WO1989004647A1 - Prophylactic articles with biocompatible coatings - Google Patents
Prophylactic articles with biocompatible coatings Download PDFInfo
- 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
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 230000000069 prophylactic effect Effects 0.000 title claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 35
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 30
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 30
- 229920001194 natural rubber Polymers 0.000 claims abstract description 30
- 230000004888 barrier function Effects 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 18
- 229920002635 polyurethane Polymers 0.000 claims abstract description 18
- 239000004814 polyurethane Substances 0.000 claims abstract description 18
- 229920001971 elastomer Polymers 0.000 claims abstract description 12
- 239000000560 biocompatible material Substances 0.000 claims abstract description 10
- 239000000806 elastomer Substances 0.000 claims abstract description 9
- 238000007598 dipping method Methods 0.000 claims abstract description 8
- 229920002529 medical grade silicone Polymers 0.000 claims abstract description 7
- 239000013536 elastomeric material Substances 0.000 claims abstract description 5
- 239000012815 thermoplastic material Substances 0.000 claims abstract description 4
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000000701 coagulant Substances 0.000 claims description 4
- 239000003814 drug Substances 0.000 claims description 4
- 235000015097 nutrients Nutrition 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000004599 antimicrobial Substances 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 229940124597 therapeutic agent Drugs 0.000 claims description 2
- 239000004446 fluoropolymer coating Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 229920001169 thermoplastic Polymers 0.000 abstract description 10
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 10
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 239000012678 infectious agent Substances 0.000 abstract description 5
- 229920001296 polysiloxane Polymers 0.000 description 33
- 239000002904 solvent Substances 0.000 description 20
- 239000006185 dispersion Substances 0.000 description 14
- 229920000126 latex Polymers 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000004816 latex Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229920002379 silicone rubber Polymers 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 210000000582 semen Anatomy 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 208000019802 Sexually transmitted disease Diseases 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 229920003225 polyurethane elastomer Polymers 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000002085 irritant Substances 0.000 description 2
- 231100000021 irritant Toxicity 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920003008 liquid latex Polymers 0.000 description 2
- 230000033001 locomotion Effects 0.000 description 2
- VKCYHJWLYTUGCC-UHFFFAOYSA-N nonan-2-one Chemical compound CCCCCCCC(C)=O VKCYHJWLYTUGCC-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229920002631 room-temperature vulcanizate silicone Polymers 0.000 description 2
- 229920000260 silastic Polymers 0.000 description 2
- 239000004447 silicone coating Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- 230000001225 therapeutic effect Effects 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 1
- 241000195947 Lycopodium Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000002009 allergenic effect Effects 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000018052 penile erection Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229940100486 rice starch Drugs 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000934 spermatocidal agent Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 239000012873 virucide Substances 0.000 description 1
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
- A61L31/00—Materials 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
- A61L31/08—Materials for coatings
- A61L31/10—Macromolecular materials
-
- 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
- A61F6/00—Contraceptive devices; Pessaries; Applicators therefor
- A61F6/02—Contraceptive devices; Pessaries; Applicators therefor for use by males
- A61F6/04—Condoms, 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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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
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.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12007287A | 1987-11-13 | 1987-11-13 | |
US120,072 | 1987-11-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1989004647A1 true WO1989004647A1 (en) | 1989-06-01 |
Family
ID=22388102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1988/004062 WO1989004647A1 (en) | 1987-11-13 | 1988-11-14 | Prophylactic articles with biocompatible coatings |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU2727588A (en) |
WO (1) | WO1989004647A1 (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3626517A (en) * | 1964-11-16 | 1971-12-14 | Sutures Inc | Rubber articles |
US4119094A (en) * | 1977-08-08 | 1978-10-10 | Biosearch Medical Products Inc. | Coated substrate having a low coefficient of friction hydrophilic coating and a method of making the same |
WO1981000345A1 (en) * | 1979-07-30 | 1981-02-19 | American Hospital Supply Corp | Hypoallergenic slip resistant gloves and methods of making same |
EP0113526A1 (en) * | 1982-11-30 | 1984-07-18 | Lrc Products Limited | Method of coating rubber or polymer articles |
-
1988
- 1988-11-14 AU AU27275/88A patent/AU2727588A/en not_active Abandoned
- 1988-11-14 WO PCT/US1988/004062 patent/WO1989004647A1/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3626517A (en) * | 1964-11-16 | 1971-12-14 | Sutures Inc | Rubber articles |
US4119094A (en) * | 1977-08-08 | 1978-10-10 | Biosearch Medical Products Inc. | Coated substrate having a low coefficient of friction hydrophilic coating and a method of making the same |
WO1981000345A1 (en) * | 1979-07-30 | 1981-02-19 | American Hospital Supply Corp | Hypoallergenic slip resistant gloves and methods of making same |
EP0113526A1 (en) * | 1982-11-30 | 1984-07-18 | Lrc Products Limited | Method of coating rubber or polymer articles |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Also Published As
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AU2727588A (en) | 1989-06-14 |
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