CA2000548C - Conformable bandage and coating material - Google Patents
Conformable bandage and coating material Download PDFInfo
- Publication number
- CA2000548C CA2000548C CA002000548A CA2000548A CA2000548C CA 2000548 C CA2000548 C CA 2000548C CA 002000548 A CA002000548 A CA 002000548A CA 2000548 A CA2000548 A CA 2000548A CA 2000548 C CA2000548 C CA 2000548C
- Authority
- CA
- Canada
- Prior art keywords
- methacrylate
- acrylate
- polymer
- liquid polymer
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0019—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
- A61F13/00—Bandages or dressings; Absorbent pads
- A61F13/02—Adhesive plasters or dressings
- A61F13/023—Adhesive plasters or dressings wound covering film layers without a fluid handling layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S128/00—Surgery
- Y10S128/21—Silicone
Abstract
SS/sas 5696s ABSTRACT
Combinations of alkyl siloxy siloxane-containing polymers admixed with liquid polydimethylsiloxanes are excellent non-stinging, non-irritating liquid coating material for forming films which act as conformable bandages adhering to and protecting nails, skin and mucous membrane wounds from abrasion, contamination, and desiccation, while stopping pain from exposed nerve ends and allowing body fluid evaporation.
Combinations of alkyl siloxy siloxane-containing polymers admixed with liquid polydimethylsiloxanes are excellent non-stinging, non-irritating liquid coating material for forming films which act as conformable bandages adhering to and protecting nails, skin and mucous membrane wounds from abrasion, contamination, and desiccation, while stopping pain from exposed nerve ends and allowing body fluid evaporation.
Description
~~~~~~48 SS/sas 5696s CONFORMABLE BANDAGE AND COATING MATERIAL
RELATED APPLICATION
This Application is a Continuation-in-Part of U.S. Patent P:,pplication 07,256,651, filed October 12, 1988.
BACKGROUND OF THE INVENTION
The invention pertains to liquid adhesive materials which are useful for protecting surfaces such as biological surfaces, including skin and mucous membranes. The polymer component of the liquid adhesive material comprises an ethylenically unsaturated addition polymerizable monomer containing at. least one alkyl siloxy silane. The polymer may avlso include other monomers.
The polymer, when incorporated into volatile liquid polydi.methylsiloxanes, preferably with a small amount of polar liquids or solvents, provides for a fast drying, flexible, waterproof, breathable, non-stinging liquid adhesive coating or bandage.
This liquid adhesive coating may contain medicants or other active materials which may be gradually released onto targeted areas, if desired.
~~~.~~ a~4~
SS/sas 5696s _2_ ~ornn aim Naturally-occurring and derivatized naturally-occurring polymers have been tested as liquid adhesive coatings for bandage applications and, in some cases, utilized commercially. Typical examples are nitrocellulose in various solvents (e. g., New Skin-Medtech Laboratories, Inca, Cody, Wyoming), agar in water and diethylene glycol (U. S.
4,291,025) carrageenan and hydroxypropylmethyl ' cellulose in water (U.S. 4,318,746), and alginate in glycerin (U. S, 4,393,048). All of these natural polymers can support microbial growth, hence requiring the addition of a preservative or antimicrobial agent to the product. The liquid bandages based on water, diethylene glycol, glycerin;- etc. are not only susceptible to microbial growth, but are often also slow drying due to high heats of vaporization; and are often water sensitive, which can result in problems when used on areas of the body exposed to water. One commercial product, New Skin, does dry rapidly and is not water sensitive. but can cause stinging and further irritation of the skin upon application.
SS/sas 09/16/89 .
5696s _3-A few synthetic polymers have been patented for .
use as liquid adhesive coatings for bandage applications, most notably polymers containing 2-hydroxyethyl methacrylate (U. S. 4,303,066). These bandages based on the use of solvents can sting abraded areas; and the films can swell and wash off when in contact with water. U.S. 4,569,784 claims an ointment, not a long lasting bandage composed of an emulsion of water and silicone fluids, among other fluids. This reference can provide for an immediate soothing, but often not long lasting, treatment of the skin or mucous membranes. It also does not provide for fast drying, abrasion resistance, and other attributes which a polymer film can provide.
Additionally, traditional wound and surgical bandages, such as Band-Aids (Johnson & Johnson, New Brunswick; NJ), comprised of film backings with adhesive, may contain silicones as part of either the adhesive or the backing (e. g. U.S. 4,650,817).
These products are not applied as liquid adhesive coating where films form and adhere directly on the skin.
SS/sas 5696s SUMMARY OF THE INVENTI
It is an object of the invention to provide a , liquid polymer-containing coating material which can act as a bandage or dressing to protect wounds; when applied in liquid form and air dried on the wound to form an adherent, solid protective film without significant stinging to the skin or mucous membranes of the user.
It is a further object of the invention to provide a coating which will prevent further microorganism or particulate contamination to skin or mucous membrane wounds or incisions.
It is a further object of the invention to provide a non-tacky, L_ransparent covering which does not attract or hold dirt and can remain colorless and clear for wound view:~ng as well as cosmetic attractiveness.
It is a Further object'of the invention to provide a coating which; when applied, will control body fluid loss from an abraded area:
It is a further object of the invention to provide a polymer film in which medicants or other active agents, e.g. perfumes, may be incorporated for gradual release into targeted areas.
Tt is a further object of the invention to provide a coating which, when applied, repels liquid H20, but also allows H20 vapor to pass through.
SS/sas 5696s _S-It as a further object of the invention to provide a low-surface tension covering which can reduce drag.
The liquid polymer containing coating materials of this invention consist essentially of a siloxane containing polymer and a solvent system comprising a polar solvent in small amount and a volatile liquid which is non-stinging to a user but provides bulk and formability to the liquid. Preferably the polymer is present from 1 to 40% by weight, the volatile liquid from 59.9 to 98.9% by weight and the polar solvent from 0.1 to 10% by weight. When the polar solvent is el~.minated, the volatile liquid can be in amounts of 60 to 99%. The solvent is minimized to obtain flowability desired at the lowest solvent level feasable which minimizes stinging. The material forms a coating or bandage in the form of a dried film when applied to a surface or the skin of a user.
Preferably, the siloxane containing polymer comprises at least one vinyl-containing alkylsiloxysilane and an addition polymerizable comonomer. The volatile liquid is preferably a polydimethylsiloxane.
It is a feature of the invention that the liquid materials can act at room temperature (20°C) when ~~~~!~~4~
Roa9~/7ooa ss/sas 09/16/$9 .
5696s _ _6_ applied to skin, nails, or mucous membranes of a user to form films in minutes which films are excellent bandages. They are not a nutrient source for microorganisms, are conformable, comfortable and can be elastic and flexible. The films do not irritate the skin and mucous membrane when sprayed or deposited in any way during application and in use after drying. The bandages are substanially painless and can be easily removed substantially without pain. The dried bandages formed are substantially non-water-sensitive, and waterproof and have high water vapor and oxygen gas transmission therethrough. The bandages form when applied over surfaces wet with water , blood or body fluids, in short times at standard room temperature and reasonable variants thereof. The liquid composition and/or dried polymer film can have various medicaments or other agents incorporated therein for maintaining sterility and/or for release to the underlying area of the body of a user. For example, perfumes, antibacterial or similar materials can be released from the coatings.
SS/sas 5696s DESCRIPTION OF PREFERRED EMBODIMENTS
The siloxane-containing polymers of this invention can comprise vinyl-containing alkylsiloxysilanes alone or as co-, ter- or multi-component polymers which can include other polymerizable monomers that do not make the polymers hydrophilic.
Typical vinylalkylsiloxysilanes that may be utilized are:
RELATED APPLICATION
This Application is a Continuation-in-Part of U.S. Patent P:,pplication 07,256,651, filed October 12, 1988.
BACKGROUND OF THE INVENTION
The invention pertains to liquid adhesive materials which are useful for protecting surfaces such as biological surfaces, including skin and mucous membranes. The polymer component of the liquid adhesive material comprises an ethylenically unsaturated addition polymerizable monomer containing at. least one alkyl siloxy silane. The polymer may avlso include other monomers.
The polymer, when incorporated into volatile liquid polydi.methylsiloxanes, preferably with a small amount of polar liquids or solvents, provides for a fast drying, flexible, waterproof, breathable, non-stinging liquid adhesive coating or bandage.
This liquid adhesive coating may contain medicants or other active materials which may be gradually released onto targeted areas, if desired.
~~~.~~ a~4~
SS/sas 5696s _2_ ~ornn aim Naturally-occurring and derivatized naturally-occurring polymers have been tested as liquid adhesive coatings for bandage applications and, in some cases, utilized commercially. Typical examples are nitrocellulose in various solvents (e. g., New Skin-Medtech Laboratories, Inca, Cody, Wyoming), agar in water and diethylene glycol (U. S.
4,291,025) carrageenan and hydroxypropylmethyl ' cellulose in water (U.S. 4,318,746), and alginate in glycerin (U. S, 4,393,048). All of these natural polymers can support microbial growth, hence requiring the addition of a preservative or antimicrobial agent to the product. The liquid bandages based on water, diethylene glycol, glycerin;- etc. are not only susceptible to microbial growth, but are often also slow drying due to high heats of vaporization; and are often water sensitive, which can result in problems when used on areas of the body exposed to water. One commercial product, New Skin, does dry rapidly and is not water sensitive. but can cause stinging and further irritation of the skin upon application.
SS/sas 09/16/89 .
5696s _3-A few synthetic polymers have been patented for .
use as liquid adhesive coatings for bandage applications, most notably polymers containing 2-hydroxyethyl methacrylate (U. S. 4,303,066). These bandages based on the use of solvents can sting abraded areas; and the films can swell and wash off when in contact with water. U.S. 4,569,784 claims an ointment, not a long lasting bandage composed of an emulsion of water and silicone fluids, among other fluids. This reference can provide for an immediate soothing, but often not long lasting, treatment of the skin or mucous membranes. It also does not provide for fast drying, abrasion resistance, and other attributes which a polymer film can provide.
Additionally, traditional wound and surgical bandages, such as Band-Aids (Johnson & Johnson, New Brunswick; NJ), comprised of film backings with adhesive, may contain silicones as part of either the adhesive or the backing (e. g. U.S. 4,650,817).
These products are not applied as liquid adhesive coating where films form and adhere directly on the skin.
SS/sas 5696s SUMMARY OF THE INVENTI
It is an object of the invention to provide a , liquid polymer-containing coating material which can act as a bandage or dressing to protect wounds; when applied in liquid form and air dried on the wound to form an adherent, solid protective film without significant stinging to the skin or mucous membranes of the user.
It is a further object of the invention to provide a coating which will prevent further microorganism or particulate contamination to skin or mucous membrane wounds or incisions.
It is a further object of the invention to provide a non-tacky, L_ransparent covering which does not attract or hold dirt and can remain colorless and clear for wound view:~ng as well as cosmetic attractiveness.
It is a Further object'of the invention to provide a coating which; when applied, will control body fluid loss from an abraded area:
It is a further object of the invention to provide a polymer film in which medicants or other active agents, e.g. perfumes, may be incorporated for gradual release into targeted areas.
Tt is a further object of the invention to provide a coating which, when applied, repels liquid H20, but also allows H20 vapor to pass through.
SS/sas 5696s _S-It as a further object of the invention to provide a low-surface tension covering which can reduce drag.
The liquid polymer containing coating materials of this invention consist essentially of a siloxane containing polymer and a solvent system comprising a polar solvent in small amount and a volatile liquid which is non-stinging to a user but provides bulk and formability to the liquid. Preferably the polymer is present from 1 to 40% by weight, the volatile liquid from 59.9 to 98.9% by weight and the polar solvent from 0.1 to 10% by weight. When the polar solvent is el~.minated, the volatile liquid can be in amounts of 60 to 99%. The solvent is minimized to obtain flowability desired at the lowest solvent level feasable which minimizes stinging. The material forms a coating or bandage in the form of a dried film when applied to a surface or the skin of a user.
Preferably, the siloxane containing polymer comprises at least one vinyl-containing alkylsiloxysilane and an addition polymerizable comonomer. The volatile liquid is preferably a polydimethylsiloxane.
It is a feature of the invention that the liquid materials can act at room temperature (20°C) when ~~~~!~~4~
Roa9~/7ooa ss/sas 09/16/$9 .
5696s _ _6_ applied to skin, nails, or mucous membranes of a user to form films in minutes which films are excellent bandages. They are not a nutrient source for microorganisms, are conformable, comfortable and can be elastic and flexible. The films do not irritate the skin and mucous membrane when sprayed or deposited in any way during application and in use after drying. The bandages are substanially painless and can be easily removed substantially without pain. The dried bandages formed are substantially non-water-sensitive, and waterproof and have high water vapor and oxygen gas transmission therethrough. The bandages form when applied over surfaces wet with water , blood or body fluids, in short times at standard room temperature and reasonable variants thereof. The liquid composition and/or dried polymer film can have various medicaments or other agents incorporated therein for maintaining sterility and/or for release to the underlying area of the body of a user. For example, perfumes, antibacterial or similar materials can be released from the coatings.
SS/sas 5696s DESCRIPTION OF PREFERRED EMBODIMENTS
The siloxane-containing polymers of this invention can comprise vinyl-containing alkylsiloxysilanes alone or as co-, ter- or multi-component polymers which can include other polymerizable monomers that do not make the polymers hydrophilic.
Typical vinylalkylsiloxysilanes that may be utilized are:
3-methacryloyloxypropyltris(trimethylsiloxy)silane (TRIS);
3-methacryloyloxypropylpentamethyldisiloxane;
3-methacryloyloxypropylbis(trimethylsiloxy)methyl-silane;
3-acryloyloxypropylmethylbis(trimethylsiloxy)silane;
3-acryloyloxypropyltris(trimethylsiloxy)silane; and others.
Typical addition polymerizable monomers which may be reacted with the vinylalkylsiloxysilanes to form multipolymers are: methyl methacrylate, methyl acrylate, tetrahydrofurfuryl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, n-lauryl acrylate, n-lauzyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isodecyl acrylate, isodecyl SS/sas 5696s _ _8-methacrylate, isooctyl acrylate, isooctyl methacrylate, isobornyl acrylate, isobornyl rrethacrylate, benzyl methacrylate, benzyl acrylate, 2-phenyl ethyl acrylate, n-tridecyl acrylate, 2-butoxyethyl rr~thacrylate, furfuzyl aczylate, 2-butoxyethyl.acrylate, n-butyl acrylate, n-butyl methaczylate, itaconate, di-n-butyl itaconate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, furfuryl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, isobutyl acrylate, isobutyl .
methacrylate, isopropyl rr~thacrylate, isopropyl acrylate, methyl acrylate, alpha methyl styrene, styrene, p-t-butyl styrene, 4-methoxystyrene, n-octadecyl acrylate, n-octadecyl methacrylate, 2-phenylethyl methacrylate, n-tridecyl methacrylate, vinyl benzoate, vinyl naphthalene. In addition fluorinated siloxanes, fluorinated itaconates, fluorinated methacrylates or acrylates, such as hexafluoroisopropyl methacrylate, can be used.
Any hydrophobic polymerizable monomer can be used as long as the resulting copolymer has desired 02 and H20 vapor permeability. These additional polymerizable comonomers can be present _ in amounts up to 0.85 mole fraction.
The polymers of the invention are preferably in proportions between about 15-100 mole%
vinylalkylsiloxysilane which component maintains the ~~~~~'~4~
SS/sas 09/16/89 .
5696s _ _9_ desired compatibilty of the polymer in the volatile liquid polydimethylsiloxanes with polar additives, provides high moisture and oxygen permeability, and provides biocompatibility. A range o~ 20 to 40 mole % of the vinylalkylsiloxysilane in the polymer is preferred in the polymer of this invention. Other addition polymerizable monomers may be copolymerized with the vinylalkylsiloxysilanes between about 0-85%
mole of the polymer composition to adjust permeability, adhesion, toughness, elasticity, temperature stability, and impact resistance, among other film qualities.
The polymers may be linear, branched, or slightly cross-linked and can be homo-, co-, ter- or multi-polymers. They may be random copolymers or segmental in nature.
Typical vinylalkylsiloxysilane monomers can have the following formulas.
Roa9a/~ooa SS/sas 5696s CHZ=C(R1)COORaSiR3R4R5 Where Rl -. H, CH3. or CH2COOR', , Where R2 - alkyl (C1 - C4) or CH2CH(OH)CH2, Where R3, R4, R5 = OSi(Y)3, or alkyl (C1 - C6).
Wherein, at least one of R3, R4, R5 -OSi(Y)3 Where Y = alkyl (C1 - C6) OSi(Z)8 or R200C( R1 ) C-=CHa , Where Z = alkyl (C1 - C6), aryl, and Where R' = R~SiR3R~R5 ss/sas 09/16/x9 .
5696s The polymers may have molecular weights from 50,000 to several million. The preferred molecular weight range is 50,000 to 500,000 weight average molecular weight. Lower molecular weight polymers have notably higher solubility in the solvents and solvent systems of this invention and hence, while they can be film formers, they generally are slow to dry and remain tacky. Higher molecular weight polymers are not soluble or dispensable in the solvents or solvent systems of this invention and therefore do not provide optimum film formation or flow properties. It is important for quick, non-tacky drying of the wound dressing that the polymer be in a poor solvent system. This is achieved by monomer choice, molecular weight control, and solvent system choice. The molecular weight of the polymers may be controlled by varing initiator, initiator concentration, reaction temperature, reaction solvent, and/or reaction method.
Any free radical initiator can be used in forming the polymers including azobisisobutyronitrile;
2,2'-azobis-(2,4-dimethylpentanenitrile);
2,2'-azobis- (2-methylbutanenitrile); potassium persulfate; ammonium persulfate; benzoyl peroxide;
2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane;
SS/sas 5s96s and the like. The polymerization can be carried out by solution, emulsion, or suspension techniques.
The polymers of the invention are incorporated into a solvent system comprising volatile liquid silicones. preferably polydimethylsiloxane (preferably having a solubility parameter of 6.8 -7.2 (cal/cm3 1/~) and if desired, a small amount (0.1-10 wt~) of polar liquid (preferably having a solubility parameter greater than or equal to 9 (cal/cm3 1/2), By utilizing a solvent system of this nature, the cast films dry more rapidly and are less sticky during drying. Moreover, the polar liquid or solvent can be used in minimized amount to minimize stinging. Volatile polydimethylsiloxanes (e. g. hexamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane or octamethyl trisiloxanes and the like), are non-stinging, have a low heat of vaporization, are inert, and are non-irritating. The use of these ' liquids simply or in combination as the primary liquid phase of the liquid coating provides for comfort to a wounded area when used as a bandage, rather than further irritation and also allows for a higher oxygen and moisture vapor permeation rate while present.
SS/sas 5696s The polar liquid or solvent when used preferably is a substance with a solubility parameter greater than or equal to 11.0 (cal/cm3 1/2), such as:
ethanol, 95% ethanol-5% water, isopropanol, propanol, diethylene glycol, propylene glycol, triethylene glycol, ethylene glycol, N-methyl pyrrolidone or glycerol.
Alcohols, esters, such as acetates, and organic acids, such as acetic acid, can also be used as the polar solvent. The polar liquids can function to further chain extend the polymer incorporated into the liquid polydimethylsiloxanes. The polydimethylsiloxanes are not true solvents for the polymers of the invention and the preferred polar liquids are solvents. The combination of the polydimethylsiloxanes and the polar solvents causes the polymers to chain extend and flow as liquids.
In some cases, the polar liquid need not be used where solubility modification is not required. When polymers of the invention are of lower molecular weight in the range of 100,000 or lower, they generally can be incorporated into the polydimethylsiloxane solvent without the_ addition of adjunctive polar solvent. Also, if the polymers of the invention are not purified by precipitation, but rather distillation, when the reaction liquor is polydimethysiloxane, the polymers of the invention ~S/sas 5696s _14_ remain incorporated and do not require adjunctive polar solvent. Thus, the coating of this invention can be made without the use of polar liquids in some cases. The polymers can be synthesized in the organic liquid such as neat hexamethylene disiloxane, without precipitation or separation of the polymer phase. The unreacted monomers can then be distilled out of the reaction liquor, after polymerization is essentially complete, leaving the polymer dissolved in the reaction liquor to produce useful, non-toxic coating compositions.
Polymer films of the invention cast from liquids containing good solvents with solubility parameters of between about 9 to 10 (cal/cm 3 1/2)~ (e. g.
tetrahydrofuran and ethyl acetate) will function, but are generally slow to dry and remain tacky for extended periods.
Other substances may be added to the liquid material or formulation for plasticization, improved adhesion, or rheology control, and the like.
Typical plasticizer/adhesion promoters are dibutylphthalate, acetyl tributyl citrate, sucrose acetate isobutyrate, sucrose benzoate, acetyltriethyl citrate, mineral oil, decamethyl cyclopentasiloxane, octamethyl cyclotetrasiloxane, butyl glycolate, and others.
~~~'~~~!~8 SS/sas Typical rheolagy additives that may be utilized are fumed silica, bentonite and other clay derivatives,and saturated fatty acids, such as hydrated ricinoleic acid.
The liquid adhesive material, composed of the polymer, solvent system, and additives, is useful for protecting or treating skin, nails and mucous membranes, e.g., skin cuts, abrasions, incisions and blisters; dry cracked skin; abraded gums and other oral sufaces; hemorrhoids and abraded body areas;
inflammed digestive tract; and, other mucosal membrane incision and wounds.
As the liquid bandage is non-stinging and instantly covers exposed nerve endings, pain is stopped immediately. The bandage remazns adherent to the skin/mucosa.l surface for 1-3 days, relieving pain and gradually lifting off without creating damage or further irritation.
Normal unabraded skin looses moisture vapor at an average rate of 200 g/m2/day in most areas; the palms of the hand and soles of the feet respire at an average of 500 g/m2/day. The liquid adhesive bandages of this invention have moisture vapor transmission rates of 200-700 g/m2/day depending on protective polymer film thicknesses (0.0005-O.OlO inches), thus preventing both SS/sas 5696s dehydration of wounded areas and occlusion of body fluids. The polymers of this invention have exceptional oxygen permeability (DK) of about 60 to 180 x 10-a (cr~/sec) (ml OZ/ml mm Hg) and preferably about 120 x 10-u (crr~/sec) (ml Oz/ml mm Hg) and the liquid adhesive coatings and bandages incorporating these polymers have oxygen permeability of about 80 x 10-11 (cm2/sec) (ml 02/ml mm Hg) at 35°c.
The liquid adhesive coatings of this invention may be applied to the skin, mucous membranes, etc.
in liquid form by utilization of a brush, rod, finger, sponge, cloth, dropper, etc; in spray or mist form; or any other usable technique for applying a liquid to a surface.
Medicants may be incorporated into the liquid or solid, dried film bandages for ready or continual release as the invention provides for an inert, longlasting, highly permeable film which can contain medicant or other active agents to be applied to the skin, mucous membranes, and other body areas on which it is desired to release the active agent over an extended period of time. Examples of useful medicants are fungicides, antibacterial agents, antiviral agents, antitumor agents, blood pressure and heart regulators, and many more. Other types of active agents which may be desirable to incorporate ~~I~~~~~~
SS/sas 09/~.6/s9 5696s include perfumes, plant growth regulators, plant insecticides, UV and IR absorbers, etc.
The liquid adhesive coating of this intention could be used for applications other than medical body care. For instance, the coating could be used as a water repellent, yet H20 vapor permeable, film applied to sanitary napkins, diapers, or panties. With the incorporation of mildewcides, the liduid adhesive coating could be used to cover grout in tiled surfaces. The liquid adhesive is also useful as an insulative layer in the manufacture of electronic devices such as printed circuits, integrated circuits and interconnects. The liquid adhesive coating is further useful as a sunscreen with the incorporation of W absorbers. Still other uses include forming films for use in eliminating chapped lips, treating skin and internal body surfaces, and providing protection to skin and other surfaces which may be medicated prior to application.
The following examples and test results are illustrative of the invention but are not meant to be limiting thereof:
~srarurnr.~ ~
A 500 ml resin kettle with overhead stirrer, N2 inlet, condenser, and oil bath was set up in a SS/sas 5696s _18_ hood. 14.25 g (0.034 mol) of 3-methacryloyloxypropyl(trimethylsiloxy)silane (TRIS) and 0.75 g (0.008 mol) of methyl methacrylate were dissolved in 150 g ethyl acetate. After charging this solution to the resin kettle and heating to 78 ° C, a solution of O.1S g azobisisobutyronitrile (AIBN) in 10 g ethyl acetate was charged. The polymerization ran for 4 hours at 78° C. The low molecular weight product was precipitated into methanol, oven-dried and dissolved in hexamethyl disiloxane. When cast onto glass, the polymer in hexamethyl disiloxane produced an adherent, tacky film which can be used as a pressure sensitive adhesive for a variety of substrates such as glass, or can be used as an adhesive for a bandage of cloth or plastic substrate.
A 50m1 reaction flask was charged with 2.5 g ethyl acetate, 2.5g (0.006 mol) (TRIS) and 0.09 g 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane;
flushed with nitrogen for 15 minutes, and completely closed to air. The polymerization was run for 94 hours at 65° C. The low molecular weight product when cast provided an elastic, waxy continuous film which was readily soluble in hexamethyl disiloxane.
~d~~~~~~
SS/sas 5696s To a 50 ml reaction flask was charged 19.76 g ethyl acetate; 4.28 g (0.010 mol) TRIS, 0.788 (0.008 mol) methyl methacrylate, 0.29 g (0.002 mol) cyclohexyl methacrylate, and 0.003 g azobis(isobutyronitrile). The reaction mixture was flushed with nitrogen for 20 minutes and then stoppered. The polymerization was run at 60-70°C
fox approximately l0 days. A film cast from the mother liquor was non-tacky, elastic, and relatively tough. The dried polymer was marginally soluble in hexamethyl disiloxane.
To a 50 ml reaction flask was charged 20.16 g ethyl acetate, 2.51 g (0.006 mol) TRIS, 2.01 g (0.02 mol) methyl methacrylate, 0:25 g (0.001 mol) 2-ethylhexyl acrylate, and 0.003 g azbis(isobutyronitrile). The reaction mixture was flushed with nitrogen and then stoppered. The polymerization was run at 60-70° C for 4 days. A
film cast from the mother liquor was clear, adherent, flexible and tough. The dried polymer was ~~~~.:~~~~~
SS/sas 5696s -20- _ marginally soluble in hexamethyl disiloxane, A
0.016 in. thick film past from the mother liquor had a moisture vapor transmission rate of 83 g/m2/24 h; a 0.0045-0.005 in. thick film had a moisture transmission rate of 126 g/m2/24h; and, a 0.0025-0.003 in. thick film had a moisture vapor transmission rate of 180 g/m2/24h.
To a 50 ml reaction flask was charged 19.19 g ethyl acetate, 2.2g (0.005 mol) TRIS, 3.78 g (0.027 mol) n--butyl methacrylate, and 0.002 g azobisisobutyronitrile. After flushing with nitrogen, the flask was stoppered, the reaction run at 60-70° C for 6 days. The resultant polymer was precipitated into methanol and dried at 110° C for 4 hours. The dried polymer was incorporated into hexamethyl disiloxane. A 0.025 in. thick film of the polymer cast from the mother liquor gave a moisture vapor transmission rate of 37.9 g/m2/24h.
A 50o ml resin kettle, equipped as in Example 1, was charged with 27.40 g (0.065 mol) TRIS, 18.54 g (0.185 mol) methyl methacrylate, 4.10 g (0.022 mol) SS/sas 5696s 2- ethylhexyl acrylate, and 194 g ethyl acetate.
After heating to 48°C, 0.01 g of 2,2'-azobis (2,4-dimethylpentanenitril2) dissolved in 3.09 g ethyl acetate was added and the polymerization run for 16 hours. At which time, 0.01 g of 2,2'-azobis (2,4-dimethylpentanenitrile) dissolved in 3.09 g ethyl acetate was again added to the reaction continued to run for another 24 hours. The product was precipitated in methanol and air dried. The dried product was partially soluble in hexamethyl disiloxane.
Preciptated and dried polymer (1.02 g) from Example 6 was dissolved in 4.02 g ethyl acetate, when cast into a 0.004 in film, provided a moisture vapor rate of 126 g/m2/42h.
EXAMPLE g Preciptated dried polymer (1.01 g) from Example 6 was dissolved in 5.40 g ethyl acetate with sucrose acetate isobutyrate (0.34g). This formulation provided an adherent, non-tacky film with a moisture SS/sas 5696s -22- _ vapor transmission rate of 180 g/m2/24h at a 0.0035 in. film thickness, and 613 g/m2/24h at 0.0005-0.001 in. film thickness.
Precipitated dried polymer (1.05 g) from Example 6 was dissolved in 5.44 g ethyl acetate and 0.31 g decamethyl cyclopentasiloxane, and then cast into a 0.004 in, film provided a moisture vapor transmission rate of 180 g/m2/24h.
Precipitated dried polymer (1.04 g) from Example 6 was dissolved in 6.76 g ethyl acetate and 0.65 g decamethyl cyclopentasiloxane, and when cast into a 0.0002 in film provided a moisture vapor transmission rate of 866 g/m2124h.
A 50 ml reaction flask was charged with 30 g ethyl acetate, 5 g (0.012 mol)TRIS, 0.8 g (0.004 mol) 2-ethylhexyl acrylate, 4.2 g (0.029 mol)n-butylmethacrylate, and 0.4 g of a 0.36%
SS/sas 5696s solution of 2,2'-azobis(2,4-dimethylpentanenitrile) in ethyl acetate. After nitrogen flushing for 20 minutes, the flask was stoppered and placed in a 40°C oven for 5 days, After precipitation in methanol and air drying, the resultant polymer was soluble in hexamethyl disiloxane containing some methanol.
To a reaction, equipped as in Example 1, was charged 10.35 g (0.025 mol) TR2S, 3.87 g (0.039 mol) methyl methacrylate, 3.87 g (0.034 mol) ethyl methacrylate, 0.02 g 2,2'-azobis (2-methyl butanenitrile), and 42.0 g hexamethyldisiloxane (HMDS). The polymerization was run 6 hours at 80°
C and then terminated by the addition of air. The polymer was precipitated into cold methanol with a resultant 86% yield of polymer, Films (0.0014-0.0018 in. thick) cast from the mother liquor produced moisture vapor transmission rates of 630 g/m2/24 h.
To a reaction, equipped as in Example 1, was Charged 49.5 g (0.117 mol) TRIS, 20.0 g (0.2 mol) SS/sas 5696s -24- .
methyl methacrylate, 20.7 g (0.18 mot) ethyl methacrylate, 0.08 g 2,2'-azobis(2-methyl-butanenitrile), 105.01 g 95% ethanol, and 105.03 g HMDS. The polymerization was run for 24 hours at reflux, 74° C. The polymer was then precipitated into water, washed repeatedly, and oven dried at 250°F for 6 hours to produce an 86% yield. The resultant polymer had a l~ of 164,200, Mn of 114,600 and a polydispersity ratio of 1.43.
A 1000 ml resin kettle equipped as in Example 1 was charged with 210 g hexamethyl disiloxane, 210 g 95% ethanol, 99.21 g (0.235 mol) TRIS, 40.09 g (0.400 mol) methyl methacrylate, 40.09 g (0.351 mol) ethyl methacrylate, and 0.16 g 2,2'-azobis-(2-methylbutanenitrile) and the reaction ran at 75° C for 22 hours. The polymer was then precipitated into water and dried for 12 hours at 110° C to give an 89% yield. When incorporated into ' 435 g hexamethyl disiloxane and 5.06 g 95% Pthanol, the polymer (65.80 g) provided a cast film with an oxygen permeability of 120 x 10 11 (cm2/sec) (ml 02/ml mm Hg) at 35° C.
SS/sas 5696s The polymer (1.26 g) of Example 14 was incorporated into a liquid adhesive bandage composition composed of 0.10 g 95% ethanol, 0.15 g sucrose acetate isobutyrate, 8.22 g hexamethyl disiloxane, and O.Ol g Thixin R (NL Chemicals, Hightstown, NJ). The resultant cast film; after two weeks of aging at room temperature, has an oxygen permeabilty of 80 x 10 11 (cm2/sec) 4m1 02/ml mm Hg) at 35°C.
The resultant dried polymer (2.34 g) from Example 14 was added to 15.30 g hexamethyl disiloxane, 0.36 g ethanol, and 0.18 g sucrose acetate isbutyrate. Films (0.002-0.003 in. thick) cast from'thisliquid coating formulation produced moisture vapor transport rates of 340 +/- 20 g/m2/24 h.
ExAMPLE 17 To 3.97 g of polymer prepared as in Example 14 were added 0.29 g 95% ethanol, 0.61 g octamethyl cyclotetrasiloxane, 0.29 g sucrose acetate SS/sas 5696s .-2s-isobutyrate, and 23.65 g hexamethyldisiloxane. The liquid adhesive bandage composition produced moisture vapor transport rates of 285 g/m2/24 h from a 0.004 in film, 560 g/m2/24 hr from a 0.001 in film, and 610 g/m2/24 hr from a 0.0005 in film.
Liquid adhesive coating formulations prepared as in Example 17 were used on numerous occasions on minor cuts and abrasions by male and female human adults for the relief of pain. In each case, wound pain was relieved immediately upon application of the liquid bandage. The individuals had full use of the wounded areas without pain during healing.
An adult male accidentally cut off the tips of his right middle and index fingers excising at least the epidermis and the dermis; he applied the liquid bandage formulation as prepared in Example 17 and found immediate complete relief from pain. He reapplied the bandage once a day. During healing he had full use of his fingers without pain. The wound did not form a scab and healed without scarring.
Roa9a/7ooa salsas 5696s _27_ EXAMPLE a0 An adult male accidentally sheared off the back of one of his teeth exposing the nerve. Upon application of the liquid bandage, as prepared in Example 17, he found immediate relief of pain. He applied the bandage once a day for two days until he could see a dentist for repair to the tooth. The bandage remained adherent to the tooth and surrounding gingival and periodontal tissue during utilization.
EXAMPLE 21.
Two teenage males and one teenage female covered poison ivy inflammations with a liquid bandage, prepared as in Example 17 except in aerosol farm, and found~immediate complete relief from itching.
They treated the poison ivy throughout its term and were not bothered by itching.
An adult male accidentally cut himself with a knife on his left index finger, upon applying liquid bandage prepared as in Example 17, the wound pain i~~~~~~s~~~
SS/sas 5696s was relieved immediately. The wound healed in two to three days with no scab formation or scarring.
An adult male applied a liquid bandage, prepared as in Example 17 except in aerosol form, to hemorrhoids and obtained relief from the pain caused by the condition.
An adult male applied a liquid bandage, prepared as in Example 17 except in aerosol form, to mosquito bites and completely relieved all itching associated with these bites.
To 22.08 g of liquid bandage prepared as in Example 17 was added 0.41 g of isopropyl xanthic disulfide, a fungicide. The isopropyl xanthic disulfide was completely soluble in the liquid bandage formulation both in liquid form and when dried. The dried film was transparent yellow in color.
SS/sas 5696s . -29-A 1000 ml. reaction kettle equipped with an overhead stirrer, N2 purge, condenser; and heating mantle is charged with 70 g hexamethyl disiloxane, 16.5 g (0.039 mol.) TRIS, 13.2 g (0.1.32 mol.) methylmethacrylate, 0.30 g (0.002 mol.) iso-octyl acrylate, and 0.026 g 2,5-dimethyl-2,5-bis(2-ethyl-hexanoylperoxy)hexane is charged, After the reaction is terminated by the addition of air and lowering of temperature, the reaction liquor is added to water. The hexamethyldisiloxane is evaporated and the precipitated polymer dried at 105°C for 12 hours to give a 69~% yield. The resultant polymer (2.99 g) when incorporated into 11.96 g hexamethyldisiloxane and .04 g. 95% ethyl alcohol produces a tough, elastic, adherent film.
The reaction of Example 26 is terminated after 18 hours at 74°C by the addition of air. The temperature is then raised to 100°C to allow distillation of the hexamethyldisiloxane containing unreacted methylmethacrylate and isooctylacrylate.
The distillate is filtered through a charcoal-containing column to trap unreacted ~~~~~~ o9~S
SS/sas 09/16/8) 5696s _g0_ monomers and circulated back to the reaction kettle. The resultant purified liquid product produces a tough, elastic, adherent film when cast.
The above examples are representative of specific embodiments of the present invention.
However, many variations are possible. In all forms, the liquid polymer containing coating material of this invention contains a siloxane-containing polymer and a solvent system comprising a major portion of a polydimethylsiloxane or mixture of such siloxanes and, if desired, a minor portion of a polar liquid or solvent or mixture thereof. In all cases the invention provides a method of forming a bandage on the body by applying a liquid polymer containing bandage formulation or material to the body and volatilizing the solvent system to form a bandage, which is adherent to the body while providing good moisture transmission properties and projecting the skin or body surface of the user.
3-methacryloyloxypropylpentamethyldisiloxane;
3-methacryloyloxypropylbis(trimethylsiloxy)methyl-silane;
3-acryloyloxypropylmethylbis(trimethylsiloxy)silane;
3-acryloyloxypropyltris(trimethylsiloxy)silane; and others.
Typical addition polymerizable monomers which may be reacted with the vinylalkylsiloxysilanes to form multipolymers are: methyl methacrylate, methyl acrylate, tetrahydrofurfuryl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, n-lauryl acrylate, n-lauzyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, isodecyl acrylate, isodecyl SS/sas 5696s _ _8-methacrylate, isooctyl acrylate, isooctyl methacrylate, isobornyl acrylate, isobornyl rrethacrylate, benzyl methacrylate, benzyl acrylate, 2-phenyl ethyl acrylate, n-tridecyl acrylate, 2-butoxyethyl rr~thacrylate, furfuzyl aczylate, 2-butoxyethyl.acrylate, n-butyl acrylate, n-butyl methaczylate, itaconate, di-n-butyl itaconate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, furfuryl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, isobutyl acrylate, isobutyl .
methacrylate, isopropyl rr~thacrylate, isopropyl acrylate, methyl acrylate, alpha methyl styrene, styrene, p-t-butyl styrene, 4-methoxystyrene, n-octadecyl acrylate, n-octadecyl methacrylate, 2-phenylethyl methacrylate, n-tridecyl methacrylate, vinyl benzoate, vinyl naphthalene. In addition fluorinated siloxanes, fluorinated itaconates, fluorinated methacrylates or acrylates, such as hexafluoroisopropyl methacrylate, can be used.
Any hydrophobic polymerizable monomer can be used as long as the resulting copolymer has desired 02 and H20 vapor permeability. These additional polymerizable comonomers can be present _ in amounts up to 0.85 mole fraction.
The polymers of the invention are preferably in proportions between about 15-100 mole%
vinylalkylsiloxysilane which component maintains the ~~~~~'~4~
SS/sas 09/16/89 .
5696s _ _9_ desired compatibilty of the polymer in the volatile liquid polydimethylsiloxanes with polar additives, provides high moisture and oxygen permeability, and provides biocompatibility. A range o~ 20 to 40 mole % of the vinylalkylsiloxysilane in the polymer is preferred in the polymer of this invention. Other addition polymerizable monomers may be copolymerized with the vinylalkylsiloxysilanes between about 0-85%
mole of the polymer composition to adjust permeability, adhesion, toughness, elasticity, temperature stability, and impact resistance, among other film qualities.
The polymers may be linear, branched, or slightly cross-linked and can be homo-, co-, ter- or multi-polymers. They may be random copolymers or segmental in nature.
Typical vinylalkylsiloxysilane monomers can have the following formulas.
Roa9a/~ooa SS/sas 5696s CHZ=C(R1)COORaSiR3R4R5 Where Rl -. H, CH3. or CH2COOR', , Where R2 - alkyl (C1 - C4) or CH2CH(OH)CH2, Where R3, R4, R5 = OSi(Y)3, or alkyl (C1 - C6).
Wherein, at least one of R3, R4, R5 -OSi(Y)3 Where Y = alkyl (C1 - C6) OSi(Z)8 or R200C( R1 ) C-=CHa , Where Z = alkyl (C1 - C6), aryl, and Where R' = R~SiR3R~R5 ss/sas 09/16/x9 .
5696s The polymers may have molecular weights from 50,000 to several million. The preferred molecular weight range is 50,000 to 500,000 weight average molecular weight. Lower molecular weight polymers have notably higher solubility in the solvents and solvent systems of this invention and hence, while they can be film formers, they generally are slow to dry and remain tacky. Higher molecular weight polymers are not soluble or dispensable in the solvents or solvent systems of this invention and therefore do not provide optimum film formation or flow properties. It is important for quick, non-tacky drying of the wound dressing that the polymer be in a poor solvent system. This is achieved by monomer choice, molecular weight control, and solvent system choice. The molecular weight of the polymers may be controlled by varing initiator, initiator concentration, reaction temperature, reaction solvent, and/or reaction method.
Any free radical initiator can be used in forming the polymers including azobisisobutyronitrile;
2,2'-azobis-(2,4-dimethylpentanenitrile);
2,2'-azobis- (2-methylbutanenitrile); potassium persulfate; ammonium persulfate; benzoyl peroxide;
2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane;
SS/sas 5s96s and the like. The polymerization can be carried out by solution, emulsion, or suspension techniques.
The polymers of the invention are incorporated into a solvent system comprising volatile liquid silicones. preferably polydimethylsiloxane (preferably having a solubility parameter of 6.8 -7.2 (cal/cm3 1/~) and if desired, a small amount (0.1-10 wt~) of polar liquid (preferably having a solubility parameter greater than or equal to 9 (cal/cm3 1/2), By utilizing a solvent system of this nature, the cast films dry more rapidly and are less sticky during drying. Moreover, the polar liquid or solvent can be used in minimized amount to minimize stinging. Volatile polydimethylsiloxanes (e. g. hexamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane or octamethyl trisiloxanes and the like), are non-stinging, have a low heat of vaporization, are inert, and are non-irritating. The use of these ' liquids simply or in combination as the primary liquid phase of the liquid coating provides for comfort to a wounded area when used as a bandage, rather than further irritation and also allows for a higher oxygen and moisture vapor permeation rate while present.
SS/sas 5696s The polar liquid or solvent when used preferably is a substance with a solubility parameter greater than or equal to 11.0 (cal/cm3 1/2), such as:
ethanol, 95% ethanol-5% water, isopropanol, propanol, diethylene glycol, propylene glycol, triethylene glycol, ethylene glycol, N-methyl pyrrolidone or glycerol.
Alcohols, esters, such as acetates, and organic acids, such as acetic acid, can also be used as the polar solvent. The polar liquids can function to further chain extend the polymer incorporated into the liquid polydimethylsiloxanes. The polydimethylsiloxanes are not true solvents for the polymers of the invention and the preferred polar liquids are solvents. The combination of the polydimethylsiloxanes and the polar solvents causes the polymers to chain extend and flow as liquids.
In some cases, the polar liquid need not be used where solubility modification is not required. When polymers of the invention are of lower molecular weight in the range of 100,000 or lower, they generally can be incorporated into the polydimethylsiloxane solvent without the_ addition of adjunctive polar solvent. Also, if the polymers of the invention are not purified by precipitation, but rather distillation, when the reaction liquor is polydimethysiloxane, the polymers of the invention ~S/sas 5696s _14_ remain incorporated and do not require adjunctive polar solvent. Thus, the coating of this invention can be made without the use of polar liquids in some cases. The polymers can be synthesized in the organic liquid such as neat hexamethylene disiloxane, without precipitation or separation of the polymer phase. The unreacted monomers can then be distilled out of the reaction liquor, after polymerization is essentially complete, leaving the polymer dissolved in the reaction liquor to produce useful, non-toxic coating compositions.
Polymer films of the invention cast from liquids containing good solvents with solubility parameters of between about 9 to 10 (cal/cm 3 1/2)~ (e. g.
tetrahydrofuran and ethyl acetate) will function, but are generally slow to dry and remain tacky for extended periods.
Other substances may be added to the liquid material or formulation for plasticization, improved adhesion, or rheology control, and the like.
Typical plasticizer/adhesion promoters are dibutylphthalate, acetyl tributyl citrate, sucrose acetate isobutyrate, sucrose benzoate, acetyltriethyl citrate, mineral oil, decamethyl cyclopentasiloxane, octamethyl cyclotetrasiloxane, butyl glycolate, and others.
~~~'~~~!~8 SS/sas Typical rheolagy additives that may be utilized are fumed silica, bentonite and other clay derivatives,and saturated fatty acids, such as hydrated ricinoleic acid.
The liquid adhesive material, composed of the polymer, solvent system, and additives, is useful for protecting or treating skin, nails and mucous membranes, e.g., skin cuts, abrasions, incisions and blisters; dry cracked skin; abraded gums and other oral sufaces; hemorrhoids and abraded body areas;
inflammed digestive tract; and, other mucosal membrane incision and wounds.
As the liquid bandage is non-stinging and instantly covers exposed nerve endings, pain is stopped immediately. The bandage remazns adherent to the skin/mucosa.l surface for 1-3 days, relieving pain and gradually lifting off without creating damage or further irritation.
Normal unabraded skin looses moisture vapor at an average rate of 200 g/m2/day in most areas; the palms of the hand and soles of the feet respire at an average of 500 g/m2/day. The liquid adhesive bandages of this invention have moisture vapor transmission rates of 200-700 g/m2/day depending on protective polymer film thicknesses (0.0005-O.OlO inches), thus preventing both SS/sas 5696s dehydration of wounded areas and occlusion of body fluids. The polymers of this invention have exceptional oxygen permeability (DK) of about 60 to 180 x 10-a (cr~/sec) (ml OZ/ml mm Hg) and preferably about 120 x 10-u (crr~/sec) (ml Oz/ml mm Hg) and the liquid adhesive coatings and bandages incorporating these polymers have oxygen permeability of about 80 x 10-11 (cm2/sec) (ml 02/ml mm Hg) at 35°c.
The liquid adhesive coatings of this invention may be applied to the skin, mucous membranes, etc.
in liquid form by utilization of a brush, rod, finger, sponge, cloth, dropper, etc; in spray or mist form; or any other usable technique for applying a liquid to a surface.
Medicants may be incorporated into the liquid or solid, dried film bandages for ready or continual release as the invention provides for an inert, longlasting, highly permeable film which can contain medicant or other active agents to be applied to the skin, mucous membranes, and other body areas on which it is desired to release the active agent over an extended period of time. Examples of useful medicants are fungicides, antibacterial agents, antiviral agents, antitumor agents, blood pressure and heart regulators, and many more. Other types of active agents which may be desirable to incorporate ~~I~~~~~~
SS/sas 09/~.6/s9 5696s include perfumes, plant growth regulators, plant insecticides, UV and IR absorbers, etc.
The liquid adhesive coating of this intention could be used for applications other than medical body care. For instance, the coating could be used as a water repellent, yet H20 vapor permeable, film applied to sanitary napkins, diapers, or panties. With the incorporation of mildewcides, the liduid adhesive coating could be used to cover grout in tiled surfaces. The liquid adhesive is also useful as an insulative layer in the manufacture of electronic devices such as printed circuits, integrated circuits and interconnects. The liquid adhesive coating is further useful as a sunscreen with the incorporation of W absorbers. Still other uses include forming films for use in eliminating chapped lips, treating skin and internal body surfaces, and providing protection to skin and other surfaces which may be medicated prior to application.
The following examples and test results are illustrative of the invention but are not meant to be limiting thereof:
~srarurnr.~ ~
A 500 ml resin kettle with overhead stirrer, N2 inlet, condenser, and oil bath was set up in a SS/sas 5696s _18_ hood. 14.25 g (0.034 mol) of 3-methacryloyloxypropyl(trimethylsiloxy)silane (TRIS) and 0.75 g (0.008 mol) of methyl methacrylate were dissolved in 150 g ethyl acetate. After charging this solution to the resin kettle and heating to 78 ° C, a solution of O.1S g azobisisobutyronitrile (AIBN) in 10 g ethyl acetate was charged. The polymerization ran for 4 hours at 78° C. The low molecular weight product was precipitated into methanol, oven-dried and dissolved in hexamethyl disiloxane. When cast onto glass, the polymer in hexamethyl disiloxane produced an adherent, tacky film which can be used as a pressure sensitive adhesive for a variety of substrates such as glass, or can be used as an adhesive for a bandage of cloth or plastic substrate.
A 50m1 reaction flask was charged with 2.5 g ethyl acetate, 2.5g (0.006 mol) (TRIS) and 0.09 g 2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane;
flushed with nitrogen for 15 minutes, and completely closed to air. The polymerization was run for 94 hours at 65° C. The low molecular weight product when cast provided an elastic, waxy continuous film which was readily soluble in hexamethyl disiloxane.
~d~~~~~~
SS/sas 5696s To a 50 ml reaction flask was charged 19.76 g ethyl acetate; 4.28 g (0.010 mol) TRIS, 0.788 (0.008 mol) methyl methacrylate, 0.29 g (0.002 mol) cyclohexyl methacrylate, and 0.003 g azobis(isobutyronitrile). The reaction mixture was flushed with nitrogen for 20 minutes and then stoppered. The polymerization was run at 60-70°C
fox approximately l0 days. A film cast from the mother liquor was non-tacky, elastic, and relatively tough. The dried polymer was marginally soluble in hexamethyl disiloxane.
To a 50 ml reaction flask was charged 20.16 g ethyl acetate, 2.51 g (0.006 mol) TRIS, 2.01 g (0.02 mol) methyl methacrylate, 0:25 g (0.001 mol) 2-ethylhexyl acrylate, and 0.003 g azbis(isobutyronitrile). The reaction mixture was flushed with nitrogen and then stoppered. The polymerization was run at 60-70° C for 4 days. A
film cast from the mother liquor was clear, adherent, flexible and tough. The dried polymer was ~~~~.:~~~~~
SS/sas 5696s -20- _ marginally soluble in hexamethyl disiloxane, A
0.016 in. thick film past from the mother liquor had a moisture vapor transmission rate of 83 g/m2/24 h; a 0.0045-0.005 in. thick film had a moisture transmission rate of 126 g/m2/24h; and, a 0.0025-0.003 in. thick film had a moisture vapor transmission rate of 180 g/m2/24h.
To a 50 ml reaction flask was charged 19.19 g ethyl acetate, 2.2g (0.005 mol) TRIS, 3.78 g (0.027 mol) n--butyl methacrylate, and 0.002 g azobisisobutyronitrile. After flushing with nitrogen, the flask was stoppered, the reaction run at 60-70° C for 6 days. The resultant polymer was precipitated into methanol and dried at 110° C for 4 hours. The dried polymer was incorporated into hexamethyl disiloxane. A 0.025 in. thick film of the polymer cast from the mother liquor gave a moisture vapor transmission rate of 37.9 g/m2/24h.
A 50o ml resin kettle, equipped as in Example 1, was charged with 27.40 g (0.065 mol) TRIS, 18.54 g (0.185 mol) methyl methacrylate, 4.10 g (0.022 mol) SS/sas 5696s 2- ethylhexyl acrylate, and 194 g ethyl acetate.
After heating to 48°C, 0.01 g of 2,2'-azobis (2,4-dimethylpentanenitril2) dissolved in 3.09 g ethyl acetate was added and the polymerization run for 16 hours. At which time, 0.01 g of 2,2'-azobis (2,4-dimethylpentanenitrile) dissolved in 3.09 g ethyl acetate was again added to the reaction continued to run for another 24 hours. The product was precipitated in methanol and air dried. The dried product was partially soluble in hexamethyl disiloxane.
Preciptated and dried polymer (1.02 g) from Example 6 was dissolved in 4.02 g ethyl acetate, when cast into a 0.004 in film, provided a moisture vapor rate of 126 g/m2/42h.
EXAMPLE g Preciptated dried polymer (1.01 g) from Example 6 was dissolved in 5.40 g ethyl acetate with sucrose acetate isobutyrate (0.34g). This formulation provided an adherent, non-tacky film with a moisture SS/sas 5696s -22- _ vapor transmission rate of 180 g/m2/24h at a 0.0035 in. film thickness, and 613 g/m2/24h at 0.0005-0.001 in. film thickness.
Precipitated dried polymer (1.05 g) from Example 6 was dissolved in 5.44 g ethyl acetate and 0.31 g decamethyl cyclopentasiloxane, and then cast into a 0.004 in, film provided a moisture vapor transmission rate of 180 g/m2/24h.
Precipitated dried polymer (1.04 g) from Example 6 was dissolved in 6.76 g ethyl acetate and 0.65 g decamethyl cyclopentasiloxane, and when cast into a 0.0002 in film provided a moisture vapor transmission rate of 866 g/m2124h.
A 50 ml reaction flask was charged with 30 g ethyl acetate, 5 g (0.012 mol)TRIS, 0.8 g (0.004 mol) 2-ethylhexyl acrylate, 4.2 g (0.029 mol)n-butylmethacrylate, and 0.4 g of a 0.36%
SS/sas 5696s solution of 2,2'-azobis(2,4-dimethylpentanenitrile) in ethyl acetate. After nitrogen flushing for 20 minutes, the flask was stoppered and placed in a 40°C oven for 5 days, After precipitation in methanol and air drying, the resultant polymer was soluble in hexamethyl disiloxane containing some methanol.
To a reaction, equipped as in Example 1, was charged 10.35 g (0.025 mol) TR2S, 3.87 g (0.039 mol) methyl methacrylate, 3.87 g (0.034 mol) ethyl methacrylate, 0.02 g 2,2'-azobis (2-methyl butanenitrile), and 42.0 g hexamethyldisiloxane (HMDS). The polymerization was run 6 hours at 80°
C and then terminated by the addition of air. The polymer was precipitated into cold methanol with a resultant 86% yield of polymer, Films (0.0014-0.0018 in. thick) cast from the mother liquor produced moisture vapor transmission rates of 630 g/m2/24 h.
To a reaction, equipped as in Example 1, was Charged 49.5 g (0.117 mol) TRIS, 20.0 g (0.2 mol) SS/sas 5696s -24- .
methyl methacrylate, 20.7 g (0.18 mot) ethyl methacrylate, 0.08 g 2,2'-azobis(2-methyl-butanenitrile), 105.01 g 95% ethanol, and 105.03 g HMDS. The polymerization was run for 24 hours at reflux, 74° C. The polymer was then precipitated into water, washed repeatedly, and oven dried at 250°F for 6 hours to produce an 86% yield. The resultant polymer had a l~ of 164,200, Mn of 114,600 and a polydispersity ratio of 1.43.
A 1000 ml resin kettle equipped as in Example 1 was charged with 210 g hexamethyl disiloxane, 210 g 95% ethanol, 99.21 g (0.235 mol) TRIS, 40.09 g (0.400 mol) methyl methacrylate, 40.09 g (0.351 mol) ethyl methacrylate, and 0.16 g 2,2'-azobis-(2-methylbutanenitrile) and the reaction ran at 75° C for 22 hours. The polymer was then precipitated into water and dried for 12 hours at 110° C to give an 89% yield. When incorporated into ' 435 g hexamethyl disiloxane and 5.06 g 95% Pthanol, the polymer (65.80 g) provided a cast film with an oxygen permeability of 120 x 10 11 (cm2/sec) (ml 02/ml mm Hg) at 35° C.
SS/sas 5696s The polymer (1.26 g) of Example 14 was incorporated into a liquid adhesive bandage composition composed of 0.10 g 95% ethanol, 0.15 g sucrose acetate isobutyrate, 8.22 g hexamethyl disiloxane, and O.Ol g Thixin R (NL Chemicals, Hightstown, NJ). The resultant cast film; after two weeks of aging at room temperature, has an oxygen permeabilty of 80 x 10 11 (cm2/sec) 4m1 02/ml mm Hg) at 35°C.
The resultant dried polymer (2.34 g) from Example 14 was added to 15.30 g hexamethyl disiloxane, 0.36 g ethanol, and 0.18 g sucrose acetate isbutyrate. Films (0.002-0.003 in. thick) cast from'thisliquid coating formulation produced moisture vapor transport rates of 340 +/- 20 g/m2/24 h.
ExAMPLE 17 To 3.97 g of polymer prepared as in Example 14 were added 0.29 g 95% ethanol, 0.61 g octamethyl cyclotetrasiloxane, 0.29 g sucrose acetate SS/sas 5696s .-2s-isobutyrate, and 23.65 g hexamethyldisiloxane. The liquid adhesive bandage composition produced moisture vapor transport rates of 285 g/m2/24 h from a 0.004 in film, 560 g/m2/24 hr from a 0.001 in film, and 610 g/m2/24 hr from a 0.0005 in film.
Liquid adhesive coating formulations prepared as in Example 17 were used on numerous occasions on minor cuts and abrasions by male and female human adults for the relief of pain. In each case, wound pain was relieved immediately upon application of the liquid bandage. The individuals had full use of the wounded areas without pain during healing.
An adult male accidentally cut off the tips of his right middle and index fingers excising at least the epidermis and the dermis; he applied the liquid bandage formulation as prepared in Example 17 and found immediate complete relief from pain. He reapplied the bandage once a day. During healing he had full use of his fingers without pain. The wound did not form a scab and healed without scarring.
Roa9a/7ooa salsas 5696s _27_ EXAMPLE a0 An adult male accidentally sheared off the back of one of his teeth exposing the nerve. Upon application of the liquid bandage, as prepared in Example 17, he found immediate relief of pain. He applied the bandage once a day for two days until he could see a dentist for repair to the tooth. The bandage remained adherent to the tooth and surrounding gingival and periodontal tissue during utilization.
EXAMPLE 21.
Two teenage males and one teenage female covered poison ivy inflammations with a liquid bandage, prepared as in Example 17 except in aerosol farm, and found~immediate complete relief from itching.
They treated the poison ivy throughout its term and were not bothered by itching.
An adult male accidentally cut himself with a knife on his left index finger, upon applying liquid bandage prepared as in Example 17, the wound pain i~~~~~~s~~~
SS/sas 5696s was relieved immediately. The wound healed in two to three days with no scab formation or scarring.
An adult male applied a liquid bandage, prepared as in Example 17 except in aerosol form, to hemorrhoids and obtained relief from the pain caused by the condition.
An adult male applied a liquid bandage, prepared as in Example 17 except in aerosol form, to mosquito bites and completely relieved all itching associated with these bites.
To 22.08 g of liquid bandage prepared as in Example 17 was added 0.41 g of isopropyl xanthic disulfide, a fungicide. The isopropyl xanthic disulfide was completely soluble in the liquid bandage formulation both in liquid form and when dried. The dried film was transparent yellow in color.
SS/sas 5696s . -29-A 1000 ml. reaction kettle equipped with an overhead stirrer, N2 purge, condenser; and heating mantle is charged with 70 g hexamethyl disiloxane, 16.5 g (0.039 mol.) TRIS, 13.2 g (0.1.32 mol.) methylmethacrylate, 0.30 g (0.002 mol.) iso-octyl acrylate, and 0.026 g 2,5-dimethyl-2,5-bis(2-ethyl-hexanoylperoxy)hexane is charged, After the reaction is terminated by the addition of air and lowering of temperature, the reaction liquor is added to water. The hexamethyldisiloxane is evaporated and the precipitated polymer dried at 105°C for 12 hours to give a 69~% yield. The resultant polymer (2.99 g) when incorporated into 11.96 g hexamethyldisiloxane and .04 g. 95% ethyl alcohol produces a tough, elastic, adherent film.
The reaction of Example 26 is terminated after 18 hours at 74°C by the addition of air. The temperature is then raised to 100°C to allow distillation of the hexamethyldisiloxane containing unreacted methylmethacrylate and isooctylacrylate.
The distillate is filtered through a charcoal-containing column to trap unreacted ~~~~~~ o9~S
SS/sas 09/16/8) 5696s _g0_ monomers and circulated back to the reaction kettle. The resultant purified liquid product produces a tough, elastic, adherent film when cast.
The above examples are representative of specific embodiments of the present invention.
However, many variations are possible. In all forms, the liquid polymer containing coating material of this invention contains a siloxane-containing polymer and a solvent system comprising a major portion of a polydimethylsiloxane or mixture of such siloxanes and, if desired, a minor portion of a polar liquid or solvent or mixture thereof. In all cases the invention provides a method of forming a bandage on the body by applying a liquid polymer containing bandage formulation or material to the body and volatilizing the solvent system to form a bandage, which is adherent to the body while providing good moisture transmission properties and projecting the skin or body surface of the user.
Claims (23)
1. A liquid polymer-containing bandage material comprising from 1 to 40 wt. % siloxane-containing polymer, 59.9 to 95.9 wt. % volatile polydimethylsiloxane, and 0.1 to 10 wt% polar liquid; said bandage material being substantially non-stinging and film forming at room temperature to form an adherent conformable moisture vapor permeable bandage directly on a user.
2. A liquid polymer-containing bandage material in accordance with claim 1 wherein said siloxane-containing polymer comprises at least one vinyl-containing alkylsiloxysilane monomer being present in a mole fraction of 1.0 to about 0.15 and having the following structure:
CH2=C(R1)COOR2SiR3R4R5 Where R1 - H;
CH3, or CH2COOR', Where R2 = alkyl (C1 - C4), aryl, or CH2CH(OH)CH2, Where R3, R4, R5 = OSi(Y)3, or alkyl (C1 - C6), Wherein, at least one of R3, R4, R5 =
OSi(Y)3 Where Y = alkyl (C1 - C6) OSi(Z)3 or R2OOC(R1)C=CH2 Where Z = alkyl (C1 - C6), and Where R' = R2SiR3R4R5
CH2=C(R1)COOR2SiR3R4R5 Where R1 - H;
CH3, or CH2COOR', Where R2 = alkyl (C1 - C4), aryl, or CH2CH(OH)CH2, Where R3, R4, R5 = OSi(Y)3, or alkyl (C1 - C6), Wherein, at least one of R3, R4, R5 =
OSi(Y)3 Where Y = alkyl (C1 - C6) OSi(Z)3 or R2OOC(R1)C=CH2 Where Z = alkyl (C1 - C6), and Where R' = R2SiR3R4R5
3. A liquid polymer-containing bandage material according to claim 2 wherein said siloxane-containing polymer comprises an addition polymerizable comonomer being present in a mole fraction of up to about 0.85 and is selected from the group consisting of methyl acrylate, methyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, n-lauryl acrylate, n-lauryl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, 2-phenylethyl acrylate, 2-phenylethyl methacrylate, n-tridecyl acrylate, n-tridecyl methacrylate, isodecyl acrylate, isodecyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl acrylate, benzyl methacrylate, 2-butoxyethyl acrylate, 2-butoxyethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate;
2-ethylhexyl methacrylate, furfuryl acrylate, furfuryl methacrylate, n-hexyl acrylate, n-hexyl-methacrylate, n-octadecyl acrylate, octadecyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isopropyl acrylate, isopropyl methacrylate, .alpha.-methyl styrene, styrene, p-t-butyl styrene, 4-methoxystyrene, vinyl benzoate, vinyl naphthalene, hexafluoroisopropyl methacrylate, fluorinated itaconates and admixtures thereof.
2-ethylhexyl methacrylate, furfuryl acrylate, furfuryl methacrylate, n-hexyl acrylate, n-hexyl-methacrylate, n-octadecyl acrylate, octadecyl methacrylate, isobutyl acrylate, isobutyl methacrylate, isopropyl acrylate, isopropyl methacrylate, .alpha.-methyl styrene, styrene, p-t-butyl styrene, 4-methoxystyrene, vinyl benzoate, vinyl naphthalene, hexafluoroisopropyl methacrylate, fluorinated itaconates and admixtures thereof.
4. A liquid polymer-containing bandage material according to claim 2 wherein said vinyl-containing alkylsiloxysilane monomer is 3-methacryloyloxypropyltris(trimethylsiloxy)silane.
5. A liquid polymer-containing bandage material according to claim 3 wherein said addition polymerizable comonomer is a member selected from the group consisting of methyl methacrylate, ethyl methacrylate and admixtures thereof.
6. A liquid polymer-containing bandage material according to claim 5 wherein 3-methacryloyloxypropyltris(trimethylsiloxy)silane is present in a mole fraction of about 0.2 to 0.4, methyl methacrylate is present in a mole fraction of about 0.3 to 0.4, and ethyl methacrylate is present in a mole fraction of about 0.3 to 0.4.
7. A liquid polymer-containing bandage material according to claim 1 wherein said volatile polydimethylsiloxane has a solubility parameter of about 7 (cal/cm3 1/2) and is selected from the group consisting of hexamethyl disiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, octamethyl trisiloxane and admixtures thereof.
8. A liquid polymer-containing bandage material according to claim 7 wherein said volatile polydimethylsiloxane is a mixture of hexamethyl disiloxane and octamethyl cyclotetrasiloxane.
9. A liquid polymer-containing bandage material according to claim 1 wherein said polar liquid has solubility parameters of greater than 9 (cal/cm3 1/2).
10. A liquid polymer-containing bandage material according to claim 9 wherein said polar liquid has a solubility parameter of greater than or equal to
11.0 (cal/cm3 1/2) and is selected from the group consisting of ethanol, 95% ethanol, isopropanol, propanol, diethylene glycol, propylene glycol, triethylene glycol, N-methyl pyrrolidone, glycerol, and admixtures thereof.
11. A liquid polymer-containing bandage material according to claim 10 wherein said polar liquid is 95% ethanol.
11. A liquid polymer-containing bandage material according to claim 10 wherein said polar liquid is 95% ethanol.
12. A liquid polymer-containing bandage material according to claim 6 comprising of about 10 to 25 wt% said siloxane-containing polymer, about 0.5 to 5.0 wt% octamethyl cyclotetrasiloxane, about 0.5 to 5.0 wt% 95% ethanol, and about 65 to 89 wt%
hexamethyl disiloxane; and having a moisture vapor permeability of from 200 to 700 g/m2/24 hr and an oxygen permeability of 60 to 180 x 10-11 (cm2/sec) (ml 02/ ml mm Hg).
hexamethyl disiloxane; and having a moisture vapor permeability of from 200 to 700 g/m2/24 hr and an oxygen permeability of 60 to 180 x 10-11 (cm2/sec) (ml 02/ ml mm Hg).
13. A liquid polymer-containing bandage material according to claim 1 comprising about 10 to 25 wt% said siloxane-containing polymer, about 0.5 to 5.0 wt% octamethyl cyclotetrasiloxane, about 0.5 to 5.0 wt% 95% ethanol, about 0.5 to 5.0 wt%
sucrose acetate isobutyrate, and about 60 to 88.5 wt% hexamethyl disiloxane; and having a moisture vapor permeability of from 200 to 700 g/m2/24hr and an oxygen permeability of 60 to 180 x 10-11 (cm2/sec) (ml o2/ml mm Hg).
sucrose acetate isobutyrate, and about 60 to 88.5 wt% hexamethyl disiloxane; and having a moisture vapor permeability of from 200 to 700 g/m2/24hr and an oxygen permeability of 60 to 180 x 10-11 (cm2/sec) (ml o2/ml mm Hg).
14. A dried film bandage formed from the liquid polymer-containing bandage material according to claim 1.
15. A dried film bandage formed from the liquid polymer-containing bandage material according to claim 12.
16. A dried film bandage formed from the liquid polymer-containing bandage material according to claim 13.
17. A method of forming a conformable adherent bandage on the body of a user comprising, applying a liquid polymer-containing bandage material consisting essentially of a siloxane-containing polymer, a major amount of a volatile polydimethylsiloxane and a minor amount of a polar liquid to the body, and evaporating said polydimethylsiloxane and volatile liquid to foam a conformable adherent bandage having sufficient moisture vapor transmission properties, abrasion resistant properties and other necessary properties for use as a protective bandaging layer over the body.
18. A liquid polymer-containing coating material comprising from 1 to 40 wt.
siloxane-containing polymer, 60 to 99 wt. % volatile polydimethylsiloxane, said coating material being substantially non-stinging, quick-drying and film forming at room temperature to form an adherent comformable moisture vapor permeable coating directly on a surface.
siloxane-containing polymer, 60 to 99 wt. % volatile polydimethylsiloxane, said coating material being substantially non-stinging, quick-drying and film forming at room temperature to form an adherent comformable moisture vapor permeable coating directly on a surface.
19. A liquid polymer-containing coating material in accordance with Claim 18, and further comprising from about 0.1 to about 10% wt. % of a polar liquid.
20. A liquid polymer-containing coating material in accordance with Claim 18 in the form of a polymerized coating adherent to a body surface.
21. A liquid polymer-containing coating material in accordance with Claim 20 in the form of a polymerized coating carrying an active agent therein for release to an underlying surface.
22. A liquid polymer-containing coating material in accordance with Claim 1 in the form of a polymerized coating adherent to a body surface.
23. A liquid polymer-containing coating material in accordance with Claim 22 in the form of a polymerized coating carrying an active agent therein for release to an underlying surface.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US25665188A | 1988-10-12 | 1988-10-12 | |
US07/256,651 | 1988-10-12 | ||
US07/416,924 US4987893A (en) | 1988-10-12 | 1989-10-04 | Conformable bandage and coating material |
US07/416,924 | 1989-10-04 |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2000548A1 CA2000548A1 (en) | 1990-04-12 |
CA2000548C true CA2000548C (en) | 2000-12-05 |
Family
ID=26945505
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002000548A Expired - Lifetime CA2000548C (en) | 1988-10-12 | 1989-10-12 | Conformable bandage and coating material |
Country Status (8)
Country | Link |
---|---|
US (1) | US4987893A (en) |
EP (1) | EP0438496B1 (en) |
JP (1) | JP2918263B2 (en) |
AU (1) | AU620653B2 (en) |
CA (1) | CA2000548C (en) |
DE (1) | DE68923456T2 (en) |
HK (1) | HK1007690A1 (en) |
WO (1) | WO1990003809A1 (en) |
Families Citing this family (113)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5474783A (en) * | 1988-03-04 | 1995-12-12 | Noven Pharmaceuticals, Inc. | Solubility parameter based drug delivery system and method for altering drug saturation concentration |
US5656286A (en) * | 1988-03-04 | 1997-08-12 | Noven Pharmaceuticals, Inc. | Solubility parameter based drug delivery system and method for altering drug saturation concentration |
US5103812A (en) * | 1988-10-12 | 1992-04-14 | Rochal Industries, Inc. | Conformable bandage and coating material |
US5246705A (en) * | 1992-04-08 | 1993-09-21 | Cygnus Therapeutic System | Occlusive, elastomeric backing materials in transdermal drug delivery systems, and associated methods of manufacture and use |
US5288827A (en) * | 1993-02-17 | 1994-02-22 | Ciba-Geigy Corporation | Copolymer of (meth)acryloxy-alkyl-siloxysilane and alkyl(meth)acrylates and the use thereof as pressure sensitive adhesives |
GB9411530D0 (en) * | 1994-06-09 | 1994-08-03 | Quayle Rachel A | Use of polymers as film-forming barrier materials |
US7833543B2 (en) | 1995-06-07 | 2010-11-16 | Durect Corporation | High viscosity liquid controlled delivery system and medical or surgical device |
JP4330175B2 (en) * | 1995-06-07 | 2009-09-16 | デュレクト コーポレイション | Controlled delivery system with high viscosity liquid |
US6730380B2 (en) | 1996-02-20 | 2004-05-04 | Safeskin Corp. | Readily-donned elastomeric articles |
US5948400A (en) * | 1997-11-20 | 1999-09-07 | Smith & Nephew Inc. | Method of applying a pressure-sensitive adhesive wound dressing and water-based skin treatment composition |
AU1800099A (en) * | 1997-11-25 | 1999-06-15 | Theratech, Inc. | Transdermal delivery devices containing polydiorganosiloxane polymers to regulate adhesive properties |
DK1162943T3 (en) * | 1999-03-25 | 2007-01-15 | 3M Innovative Properties Co | Non-firming coating composition |
US6471985B2 (en) * | 1999-06-04 | 2002-10-29 | Bahman Guyuron | Use of RTV silicone compositions for wound dressing |
GB0003632D0 (en) * | 2000-02-16 | 2000-04-05 | Univ Hong Kong Science & Techn | Dimeric compounds |
US6512072B1 (en) | 2000-06-12 | 2003-01-28 | Dow Corning Corporation | Fast cure film forming formulation |
US6902734B2 (en) | 2000-08-07 | 2005-06-07 | Centocor, Inc. | Anti-IL-12 antibodies and compositions thereof |
UA81743C2 (en) | 2000-08-07 | 2008-02-11 | Центокор, Инк. | HUMAN MONOCLONAL ANTIBODY WHICH SPECIFICALLY BINDS TUMOR NECROSIS FACTOR ALFA (TNFα), PHARMACEUTICAL MIXTURE CONTAINING THEREOF, AND METHOD FOR TREATING ARTHRITIS |
US6746667B2 (en) | 2001-07-05 | 2004-06-08 | Closure Medical Corporation | Adhesive treatment for tinea pedis |
US6602496B2 (en) | 2001-07-05 | 2003-08-05 | Closure Medical Corporation | Adhesive treatment for tinea corporis |
US6585967B2 (en) | 2001-07-05 | 2003-07-01 | Closure Medical Corporation | Adhesive treatment for tinea cruris |
US6942875B2 (en) * | 2001-07-05 | 2005-09-13 | Closure Medical Corporation | Adhesive treatment for skin yeast infections |
US20040001889A1 (en) | 2002-06-25 | 2004-01-01 | Guohua Chen | Short duration depot formulations |
ES2553136T3 (en) | 2002-12-13 | 2015-12-04 | Durect Corporation | Oral drug delivery system comprising high viscosity liquid vehicle materials |
US20040122382A1 (en) * | 2002-12-23 | 2004-06-24 | Kimberly-Clark Worldwide, Inc. | Elastomeric articles with beneficial coating on a surface |
US9708410B2 (en) | 2003-05-30 | 2017-07-18 | Janssen Biotech, Inc. | Anti-tissue factor antibodies and compositions |
US20050031817A1 (en) * | 2003-08-07 | 2005-02-10 | Littleton Kermit R. | Readily donned, powder-free elastomeric article |
US20050129937A1 (en) * | 2003-12-16 | 2005-06-16 | Eastman Kodak Company | Antimicrobial web for application to a surface |
US7842749B2 (en) * | 2004-08-02 | 2010-11-30 | Poly-Med, Inc. | Tissue protecting spray-on copolymeric film composition |
US20060030808A1 (en) * | 2004-08-09 | 2006-02-09 | Aso Corporation | Liquid bandage and tissue sealant |
US8753665B2 (en) | 2004-09-17 | 2014-06-17 | Durect Corporation | Controlled delivery system |
CN101084275B (en) | 2004-12-23 | 2011-09-14 | 陶氏康宁公司 | Crosslinkable saccharide-siloxane compositions, and networks, coatings and articles formed therefrom |
JP4704764B2 (en) * | 2005-02-03 | 2011-06-22 | 日東電工株式会社 | Nail adhesive composition and nail patch |
US7318937B2 (en) * | 2005-03-18 | 2008-01-15 | Closure Medical Corporation | Liquid coating compositions |
KR101261256B1 (en) | 2005-05-23 | 2013-05-07 | 다우 코닝 코포레이션 | Personal care compositions comprising saccharide-siloxane copolymers |
US20070027105A1 (en) | 2005-07-26 | 2007-02-01 | Alza Corporation | Peroxide removal from drug delivery vehicle |
AU2006279369B2 (en) | 2005-08-17 | 2011-09-08 | Rochal Partners, Llp | Conformable solvent-based bandage and coating material |
DE602006020490D1 (en) * | 2005-12-07 | 2011-04-14 | Rochal Ind Llp | ADJUSTABLE FASTENER AND COVER MATERIAL |
JP5185259B2 (en) | 2006-05-23 | 2013-04-17 | ダウ・コーニング・コーポレイション | Novel silicone film forming agent for active ingredient delivery |
CN103480026A (en) * | 2007-03-08 | 2014-01-01 | 莫科治疗有限公司 | Scar dressing formulation |
WO2008133868A1 (en) * | 2007-04-23 | 2008-11-06 | Safe N' Simple | Stoma wipe and adhesive remover and method |
US20080302827A1 (en) * | 2007-06-06 | 2008-12-11 | Gerrish Donald L | Spray dispenser |
AU2008335809A1 (en) | 2007-12-06 | 2009-06-18 | Durect Corporation | Methods useful for the treatment of pain, arthritic conditions, or inflammation associated with a chronic condition |
US8828358B2 (en) * | 2008-03-11 | 2014-09-09 | Materials Modifications, Inc. | In situ formation of an artificial blockage to control bleeding by polymer expansion with hydrogen peroxide |
US8852558B2 (en) * | 2008-03-11 | 2014-10-07 | Materials Modification, Inc. | In situ formation of an artificial blockage to control bleeding by polymer expansion with hydrogen peroxide and platinum catalyst |
MX2010014358A (en) | 2008-06-20 | 2011-07-04 | Wyeth Llc | Compositions and methods of use of orf1358 from beta-hemolytic streptococcal strains. |
US8003132B2 (en) | 2008-06-30 | 2011-08-23 | Johnson & Johnson Consumer Companies, Inc. | Compositions comprising an ultraviolet radiation-absorbing polymer |
EA026110B1 (en) | 2008-08-14 | 2017-03-31 | Сефалон Острэйлиа Пти Лтд. | Anti-il-12/il-23 antibodies |
DE102008048338A1 (en) | 2008-09-22 | 2010-03-25 | Beiersdorf Ag | Wound care preparation with reduced skin irritation |
US20100260844A1 (en) | 2008-11-03 | 2010-10-14 | Scicinski Jan J | Oral pharmaceutical dosage forms |
DE102008060904A1 (en) * | 2008-12-09 | 2010-06-10 | Beiersdorf Ag | Water-soluble active ingredients in spray plaster |
ES2626433T3 (en) | 2009-04-27 | 2017-07-25 | Avery Dennison Corporation | Releasable adhesive that has a multilayer substrate |
US8957277B2 (en) | 2009-04-27 | 2015-02-17 | Avery Dennison Corporation | Disruptable adhesive layer for fluid activated debonding |
US8828425B2 (en) * | 2010-02-02 | 2014-09-09 | Poly-Med, Inc. | In situ-formed bioactive tissue adherent films of absorbable crystallizable polymers |
US8475774B2 (en) | 2010-02-08 | 2013-07-02 | Johnson & Johnson Consumer Companies, Inc. | Sunscreen compositions comprising an ultraviolet radiation-absorbing polymer |
KR101858022B1 (en) | 2010-08-23 | 2018-05-16 | 다우 실리콘즈 코포레이션 | Saccharide siloxanes stable in aqueous environtments and methods for the preparation and use of such saccharide siloxanes |
JP5754665B2 (en) * | 2010-10-22 | 2015-07-29 | アルケア株式会社 | Film-forming composition for alleviating skin pain |
CA2843739A1 (en) | 2011-08-14 | 2013-02-21 | Materials Modification, Inc. | Method and composition for in situ formation of an artificial blockage to control blood loss |
BR112014007522A2 (en) | 2011-09-30 | 2017-04-25 | 3M Innovative Properties Co | "conforming coating composition and conforming film" |
US8263720B1 (en) * | 2011-10-05 | 2012-09-11 | Rochal Industries, Llp | Sacrificial adhesive coatings |
DK2773304T3 (en) | 2011-10-31 | 2016-05-02 | Avery Dennison Corp | Adhesive layers, which can be torn apart, to the fluid-activated solution. |
CN104870567B (en) | 2012-10-22 | 2018-09-07 | 艾利丹尼森公司 | It is dispersed in the hybrid material of the crosslinked micro-gel particles in adhesive |
WO2014064703A1 (en) * | 2012-10-28 | 2014-05-01 | Peritech Pharma Ltd. | Pharmaceutical liquid adhesive compositions for treatment of anorectal disorders |
JP6267218B2 (en) | 2012-11-06 | 2018-01-24 | ロチャル インダストリーズ,エルエルシー | Delivery of biologically active agents using volatile and hydrophobic solvents |
CA2904507C (en) | 2013-03-10 | 2021-05-04 | Peritech Pharma Ltd. | Topical compositions and methods of treatment of topical disorders |
CN105120659A (en) | 2013-03-15 | 2015-12-02 | 度瑞公司 | Compositions with a rheological modifier to reduce dissolution variability |
US20140272129A1 (en) * | 2013-03-15 | 2014-09-18 | Apple Inc. | Compliant permeable glue applicator |
US9901366B2 (en) * | 2013-07-27 | 2018-02-27 | Lawrence A. Colby | Systems and methods for enhancing the visibility of medical items |
US8877882B1 (en) | 2013-10-04 | 2014-11-04 | Rochal Industries Llp | Non-self-adherent coating materials |
KR102344991B1 (en) | 2013-12-24 | 2021-12-28 | 잔센파마슈티카엔.브이. | Anti-vista antibodies and fragments |
CN106103613B (en) | 2014-03-10 | 2019-07-09 | 3M创新有限公司 | Conformal coating composition |
CN107406593A (en) * | 2014-12-30 | 2017-11-28 | 莫门蒂夫性能材料股份有限公司 | Siloxanes coordination polymer |
US9815045B2 (en) | 2015-03-23 | 2017-11-14 | Clariant Corporation | Metal oxide catalyst material and processes for making and using same |
EP3280461B1 (en) | 2015-04-06 | 2020-06-17 | 3M Innovative Properties Company | Removable film forming gel compositions and methods for their application |
CA2990360C (en) | 2015-06-24 | 2024-02-13 | Janssen Pharmaceutica Nv | Anti-vista antibodies and fragments |
TWI756204B (en) | 2016-02-12 | 2022-03-01 | 比利時商楊森製藥公司 | Anti-vista antibodies and fragments, uses thereof, and methods of identifying same |
CA3019164A1 (en) | 2016-03-29 | 2017-10-05 | Janssen Biotech, Inc. | Method of treating psoriasis with increased interval dosing of anti-il12/23 antibody |
WO2017175058A1 (en) | 2016-04-07 | 2017-10-12 | Janssen Pharmaceutica Nv | Anti-vista antibodies and fragments, uses thereof, and methods of identifying same |
MX2019003703A (en) | 2016-09-30 | 2020-08-13 | Janssen Biotech Inc | Safe and effective method of treating psoriasis with anti-il23 specific antibody. |
US20190381208A1 (en) | 2016-10-13 | 2019-12-19 | 3M Innovative Properties Company | Removable Film Forming Gel Compositions Featuring Adhesion Promoters |
AU2017362222A1 (en) | 2016-11-16 | 2019-05-30 | Janssen Biotech, Inc. | Method of treating psoriasis with anti-IL-23 specific antibody |
DE102017100443A1 (en) * | 2017-01-11 | 2018-07-12 | Madeleine Elixmann | Liquid plaster, applicator and their use |
MA47362A (en) | 2017-01-30 | 2019-12-04 | Janssen Biotech Inc | ANTI-TNF ANTIBODIES, COMPOSITIONS AND METHODS FOR THE TREATMENT OF ACTIVE PSORIASIC RHEUMATISM |
WO2018147915A1 (en) | 2017-02-07 | 2018-08-16 | Janssen Biotech, Inc. | Anti-tnf antibodies, compositions, and methods for the treatment of active ankylosing spondylitis |
TW201922780A (en) | 2017-09-25 | 2019-06-16 | 美商健生生物科技公司 | Safe and effective method of treating Lupus with anti-IL12/IL23 antibody |
CA3092551A1 (en) | 2018-03-05 | 2019-09-12 | Janssen Biotech, Inc. | Methods of treating crohn's disease with anti-il23 specific antibody |
EP3824295A4 (en) | 2018-07-18 | 2022-04-27 | Janssen Biotech, Inc. | Sustained response predictors after treatment with anti-il23 specific antibody |
KR20230148273A (en) | 2018-09-24 | 2023-10-24 | 얀센 바이오테크 인코포레이티드 | Safe and effective method of treating ulcerative colitis with anti-IL12/IL23 antibody |
WO2020104943A2 (en) | 2018-11-20 | 2020-05-28 | Janssen Biotech, Inc. | Safe and effective method of treating psoriasis with anti-il-23 specific antibody |
US20200197517A1 (en) | 2018-12-18 | 2020-06-25 | Janssen Biotech, Inc. | Safe and Effective Method of Treating Lupus with Anti-IL12/IL23 Antibody |
AU2020208828A1 (en) | 2019-01-15 | 2021-08-05 | Janssen Biotech, Inc. | Anti-TNF antibody compositions and methods for the treatment of juvenile idiopathic arthritis |
EP3914618A1 (en) | 2019-01-23 | 2021-12-01 | Janssen Biotech, Inc. | Anti-tnf antibody compositions for use in methods for the treatment of psoriatic arthritis |
US20220144934A1 (en) | 2019-03-14 | 2022-05-12 | Janssen Biotech, Inc. | Methods for Producing Anti-TNF Antibody Compositions |
EP3938384A4 (en) | 2019-03-14 | 2022-12-28 | Janssen Biotech, Inc. | Manufacturing methods for producing anti-il12/il23 antibody compositions |
US20220153830A1 (en) | 2019-03-14 | 2022-05-19 | Janssen Biotech, Inc. | Manufacturing Methods for Producing Anti-TNF Antibody Compositions |
EA202192508A1 (en) | 2019-03-14 | 2022-03-29 | Янссен Байотек, Инк. | METHODS FOR OBTAINING COMPOSITIONS OF ANTIBODIES TO TNF |
WO2020188466A1 (en) | 2019-03-18 | 2020-09-24 | Janssen Biotech, Inc. | Method of treating psoriasis in pediatric subjects with anti-il12/il23 antibody |
CA3138241A1 (en) | 2019-05-23 | 2020-11-26 | Janssen Biotech, Inc. | Method of treating inflammatory bowel disease with a combination therapy of antibodies to il-23 and tnf alpha |
CN113939531A (en) | 2019-06-03 | 2022-01-14 | 詹森生物科技公司 | anti-TNF antibody compositions and methods for treating psoriatic arthritis |
CA3142580A1 (en) | 2019-06-03 | 2020-12-10 | Janssen Biotech, Inc. | Anti-tnf antibodies, compositions, and methods for the treatment of active ankylosing spondylitis |
WO2021028752A1 (en) | 2019-08-15 | 2021-02-18 | Janssen Biotech, Inc. | Anti-tfn antibodies for treating type i diabetes |
KR20220140711A (en) | 2020-01-13 | 2022-10-18 | 듀렉트 코퍼레이션 | Reduced Impurity Sustained Release Drug Delivery Systems and Related Methods |
CN111450310A (en) * | 2020-03-03 | 2020-07-28 | 劳龙斯(上海)医药科技有限公司 | Novel liquid wound dressing and preparation method thereof |
CN111714692B (en) * | 2020-07-07 | 2022-04-15 | 华熙生物科技股份有限公司 | Skin wound surface protection composition and preparation method thereof |
AU2022233792A1 (en) | 2021-03-12 | 2023-10-26 | Janssen Biotech, Inc. | Safe and effective method of treating psoriatic arthritis with anti-il23 specific antibody |
KR20230156764A (en) | 2021-03-12 | 2023-11-14 | 얀센 바이오테크 인코포레이티드 | Method for treating psoriatic arthritis patients with inadequate response to TNF therapy by anti-IL23 specific antibody |
AU2022308201A1 (en) | 2021-07-09 | 2024-02-22 | Janssen Biotech, Inc. | Manufacturing methods for producing anti-tnf antibody compositions |
WO2023281462A1 (en) | 2021-07-09 | 2023-01-12 | Janssen Biotech, Inc. | Manufacturing methods for producing anti-tnf antibody compositions |
WO2023281466A1 (en) | 2021-07-09 | 2023-01-12 | Janssen Biotech, Inc. | Manufacturing methods for producing anti-il12/il23 antibody compositions |
WO2023073615A1 (en) | 2021-10-29 | 2023-05-04 | Janssen Biotech, Inc. | Methods of treating crohn's disease with anti-il23 specific antibody |
US20230151087A1 (en) | 2021-11-15 | 2023-05-18 | Janssen Biotech, Inc. | Methods of Treating Crohn's Disease with Anti-IL23 Specific Antibody |
US20230159633A1 (en) | 2021-11-23 | 2023-05-25 | Janssen Biotech, Inc. | Method of Treating Ulcerative Colitis with Anti-IL23 Specific Antibody |
US20230312703A1 (en) | 2022-03-30 | 2023-10-05 | Janssen Biotech, Inc. | Method of Treating Psoriasis with IL-23 Specific Antibody |
US20230374122A1 (en) | 2022-05-18 | 2023-11-23 | Janssen Biotech, Inc. | Method for Evaluating and Treating Psoriatic Arthritis with IL23 Antibody |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3577516A (en) * | 1969-12-02 | 1971-05-04 | Nat Patent Dev Corp | Preparation of spray on bandage |
US3836647A (en) * | 1970-10-22 | 1974-09-17 | Dow Corning | Wash-resistant skin preparation |
CA1039189A (en) * | 1973-08-31 | 1978-09-26 | Beiersdorf Aktiengesellschaft | Film-forming sprayable polymer-solution for producing a wound-dressing |
JPS5528918A (en) * | 1978-08-18 | 1980-02-29 | Kuraray Co Ltd | Coating material |
US4303066A (en) * | 1979-06-28 | 1981-12-01 | National Patent Development Corporation | Burn dressing |
US4318746A (en) * | 1980-01-08 | 1982-03-09 | Ipco Corporation | Highly stable gel, its use and manufacture |
US4393048A (en) * | 1980-02-15 | 1983-07-12 | The United States Of America As Represented By The Secretary Of The Army | Protective gel composition for wounds |
US4291025A (en) * | 1980-04-11 | 1981-09-22 | Laclede Professional Products, Inc. | Agar gel topical dressing |
US4569784A (en) * | 1980-11-17 | 1986-02-11 | Adamantech, Inc. | Preparation of a gel having gas transporting capability |
US4650817A (en) * | 1982-07-16 | 1987-03-17 | C. R. Bard, Inc. | Physiologically compatible adhesive composition |
FR2589737A1 (en) * | 1985-11-12 | 1987-05-15 | Dow Corning Sa | METHODS OF MANUFACTURING DRESSINGS |
GB2192142B (en) * | 1986-07-04 | 1990-11-28 | Johnson & Johnson | Wound dressing |
-
1989
- 1989-10-04 US US07/416,924 patent/US4987893A/en not_active Expired - Lifetime
- 1989-10-10 JP JP1511065A patent/JP2918263B2/en not_active Expired - Lifetime
- 1989-10-10 DE DE68923456T patent/DE68923456T2/en not_active Expired - Lifetime
- 1989-10-10 WO PCT/US1989/004543 patent/WO1990003809A1/en active IP Right Grant
- 1989-10-10 AU AU44237/89A patent/AU620653B2/en not_active Expired
- 1989-10-10 EP EP89911950A patent/EP0438496B1/en not_active Expired - Lifetime
- 1989-10-12 CA CA002000548A patent/CA2000548C/en not_active Expired - Lifetime
-
1998
- 1998-06-26 HK HK98106878A patent/HK1007690A1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
HK1007690A1 (en) | 1999-04-23 |
AU620653B2 (en) | 1992-02-20 |
DE68923456D1 (en) | 1995-08-17 |
EP0438496A1 (en) | 1991-07-31 |
AU4423789A (en) | 1990-05-01 |
EP0438496A4 (en) | 1991-10-09 |
EP0438496B1 (en) | 1995-07-12 |
JP2918263B2 (en) | 1999-07-12 |
JPH04501076A (en) | 1992-02-27 |
DE68923456T2 (en) | 1995-12-14 |
CA2000548A1 (en) | 1990-04-12 |
WO1990003809A1 (en) | 1990-04-19 |
US4987893A (en) | 1991-01-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2000548C (en) | Conformable bandage and coating material | |
EP0572416B1 (en) | Conformable bandage and coating material | |
US7318937B2 (en) | Liquid coating compositions | |
US8263720B1 (en) | Sacrificial adhesive coatings | |
AU2008308849B2 (en) | Silicone gel-based compositions for wound healing and scar reduction | |
CA2926294C (en) | Non-self-adherent coating materials | |
US7842749B2 (en) | Tissue protecting spray-on copolymeric film composition | |
EP1322349B1 (en) | Protectant film for skin | |
US20080152614A1 (en) | Method and kit for skin lesion prevention and/or protection | |
EP3824005B1 (en) | Liquid wound dressing composition | |
EP1904574A2 (en) | Tissue protecting spray-on copolymer film composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
EEER | Examination request | ||
MKEX | Expiry |