250 *Jul 20, 1977Jan 23, 1979Ciba-Geigy CorporationCrosslinked, addition monomer or polymer
US4172149 *Jan 30, 1978Oct 23, 1979Westwood Pharmaceuticals, Inc.Method for treating living skin exhibiting excessive sebum secretion
US4186190 *Nov 13, 1978Jan 29, 1980The United States Of America As Represented By The Secretary Of The NavyMethod of treating burns using a poly-ε-caprolactone
US4241048 *May 1, 1979Dec 23, 1980Bristol-Myers CompanyVinyl pyrrolidone-alpha olefin copolymer crystal growth inhibitor
US4272518 *Jul 10, 1979Jun 9, 1981Moro Daniel GPlastic wound bandage
US4287177 *Aug 15, 1979Sep 1, 1981Kuraray Co., Ltd.Wound covering material
US4303066 *Jun 28, 1979Dec 1, 1981National Patent Development CorporationBurn dressing
US4310509 *Jul 31, 1979Jan 12, 1982Minnesota Mining And Manufacturing CompanyPressure-sensitive adhesive having a broad spectrum antimicrobial therein
US4323557 *Jul 31, 1979Apr 6, 1982Minnesota Mining & Manufacturing CompanyPressure-sensitive adhesive containing iodine
US4367227 *Dec 26, 1978Jan 4, 1983Lever Brothers CompanyMethod and cosmetic composition for reducing sebum secretion
US4492685 *Jan 30, 1984Jan 8, 1985Key Pharmaceuticals, Inc.Portection of burned or wounded patients
US4563184 *Oct 17, 1983Jan 7, 1986Bernard KorolSynthetic resin wound dressing and method of treatment using same
US4584192 *Jun 4, 1984Apr 22, 1986Minnesota Mining & Manufacturing CompanyFilm-forming composition containing an antimicrobial agent and methods of use
US4587129 *Jun 1, 1982May 6, 1986National Patent Development Co.Hydrophilic gels containing high amounts of fragrance
US4699133 *May 23, 1985Oct 13, 1987Firma Karl Otto Braun KgProcess for producing a cohesive, self-adhesive, rigid or elastic bandage for fixing, compression and support dressings for medical purposes and bandage produced by this process
US4725271 *Nov 27, 1985Feb 16, 1988Enquay Pharmaceutical AssociatesPolymer, solvent, hydrogen bonding plasticizer; preformed or cured in situ; timed release
US4732755 *Apr 28, 1983Mar 22, 1988University Of Health Sciences/The Chicago Medical SchoolSodium polyacrylate solutions
US4743440 *Jul 29, 1981May 10, 1988Lever Brothers CompanySkin composition
US4822596 *Nov 6, 1985Apr 18, 1989Lever Brothers CompanySkin composition
US4874540 *Sep 3, 1987Oct 17, 1989Ecolab Inc.Water treatment
US4880617 *Oct 6, 1986Nov 14, 1989Dow Corning CorporationLattice-entrapped composition
US4882166 *Aug 20, 1987Nov 21, 1989National Research Development CorporationSustained release; in situ cationic polymerization
US4883828 *Jan 30, 1989Nov 28, 1989Ecolab Inc.Disinfectant polymeric coatings for hard surfaces
US4908381 *Dec 5, 1988Mar 13, 1990Ecolab Inc.Antimicrobial film-forming compositions
US4921691 *Aug 22, 1985May 1, 1990Stockel Richard FSpray on wound dressing compositions
US4978527 *Apr 10, 1989Dec 18, 1990Minnesota Mining And Manufacturing CompanyAqueous mixture with iodine-containing copolymers forms hydrophobic wear resistant film on skin; drug delivery
US4987893 *Oct 4, 1989Jan 29, 1991Rochal Industries, Inc.Addition polymer containing pendant siloxane group, a volatile polydimethylsiloxane and a polar liquid; transparent and durable protective coating
US5011493 *Oct 2, 1987Apr 30, 1991Belykh Sergei IMaterial for connecting members for inner soft tissues and organs
US5061485 *Feb 16, 1989Oct 29, 1991Ecolab Inc.Film forming acrylic polymer
US5078129 *Mar 8, 1990Jan 7, 1992Research Foundation Of State University Of New YorkDevice for stimulating salivation
US5103812 *Feb 19, 1991Apr 14, 1992Rochal Industries, Inc.An alkyl siloxy siloxane-containing polymer in a liquid polydimethylsiloxane; non-stinging, film-forming; stops pain while protecting wounds
US5108740 *Nov 13, 1989Apr 28, 1992Ecolab Inc.Antimicrobial film-forming compositions containing polymers having pendant pyran groups
US5154920 *Oct 21, 1987Oct 13, 1992Ecolab Inc.Disinfectant polymeric coatings for hard surfaces
US5164179 *Jan 10, 1991Nov 17, 1992Kao CorporationBiocide activator
US5173291 *Sep 10, 1990Dec 22, 1992Minnesota Mining And Manufacturing CompanyDried hydrophobic film of addition polymer complexed with iodine; surgery; bandages; sterilization of skin
US5196185 *Sep 11, 1989Mar 23, 1993Micro-Collagen Pharmaceutics, Ltd.Collagen-based wound dressing and method for applying same
US5383899 *Feb 23, 1994Jan 24, 1995Hammerslag; Julius G.Method of using a surface opening adhesive sealer
US5419913 *Mar 5, 1992May 30, 1995Podell; Howard I.Adhesive bandages, wound dressings, sutures, drapes, orthodontic rubber bands, toothbrushes, and the like
US5429590 *Nov 30, 1993Jul 4, 1995Nitto Denko CorporationMedical water-absorptive polymer and dressing for wound and medical bandage using the same
US5529577 *Jul 21, 1994Jun 25, 1996Hemodynamics, Inc.Surface opening adhesive sealer
US5605541 *Dec 7, 1994Feb 25, 1997E. R. Squibb And Sons, Inc.Using a gas
US5620702 *May 9, 1995Apr 15, 1997Podell; Howard I.Adhesive bandages, wound dressings, sutures, drapes orthodontic rubber bands, toothbrushes, and the like
US5632727 *Jun 7, 1995May 27, 1997Atrix Laboratories, Inc.Biodegradable film dressing and method for its formation
US5653730 *Sep 28, 1994Aug 5, 1997Hemodynamics, Inc.Surface opening adhesive sealer
US5665106 *Sep 7, 1995Sep 9, 1997Hemodynamics, Inc.Vascular patch applicator
US5665107 *Sep 7, 1995Sep 9, 1997Hemodynamics, Inc.Surface opening adhesive sealer
US5722950 *Jun 7, 1995Mar 3, 1998Atrix Laboratories, Inc.Method for remote delivery of an aerosolized liquid
US5725491 *Nov 8, 1994Mar 10, 1998Atrix Laboratories, Inc.Spraying thermoplastic polymer in solvent
US5759194 *Oct 23, 1996Jun 2, 1998Hemodynamics, Inc.Vascular patch applicator
US5792469 *Jun 7, 1995Aug 11, 1998Atrix Laboratories, Inc.Liquid formulation of thermoplastic polymer and organic solvent
US5810786 *Mar 25, 1996Sep 22, 1998Richard R. JacksonTissue-numbing anesthetic articles
US5843124 *Aug 21, 1996Dec 1, 1998Hemodynamics, Inc.Surface opening adhesive sealer
US6210688 *Jun 9, 1995Apr 3, 2001Rachel Ann QuayleUse of polymers as film-forming barrier materials
US6242042Sep 14, 1998Jun 5, 2001Lrc Products Ltd.Immersion in aqueous solution of hydrophilic resin
US6287323Dec 1, 1998Sep 11, 2001Hemodynamics, Inc.Method of catheterization and inhibition of arterial bleeding
US6454786Nov 14, 1997Sep 24, 2002Bristol-Myers Squibb CompanySurgical sealant; fibrin monomer liquid and a thrombin solution
US6520942 *Oct 27, 1997Feb 18, 2003Edward L PutmanA gel is bottled in a plastic container and the top fitted with a pump for delivery of a small quantity of the gel onto dry toilet paper. The gel can thus be hygienically applied to the peri-anal area using the thus moistened toilet paper, and
US6585967Jul 5, 2001Jul 1, 2003Closure Medical CorporationAdhesive treatment for tinea cruris
US6602496Jul 5, 2001Aug 5, 2003Closure Medical CorporationApplying polymerizable monomer and fungicide; applying to skins
US6613020Dec 6, 1996Sep 2, 2003Bristol-Myers Squibb CompanyMethod of applying a mixture of two liquid components as well as a device for carrying out the method
US6706313Sep 14, 1999Mar 16, 2004Lrc Products Ltd.Immersing article in aqueous solution of 2-hydroxyethyl acrylate- 2-hydroxyethyl methacrylate co- or terpolymer, heat curing and vulcanizing rubber or latex
US6746667Jul 5, 2001Jun 8, 2004Closure Medical CorporationAdhesive treatment for tinea pedis
US6767552Jul 5, 2001Jul 27, 2004Closure Medical CorporationAdhesive treatment for oral fungal infection
US6942875Jul 5, 2001Sep 13, 2005Closure Medical CorporationApplying polymerizable monomer and fungicide; applying to skins
US7842749 *Jul 5, 2005Nov 30, 2010Poly-Med, Inc.Tissue protecting spray-on copolymeric film composition
US7879942Oct 5, 2006Feb 1, 2011Eastman Chemical CompanySwitchable adhesive article for attachment to skin and method of using the same
US8762067Oct 31, 2008Jun 24, 2014The Invention Science Fund I, LlcMethods and systems for ablation or abrasion with frozen particles and comparing tissue surface ablation or abrasion data to clinical outcome data
US20120101738 *Mar 31, 2009Apr 26, 2012Searete Llc, A Limited Liability Corporation Of The State Of DelawareCompositions and methods for biological remodeling with frozen particle compositions
USRE33429 *Feb 3, 1989Nov 6, 1990Dow Corning CorporationCrosslinked polymer beAD
EP0164999A2 *Jun 4, 1985Dec 18, 1985Minnesota Mining And Manufacturing CompanyFilm-forming composition containing an antimicrobial agent
EP0601463A1Dec 1, 1993Jun 15, 1994Nitto Denko CorporationMedical water-absorptive polymer and dressing for wound and medical bandage using the same
WO1982000099A1 *Jun 26, 1981Jan 21, 1982Key PharmaPolymeric diffusion matrix for administration of drugs
WO1990003809A1 *Oct 10, 1989Apr 19, 1990Rochal Ind IncConformable bandage and coating material
WO1998039042A1 *Mar 25, 1997Sep 11, 1998Richard R JacksonAnesthetizing plastics, drug delivery plastics, and related medical products, systems and methods
WO2007000598A1 *Jun 28, 2006Jan 4, 2007Manel TorresNon-woven fabric
WO2007005029A2 *Jul 8, 2005Jan 11, 2007James M Lindsey IiiTissue protecting spray-on copolymer film composition
Classifications
U.S. Classification424/46, 602/48, 424/78.6, 602/904, 128/888, 424/443, 604/304, 424/45, 623/66.1, 427/4, 604/290, 128/849
International ClassificationC08J7/04, A61D9/00, A61F13/00, A61L15/46, A61L26/00
Cooperative ClassificationA61F13/00063, A61L26/0066, A61L2300/41, A61L26/0076, A61L2300/404, A61F2013/00876, A61L26/0014, A61F2013/00263, A61F2013/0011, A61F13/00008, A61L15/46, A61L2300/222, A61L2300/402, Y10S602/904
European ClassificationA61F13/00A2, A61F13/00B6, A61L15/46, A61L26/00B2, A61L26/00H6, A61L26/00H2