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WO1989004647A1 - Prophylactic articles with biocompatible coatings - Google Patents

Prophylactic articles with biocompatible coatings Download PDF

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Publication number
WO1989004647A1
WO1989004647A1 PCT/US1988/004062 US8804062W WO8904647A1 WO 1989004647 A1 WO1989004647 A1 WO 1989004647A1 US 8804062 W US8804062 W US 8804062W WO 8904647 A1 WO8904647 A1 WO 8904647A1
Authority
WO
WIPO (PCT)
Prior art keywords
biocompatible
prophylactic device
prophylactic
coating
elastomeric
Prior art date
Application number
PCT/US1988/004062
Other languages
French (fr)
Inventor
Michael S. Nawash
Original Assignee
Stillman, Suzanne
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Stillman, Suzanne filed Critical Stillman, Suzanne
Publication of WO1989004647A1 publication Critical patent/WO1989004647A1/en

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Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS 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
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08Materials for coatings
    • A61L31/10Macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61FFILTERS 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
    • A61F6/00Contraceptive devices; Pessaries; Applicators therefor
    • A61F6/02Contraceptive devices; Pessaries; Applicators therefor for use by males
    • A61F6/04Condoms, sheaths or the like, e.g. combined with devices protecting against contagion

Definitions

  • Prophylactic devices such as condoms, finger cots, surgical gloves and examination gloves, are commonly made of elastomeric materials, such as natural rubber or thermoplastic resin.
  • plasticizers and other chemicals may be present in the finished article and may leach out of the article over time. Such chemicals may be allergenic, irritating, and are sometimes toxic, to tissues and cells.
  • vulcanized natural rubber and some thermoplastics The toxicity of some chemicals present in vulcanized natural rubber and some thermoplastics is of special importance when these materials come into direct contact with cells, tissues or organisms. Some chemicals present in vulcanized natural rubber and some thermoplastics have been found to be particularly toxic to sperm collected in condoms and like devices. These articles, and specifically condoms, have in the past frequently been used as seminal collection devices for conducting sperm counts to assess the fertility of males. The detrimental effect on sperm of compounds present in natural rubber and some thermoplastics has resulted in erroneous counts. Therefore, it is now commonly recognized that condoms and like articles made of natural rubber or some thermoplastics are not most appropriate for seminal collection.
  • prophylactic devices which provide increased protection from the transmission of infectious agents, such as bacteria and viruses.
  • Conventional prophylactic devices, while useful, are thought to exhibit unacceptable' failure rates.
  • An object of this invention is to provide an article made of vulcanized natural rubber or other material; such article will have comparable properties, cause less tissue irritation and be more compatible with living cells in general. It is a further object of this invention to make natural rubber condoms, in particular, more suitable for seminal collection and seminal storage. A further object of this invention is to provide prophylactic articles with substantially improved biocompatibility, barrier properties and reduced failure rates.
  • prophylactic articles such as condoms made of an elastomeric base material such as natural rubber, - thermoplastics, or the like with a biocompatib-Le barrier coating (s) .
  • a biocompatib-Le barrier coating s
  • the presence of an additional layer of material further reduces the probability of structural flaws that may lead to failure of the device.
  • the coating of a prophylactic article such as a condom with a biocompatible material renders the article non-injurious to healthy tissue and also minimizes further insults on traumatized or diseased tissue when such tissue comes into contact with the article.
  • the contact of a biocompatible material with an injured tissue does not interfere with the healing process of the tissue. Thus, either the natural healing process or the course of any special therapeutic treatment proceeds uninterrupted.
  • the coating also renders the article noncytopathic.
  • the coating is selected to be non-adherent to tissues, cells or other matters that come into contact with it. Thus, tissues, cells and other matters may be removed from the article without physical damage. When adhesion is desired, however, an adhesive material may be applied to the appropriate surface area of the article.
  • the coating ⁇ as in the case of a medical silicone elastomer — ⁇ also has low surface tension, which makes the article virtually self-lubricating especially when used in an aqueous environment.
  • the coating also prolongs the shelf life of the coated article; for example, the above noted silicone is substantially unaffected by ordinary environmental . elements or time.
  • the coating will render the article non-sensitizing, especially in cases where prolonged contact with tissue or cells is required.
  • the article of this invention is provided with the biocompatible barrier coating on at least a portion of one major surface.
  • a “major surface” it is meant the inside or outside surface of a prophylactic article.
  • the article has both its inside and outside surfaces or portion(s) thereof coated with a layer of the biocompatible material.
  • the base layer in general, comprises an elastomeric material, such as vulcanized natural rubber or synthetic thermoplastic material. Examples of the latter include polyethylene, polystyrene, polyurethane, butyl rubber, etc. For most uses, vulcanized natural rubber is the preferred material for making the base layer of the article of this invention.
  • a “biocompatible coating” it is meant any suitable form and any suitable substance that will accomplish the objective of protecting cells, tissues or organisms from a non-biocompatible material used in constructing an article, from the chemicals that are present in such article or from chemicals that might develop in the material with time.
  • the barrier coating material described herein is preferably a biocompatible medical grade silicone elastomer, but is not necessarily limited to this material or form. Biocompatible grade polyurethane, fluorinated * elastomers and some biocompatible thermoplastic copolymers, for example, may be used in place of medical grade silicone.
  • the elastomeric base material determines the type of silicone which is most suitable.
  • exemplary embodiment includes alcohol condensation reaction type silicones; acetic acid condensation reaction type silicones; platinum vulcanized silicones, of either the room temperature vulcanizing (RTV) or hot air vulcanizing (HAV) type; peroxide vulcanized type silicones; acid vulcanized type silicones; and ultraviolet light vulcanizing type silicones-,
  • Silicone elastomer stocks that are especially made for biomedical usage are available from Dow Corning Corporation of Midland, Michigan. Available compositions include Silastic MDX 4-4515, a hot air vulcanizing peroxide cure reaction type silicone; Silastic Medical Adhesive Type A, an RTV acetic acid condensation reaction type silicone; and Dow Corning 3110 RTV, an alcohol condensation reaction type room temperature vulcanizing silicone.
  • the more preferred at present is the two component RTV silicone, wherein one component comprises elastomeric base dimethylpolysiloxane, strengthening silica filler and a crosslinking agent such as propyl orthosilicate, while the second component comprises an organometallic compound which functions as the curing agent/catalyst.
  • Dibutyl tin diacetate is the preferred catalyst for this reaction.
  • An adhesion promoter may optionally be used to induce a stronger bond between the silicone elastomer layers and the elastomeric base layer.
  • primers are described in, e.g., U.S. Patent 3,434,869 (the disclosure of which is hereby incorporated by reference) and Canadian Patent 682,769.
  • Polyurethanes also have the potential to fill the prerequisites for use as a biocompatible coating in accordance with this invention.
  • segmented polyurethanes derived from long chain diols in which the amount of the hard segment and the degree of cross-linking are balanced such that the polymer is essentially non-crystalline and has low modulus and low set properties.
  • Segmented polyurethanes are block copolymers constituted by alternating segments of hard, rigid segments and soft, flexible segments.
  • One discussion of their chemistry is found in Polymer Science and Technology, "Polymers in Medicine and Surgery,"- Kronenthal et al.. Volume 8, pp. 45-75.
  • the hard and soft segments in these polymers are incompatible, so that icrophase separation or domain formation occurs.
  • the soft segment is dominant, the hard segment domains serve as a physical cross-link and give the polymers elastomeric properties.
  • Polyurethane polymers suitable for the purposes of this invention are those which, upon curing, will form elastomeric layers or coatings having physical properties sufficiently similar to those of the substrate, such as the latex rubber layer, to avoid failure of the elastomeric coating upon stretching within the limits of its ultimate elongation,
  • the polyurethane elastomers used in accordance with this invention may be prepared by the methods • known and described in the prior art.
  • the polyurethane elastomers are usually prepared from a long chain diol such as a linear polyester or polyether, preferably of molecular weight 1000 to 3000, a polyisocyanate, preferably a diisocyanate, and a low molecular weight chain extender such as a glycol or a diamine.
  • reaction sequences are known to the art and thus may be used to prepare the polyurethane elastomers, one of the most successful is the "prepolymer" method.
  • the diol is caused to react with an excess of diisocyanate and the reaction product thus obtained is a liquid or low melting solid of a moderate molecular weight and which is referred to as a "prepolymer.”
  • the second step of this method is the addition of a low molecular weight glycol or diamine, with the ratio of reactants usually being chosen so that a slight excess of isocyanate groups is present.
  • These isocyanate terminated prepolymers may advantageously be blocked or capped.
  • the terminal isocyanate groups may be reacted to stabilize the prepolymer against premature cure by atmospheric moisture.
  • the capping agents may be any active hydrogen substance which may be volatilized or removed upon regeneration to free isocyanate groups at temperatures below those adverse to the substrate.
  • these isocyanate precursors should decompose at a temperature not above about 250 to 300°F, and preferably between about 200 to 275°F.
  • blocking agents are diethylmalonate, acetonate, acetyl acetone, sodium bisulfite and acetone oxime.
  • the prepolymer is dissolved in a solvent to satisfy the prerequisites for establishing a uniform layer of polyurethane of predetermined thickness on the rubber substrate.
  • a solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like.
  • the latter solvents alone may not be ideal for manufacturing purposes for reasons of low volatility, cost, viscosity, or toxicity.
  • diluents or blending solvents can be selected to improve these properties.
  • Blending solvents which can be utilized are toluene, xylene, and other aromatic fractions.
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl heptyl ketone, and cyclohexanone are illustrative of ketones miscible with the aforementioned polymer solvents.
  • Chlorinated solvents such as methylene chloride, trichloroethylene and 1, 1, 1-trichloroethane are examples of blending solvents or diluents for the polymer solvents.
  • the latter chlorinated solvents can be sole solvent for some segmented polyurethane prepolymers suitable for use in this invention.
  • a preferred solvent with high solubility for the prepolymer, a low boiling point and low toxicity is the chlorinated solvent methylene dichloride.
  • Typical solution coating compositions contain approximately 15- 20 percent solids for optimum dip properties.
  • Segmented polyurethanes that can be used in this invention are described in U.S. Patent Nos. 3,382,138 and 4,463,156, the disclosures of which are hereby incorporated by reference.
  • a primer dip can be utilized to enhance the adhesion of the polyurethane to the natural rubber.
  • the primer is, for example, a diisocyanate dissolved in a suitable solvent and dipped or sprayed onto the dry rubber surface prior to the polyurethane dip.
  • Diisocyanates which can be utilized as primer in this step include aromatic and alicyclic diisocyanates such as 4,4'-diphenyl methane diisocyanate (MDI) , toluene diisocyanate (TDI) , isophorone diisocyanate (IPDI) , methylene bis (4- cyclohexylisocyanate) (HMDI) , etc.
  • MDI 4,4'-diphenyl methane diisocyanate
  • TDI toluene diisocyanate
  • IPDI isophorone diisocyanate
  • HMDI methylene bis (4- cyclohexylisocyanate
  • a laminated product comprising base material and biocompatible coating according to the present invention is prepared by dipping, molding, spraying, bonding or other known methods.
  • the desired portion of inside surface of such article is, for example, coated by placing the coating material in the cavity of the article and then setting the article or its contents in a fixed position or subjecting it to any type of motion that will induce or facilitate the spread of the coating material on the desired portion of the inside surface of the article.
  • a mandrel of appropriate size and configuration made of an appropriate material is dipped in a dispersion of medical silicone elastomer or other suitable biocompatible material.
  • the dispersing media must not dissolve the central layer or cause it to swell.
  • Water or other suitable solvent is generally employed; aromatic solvents, such as xylene and toluene or aliphatic solvents, such as heptane and hexane, are preferred.
  • the solids content of the dispersion varies depending on the desired dwell time for the mandrel in the dispersion and on the desired thickness of the layer picked up by the mandrel from the dispersion with each dip.
  • the first dip of the mandrel into the dispersion material forms the inside surface of the condom or other article.
  • this first layer may need to be vulcanized before subsequent dips.
  • the vulcanization may be accomplished by heating.
  • RTV silicone of the one component or two component type be used.
  • the next dip is in a dispersion of natural rubber or thermoplastic. Again, the speed of dipping the mandrel, the dwell time of the mandrel, and the speed of withdrawal are adjusted to provide the desired thickness of the layer resulting from this dip.
  • the solids content of the natural rubber dispersion also affects the thickness of the natural rubber layer.
  • the natural rubber portion of the laminate may, in general, constitute the major portion of the total wall thickness of the article, primarily because of the strength of natural rubber. If the device is of the type where only the inner surface contacts cells or tissues, the manufacture of the article is completed by vulcanizing the natural rubber layer described above. Examples of such articles are gloves designed specifically for the protection of hands of the wearer and tissue or cell collection devices such as seminal collection devices, etc. If, however, the outer surface of the article also needs to be non-toxic and non-irritant, further dips in silicone or the like material are necessary subsequent to the natural rubber dip described above.
  • a finished natural rubber article such as a condom is mounted on a mandrel and then dipped into silicone dispersion to coat the desired portion of the outer surface. If only the outer surface is to be coated, the product is finished at this stage. If only the inner surface is to be coated, the article is inverted to achieve this objective. If both surfaces are to be coated, the article is inverted after coating the outer surface, then the article is mounted on a mandrel and again dipped into a dispersion of non-toxic, non-irritant material. In this manner, both surfaces of the natural rubber article are coated with the biocompatible material.
  • Spraying of the dispersion material is a third example of how the desired laminated article is fabricated.
  • the desired article is built sequentially.
  • a finished natural rubber article is sprayed inside and out with a dispersion of a non-toxic coating material to create the barrier layer or layers desired.
  • Condoms are customarily "straight" dipped, which means that glass, glazed porcelain,, plastic or polished metal molds (also referred to as forms or mandrils) are dipped into the latex compound without the use of coagulants which would tend to deposit too much rubber.
  • the prewarmed molds enter and exit the latex compound at an orientation and speed designed to avoid entrapment of air bubbles and to minimize any run-backs of the liquid latex.
  • the latex film is dried while the forms are rotating on two axes. The latter movements are necessary to equilibrate the flow patterns of the liquid latex during drying.
  • a second or more dips are desirable, after the first- dip is dry, the molds are reimmersed into a latex compound similar or identical to the first compound then the dip and dry sequences are repeated. The two or more straight dips minimize the possibilities of pinholes being present in the product.
  • a bead is rolled onto the condoms by impinging angled rotating brushes against the rotating molds and the top edge of the dipped product. After beading, the condoms are vulcanized in hot air ovens. Often, anti-blocking or lubricating finishes are applied either before or after the vulcanization and then the condoms are removed from the molds, inspected, and packaged.
  • the composite construction condoms are beaded and cured using the same sequences developed for conventional condoms.
  • the polyurethane or silicone surface must be oriented to be the inside of the finished condom. urethane or silicone applied to both surfaces; - -
  • primer applications can be inserted prior to each succeeding dip.
  • Primer may be dipped or spray applied and dried in an analogous manner to the other dips.
  • the thickness of the biocompatible barrier layer is not critical, as long as the layer functions to create the desired protective barrier. Generally, coatings as thin as one mil (1/1000 inch) or even less may be sufficient. Whereas coatings as thick as 250 mils may be suitable when the device is intended for collection or storage of semen.
  • the coatings on prophylactic devices for use in minimizing or preventing the transmission of sexually transmitted diseases (STDs) will be substantially thinner so as to preserve the requisite handling properties of the device. In the latter case, thicknesses on the order of up to 10 mils would be sufficient. If a therapeutic agent, preservative or nutrient is desired on a surface that comes into contact with tissues or cells, such preparations may be added to the silicone dispersion or the like material. These preparations become incorporated into the polymer portion of the dispersion and become entrapped in the surface coating.
  • drugs or similar preparations eventually migrate from the polymeric matrix to the surface and impart their therapeutic or other effect on the tissue or cells that come into contact therewith.
  • antimicrobial agents such as spermatocides, germicides or virucides, are suitably incorporated into the layer made of silicone
  • a slow release lubricant is also suitably incorporated into the barrier layer or layers, so that the device will be permanently self-lubricating. Due to the non-wettable nature of silicone, dry lubricants are quite effective. Dry lubricants are conveniently pre-applied on a condom or packaged therewith to be applied just prior to use. The unique non-wettability of silicone actually reduces or eliminates the need for lubricant when the article is used in an aqueous environment.
  • an absorbent suitably a powder, is placed inside the condom in a position and quantity to absorb the liquid portion of the semen, thus immobilizing the sperm and other microorganisms, viruses or any infectious agents that rely on fluid media for mobility and survival.
  • This absorbent will also immobilize and impair the survival of infectious agents that might be able to penetrate the condom from the outside.
  • the absorption of the seminal fluid by an agent within the cavity of the condom will also prevent spillage of such fluid due to loss of penile erection etc.
  • a biocompatible coagulant may be placed in the seminal collection device. This will change the consistency of the seminal fluid to a gelatinous form, thereby concentrating the seminal fluid and the sperm it contains rather than allowing the spread of the fluid and the sperm on the walls of the device.
  • Glazed porcelain condom molds were cleaned for 60 seconds with an appropriate commercial cleaner (e.g. Oaklite Rust Stripper - 2 oz./gallon) at 160°F in an ultrasonic cleaning tank.
  • the clean forms were dried in a 158°F oven for 10-15 minutes.
  • the dried forms were equilibrated to 110+10°F and dipped into a 61% solids prev ⁇ lcanized natural latex designated as Revertex L.A. R (made by Revertex Ltd. of Harlow, Essex, England and available from Joseph Appleby Company, Chattanooga, Tennessee). Dipping was at insertion and withdrawal speeds designed to avoid air entrapment and to minimize latex run-backs.
  • the forms were rotated until the wet film gelled sufficiently so as no longer to flow on the form.
  • the latex film was dried for 15 minutes at 158 ⁇ F or until all evidence (whiteness from moisture) of retained water had left the film.
  • silicone coating a system that is commercially available from Dow Corning Corporation of Midland, Michigan was used.
  • the system consists of:
  • the latex coated forms were dipped slowly (to avoid air entrapment) into the silicone elastomer compound to a level of 1/2 inch from the latex dip line (to allow bead formation) .
  • the form was withdrawn slowly to minimize run-backs of the silicone elastomer solution.
  • the form was rotated until the silicone polymer was dry.
  • the 1/2 inch latex band at the distal end of the condom was rolled into a bead.
  • the condoms were dried for 15 minutes at 158°F and then cured for 15 minutes at 235°F.
  • the cured condoms were then dipped into a slurry of cross-linked rice starch or lycopodium powder which contained 0.5 to 1.0% active dimethyl polysiloxane silicone fluid.
  • the latter was added in an emulsion form (e.g. Dow Corning 347 emulsion) .
  • emulsion form e.g. Dow Corning 347 emulsion
  • Clean glazed porcelain forms were coated with a semi-permanent fluoropoly er coating such as Vydax or Teflon R (made by and available from Ed. DuPont Corporation, Wilmington, Delaware) or equivalent.
  • a commercial brand used with some success was S oner's Ink Co. fluorocarbon release coating, applied from a spray can.
  • the forms were dipped into the silicone elastomer solution and using the dip techniques as described in Example 1. After the elastomer had completely dried, all of the steps outlined for one side coating were undertaken to result in a condom which is a laminate construction of silicone elastomer/natural rubber/silicone elastomer-, The starch/silicone fluid slurry provides antiblocking analogous to one-side coated condoms.

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  • Health & Medical Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Vascular Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Heart & Thoracic Surgery (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Surgery (AREA)
  • Epidemiology (AREA)
  • Reproductive Health (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Orthopedics, Nursing, And Contraception (AREA)

Abstract

A prophylactic device is disclosed, comprising an elastomeric base material and a biocompatible barrier coating provided on at least a portion of the inside and/or outside surface of the device. The base layer comprises an elastomeric material, such as vulcanized natural rubber or synthetic thermoplastic material. The biocompatible coating provides an additional barrier layer to prevent transmission of infectious agents and protects cells, tissues or organisms from non-biocompatible materials used in constructing the device, such as chemicals that are present in or might develop in the base layer with time. Suitably, the biocompatible coating comprises a medical grade silicone elastomer, polyurethane, fluorinated elastomer or biocompatible thermoplastic copolymer. Additional materials may be incorporated into the biocompatible layer and/or provided within the interior of the device, depending on the desired use. Methods for preparing the prophylactic device, such as by dipping, are also disclosed.

Description

PROPHYLACTIC ARTICLES WITH BIOCOMPATIBLE COATINGS
Prophylactic devices, such as condoms, finger cots, surgical gloves and examination gloves, are commonly made of elastomeric materials, such as natural rubber or thermoplastic resin. In view of the process steps and chemical reactions necessary to vulcanize natural rubber or prepare thermoplastic products, plasticizers and other chemicals may be present in the finished article and may leach out of the article over time. Such chemicals may be allergenic, irritating, and are sometimes toxic, to tissues and cells.
The toxicity of some chemicals present in vulcanized natural rubber and some thermoplastics is of special importance when these materials come into direct contact with cells, tissues or organisms. Some chemicals present in vulcanized natural rubber and some thermoplastics have been found to be particularly toxic to sperm collected in condoms and like devices. These articles, and specifically condoms, have in the past frequently been used as seminal collection devices for conducting sperm counts to assess the fertility of males. The detrimental effect on sperm of compounds present in natural rubber and some thermoplastics has resulted in erroneous counts. Therefore, it is now commonly recognized that condoms and like articles made of natural rubber or some thermoplastics are not most appropriate for seminal collection.
In addition, it would be desirable to produce prophylactic devices which provide increased protection from the transmission of infectious agents, such as bacteria and viruses. Conventional prophylactic devices, while useful, are thought to exhibit unacceptable' failure rates.
An object of this invention is to provide an article made of vulcanized natural rubber or other material; such article will have comparable properties, cause less tissue irritation and be more compatible with living cells in general. It is a further object of this invention to make natural rubber condoms, in particular, more suitable for seminal collection and seminal storage. A further object of this invention is to provide prophylactic articles with substantially improved biocompatibility, barrier properties and reduced failure rates.
These and other objects of the invention are achieved through the laminating and/or coating of prophylactic articles such as condoms made of an elastomeric base material such as natural rubber, - thermoplastics, or the like with a biocompatib-Le barrier coating (s) . In this manner, it is possible to create a permanent, non-flowable and non-soluble barrier between the natural rubber or thermoplastic material and the chemicals that might leach out therefrom on the one side, and the tissues or organisms on the other side. In addition, when the device is used as a barrier to prevent transmission of infectious agents, the presence of an additional layer of material further reduces the probability of structural flaws that may lead to failure of the device.
The coating of a prophylactic article such as a condom with a biocompatible material renders the article non-injurious to healthy tissue and also minimizes further insults on traumatized or diseased tissue when such tissue comes into contact with the article. The contact of a biocompatible material with an injured tissue does not interfere with the healing process of the tissue. Thus, either the natural healing process or the course of any special therapeutic treatment proceeds uninterrupted. The coating also renders the article noncytopathic. The coating is selected to be non-adherent to tissues, cells or other matters that come into contact with it. Thus, tissues, cells and other matters may be removed from the article without physical damage. When adhesion is desired, however, an adhesive material may be applied to the appropriate surface area of the article. The coating ~ as in the case of a medical silicone elastomer — also has low surface tension, which makes the article virtually self-lubricating especially when used in an aqueous environment. The coating also prolongs the shelf life of the coated article; for example, the above noted silicone is substantially unaffected by ordinary environmental . elements or time. Finally, the coating will render the article non-sensitizing, especially in cases where prolonged contact with tissue or cells is required.
The article of this invention is provided with the biocompatible barrier coating on at least a portion of one major surface. By a "major surface" it is meant the inside or outside surface of a prophylactic article. Preferably, the article has both its inside and outside surfaces or portion(s) thereof coated with a layer of the biocompatible material.
Depending on the particular purpose for which the article is employed, it would of course not be necessary to provide the biocompatible barrier coating over an entire major surface thereof. For example, a glove may suitably be covered over only the finger portions. Depending on the desired end use, one skilled in the art may readily determine the location and extent of the biocompatible barrier coating to be provided. Thus, a condom may be prepared with a coating only on the tip, only on the shaft, only on portions of the tip and/or shaft, or over one or both entire surfaces. The base layer, in general, comprises an elastomeric material, such as vulcanized natural rubber or synthetic thermoplastic material. Examples of the latter include polyethylene, polystyrene, polyurethane, butyl rubber, etc. For most uses, vulcanized natural rubber is the preferred material for making the base layer of the article of this invention.
By a "biocompatible coating" it is meant any suitable form and any suitable substance that will accomplish the objective of protecting cells, tissues or organisms from a non-biocompatible material used in constructing an article, from the chemicals that are present in such article or from chemicals that might develop in the material with time. The barrier coating material described herein is preferably a biocompatible medical grade silicone elastomer, but is not necessarily limited to this material or form. Biocompatible grade polyurethane, fluorinated * elastomers and some biocompatible thermoplastic copolymers, for example, may be used in place of medical grade silicone.
Several silicone formulations are useful in forming the biocompatible barrier coating. The elastomeric base material in part determines the type of silicone which is most suitable. Exemplary embodiment includes alcohol condensation reaction type silicones; acetic acid condensation reaction type silicones; platinum vulcanized silicones, of either the room temperature vulcanizing (RTV) or hot air vulcanizing (HAV) type; peroxide vulcanized type silicones; acid vulcanized type silicones; and ultraviolet light vulcanizing type silicones-,
The different types of silicones mentioned above are well described in the literature and are commercially available and a detailed discussion of their composition is unnecessary. Silicone elastomer stocks that are especially made for biomedical usage are available from Dow Corning Corporation of Midland, Michigan. Available compositions include Silastic MDX 4-4515, a hot air vulcanizing peroxide cure reaction type silicone; Silastic Medical Adhesive Type A, an RTV acetic acid condensation reaction type silicone; and Dow Corning 3110 RTV, an alcohol condensation reaction type room temperature vulcanizing silicone.
Of the indicated silicones, the more preferred at present is the two component RTV silicone, wherein one component comprises elastomeric base dimethylpolysiloxane, strengthening silica filler and a crosslinking agent such as propyl orthosilicate, while the second component comprises an organometallic compound which functions as the curing agent/catalyst. Dibutyl tin diacetate is the preferred catalyst for this reaction.
An adhesion promoter (primer) may optionally be used to induce a stronger bond between the silicone elastomer layers and the elastomeric base layer. Such primers are described in, e.g., U.S. Patent 3,434,869 (the disclosure of which is hereby incorporated by reference) and Canadian Patent 682,769.
Polyurethanes also have the potential to fill the prerequisites for use as a biocompatible coating in accordance with this invention. Of particular interest are segmented polyurethanes derived from long chain diols in which the amount of the hard segment and the degree of cross-linking are balanced such that the polymer is essentially non-crystalline and has low modulus and low set properties.
Segmented polyurethanes are block copolymers constituted by alternating segments of hard, rigid segments and soft, flexible segments. One discussion of their chemistry is found in Polymer Science and Technology, "Polymers in Medicine and Surgery,"- Kronenthal et al.. Volume 8, pp. 45-75. Generally, the hard and soft segments in these polymers are incompatible, so that icrophase separation or domain formation occurs. Where the soft segment is dominant, the hard segment domains serve as a physical cross-link and give the polymers elastomeric properties.
Polyurethane polymers suitable for the purposes of this invention are those which, upon curing, will form elastomeric layers or coatings having physical properties sufficiently similar to those of the substrate, such as the latex rubber layer, to avoid failure of the elastomeric coating upon stretching within the limits of its ultimate elongation,,
The polyurethane elastomers used in accordance with this invention may be prepared by the methods known and described in the prior art. The polyurethane elastomers are usually prepared from a long chain diol such as a linear polyester or polyether, preferably of molecular weight 1000 to 3000, a polyisocyanate, preferably a diisocyanate, and a low molecular weight chain extender such as a glycol or a diamine.
While several reaction sequences are known to the art and thus may be used to prepare the polyurethane elastomers, one of the most successful is the "prepolymer" method. In the first step of this method, the diol is caused to react with an excess of diisocyanate and the reaction product thus obtained is a liquid or low melting solid of a moderate molecular weight and which is referred to as a "prepolymer." The second step of this method is the addition of a low molecular weight glycol or diamine, with the ratio of reactants usually being chosen so that a slight excess of isocyanate groups is present. These isocyanate terminated prepolymers may advantageously be blocked or capped. That is, the terminal isocyanate groups may be reacted to stabilize the prepolymer against premature cure by atmospheric moisture. The capping agents may be any active hydrogen substance which may be volatilized or removed upon regeneration to free isocyanate groups at temperatures below those adverse to the substrate. Preferably, these isocyanate precursors should decompose at a temperature not above about 250 to 300°F, and preferably between about 200 to 275°F. Examples of such blocking agents are diethylmalonate, acetonate, acetyl acetone, sodium bisulfite and acetone oxime.
The prepolymer is dissolved in a solvent to satisfy the prerequisites for establishing a uniform layer of polyurethane of predetermined thickness on the rubber substrate. By careful selection of the solvent or solvent blend, drying time and adhesion to substrate can be optimized. Some polyurethane prepolymers require polymer solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like. The latter solvents alone may not be ideal for manufacturing purposes for reasons of low volatility, cost, viscosity, or toxicity. Usually, diluents or blending solvents can be selected to improve these properties. Blending solvents which can be utilized are toluene, xylene, and other aromatic fractions. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl heptyl ketone, and cyclohexanone are illustrative of ketones miscible with the aforementioned polymer solvents. Chlorinated solvents such as methylene chloride, trichloroethylene and 1, 1, 1-trichloroethane are examples of blending solvents or diluents for the polymer solvents. The latter chlorinated solvents can be sole solvent for some segmented polyurethane prepolymers suitable for use in this invention. Where possible, a preferred solvent with high solubility for the prepolymer, a low boiling point and low toxicity is the chlorinated solvent methylene dichloride. Typical solution coating compositions contain approximately 15- 20 percent solids for optimum dip properties.
Segmented polyurethanes that can be used in this invention are described in U.S. Patent Nos. 3,382,138 and 4,463,156, the disclosures of which are hereby incorporated by reference.
While the adhesion of some polyurethanes to, for example, a natural rubber substrate will be adequate, the adhesion of other polyurethanes may not. A primer dip can be utilized to enhance the adhesion of the polyurethane to the natural rubber. The primer is, for example, a diisocyanate dissolved in a suitable solvent and dipped or sprayed onto the dry rubber surface prior to the polyurethane dip. Diisocyanates which can be utilized as primer in this step include aromatic and alicyclic diisocyanates such as 4,4'-diphenyl methane diisocyanate (MDI) , toluene diisocyanate (TDI) , isophorone diisocyanate (IPDI) , methylene bis (4- cyclohexylisocyanate) (HMDI) , etc.
A laminated product comprising base material and biocompatible coating according to the present invention is prepared by dipping, molding, spraying, bonding or other known methods. In the case of a hollow article such as a condom, the desired portion of inside surface of such article is, for example, coated by placing the coating material in the cavity of the article and then setting the article or its contents in a fixed position or subjecting it to any type of motion that will induce or facilitate the spread of the coating material on the desired portion of the inside surface of the article.
As an example of the manufacturing process in the case of a condom, a mandrel of appropriate size and configuration made of an appropriate material is dipped in a dispersion of medical silicone elastomer or other suitable biocompatible material. The dispersing media must not dissolve the central layer or cause it to swell. Water or other suitable solvent is generally employed; aromatic solvents, such as xylene and toluene or aliphatic solvents, such as heptane and hexane, are preferred. The solids content of the dispersion varies depending on the desired dwell time for the mandrel in the dispersion and on the desired thickness of the layer picked up by the mandrel from the dispersion with each dip. Presently preferred are a 10 to 50 percent by weight of solid silicone dispersion and a mandrel dwell time of 15 to 60 seconds. Emersion and withdrawal of the mandrel should be relatively slow; a speed of 6 to 10 inches per minute is suitable to insure uniform silicone coating.
In this embodiment of the inventive process, the first dip of the mandrel into the dispersion material forms the inside surface of the condom or other article. Depending on the chemistry of the silicone or other material, this first layer may need to be vulcanized before subsequent dips. The vulcanization may be accomplished by heating. As natural rubber or thermoplastics may deteriorate when heated, it is preferred that RTV silicone of the one component or two component type be used. The next dip is in a dispersion of natural rubber or thermoplastic. Again, the speed of dipping the mandrel, the dwell time of the mandrel, and the speed of withdrawal are adjusted to provide the desired thickness of the layer resulting from this dip. The solids content of the natural rubber dispersion also affects the thickness of the natural rubber layer. The natural rubber portion of the laminate may, in general, constitute the major portion of the total wall thickness of the article, primarily because of the strength of natural rubber. If the device is of the type where only the inner surface contacts cells or tissues, the manufacture of the article is completed by vulcanizing the natural rubber layer described above. Examples of such articles are gloves designed specifically for the protection of hands of the wearer and tissue or cell collection devices such as seminal collection devices, etc. If, however, the outer surface of the article also needs to be non-toxic and non-irritant, further dips in silicone or the like material are necessary subsequent to the natural rubber dip described above.
In an alternate process for manufacturing the product of this invention, a finished natural rubber article such as a condom is mounted on a mandrel and then dipped into silicone dispersion to coat the desired portion of the outer surface. If only the outer surface is to be coated, the product is finished at this stage. If only the inner surface is to be coated, the article is inverted to achieve this objective. If both surfaces are to be coated, the article is inverted after coating the outer surface, then the article is mounted on a mandrel and again dipped into a dispersion of non-toxic, non-irritant material. In this manner, both surfaces of the natural rubber article are coated with the biocompatible material.
Spraying of the dispersion material is a third example of how the desired laminated article is fabricated. By following a certain sequence of sprays onto a mandrel, the desired article is built sequentially. Alternatively, a finished natural rubber article is sprayed inside and out with a dispersion of a non-toxic coating material to create the barrier layer or layers desired. Condoms are customarily "straight" dipped, which means that glass, glazed porcelain,, plastic or polished metal molds (also referred to as forms or mandrils) are dipped into the latex compound without the use of coagulants which would tend to deposit too much rubber. The prewarmed molds enter and exit the latex compound at an orientation and speed designed to avoid entrapment of air bubbles and to minimize any run-backs of the liquid latex. After dipping, the latex film is dried while the forms are rotating on two axes. The latter movements are necessary to equilibrate the flow patterns of the liquid latex during drying. If a second or more dips are desirable, after the first- dip is dry, the molds are reimmersed into a latex compound similar or identical to the first compound then the dip and dry sequences are repeated. The two or more straight dips minimize the possibilities of pinholes being present in the product. After the dips are dry, a bead is rolled onto the condoms by impinging angled rotating brushes against the rotating molds and the top edge of the dipped product. After beading, the condoms are vulcanized in hot air ovens. Often, anti-blocking or lubricating finishes are applied either before or after the vulcanization and then the condoms are removed from the molds, inspected, and packaged.
Exemplary sequences applicable in this invention are as follows:
Urethane or silicone applied to one surface;
1) Clean prewarmed molds are dipped into the natural rubber latex compound and the film is established and dried in the same manner described for conventional condoms.
2) The dried natural rubber first dip is overdipped with a silicone or polyurethane in solvent solution. 3) The latter dip is dried using multi-axis rotation as described for conventional condoms.
4) The composite construction condoms are beaded and cured using the same sequences developed for conventional condoms. To be utilized for sperm collection, the polyurethane or silicone surface must be oriented to be the inside of the finished condom. urethane or silicone applied to both surfaces; - -
1) Clean prewarmed molds are dipped into a polyurethane or silicone in solvent solution.
2) The dipped films are dried while rotating in two directions as described earlier.
3) After the first dip is dry, the molds are dipped into the latex compound and this film is established and dried as described earlier.
4) A third dip of polyurethane or silicone is applied and dried using parameters described earlier.
To improve the laminate construction and adhesion of layer to layer, primer applications can be inserted prior to each succeeding dip. Primer may be dipped or spray applied and dried in an analogous manner to the other dips.
The thickness of the biocompatible barrier layer is not critical, as long as the layer functions to create the desired protective barrier. Generally, coatings as thin as one mil (1/1000 inch) or even less may be sufficient. Whereas coatings as thick as 250 mils may be suitable when the device is intended for collection or storage of semen. The coatings on prophylactic devices for use in minimizing or preventing the transmission of sexually transmitted diseases (STDs) will be substantially thinner so as to preserve the requisite handling properties of the device. In the latter case, thicknesses on the order of up to 10 mils would be sufficient. If a therapeutic agent, preservative or nutrient is desired on a surface that comes into contact with tissues or cells, such preparations may be added to the silicone dispersion or the like material. These preparations become incorporated into the polymer portion of the dispersion and become entrapped in the surface coating.
In view of the semi-permeable nature of a film made of silicone or certain other polymers, drugs or similar preparations eventually migrate from the polymeric matrix to the surface and impart their therapeutic or other effect on the tissue or cells that come into contact therewith. In the case of a condom that is designed as a prophylactic device for preventing transmission of STDs, antimicrobial agents such as spermatocides, germicides or virucides, are suitably incorporated into the layer made of silicone
« or the like material.
A slow release lubricant is also suitably incorporated into the barrier layer or layers, so that the device will be permanently self-lubricating. Due to the non-wettable nature of silicone, dry lubricants are quite effective. Dry lubricants are conveniently pre-applied on a condom or packaged therewith to be applied just prior to use. The unique non-wettability of silicone actually reduces or eliminates the need for lubricant when the article is used in an aqueous environment.
In the case of a prophylactic condom for preventing transmission of STDs, an absorbent, suitably a powder, is placed inside the condom in a position and quantity to absorb the liquid portion of the semen, thus immobilizing the sperm and other microorganisms, viruses or any infectious agents that rely on fluid media for mobility and survival. This absorbent will also immobilize and impair the survival of infectious agents that might be able to penetrate the condom from the outside. The absorption of the seminal fluid by an agent within the cavity of the condom will also prevent spillage of such fluid due to loss of penile erection etc.
A biocompatible coagulant may be placed in the seminal collection device. This will change the consistency of the seminal fluid to a gelatinous form, thereby concentrating the seminal fluid and the sperm it contains rather than allowing the spread of the fluid and the sperm on the walls of the device. By maintaining an appropriate solid/fluid ratio in the coagulated material, incorporating a nutrient into the mixture and "maintaining the specimen at body temperature, it is possible to store sperm in this fashion for several hours.
Although condoms, finger cots and gloves are specifically mentioned in connection with this invention, and the utilization of biocompatible medical grade silicone in particular is discussed throughout this isclosure, it is not intended for this invention to be limited to these articles or to silicone materials, which are merely exemplary. Other articles and polymeric materials will be obvious to those of ordinary skill in the art.
The invention may be better understood with reference to the following examples, which are intended to illustrate the invention without in any way limiting the scope of the appended claims.
EXAMPLE 1
Glazed porcelain condom molds were cleaned for 60 seconds with an appropriate commercial cleaner (e.g. Oaklite Rust Stripper - 2 oz./gallon) at 160°F in an ultrasonic cleaning tank. The clean forms were dried in a 158°F oven for 10-15 minutes. The dried forms were equilibrated to 110+10°F and dipped into a 61% solids prevύlcanized natural latex designated as Revertex L.A. R (made by Revertex Ltd. of Harlow, Essex, England and available from Joseph Appleby Company, Chattanooga, Tennessee). Dipping was at insertion and withdrawal speeds designed to avoid air entrapment and to minimize latex run-backs. The forms were rotated until the wet film gelled sufficiently so as no longer to flow on the form. The latex film was dried for 15 minutes at 158βF or until all evidence (whiteness from moisture) of retained water had left the film.
For the silicone coating, a system that is commercially available from Dow Corning Corporation of Midland, Michigan was used. The system consists of:
(a) the base elastomer available as Dow Corning Q7-2630 — 50.0 parts by weight;
(b) the catalyst and cross linker available as Dow Corning Q7-2640 — 1.0 parts by weight; and
(c) a thinning agent available as Dow Corning Q7- 2650 ~ 50.0 parts by weight.
The latex coated forms were dipped slowly (to avoid air entrapment) into the silicone elastomer compound to a level of 1/2 inch from the latex dip line (to allow bead formation) . The form was withdrawn slowly to minimize run-backs of the silicone elastomer solution. The form was rotated until the silicone polymer was dry. The 1/2 inch latex band at the distal end of the condom was rolled into a bead.
The condoms were dried for 15 minutes at 158°F and then cured for 15 minutes at 235°F. The cured condoms were then dipped into a slurry of cross-linked rice starch or lycopodium powder which contained 0.5 to 1.0% active dimethyl polysiloxane silicone fluid. The latter was added in an emulsion form (e.g. Dow Corning 347 emulsion) . As the condom was rolled off the forms. some of the starch and silicone was transferred from the outside to the natural rubber inner surface, inhibiting blocking of both surfaces.
EXAMPLE 2
Clean glazed porcelain forms were coated with a semi-permanent fluoropoly er coating such as Vydax or Teflon R (made by and available from Ed. DuPont Corporation, Wilmington, Delaware) or equivalent. A commercial brand used with some success was S oner's Ink Co. fluorocarbon release coating, applied from a spray can.
The forms were dipped into the silicone elastomer solution and using the dip techniques as described in Example 1. After the elastomer had completely dried, all of the steps outlined for one side coating were undertaken to result in a condom which is a laminate construction of silicone elastomer/natural rubber/silicone elastomer-, The starch/silicone fluid slurry provides antiblocking analogous to one-side coated condoms.
Some of the condoms were stretched until they tore and the remnants were examined under a low-power microscope for delamination. None was apparent under these tests.

Claims

WHAT IS CLAIMED IS:
1. A prophylactic device comprising an elastomeric base material and a biocompatible barrier coating provided on at least a portion of one major surface thereof.
2. A prophylactic device according to claim 1 in the form of a condom.
3. A prophylactic device according to claim 1 wherein said biocompatible barrier coating comprises medical silicone elastomer.
»
4. A prophylactic device according to claim 1 wherein said biocompatible barrier coating comprises a fluoropolymer coating.
5. A prophylactic device according to claim 1 wherein said biocompatible barrier coating comprises polyurethane.
6. A prophylactic device according to claim 1 wherein said elastomeric base material comprises natural rubber.
7. A prophylactic device according to claim 1 wherein said elastomeric base material comprises a thermoplastic material.
8. A prophylactic device according to claim 1 wherein said major surface comprises an inner surface of said device.
9. A prophylactic device according to claim 8 further comprising an absorbant provided within a cavity formed by said inner surface.
10. A prophylactic device according to claim 8 further comprising a biocompatible coagulant provided within a cavity formed by said inner surface.
lie A prophylactic device according to claim 1 wherein said major surface comprises an outer surface of said device.
12c A prophylactic device according to claim 11 wherein said biocompatible barrier coating further includes a lubricant.
13. A prophylactic device according to claim 1 wherein said biocompatible barrier coating is provided on both inner and outer surfaces of said device.
14. A prophylactic device according to claim 13 wherein said biocompatible barrier coating further includes at least one component selected from the group consisting of therapeutic agents, anti-microbial agents, preservatives, nutrients and biocompatible coagulants.
15. A method for preparing a prophylactic device which comprises: providing a biocompatible barrier layer on at least a portion of one major surface of a preformed device comprising an elastomeric base material.
16. A method according to claim 15, wherein said biocompatible barrier layer is formed by dipping.
17. A method according to claim 15, wherein said biocompatible barrier layer is formed by spraying.
18. A method for preparing a prophylactic device which comprises: forming an elastomeric base material into a desired shape; and providing a biocompatible barrier layer on at least a portion of one major surface of said preformed elastomeric base material.
19. A method according to claim 18, wherein said elastomeric base material is formed by dipping.
20. A method according to claim 18, wherein said biocompatible barrier layer is applied by dipping.
21. A method for preparing a prophylactic device which comprises: forming a biocompatible material with elastomeric properties into a desired shape; and providing a coating of an elastomeric material on at least a first major surface of said preformed biocompatible material.
22. A method according to claim 21, further comprising providing a coating of biocompatible material over said elastomeric material on at least a portion of a second major surface of said elastomeric material opposite said first major surface.
PCT/US1988/004062 1987-11-13 1988-11-14 Prophylactic articles with biocompatible coatings WO1989004647A1 (en)

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EP0379271A3 (en) * 1989-01-18 1990-12-12 Becton Dickinson And Company Anti-infective and lubricious medical articles and method for their preparation
EP0427997A3 (en) * 1989-11-10 1991-08-07 Germo S.P.A. Condom
EP0441406A1 (en) * 1990-02-08 1991-08-14 London International U.S. Holdings Inc. Condom composition
EP0457127A3 (en) * 1990-05-15 1993-03-24 Bayer Ag Spermicidal coating
EP0557625A1 (en) * 1991-12-20 1993-09-01 Robin Renee Thill Shlenker Method of making latex articles
US5261421A (en) * 1988-04-23 1993-11-16 Smith & Nephew Plc Gloves, their manufacture and use
WO1994000166A1 (en) * 1992-06-30 1994-01-06 Government Of The United States As Represented By Secretary Department Of Health And Human Services Method for producing viral protective barrier materials
WO1995012420A1 (en) * 1993-11-04 1995-05-11 Bsi Corporation Barrier coatings for surfaces
WO1996023643A1 (en) * 1995-02-02 1996-08-08 Baxter International Inc. A process for making a glove having a polyurethane coating
WO1996023428A1 (en) * 1995-02-02 1996-08-08 Baxter International Inc. A multiple layered antimicrobial or antiviral glove
AU704557B2 (en) * 1995-03-31 1999-04-29 Mentor Corporation Two piece male condom catheter and method for manufacture
WO2003056955A1 (en) * 2001-12-21 2003-07-17 Kimberly-Clark Worldwide, Inc. Elastomeric articles having improved chemical resistance
DE10222268A1 (en) * 2002-05-18 2003-12-04 Mapa Gmbh Gummi Plastikwerke Condom and method of making a condom
DE10222990A1 (en) * 2001-05-31 2003-12-11 Viola Szabo Latex products for preventing and curbing infections are provided on their inner and/or outer surface with a preparation containing propolis
WO2004060432A1 (en) * 2002-12-23 2004-07-22 Kimberly-Clark Worldwide, Inc. Elastomeric articles with beneficial coating on skin-containing surface
US7052642B2 (en) 2003-06-11 2006-05-30 Kimberly-Clark Worldwide, Inc. Composition for forming an elastomeric article
WO2007070094A3 (en) * 2005-12-14 2007-11-22 Kimberly Clark Co Protective and therapeutic article
US20170172786A1 (en) * 2015-12-21 2017-06-22 Ansell Limited Coated condom
US10857026B2 (en) 2011-12-01 2020-12-08 Lrc Products Limited Coated condom

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US5261421A (en) * 1988-04-23 1993-11-16 Smith & Nephew Plc Gloves, their manufacture and use
EP0379271A3 (en) * 1989-01-18 1990-12-12 Becton Dickinson And Company Anti-infective and lubricious medical articles and method for their preparation
EP0427997A3 (en) * 1989-11-10 1991-08-07 Germo S.P.A. Condom
EP0441406A1 (en) * 1990-02-08 1991-08-14 London International U.S. Holdings Inc. Condom composition
EP0457127A3 (en) * 1990-05-15 1993-03-24 Bayer Ag Spermicidal coating
US5304375A (en) * 1990-05-15 1994-04-19 Bayer Aktiengesellschaft Spermicidal coating composition
EP0557625A1 (en) * 1991-12-20 1993-09-01 Robin Renee Thill Shlenker Method of making latex articles
EP1285743A1 (en) * 1991-12-20 2003-02-26 Robin Thill Beck Latex article
EP0924061A1 (en) * 1991-12-20 1999-06-23 Robin Thill Beck Latex article
WO1994000166A1 (en) * 1992-06-30 1994-01-06 Government Of The United States As Represented By Secretary Department Of Health And Human Services Method for producing viral protective barrier materials
US5671754A (en) * 1992-06-30 1997-09-30 The United States Of America As Represented By The Department Of Health And Human Services Viral-proofing a protective barrier
WO1995012420A1 (en) * 1993-11-04 1995-05-11 Bsi Corporation Barrier coatings for surfaces
WO1996023428A1 (en) * 1995-02-02 1996-08-08 Baxter International Inc. A multiple layered antimicrobial or antiviral glove
WO1996023643A1 (en) * 1995-02-02 1996-08-08 Baxter International Inc. A process for making a glove having a polyurethane coating
AU704557B2 (en) * 1995-03-31 1999-04-29 Mentor Corporation Two piece male condom catheter and method for manufacture
DE10222990A1 (en) * 2001-05-31 2003-12-11 Viola Szabo Latex products for preventing and curbing infections are provided on their inner and/or outer surface with a preparation containing propolis
WO2003056955A1 (en) * 2001-12-21 2003-07-17 Kimberly-Clark Worldwide, Inc. Elastomeric articles having improved chemical resistance
US7329442B2 (en) 2001-12-21 2008-02-12 Kimberly-Clark Worldwide, Inc. Elastomeric gloves having improved donnability
DE10222268A1 (en) * 2002-05-18 2003-12-04 Mapa Gmbh Gummi Plastikwerke Condom and method of making a condom
DE10222268B4 (en) * 2002-05-18 2004-07-15 Mapa Gmbh Gummi- Und Plastikwerke Condom and method of making a condom
WO2004060432A1 (en) * 2002-12-23 2004-07-22 Kimberly-Clark Worldwide, Inc. Elastomeric articles with beneficial coating on skin-containing surface
US7052642B2 (en) 2003-06-11 2006-05-30 Kimberly-Clark Worldwide, Inc. Composition for forming an elastomeric article
WO2007070094A3 (en) * 2005-12-14 2007-11-22 Kimberly Clark Co Protective and therapeutic article
US10857026B2 (en) 2011-12-01 2020-12-08 Lrc Products Limited Coated condom
US12090085B2 (en) 2011-12-01 2024-09-17 Lrc Products Limited Coated condom
US20170172786A1 (en) * 2015-12-21 2017-06-22 Ansell Limited Coated condom

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