Flexible rubber article and method of making

Abstract: A multi-layer flexible article includes a first layer of natural rubber, a second layer of natural rubber, polyurethane, poly(acrylamide/acrylic acid) and polyethylene oxide and a third layer of acrylic copolymer and fluorocarbon telomer resin. The article is preferably a glove formed by the method of dipping a hand shaped mold into baths containing aqueous emulsions of the components used to form the layers. Gloves manufactured according to the method are substantially wet-hand and dry-hand donnable as compared to powdered latex gloves of similar size. The finished gloved is water washed and wet autoclaved to substantially reduce the protein content from the natural rubber and substantially remove other water extractable allergenic moieties. The washing and autoclaving renders the glove substantially hypoallergenic as compared to gloves not so treated.

Description: Field of Invention This invention relates to multi-layer gloves for use in medical procedures and the method of making same. Background of the Invention Flexible surgeon's gloves have very demanding requirements. They should have strength to resist tearing and should be thin and flexible to allow touch sensitivity. Further, they should be easy to don with wet or dry hands, but not be slippery for handling instruments. Traditionally, surgeon's gloves have been manufactured by dipping molds or forms shaped like hands into baths containing natural rubber latex emulsions to form a film of the desired thickness. The film is then cured and the glove is removed from the mold. There are numerous problems with the manufacture and use of natural rubber gloves, an important one of which is the step of removal from the mold form. Removal from the mold can be difficult because the cured latex tends to be tacky and may adhere to the mold. Further, plain natural rubber latex gloves adhere to themselves and tend to be very difficult for a surgeon to don. This is particularly true in actual use situations where a sterility protocol is followed with the surgeon having wet hands. Techniques for addressing these problems have developed over the years. Initially, mold-release powders were dusted onto the surface of the mold forms to facilitate the removal of the glove from the form. Since the gloves are generally turned inside out as they are stripped from the form, these powders then aided the subsequent donning of the glove by the surgeon. A wide variety of powders including talc, lycopodium, calcium carbonate, starch and modified starches has been used. Problems were identified with granuloma formation in patients and attributed to powders, particularly talc and its use has long been abandoned. Powdered gloves are still widely accepted today with epichlorohydrin modified starches being used quite successfully as powders for gloves by carefully controlling the material used and the amounts present on each glove. As an alternate to powder, there are many disclosures of coating or treatments of gloves to modify their surface properties. These surface modifications have enjoyed varying degrees of success, as high quality powdered gloves are still considered optimum in terms of strength, tactility and ease of donning and removal. There are two general ways of achieving natural rubber latex gloves which do not require powder for donning, chemical treatment of the rubber surface and adding materials onto a natural rubber surface. Representative of the chemical treatment is halogenation. Halogenation renders a rubber surface slippery, but it is most effective in conjunction with dry hands and additionally, the treatment may weaken and embrittle the overall film. It may also adversely affect the shelf life of a sterile glove. There are many disclosures relating to adding materials to a rubber surface to improve its slip characteristics with both wet and dry skin. US 4,027,060 to Esemplare et al . discloses an article such as a rubber glove provided with an adherent slip comprising a rubber surface provided with an adherent slip coating of a synthetic polymer latex composition consisting essentially of about 5 to 95% by weight of a film-forming, non-elastomeric synthetic polymer component (1) having an elongation of at least about 200% and about 5 to 95% of a normally solid, non-elastomeric, synthetic polymer component (2) exhibiting an elongation of below about 20% and a coefficient of friction of up to about 0.20, said slip coating having an elongation of at least about 200 up to 700%, a coefficient of friction of up to about 0.25 and a thickness of below about 0.0127 mm (0.0005 inch.). Also representative of the disclosures, United States Patent 4,575,476 to Podell et al. Podell et al. teaches a dipped rubber article having a skin contacting surface layer formed of a hydrogel polymer, such as polyvinyl pyrrolidone, polyhydroxyethyl acrylate or methacrylate and copolymers of these with each other or with acrylic or methacrylic acid, or with 2-ethylhexyl acrylate or a ternary copolymer of 2-hydroxyethyl methacrylate, methacrylic acid and 2-ethylhexyl acrylate. Gloves prepared according to the teaching of Podell et al. can be shown to have less mechanical strength and reduced resistance to accelerated aging after sterilization compared to conventional powdered latex gloves. Under conditions of mechanical stress, such as extreme elongation as could occur during donning, they may partially delaminate and lose particles from the hydrogel coating. Further, they tend to be somewhat thicker than many powdered latex gloves thereby adversely affecting tactile sensitivity. Object of the Invention The object of the invention is to provide an improved multi-layer glove for use in medical procedures and a method for making such a glove. Summary of the Invention The present invention provides a multi-layer glove comprising: a patient contacting layer formed as a film from an aqueous natural rubber latex emulsion; a wearer contacting layer formed as a film from an aqueous emulsion comprising an acrylic copolymer and a fluorocarbon telomer resin; and a layer, intermediate said patient contacting layer and said wearer contacting layer, formed as a film from an aqueous emulsion comprising natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide. The present invention further provides a multilayer glove as defined in claim 5. The present invention also provides a method for making a multi-layer glove for use in medical procedures comprising: dipping a cleaned and coagulant coated hand mold having a surface in a first bath comprising an anionic emulsion of aqueous natural rubber latex; forming a first film of said latex on said surface; removing said mold having said film from said first bath; dipping said mold having said first film in a second bath comprising an aqueous emulsion of anionic natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide;forming a second film from said emulsion of said second bath over said first film; removing said mold having said second film over said first film from said second bath; dipping said mold having said first film and said second film into a third bath containing an aqueous emulsion of an acrylic copolymer and a fluorocarbon telomer resin; forming a third film over said second film and said first film from said third bath emulsion; removing said mold having said third film over said second film and said first film from said third bath; drying and curing said films on said mold to form a multi-layer unitary structure having a surface for contacting a wearer; stripping and everting said unitary structure for said mold thereby exposing on said multi-layer unitary structure a surface for contacting a patient; applying a coating of lubricant to at least one of said contact surfaces of said multi-layer unitary structure; washing and autoclaving said multi-layer unitary structure; and tumbling dry said multi-layer unitary structure, wherein said method results in formation of a glove. The multi-layer glove may be formed by dipping a hand shaped mold form in a series of baths. The preferred gloves are wet hand and dry hand donnable without the need for powder, and have greater strength compared to existing gloves of similar thickness. The structure of the gloves substantially reduces the incidence of air pinhole defects in manufacture of the gloves when compared to natural rubber latex gloves of similar thickness. Detailed Description In accordance with the present invention, a preferred embodiment is a surgeon's glove formed on the surface of a mold. The manufacture begins with a surface of a cleaned and coagulant treated mold form which is coated by dipping the mold in a bath containing a natural latex rubber emulsion. The glove molds are individual for the right and left hands. The molds are made in a variety of sizes and shapes corresponding to the various hand sizes for which the gloves are intended. The molds are preferably made of ceramic, most preferably porcelain, bisque or glazed, but other materials such as stainless steel, glass, hard woods and plastic may also be used. Suitable coagulants include, but are not limited to, calcium nitrate, calcium chloride, acetic acid, magnesium acetate, and the like. A bath with an aqueous solution of about 20 to 25%, preferably 22.5%, calcium chloride with about 0.1 to 0.2% octoxynol, preferably 0.15%, is preferred for coating the molds with coagulant. When the mold is dipped in the latex bath, the latex forms a patient contacting film on the surface of the coagulant coated mold which serves as a substrate for subsequent layers. The thickness of the substrate film and the subsequently applied layers is generally governed by the solids content of the emulsions, the quantity of the coagulant deposited on the mold, the temperature of the mold and the residence time of the mold in the baths. In a preferred embodiment, where the substrate is formed from natural rubber latex, the porcelain molds are cleaned in a bath with aqueous sodium hypochlorite of concentration about 2.5 to 5%, preferably 3.0%, then rinsed with 49 to 66°C (120 to 150°F.), preferably 57°C (135°F.), water and allowed to drain. The rinsed and drained molds are then dipped in the calcium chloride coagulant bath with a temperature preferably about 43 to 54°C (110 to 130°F.), most preferably 49°C (120°F.). The molds with the coagulant on their surface are dried at about 99 to 132°C (210 to 270°F.) for about 8 to 10 minutes, preferably 121°C (250° F.) for 8.5 minutes, then dipped into a bath containing an aqueous anionic natural rubber latex emulsion. The latex bath has a total solids content preferably about 25 to 35%, most preferably 30%, a temperature of preferably about 24 to 32°C (75 to 90°F.), most preferably 28°C (82°F.), and a pH about 9.5 to 10.6, most preferably, 10.1. The mold remains in the bath preferably about 20 to 30 seconds, most preferably 25 seconds, and is then removed, and preferably a minimum of 25 seconds is allowed for the latex film to gel. This forms the substrate layer. The mold with the substrate layer on its surface is now dipped into a second bath containing an aqueous emulsion of anionic natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide. The total solids content of the bath is preferably about 13 to 15%, most preferably 14%, at a temperature preferably about 24 to 32°C (75 to 90°F), most preferably 28°C (82°F), and a pH preferably about 7 to 10, most preferably 9. The proportions in parts per hundred of the components of the bath are anionic natural rubber latex, preferably 16 to 18, most preferably 17, polyurethane latex, preferably 11 to 13, most preferably 12, poly(acrylamide/acrylic acid) (10% carboxylic), preferably 0.35 to 0.43, most preferably 0.39, polyethylene oxide, preferably 0.26 to 0.32, most preferably 0.29, and water, preferably 69 to 71, most preferably 70. The mold is in the bath preferably about 25 to 45 seconds, most preferably 36, is then removed from the bath and dried, preferably about 71 to 93°C (160 to 200°F.), most preferably, 82°C (180°F.), preferably about 160 to 180 seconds, most preferably 180 seconds. This forms the intermediate layer. Following the formation of the intermediate layer over the substrate layer on the surface of the mold, the mold with the layers on its surface is spray washed, preferably about 10 to 20 minutes, most preferably 15 minutes, preferably with 49 to 66°C (120 to 150°F.), most preferably 54°C (130°F.), water, then air dried preferably about 1 to 3 minutes, most preferably 2.5 minutes, preferably about 93°C (200°F). After drying, the washed and dried mold with the layers on its surface has a wearer contacting layer applied over the intermediate layer by dipping the mold into a third bath containing an aqueous emulsion of acrylic copolymer and fluorocarbon telomer resin. The bath has a total solids content preferably about 2 to 3wt-%, most preferably 2.5%, and a composition in parts per hundred of acrylic copolymer preferably about 1.41 to 1.88, most preferably 1.65, fluorocarbon telomer resin preferably about 34 to 38, most preferably 36, and water, preferably about 60 to 65, most preferably 62.35. The bath has a pH preferably about 6.5 to 9, most preferably 7.3. After dipping, the mold remains in the bath preferably 25 to 45 seconds, most preferably 36 seconds, then is withdrawn. The mold with the layers on its surface is then dried and cured preferably about 40 to 50 minutes, most preferably 44 minutes, preferably about 102 to 113°C (215 to 235°F), most preferably 107°C (225°F). This drying and curing step causes the layers to form a unitary structure and completes the formation of a glove. The gloves are then stripped from the molds by everting them, having the effect of placing the last formed wearer layer on the inside. Preferably, the gloves are further treated by tumbling with a lubricant, preferably lanolin alkoxy ether, lanolin oil alkoxy ether, fluorocarbon telomer, silicone and the like, most preferably polydimethylsiloxane, preferably about 12 to 18 minutes, most preferably 15 minutes, preferably at 60 to 71°C (140 to 160°F.), most preferably 66°C (150°F) to apply a coating of the lubricant to the surface. Following the silicone treatment, the gloves are preferably water washed and subjected to a wet autoclaving cycle, preferably for 12 to 18 minutes, most preferably 15 minutes, preferably with a peak temperature about 93 to 149°C (200 to 300°F.), most preferably 121°C (250°F.), then tumble dried preferably about 20 to 30 minutes about 60 to 71°C (140 to 160° F), most preferably 30 minutes and 66°C (150°F). Natural rubber latex is known to have a protein component, which is believed to be responsible for some allergic reactions to articles formed from natural rubber. The water washing and wet autoclaving steps followed by drying produce a significant reduction in the protein component as well as substantially reducing any other water extractable allergenic moieties present compared to gloves not so treated and other commercial surgeon's gloves. The protein content was determined by the Bradford test, a widely used method for protein quantitation. There are many reports in the recent literature attributing allergic reactions, and, in some cases, anaphylaxis, to the proteins present in natural rubber latex. The instant invention's wet autoclaving step is believed to substantially remove and denature these proteins. A comparison using the Bradford test for protein level was made between gloves of the instant invention and known commercially available gloves intended for similar applications. Protein Content (ug/g of glove) Glove 5.7 Instant Invention 117.0 Surgikos MicroTouch 85.1 Baxter Triflex The ability of a material to cause irritation has historically been measured by the degree of irritation to rabbit eyes. Recent efforts to reduce the use of animals for this type of testing has led to the development of in vitro bacteria based tests. A test which has shown good correlation to the in vivo rabbit eye test for irritation potential is the luminescent bacterial toxicity test, provided under the trade name of Microtox. As shown in the table, the effective concentration (EC 50 ) is the weight of glove material in milligrams per 1000 milliliters of extraction medium required to reduce the light output of luminescent bacteria by 50%. The larger the number, the less cytotoxic the material. A comparison using the Microtox test between gloves of the instant invention and gloves produced under United States Patent 4,575,476 shows that the irritation potential of the instant invention is significantly less. Bioluminescence (EC 50 ) Glove 37,000 Instant Invention 2,568 U.S. 4,575,476 Gloves manufactured according to the above described method are substantially wet hand and dry hand donnable when compared to powdered natural rubber latex gloves of equivalent thickness and design. The intermediate layer and the wearer contacting layer applied to a natural rubber substrate can be used to impart a wet-slip and- a dry-slip property to articles other than gloves as desired. When the coating layers are coupled with the water washing and wet autoclaving process steps, the detectable protein level from the natural rubber may be substantially reduced. Further, the concentration of any other water extractable moieties having allergenic potential present in the article may be substantially reduced. The use of rubber gloves in medical practice has taken on added importance with the concern about Human Immunodeficiency Virus (HIV). The strength of a glove is an important consideration to users. The instant invention of a multi-layer glove surprisingly provides a statistically significantly higher tensile strength and tear strength compared to gloves manufactured according to the United States Patent No. 4,575,476. This improved strength is particularly surprising because the gloves of the instant invention are stronger even when their thickness is less than those produced under the US-A-4,575,476, a widely accepted powder-free glove. A comparison of physical properties is presented below using 30 samples for the instant invention and 20 samples of gloves produced under US-A-4,575,476. The test values and standard deviation for the values are shown. Comparison of Physical Properties (ASTM D3577-88, D412, D624) Instant Invention US 4,575,476 Tensile, PSI 4301 (240) 3730 (407) Tear, PLI 346 ( 44) 257 ( 39) % Elongation 903 ( 42) 898 ( 33) Modulus at 500% Elongation, PSI 548 ( 24) 425 ( 43) Thickness (Mils) Finger 8.2 10.9 Palm 8.7 9.7 Cuff 8.4 9.3 The property of high strength coupled with reduced thickness resulted in the glove being rated acceptable or better for tactile sensitivity by 91% of users in a controlled use multi-site study in comparison to other premium quality surgical gloves, both powdered and powder-free. The gloves manufactured according to the instant invention preferably have a patient contacting layer about 0.05 to 0.45 mm thick, more preferably 0.15 to 0.30 mm, an intermediate layer about 0.005 to 0.20 mm thick, more preferably 0.013 to 0.05mm and a wearer contacting layer about 0.0005 to 0.05 mm thick, more preferably 0.001 to 0.005mm. Another benefit of the instant invention is a reduced incidence of the "air pinhole" defect experienced in glove manufacture. In a well-run glove manufacturing operation, it is generally recognized that there is some running level of various defects. A defect level of about four per one thousand gloves has historically been seen for the "air pinhole" defect for natural rubber latex gloves. Most improvements to production processes are in the low percentage ranges. In the case of the instant invention, a substantial reduction of the "air pinhole" defect is achieved. In producing the instant invention a reduction in the occurrence of the "air pinhole" defect to below one in one thousand gloves may be achieved, thereby greatly increasing the yield for the process. It is believed that the application of the intermediate layer present in the instant multi-layer glove over the natural rubber substrate occludes many of the "air pinholes" present in the natural rubber layer, thereby reducing the occurrence of the "air pinhole" defect. A preferred method for manufacture of gloves of the present invention is shown as an example. It should be recognized that the components and the parameters presented here are to be considered exemplary of the principles of the invention and are not intended to limit the invention to those components and parameters illustrated. The scope of the invention will be measured by the appended claims and their equivalents. Example Gloves of the present invention were formed by executing the following steps: 1) Cleaned molds by dipping in an aqueous NaOCl (3.0%) bath, removed and rinsed with 57°C (135°F.) water; 2) Applied coagulant to molds by dipping in an aqueous bath, removed and air dried (8.5 min., 121°C (250°F.)) coagulant bath composition and conditions Parts per hundred w/w calcium chloride 22.5 Triton X-100(Rohm and Haas) 0.15 water 77.35 temperature 48.9°C (120°F.); 3) Applied aqueous natural rubber latex to molds (substrate) by dipping in a bath for 30 seconds; latex bath composition and conditions Temperature 28°C (82°F). pH 10.1 latex solids = 30%; 4) Removed from latex bath and allowed to gel for 30 seconds; 5) Applied intermediate layer over substrate by dipping molds in intermediate bath for 36 seconds; intermediate bath composition and conditions Parts per Hundred w/w Natural rubber latex (56% solids) 17.0 Polyurethane latex (Impranil DLN, Mobay) 12.0 Poly(acrylamide/acrylic acid sodium salt), 10% Carboxyl; (Polyscience 200,000 M.W.) 0.39 Polyethylene oxide (Polyox N-10 Union Carbide) 0.29 Water 70 Temperature 28°C (82°F.) pH=9 total solids = 14%; 6) Removed from intermediate bath and dried intermediate layer for 180 seconds at 93°C (200° F.); 7) spray washed with water for 15 minutes at 54°C (130°F.); 8) Dried for 2.5 minutes at 93°C (200°F.); 9) Applied wearer side coating by dipping molds in wearer side bath for 35 seconds wearer side bath composition and conditions Parts per hundred w/w Acrylic copolymer (Rhoplex HG-74; Rohm and Haas, 42.5%) 1.65 Fluorocarbon telomer resin (McLube 1829; McGee Ind., 5%) 36.0 Water 62.35 Total solids 2.5% pH =7.3 Temperature 29°C (85°F.); 10) Air dried and cured on molds; Time = 44 minutes Temperature 107°C (225°F.); 11) Gloves were removed from mold by everting; 12) Gloves were tumbled with silicone lubricant (polydimethyl siloxane, G.E. SM-2140), 15 minutes at 66°C (150°F.); 13) Gloves were water washed (5 min. at 82°C (180°F.)) and wet autoclaved for a 15 minute cycle with a peak temperature at 121°C (250° F.); and 14) Gloves were tumbled dry in 30 minutes at 66°C (150°F.) The gloves were subsequently sorted into pairs comprising a right hand and a left hand. A microorganism resistant package was formed from sealable paper laminate, and one pair of gloves was placed into each package. The package was then sealed and placed in a gamma radiation chamber for sterilization. Alternatively, packaging could be formed from non-woven, formed trays or the like, and sterilization could be conducted by steam, ethylene oxide or electron beam. The process of applying a second layer and third layer, described above as intermediate and wearer contacting layers, has been shown to have utility in cases where the first layer is a material other than a film of natural rubber latex. Articles such as vinyl examination gloves formed from plastisol Polyvinylchloride (PVC) have shown benefits in powder-free donnability and in strength when coated with the intermediate and wearer contacting layers as described in the above example for natural rubber latex substrates. Additionally, the plastisol PVC gloves have also successfully been coated with just the wearer contacting layer directly by omitting the intermediate layer, thereby acquiring powder-free donnability. Other substrate films and flexible articles made from materials such as polyurethanes, polychloroprene, styrene/butadiene copolymer, nitrile latex and the like may benefit from the wet-slip and dry-slip properties imparted to articles by the application of the intermediate film followed by the wearer contacting coating. These articles could include other medical devices such as condoms, catheters and the like. Coatings of the wet-slip and dry-slip enhancing films followed by the above disclosed water washing and wet autoclaving process may also greatly reduce the reported incidences of anaphylaxis reported with natural rubber enema probes and the like based on the protein reduction and cytotoxicity testing reported above.

Claims: A multi-layer glove for use in medical procedures comprising: a patient contacting layer formed as a film from an aqueous natural rubber latex emulsion; a wearer contacting layer formed as a film from an aqueous emulsion comprising an acrylic copolymer and a fluorocarbon telomer resin; and a layer, intermediate said patient contacting layer and said wearer contacting layer, formed as a film from an aqueous emulsion comprising natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide. The glove of claim 1 having an inner surface of said wearer contacting layer and an outer surface of said patient contacting layer and at least one of said surfaces having a coating of a lubricant. The glove of Claim 1 wherein said lubricant is selected from the group consisting of silicone, fluorocarbon telomer, lanolin oil alkoxy ethers and lanolin alkoxy ethers. The glove of claim 1 wherein said patient contacting layer is about 0.05 to 0.45 mm thick, said intermediate layer is about 0.005 to 0.20 mm thick and said wearer contacting layer is about 0.0005 to 0.05 mm thick. A multi-layer glove for use in medical procedures comprising: a patient contacting layer formed from a material selected from the group consisting of plastisol PVC, natural rubber latex, polyurethane latex, polychloroprene, styrene/butadiene copolymer and nitrile latex; a wearer contacting layer formed from an acrylic copolymer and fluorocarbon telomer resin; and a layer, intermediate said patient contacting layer and said wearer contacting layer, comprising natural rubber latex, polyurethane, poly(acrylamide/acrylic acid), and polyethylene oxide. A method for making a multi-layer glove for use in medical procedures comprising: dipping a cleaned and coagulant coated hand mold having a surface in a first bath comprising an anionic emulsion of aqueous natural rubber latex; forming a first film of said latex on said surface; removing said mold having said film from said first bath; dipping said mold having said first film in a second bath comprising an aqueous emulsion of anionic natural rubber latex, polyurethane latex, poly(acrylamide/acrylic acid) and polyethylene oxide; forming a second film from said emulsion of said second bath over said first film; removing said mold having said second film over said first film from said second bath; dipping said mold having said first film and said second film into a third bath containing an aqueous emulsion of an acrylic copolymer and a fluorocarbon telomer resin; forming a third film over said second film and said first film from said third bath emulsion; removing said mold having said third film over said second film and said first film from said third bath; drying and curing said films on said mold to form a multi-layer unitary structure having a surface for contacting a wearer; stripping and everting said unitary structure for said mold thereby exposing on said multi-layer unitary structure a surface for contacting a patient; applying a coating of lubricant to at least one of said contact surfaces of said multi-layer unitary structure; washing and autoclaving said multi-layer unitary structure; and tumbling dry said multi-layer unitary structure, wherein said method results in formation of a glove. The method of Claim 6 wherein said first bath for forming said patient contacting layer is an aqueous emulsion having about 25 to 30wt% total solids content and a pH about 9 to 11 comprising an anionic emulsion of natural rubber latex. The method of claim 6 wherein said second bath for forming said intermediate layer is an aqueous emulsion having about 10 to 20wt% total solids content and a pH about 7 to 10 comprising an anionic emulsion of natural rubber latex, an anionic emulsion of an aliphatic polyester polyurethane, a sodium salt of poly(acrylamide/acrylic acid) and polyethylene oxide. The method of claim 6 wherein said third bath for forming said patient contacting layer is an aqueous emulsion having about 1.5 to 4wt% total solids content and pH about 7 to 10 comprising acrylic copolymer and fluorocarbon telomer resin. The method of claim 5 wherein said washing and autoclaving step comprises a water wash for about 5 to 10 minutes at 66 to 93°C (about 150 to 200°F) and a wet autoclaving cycle for about 10 to 20 minutes with a peak temperature 82 to 138°C (about 180 to 280°F) which serves to substantially denature and extract proteins found in natural latex and substantially remove water extractable allergenic moieties, thereby rendering said gloves hypoallergenic compared to gloves not so treated.

Inventors: CHEN FUNG-BOR, HUANG WU-NAN, MANWILL NILES R, MUSCHELEWICZ ADANA, CHEN, FUNG-BOR, HUANG, WU-NAN, MANWILL, NILES R., MUSCHELEWICZ, ADANA
Applicants: MAXXIM MED INC, MAXXIM MEDICAL, INC.
Application year: 1993
Main classification: B29C41
IPC codes: A61B19, B29C41, B32B25