MXPA00004979A - Method of forming a membrane, especially a latex or polymer membrane, including multiple discrete layers - Google Patents

Abstract

Single and multiple layer membranes such as gloves and condoms include one or more deactivating barrier layers and/or indicating layers to indicate to a user membrane breach or the presence of a harmful substance in blood or body fluids. A membrane may include one or more permeable or semipermeable layers to disperse contained substances such as lubricants, biocides, spermicides, or indicators outwardly, and may also include permeable or semipermeable layers to allow transmission of body fluids or other environmental fluids inwardly into contact with an indicating or treating substance. An intermediate layer of a multi-layer membrane may include a substance to wipe, cleanse, sterilize, or otherwise treat a piercing needle. A membrane may include a sealing or coating to entrap indicators or other agents such as biocides therein. A method of making membranes such as gloves results in a double glove having discrete inner or outer layers joined only in a cuff region. Admixing of gentian violet with latex prior to membrane formation provides biocidal properties, anti-aging effects prolonging shelf-life and tear resistance, and reduces allergic reactions in latex-allergic users.

Description

METHOD FOR FORMING A MEMBRANE, ESPECIALLY A LATEX OR POLYMER MEMBRANE, INCLUDING MULTIPLE DISCRETE LAYERS TECHNICAL FIELD The present invention relates to membranes formed from materials including latex, polyurethane, polyethylene, rubber and other polymers and elastomers.

BACKGROUND OF THE INVENTION Known applications of such membranes include surgical and recognition gloves, condoms, diaphragms, bandages, sleeves, slippers, rubber boots, sterile garters, catheters, tubes, curtains, openings in the intestines, mouthpieces, baby pacifiers, nasal tubes. intragastric tubes, nasal gastric tubes, kidneys, referrals for eyes and brain, dental dams, dental appliances, leads for subclavian veins and arteries, and colostomy bags. Typically, during use, said membranes are in contact with the skin or other tissues of a person or an animal. In recent years, there has been a growing interest in improving these membranes to provide greater protection against the transmission of viruses such as hepatitis and HIV, as well as other pathogenic and harmful agents.

BRIEF DESCRIPTION OF THE INVENTION The present invention describes various embodiments that provide membranes with improved resistance to the transmission of viruses and other harmful agents, and capabilities to disinfect needles and other objects that traverse membranes, and also describes the provision of one or more indicator layers to detect and indicate membrane breakdown and the presence of viruses, and other pathogens, as well as harmful chemicals. In one aspect of the invention, a multi-layer construction membrane includes one or more internal layers, which serve as reservoirs for substances or agents such as biocides, lubricants or indicators, which can pass through one or more outer layers permeable, or semipermeable to make the reserve substance available on the outside of the membrane, or alternatively to prevent the external transmission of reserve substances while allowing the external substances to pass at least partially through the membrane . As an alternative to permeability, substantially impermeable layers can transmit the substance or agent by breaking or being traversed and completely containing the substances the rest of the time.

According to another aspect of the invention, a multi-layer construction membrane includes one or more internal layers, which serve as reservoirs for substances or agents such as biocides, lubricants, or indicators, which may come into contact with or interact with. another way with substances that pass through one or more outer layers of the membrane and with which they can react, indicate the presence of, or otherwise respond to, the presence of the substance originally outside the membrane. Said multi-layer membranes can be used to provide an antimicrobial action, disinfectant, or other action that kills or weakens infectious agents, microbes, viruses or bacteria, through a selective or controlled flow of substances or agents internal to the surface of the membrane. According to another aspect of the invention a multi-layered membrane provides a place for indicator materials such as a DNA probe-based reaction such as the "Branched DNA Probe" technique of Chiron, "Polymerase Chain Reaction" by Hoffman -LaRoche, or conventional color change indicator reactions, titration reactions, reactions to detect pH, and reactions to detect chemicals, viruses or other pathogens. The multilayer membrane includes one or more permeable or semipermeable covers to allow the migration of a material to be detected through one or more outer layers and in contact with a material or indicator system. One or more of the layers may be waterproof to prevent migration beyond the indicators or other reserve materials. In another aspect of the invention, indicators for detecting chemical substances, viruses or other pathogens are mixed with the membrane material, or with a layer of a multilayer membrane, or applied as a coating on an outer layer of the membrane or multi-layer membrane. Another aspect of the invention comprises providing an indicator to indicate rupture of a membrane. The indication can be provided by changing the color, changing the tone, for example, darker or lighter, changing the temperature, or changing the touch, for example, stiffness or tightness. Indicators such as cobalt chloride may indicate membrane breakdown by reaction in the presence of moisture. In another aspect of the invention, a permeable or semipermeable membrane of multilayer construction includes one or more internal layers which serve as reservoirs for substances or agents such as biocides, lubricants, hydrogels or indicators. The substances or agents can pass through the outer layer or layers to make the reserve substance available on the outside of the membrane. In another aspect of the invention, one or more semipermeable or permeable membrane layers allow the migration of a substance in a predetermined direction. For example, viruses or other pathogens can migrate inward in contact with an indicator or biocide. In addition or alternatively, biocides, lubricants, spermicides, antiseptics, or indicators, can migrate outward. In another aspect of the invention, a single layer or multiple layer membrane includes an indicator that is located on an internal or external surface to detect the presence of a virus or other harmful material disposed externally of the membrane and / or also indicates transmission. of a harmful material either partially or completely through the membrane. Another aspect of the invention includes the provision of a liquid or gel that increases the sensitivity to touch between the layers of a multilayer membrane. Another aspect of the invention comprises the distribution of microfibers or fibers such as Kevlar within or on a membrane that form a substance before or during the formation of the membrane to increase the strength and resistance to penetration thereof. In one aspect of the invention, the membrane includes an indicator that provides a rapid identifiable reaction in the presence of a harmful substance to alert the user. Examples of indicators include a DNA probe such as those developed by Chiron or Hoffman-LaRoche to detect the presence of particular viruses, or conventional color change indicator technology such as phenolphthalein reactions or pH indicator materials, chromophores, or dyes that they change in the presence of the substance to be detected.

In one aspect of the invention, a single-layer or multi-layer membrane carries out transport through one or more membrane layers by capillary or wicking action. The membrane or one or more layers may also constitute a size-selective membrane to limit the size of the viruses or microbes they traverse. In addition or alternatively, one or more of the membrane layers can be chemically selective. For example, membranes of the type used in filtration and purification processes can be used. In another aspect of the invention, a membrane including a permeable or semipermeable inner or outer layer comprises a sealing or coating treatment for trapping indicators or biocidal agents. The invention also contemplates the provision of an indicator distributed throughout the membrane or limited to a certain place or area on or in the membrane, such as in or on points or stripes. The indicator can be added to the membrane during training or after it is complete. In another aspect of the invention, a substance for treating needles in one or more internal layers of a membrane functions to clean, coat, wipe, scrub, disinfect, make less damaging or otherwise treat a needle or other object passing through. membranes. Another aspect of the invention describes a method for making a multilayer membrane, such as a glove or condom, in which the layers are joined in one or more predetermined regions, such as only in a fist or higher region. In another aspect of the invention, a method for mixing biocides that bind proteins such as gentian violet with wet latex prior to membrane formation increases the resistance thereof and / or reduces or eliminates allergic effects in allergic or sensitive persons to latex. In another aspect of the invention a patch with backing adhesive includes an antiseptic or cleansing agent that comes in contact with a needle or catheter traversing it.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 represents a schematic plan view illustrating a double glove produced in accordance with a method of the present invention. Figure 2 is a cross-sectional view illustrating the double glove of Figure 1 including a biocide disposed in an intermediate reservoir formed between the inner and outer glove layers. Figure 3 is a schematic plan view illustrating a double glove according to the present invention having an indicator strip with separate detection regions to indicate the presence of different pathogens or other harmful agents or chemicals in the user's environment of the glove. Figure 4 is a cross-sectional view illustrating an example of a multilayer membrane according to the present invention.

PREFERRED MODE OF INVENTION Needle-cover layer Needles, both hollow center and solid needles, as well as other pointed objects such as catheters, scalpels, wires, or bone fragments, have long been of concern to health care professionals and others in relationship with the infection that can transmit. The needles are usually in a sterile condition when removed from their wrappings; however, they can be inadvertently contaminated when they pass through a person's body and are potentially contaminated when they are removed from the body of an infected patient. It is common for people working in health care and hospital staff to accidentally sting with needles or other sharp objects both during and after their use. In accordance with the present invention, a material is incorporated into a multilayer membrane, such as a glove, for cleaning, coating, wiping, scrubbing, disinfecting, damaging or otherwise treating a needle or other pointed object. what happens through it. A membrane formed from liquid latexMembranes made with solvent, liquid polymers or other synthetic materials, or elastomers can be formed by immersion, the use of fluidized beds, or by spraying the liquid material in a former. After depositing one or more layers, an intermediate layer including a material having treatment properties is deposited. Then, one or more outer layers are formed and the membrane is cured or fixed according to conventional techniques. Polymers suitable for use in producing membranes according to the invention include prepolymers, ie polymers and precursors of low molecular weight polymers, prepolymers and polymer precursors dissolved in solvents, liquid monomers, and liquid monomers dissolved in solvents. Specific examples include low molecular weight polymers such as silicone rubber (polydimethylsiloxane: HO- (Si- (CH3) 2-O-) n-H) with n from 2 to 200; polymer precursors such as low molecular weight diol, for example HO - ((CH2) -O) s s) -H and low molecular weight diisocyanate, for example OCN-C6H6-CH2-C6H6-NCO which upon mixing and polymerized polyurethane form. Examples of solvents for low molecular weight polymers include xylene and n-hexane. Suitable solvents for polymer precursors include dimethylformamide and dimethyl sulfoxide. Examples of liquid monomers include alpha-alkylcyanoacrylate, wherein the alkyl group can be -methyl, -ethyl, -propyl, etc. Examples of solvents for liquid monomers include dimethylformamide. In the context of this disclosure, the terms prepolymer, polymer, and polymer precursors include mixtures of one or more prepolymers, polymers, or polymer precursors. In one embodiment of the invention, the layer for treating needles or pointed objects comprises a sticky coating such as urethane of a rubbery consistency, semi-cured latex, a gel, polymers, an adhesive, or a pituitary substance, with or without a biocide, antiseptic, or mixed sterilizing agent, as an inner layer. As the needle or other object passes through the membrane, the treatment substance tends to adhere to it, cover it, clean it, or otherwise inactivate any harmful substances that may adhere to it. The technique of the treatment of needles or sharp objects may include both chemical and mechanical aspects. For example, preferably the layer includes a biocide or antiseptic effective against pathogens. Also, the layer can also function to wipe blood and other bodily fluids from the needle as the latter passes through said layer. Alternatively, abrasive materials of a fine texture capable of physically removing or scrubbing materials with which the needle is covered can be used individually or in combination.

Examples of treatment chemicals added to a biocide in the inner needle treatment layer include polyethylene oxide, and a mixture of polyethylene oxide and glycerin. By forming latex membranes, a first layer of latex is deposited by immersion or spraying or by other conventional techniques. A biocide, such as a gentian violet solution, is thickened with a mixture of polyethylene oxide and glycerin. The thickened mixture is applied to the latex layer, allowed to dry to a certain degree, and then covered with one or more layers of latex. The needle treatment layer may also include adhesive or film-forming materials that would form a physical sheath or additional membrane over the needle or other sharp object and over the harmful agents therein. The needle treatment layer or layers may also include a detergent or other agent that modifies the surface tension properties of harmful agents in the needle making it possible for a subsequent layer to physically remove, contain, disinfect, or make less harmful the harmful agent, or to make it less likely to infect or contaminate the person or al that is on the opposite side of the membrane. The aforementioned approaches can be used individually or in combination and can be contained in the same layer or in separate layers of a multilayer membrane. There may or may not be coagulants and the use of natural latex and synthetic latex or substitutes for polymers or elastomers may be interchangeable.

Needle treatment patch The following describes a needle treatment patch and a method for its use in helping to disinfect a needle or other sharp object after or during use. In one modality, a small patch or disc with adhesive on the back can be glued to the area where the needle will penetrate. The disc may be similar to a crushed or flattened vitamin E pellet which is pierced by the needle before it passes through the skin. The disc includes an antimicrobial, antiseptic or cleansing ingredient that comes into contact with the needle before it passes through the skin and out of the skin. The disc may be transparent to help the health care professional locate a vein or other objective. In the same way, the adhesive can be arranged only around the outer periphery of the disc so that it is not carried within the puncture. The back side of the patch may include a biocide or antiseptic adapted to come into contact with the skin of a patient or al. The disc can be constructed in such a way that the texture or pattern allows penetration of the needle or syringe upon entering and then creates a wiping action by being pulled back through the disc. Preferably the patch includes an antimicrobial solution or disinfectant. The biocide or antiseptic solution contained in both embodiments may be of a gel-like and / or sticky consistency to help cover the needle or seal it when it leaves the body or patch. The patch may also be used in conjunction with insertion or fixation of catheters and ostomy products, and may be used in conjunction with long-term fixation of a catheter to inhibit the growth and / or transmission of pathogens. Adhesives for suitable patches, as set forth in the patent of E.U.A. No. 5,2345,957, the entire disclosure of which is incorporated herein by reference, include partially esterified polyacrylic acid polymers, including but not limited to, polyacrylic acid polymers entangled with a polyether polyalkenyl such as those commercially available from B.F. Goodrich, Cincinnati, Ohio, under the trademarks Carbopol 934, 934P, 940 and 941. Other suitable adhesives include natural and synthetic polysaccharides such as cellulose derivatives such as methylcellulose, cellulose acetate, carboxymethylcellulose, hydroxyethylcellulose and the like. Other suitable adhesives are pectin, a mixture of sulfated sucrose and aluminum hydroxide, hydrophilic polysaccharide gums such as exudates from natural plants, including karaya gum, gati gum, tragacanth gum, xanthan gum, jaraya gum and the like, as well as gums of seeds such as guar gum, locust bean gum, psilum seed gum and the like. Suitable biphoids for use in membranes according to the description of the present application include phenols, acridine dyes, gentian violet (crystal violet), chlorhexadine, Triclosan, Nonoxynol 9, Gluconate, dextran sulfate, benzalkonium, betadine, mercurochrome, salts of silver, and an extract of blue-green algae, in addition to a long list of other suitable biocides that are attached to this description before the claims.

Indicators and multilayer membranes In most environments where operations are performed, the doctor or surgeon does not know if the patient has a contagious disease carried by pathogens in the blood. It would be beneficial, especially for those people in the operating room and emergency room, to have an indicator on their glove that will alert them when they are in contact with the patient's blood or body fluid, the presence of a harmful, contagious or potentially fatal substance. in that fluid or blood. The present invention contemplates the provision of metering mechanisms to multiple immersion membranes or formed with solvents, including, but not limited to, gloves and condoms. The present invention describes the provision of indicators to alert the user of membrane breakage, as well as to alert the user of dangerous substances present in blood and other body fluids. As described in the patent of E.U.A. No. 4,935,260, reservoirs of fluid within a membrane may include colored, fluorescent or reactive substances that serve as an indicator if the membrane ruptures, is defective or becomes deranged. The present invention contemplates the provision of a visual indication to a user of membrane breakage by changing color or appearance of other physical means. An indicator change to a material in an inner layer of a multilayer membrane can be released by the presence of air, moisture, body fluids, harmful substances, change in electrical activity, surface tension, or partial pressure. The indicator system responds to an exposure of the indicator element to an external substance or change in the physical integrity of the surrounding membrane. Change of pH in the internal material due to exposure to substances outside the membrane can be an additional indicator mechanism. Other indicators suitable for use in membranes according to the present invention include indicator materials such as x_ a DNA probe based reaction such as the "Branched DNA Probe" technique of Chiron, "Polymerase Chain Reaction" by Hoffman-LaRoche , or conventional color change indicator reactions, to detect chemical substances, viruses or other pathogens. A multilayer membrane may include one or more permeable or semipermeable layers to allow the migration of a material to be detected through external layers and in contact with a material or indicator system. Other viral indicators and suitable indicator methods are described in the patents of E.U.A. Nos. 4,879,211; 4,942,122; 5,039,604; 5,093,230; 5,108,891; 5,149,623; 5,156,949; 5,208,321; 5,235,039; 5,260,189; 5,268,265; whose full descriptions are incorporated herein by reference. Next, a method for making a membrane including a color indicator for membrane disruption is set forth. 1.- By using conventional dipping, spraying, or other sheeting techniques, an initial layer is formed using elastomeric materials such as latex, solvent-made membranes, liquid polymers, or elastomers, or polymer films. A second layer is created by conventional techniques such as coating or dipping (with or without a coagulant) including an indicator material such as dyes, crystals, reactants, colored agents, or blocking substances. 2.- The dyes or indicators are selected to provide a remarkable change in appearance, feel, (rigidity, agglutination, consistency), or temperature, to indicate to the user that the membrane is compromised. 3. One or more additional elastomeric membrane layers are then formed to at least partially contain the indicator substance.

The present invention also contemplates the provision to a multi-layered membrane of an indicator to detect and indicate the presence of pathogens in the blood or other body fluids. The outer membrane layers are selected to be either waterproof, permeable, or selectively permeable to a substance included in a reserve created between the membrane layers, or to the substances, microbes or pathogens whose presence is to be detected. Instead of, or in addition to, the inclusion of several substances in a reservoir formed between membrane layers, the substances can be applied to internal or external surfaces of the membrane after formation. The multi-layer gloves according to the present invention, in addition to or instead of indicators, may also include one or more reserves disposed between adjacent membrane layers and containing one or more substances such as lubricants, biocides, spermicides, antiseptics, gels, hydrogels, pituitous substances, cleaning agents, surfactants, detergents, abrasives, coating agents, wiping agents, fibers, objects that increase sensitivity to touch, and sheet forming agents, so that said substance is substantially contained between the adjacent layers. One or more of the multiple membrane layers may be permeable or semipermeable to allow directional migration of (1) reserve substances externally to the membrane, or (2) external substances at least partially through the membrane.

An example of a multilayer membrane 50 according to the present invention is illustrated in Figure 4. The membrane 50 may, for example, comprise a condom. An inner waterproof layer 52 can be formed from latex or from a polymer material. A biocide and / or spermicide such as Nonoxynol 9 at least partially fill a reservoir 54 formed between the inner layer 52 and a medium or intermediate impermeable layer 56, which may also comprise a latex or polymer material. A lubricant fills a reservoir 58 formed between the intermediate layer 56 and an external permeable layer 60 to carry out a controlled release of the lubricant through the pores of the permeable layer 60 over time. The permeable layer 60 may comprise a membrane with pores that open to allow the lubricant in the reservoir 58 to penetrate when it is stretched under pressure. In case of rupture of the inner layer 52, the seminal fluids will initially come into contact with the biocide / spermicide in the reservoir 54, even in the event of a concurrent rupture of the intermediate layer 56. Similarly, in case of breaking of the intermediate layer 56, the vaginal fluids will initially also come into contact with the biocide / spermicide in the reservoir 54, even in the case of a concurrent rupture of the inner layer 52. The methods for introducing or forming the inner layer or one or more intermediate layers or outer layers of multi-layer membranes according to the present invention include dip forming methods and other techniques such as spray coating, sheet forming techniques, fluidized bed reservoir, steam reservoir, electric discharge reservoir, reservoir vacuum, centrifugal coating, and extrusion. Molding techniques, such as rotary molding, or other types of molding techniques employing positive or negative mold surfaces may be employed. Membranes or membrane layers according to the invention may also include latex, elastomer, or polymer or synthetic films wherein the membrane or membrane layer is coated with a desired substance such as biocides, lubricants, indicators, spermicides, antiseptics, gels, hydrogels, pituitous substances, cleaning agents, surfactants, detergents, abrasives, coating agents, cleaning agents by rubbing, fibers, objects that increase sensitivity to touch, and film-forming agents, and then treated on the surface to contain the coated substance. Examples of such surface treatment methods include treatment with a chemical such as chlorine or bromine, coating with a sealant such as silicone or an acrylic, a heat treatment process such as melting or glazing, treatment by exposure to reduced temperatures , mechanical treatment procedure such as winding, pressing, ultrasound, or radiofrequency heating. In each case the common objective is to substantially contain a desired substance on a surface of an inner, intermediate, or outer membrane layer.

The surface on one side can be designed to be impenetrable while the substance on the other side of the multilayer membrane can be designed to be permeable or selectively permeable. The indicator can be provided on an inner surface of single-layer or multi-layer membranes, or on the outer surface, where it can be exposed to a pathogenic agent or harmful substance or antibody to a harmful substance. Figure 3 illustrates an example of a glove 20 according to the present invention that includes inner 14 and outer 12 layers joined in a cuff region 16. An indicator strip 30 attached or otherwise coupled to the outer surface of glove 30 includes indicators separated in frames or regions 32, 34, and 36 to detect and indicate to the user the presence of pathogens or other harmful chemical agents or substances in the user's environment. For example, the indicator bar can show the presence of Streptococcus in Table 32, the presence of a retrovirus in Table 34 and the presence of Staphylococcus in Table 36. The indicator substance can be retained more effectively by the membrane if the same comprises a film selected from the family of polymers treated by luminescent discharge, such as polyethylene, tetrafluoroethylene PE (TFE / PE), polyethylene terephthalate (PET), TFE / PET, polytetrafluoroethylene (PTFE), PET (E / PET) treated by luminescent discharge by ethylene and PET (HMDS / PET) treated by luminescent discharge by hexamethyldisiloxane Preferably the indicator included in multi-layer membranes produces an identifiable reaction, which alerts the user to the presence of a potentially harmful substance. Indicators can be specific to any number of substances and microorganisms, including viruses (including HIV), bacteria, ys, undesirable and harmful chemicals, etc. Specific viral indicators may include DNA probe-based reactions such as the "Branched DNA Probe" technique from Chiron, "Polymerase Chain Reaction" from Hoffman-LaRoche, the elements the P-24 antigen kit, the Abbot preparation Lab or mixed preparation for GP-120. Additional examples of indicators include conventional color change indicator reactions where the material to be detected (pathogen, chemical, or other substance) could migrate through the outer membrane and reach the indicator system. Similarly, certain of these indicators could be mixed with the membrane material or a layer of the multilayer membrane or applied as a coating on the outer layer of the membrane or multi-layer membrane. For example, HIV and Hepatitis B belong to a family called the retrovirus family. The indicators that could capture the presence of HIV or its antigens in the blood are the P-24 antigen kit, and the preparation of Abbot Lab or mixed preparation for GP-120. Likewise, other tests can capture indications of the presence of a retrovirus or a lentivirus by reacting with a substance common to the virus family, such as in the cover of the virus family. The indicators can also capture antibodies to these harmful substances in body fluids such as blood, semen, or vaginal fluid. And it is particularly observed that a specific substance can be picked up instead of a family of harmful substances. Some of these indicators may be, but are not necessarily limited to, the family or group of peptides and synthetic epitopes.

Transdermal release When a glove is in use, sometimes a defect can be detected by several leak detection devices - some use changes in the electrical properties or patterns of material or surface of the material. These are not very beneficial if the user is not in a position to change their gloves and remove the defective glove or put another glove on top of it. The present invention describes a glove constructed in a multi-layered manner containing a chemical substance that can be released into the glove, close to the hand to protect the user, until he or she can take appropriate action. The technology applied to the membrane is similar to the existing transdermal patch technology. This technology is in use in nicotine patches and hormone release patches. These can provide a sustained release or a specific release due to a change in the electrical properties on the surface of the membrane or a break in the integrity of the same. Examples of transdermal patches are described in the patents of E.U.A. Nos. 4,286,592; 4,627,429; 4,839,174; 4,921, 475; 4,978,531; 5,008,110; 5,087,240; 5,163,899; 5,164,189; 5,230,896; 5,234,957; 5,262,165; 5,273,756; and 5,286,490; 5,290,561; whose full descriptions are incorporated herein by reference. The multilayer glove preferably contains an antiseptic / disinfectant pool that is released through the transdermal system when the glove film is deteriorated as indicated by a change in electrical properties, the presence of moisture or other indications of decreased the integrity of the glove.

Dual layer membrane immersion training method In many applications, the use of a double layer membrane can provide greater protection. For example, it is now an accepted practice for surgeons and other health care professionals to wear two pairs of gloves, one on top of the other to provide maximum protection from infection. In fact, some studies show that the use of two gloves together reduces the appearance of infections. Said double layer membrane configuration also creates a space that can serve as a reservoir, in particular when the layers of the membrane are joined in a fist or higher region. This reserve can be used to contain a variety of materials including biocides, materials to treat needles, liquids or gels that increase the sensitivity of touch, lubricants, spermicides, hydrogels, indicators, and scales, discs, or other materials to inhibit the penetration of needles and other pointed objects. The hydrogels can be of the type described in the U.S. patent. No. 4,499,154, the complete disclosure of which is incorporated herein by reference. Hydrogels can function to absorb a biocide and to keep the membrane layers separate, and can function as a coagulant or as a lubricant. Examples of lubricants within the scope of this application include water-soluble non-toxic chemical compounds that incorporate sodium or potassium in varied chemical combinations with carbonates, acetates, bicarbonates, acetate trihydrates and citrate dihydrates, as described in US Pat. No. 4,143,423, the complete disclosure of which is incorporated herein by reference. Other suitable lubricants include microspheres as described in the U.S.A. No. 5,073,365, the entire disclosure of which is incorporated herein by reference. It is possible to form a double glove or another double membrane in a multiple dipping manufacturing process. Latex gloves and condoms are produced in a conventional manner using an immersion forming method in which molded formers are immersed in liquid latex tanks. A method for making a double-layer latex membrane according to the present invention includes the following steps: 1. Clean the formers. 2. Heat the formers for 8 minutes at 98.8-104.4 ° C. 3. Immerse in coagulant solution such as CaCO3 plus alcohol plus NO3, (or calcium carbonate plus alcohol plus nitrate). 4. Stop rest 2-3 minutes. 5. Immerse in uncured latex. 6. Let stand 2-3 minutes 7. Leach with cold running water for 15 minutes ... let stand 2 minutes 8. Produce the rolling in the form of a ring. 9. Dry in the oven for 6 minutes. 10. Immerse in gentian violet in 1.5% solution in distilled water. (Other biocides or chemical substances can be substituted in several solutions, or optionally eliminate immersion in biocide, since it is possible to make a double glove or another membrane without the use of a biocide). 11. Dry in oven. 12. Let stand 5 minutes. 13. Immerse in 20% calcium nitrate coagulant or a higher concentration. 14. Immerse in uncured latex. 15. Let stand 8 minutes. 16. Dry in oven for 30 minutes to cure by heating the membrane to dry and acquire its final shape. 17. Sprinkle and remove the double membrane of the former. This method produces a glove inside a glove or a condom inside a condom attached to the fist or top. Figure 1 illustrates an example of a double glove 10 produced in accordance with the invention that includes a separate discrete outer layer 12 and an inner layer 14 joined in the fist region in a ring-shaped winding 16. As can easily be seen, the double glove of the invention 10 has substantial advantages in that it is easily put in comparison to separate single layer gloves. The space between the two membranes can be built with a step or additional steps of incorporation of different substances including but not limited to gels, biocides, chemicals, silicones, neutralizing chemicals, pH regulating chemicals, spermicides, lubricants, boosters, sensitivity to touch, and scales, discs, or other materials to inhibit the penetration of needles and other sharp objects. For example, as shown in Figure 2, the reservoir 15 formed between the inner layer 14 and the outer layer 12 of the glove can be filled with a biocide such as gentian violet. It should be appreciated that this double membrane configuration can also be made by the above method with a biocidal component by immersing in biocide before immersing in the coagulant, or by mixing the biocide or chemical with the coagulant.

The outstanding steps in the above method comprise: (a) depositing a first layer of latex in a former; (b) treating the first layer with an effective material such as a latex coagulant; (c) depositing on the first layer in the former a second layer of latex, with the effective coagulant to substantially prevent melting of the first and second layers; and (d) fixing or curing the first and second layers. It is particularly preferred that the coagulant is not applied to an upper or fist region extending circumferentially of the first layer so that the first and second layers are fused in the fist region to form a reserve in the remaining regions. Before the application of coagulant to the first layer, a substance can be deposited on the first layer in the former, selecting the substance from the group consisting of biocides, indicators, spermicides, antiseptics, gels, hydrogels, pituitary substances, cleaning agents, surfactants, detergents, abrasives, disks, flakes, and other materials to inhibit the penetration of needles and other pointed objects, coating agents, rubbing agents, fibers, objects that increase sensitivity to touch, and film forming agents , so that the substance is substantially contained between the first latex layer and the second latex layer. Said intermediates can also be mixed to be applied with the coagulant.

In another example of a method for making a double latex membrane according to the present invention, such as "double gloves", a glove mold or former heated at about 70 ° C is first immersed in a coagulating suspension in a conventional manner. This coating is dried in the oven at approximately 80 ° C for 5 minutes. The mold is then immersed in a latex compound, available under the name Vultex 1-N-4402 at 38% solids from General Látex and Chemical Corporation, with a residence time of approximately five seconds. The deposit is then partially dried at 80 ° C for about one minute. Then the latex tank is leached in hot water for about three minutes and dried in the oven at 100 ° C for five minutes or until the latex tank is completely dry. A coating of zinc stearate emulsion separating agent in water at about 3-5% solids is applied on the first layer of latex in the former, except in a region at 2.54-5.08 cm from the fist or flange area, by spraying or alternatively by immersion. The zinc stearate coating is then dried at about 100 ° C for about three to five minutes and a powder-free coagulant is applied on the first latex coating. This coagulant coating is then dried at about 80 ° C for five minutes and then the former is immersed again in the latex compound, adjusting the immersion rates to provide a uniform second layer. Then the second layer is partially dried for about one minute at about 80 ° C and leached in hot water for about three minutes. Then the second layer of latex is cured at 125 ° C for twenty minutes. A coating of corn starch powder is applied, and the glove is removed after the former. The resulting glove has two discrete layers, except in the region at 2.54-5.08 cm from the cuff or flange, where the glove consists of a single layer. The separating agent can be applied either after the second coagulant coating, or alternatively it can be incorporated into the second coagulant formulation for concurrent application therewith. A variety of separating agents of different potential can be employed, including: zinc stearates and other stearates, hydrogel compositions, powders such as calcium carbonate, corn starch, microspheres, wax emulsions such as paraffin and microcrystalline, silicon emulsions. , gentian violet at high concentrations, silicon oil, acrylic separating compositions, separate healing of latex layers, and chlorination of the first layer of latex before the application of the second layer. The formation of the second layer requires flexibility with respect to the immersion rates depending on the particular latex formulations, separating agent, and coagulants employed. For example, different immersion speeds can be employed in the fist region (which is not coated with the separating agent) and the main body region, and / or the second layer can be dipped twice in the main region and submerged once in the fist region. The temperatures, speeds, and residence time will also vary depending on the particular formulations employed. Another example of a method for being a multi-layer membrane according to the present invention includes the following steps: I. Cleaning the formers. 2. Heat the formers for 8 minutes at 65 ° C. 3. Immerse in latex, while rotating the formers. 4. Heat the formers for three minutes at 65 ° C. 5. Cool. 6. Immerse in uncured latex while rotating the formers. 7. Heat the formers for three minutes at 65 ° C. 8. Immerse in Cal-Dip solution (a stearate compound from Rubichem, Inc.) using 37.4 gms of Cal-Dip per 22.6 gms of isopropyl alcohol. (water can be used instead of alcohol). 9. Heat the formers for one minute at 65 ° C. 10. Immerse in latex, while rotating the formers. I I. Cure for three minutes at 65 ° C. 12. Leach with water for three minutes. 17. Dry, dust and remove the trainer's membrane. Suitable release agents or tackifiers for use in the present invention include calcium stearate, zinc stearate, and ammonium stearate as layer separating agents. In addition, the chlorination of the finished membrane or intermediate layers during formation can be employed as a release agent. A method for forming a polymeric multilayer membrane according to the present invention includes the steps of: (a) depositing in a former a material selected from the group consisting of liquid polymers and polymers dissolved in a solvent to form a first layer; (b) treating the first layer with a surfactant; (c) depositing on the first layer in the former a material selected from the group consisting of liquid polymers and polymers dissolved in a solvent to form a second layer, wherein the surfactant is effective to substantially prevent melting of the first and second layers. layers; and (d) fixing or curing the first and second layers. As in the method for making latex membranes, a variety of substances can be provided in an intermediate or reserve layer between the first and second layers. Examples of surfactants include ionic surfactants capable of emulsifying or destabilizing polymers in a known manner. In the context of this application, the term polymer includes synthetic materials based on water. It is also believed that it is possible to use other techniques to produce membranes having multiple discrete latex or polymer layers. For example, the temperatures of the mold / former and / or the latex or polymer bath, leach bath, furnace, and / or a surrounding chamber can be varied to different stages in the process. For example, the first latex or polymer layer could be cooled prior to the application of the second layer to form separate layers in the resulting membrane. In addition, the application of sound, ultrasound, or thermal shocks could be used to separate or facilitate the separation of layers. In the same way, irradiation with energy of several frequencies of the electromagnetic spectrum can be used. In the case of both latex and polymer or synthetic membranes, the first and second layers can be selectively melted or separated by selective application and / or variations in the release agent, coagulant or surfactant formulation. For example the first and second layers could be fused or joined in selected areas of a glove such as the palm, the back of the hand, the knuckles, the fingertips. A similar selective binding could be employed with other multilayer membranes such as condoms. For example, multiple layers of a condom could be selectively joined at the tip and / or intermediate region. A bubble or blister effect can also be created by melting two layers of a multilayer membrane in such a manner to create discrete sealed chambers. Said chambers may contain a variety of different solids, liquids, and gases such as lubricants, sealants, biocides, indicators, spermicides, antiseptics, gels, hydrogels, pituitary substances, cleaning agents, surfactants, detergents, abrasives, coating agents, agents cleaning by rubbing, fibers, objects that increase sensitivity to touch, and discs, scales and other materials to inhibit the penetration of needles and other sharp objects. For example, the cameras could contain liquids or gases to provide a damping effect. Alternatively, the cameras could contain materials that combine when the cameras are broken to provide an indicator effect. You could also select various materials that combine to provide a color change, heating effect, disinfectant or biocide, rigidity, softening, or alteration in touch sensitivity. It is also possible to vary the extent of separation or melting of the layers of a multilayer membrane by varying the chemistry of the latex or polymer, the chemistry of the separating agent, surfactant or coagulant, cure times and temperatures, immersion velocity and times of permanence, and through other methods, such as chlorination. The degree of separation or melting of the layers can vary from completely discrete layers to layers which, although initially glued, can be separated by detachment with a little effort.

As an alternative to dipping or spraying of latex, synthetic or polymer membranes having multiple discrete layers, the techniques described above can also be employed in connection with conventional sheet and extrusion processes to be a variety of other multi-layer membranes. For example, medical or other multi-layer tubes can be formed using an extrusion process. As in the case of immersion or spray forming techniques, the multiple layers of multi-layer membranes formed by sheeting or extrusion techniques can be joined or fused to selected and discrete or discrete regions in other selected regions. Said multi-layer membranes find applications in cases where a greater measure of safety against rupture is desired, for example in colostomy bags. The texture or other characteristics of the individual latex or polymer layers of a multilayer membrane could be different. For example, the former could be tilted and / or rotated differently by forming different layers to provide an improved strength membrane. Alternatively, different layers could be applied during the application of different electrostatic or magnetic fields. In addition, the various layers could be formed of different materials such as latexes, polymers, and synthetics, possibly treated in several different ways, such as conventional chlorination treatments of latex layers.

Incorporation of biocide into polyurethane films Luminescent discharge treatment techniques can be used to increase the uptake and retention properties of certain polymer families. Biocides can be captured and retained more effectively by certain polymer films. The film can be selected from the family of polymers treated by luminescent discharge, such as polyethylene, PE (TFE / PE) treated by luminescent discharge by tetrafluoroethylene, polyethylene terephthalate (PET), TFE / PET, polytetrafluoroethylene (PTFE), PET (E / PET) treated by luminescent discharge by ethylene and PET (HMDS / PET) treated by luminescent discharge by hexamethyldisiloxane, or any of the other polymers treated by the luminescent discharge process. The biocides can be applied directly to films treated by luminescent discharge. The resulting films may be a bit stiffer but very strong and therefore thinner films will be satisfactory for many applications. Alternatively, biocides can be fed, like a gas, into a chamber and deposited directly creating the luminescent discharge or RF discharge to facilitate depositing. In addition, the biocides can be introduced into and / or into the polymer during the manufacture of the film so that they are available to provide disinfecting properties. This can be carried out by conventional dipping or mixing, with additional layers deposited by dipping, fabrication, spray coating, vacuum storage, fluidized beds traversing, centrifugal rotation, etc. External coatings can be formed by similar techniques to contain the biocide and minimize leaching where appropriate. Coatings within the scope of the present invention include spermicides such as Nonoxynol-9 and one or more organopolysiloxane compounds that can be applied to latex membranes as described in the U.S.A. No. 5,304,375, the complete disclosure of which is incorporated herein by reference. The rubber membranes can be provided with a transparent coating of an aqueous composition containing a preformed latex binder, an emulsifying agent, an inorganic compound containing fluoro, and a thickening agent as described in the US patent. No. 5,182,142, the complete disclosure of which is incorporated herein by reference. Also, a cellulosic coating material including synthetic latex formed by emulsification of cellulosic polymers stabilized by surfactants and containing a water-soluble pore-forming agent and a plasticizer, as described in U.S. Pat. No. 5,126,146, the complete disclosure of which is incorporated herein by reference.

Incorporation of biocide into porous and non-porous polyurethane films This can be done in the four ways described below. All but the last require that the biocide have a low vapor pressure at room temperature (less than -0.013 bar). In all cases, the solvents that come into contact with the biocide must not react with or chemically alter the biocide in such a way that its antibacterial and antiviral activity is irreversibly destroyed. (1) Physical entrapment of the biocide in the pores of a porous film.

A. Introduction of the biocide during the manufacture of the film These films can be manufactured using (1) a fully polymerized polyurethane dissolved in a suitable solvent, or (2) using a polyurethane prepolymer of molecular weight 1000 to 3000 dissolved in a solvent and subsequently vulcanized or cured with an interlacing or curing agent added to the solution. In both cases, the solvents must be solvent for both the biocide and the polyurethane. The solvents for this purpose will depend on the type of polyurethane: polyether, polyester or polyester-polyamide, and the type of biocide.

Some solvents that can be used are listed in the following table.

TABLE 1 Solvents that can be used and their solubility parameters Solvent Hydrogen bonding parameter solubility Dimethylformamide (DMF) 12.1 Medium Dimethylacetamide (DMF) 10.8 Medium Tetrahydrofuran (THF) 9.1 Medium Dimethyl sulfoxide (DMS) 12 Dioxane medium 1, 4 10 Medium Strong phenol m-Cresol 10.2 Strong Formic acid 12.1 Strong Sulfuric acid Strong Methyl ethyl ketone 9.3 Medium Diethyl ketone 8.8 Medium Ethylene glycol monoethyl ether 10.5 Ethylene glycol monomethyl ether medium 11.4 Medium The use of water soluble polymers is also contemplated within the scope of the present invention. You can also use the mixtures of these solvents with each other and with non-solvents that have solubility parameters in the scale: from 8 to 24 (cals / cc) 1/2 and medium or strong hydrogen bonding. The biocide is first dissolved in said solvent or solvent mixture, to form an almost saturated solution, and then mixed with a solution of the polyurethane or urethane prepolymer in the same solvent or a similar one. In the case of solutions containing the polyurethane prepolymer, the curing agent (typically amines or alcohols with functionality of 2 or more) is added to the polymer plus the biocide solution just before making the films. The films of the resulting mixture are then manufactured using the methods described in the Gilding patents: US patents. Nos. 4,813,966 and 4,704,130, the complete descriptions of which are incorporated herein by reference, with the following modifications. During the immersion of the film made in the precipitation bath, and subsequently in the solvent extraction bath, there will be a tendency for the biocide to leach out of the rubber and into the bath solution. This leaching can be reduced in two ways (1) saturate the precipitation bath or extraction with the biocide, or (2) use low polarity liquids (having solubility parameters less than -9 (cals / cc) 1 2 and link of weak hydrogen) in the precipitation and extraction baths. Because most biocides are strongly polar, they will tend to remain in the medium to strongly polar polyurethane environment instead of being extracted in the bath. During subsequent drying and annealing, the remaining solvent is removed leaving the biocide physically trapped in the pores of the film.

B. Introduction of the biocide after manufacture of the film A porous polyurethane film can be swollen with a solvent or solvent mixture from Table 1, or with a mixture of said solvents with non-solvents, saturated with a biocide. In the case of a linear polyurethane, the proportion of non-solvent must be adjusted so that the solvent mixture swells the soft segments (polyether segments) of the urethane chain, but do not dissolve the polymer. During swelling, the solvent / swelling agent carries the biocide through the polymer structure and into the pores. After removing the film from the biocide solution, the film is dried and annealed, which removes the swelling agent and leaves the biocide trapped in the pores as well as in the polymer matrix. (2) Adsorption of the biocide on internal pore surfaces. This method is applied to porous films. The same procedures as in 1A and 1B are followed except that the extraction of solvent or swelling agent from the rubber is carried out mainly by immersion of the film in a bath of non-solvent of low polarity (for meter of lower solubility to 9 (cal / cc) 1/2 and weak hydrogen bond). In this case, the non-solvent bath is not saturated with the biocide, therefore there will be a strong tendency for the biocide to adsorb to the polyurethane pore surfaces (as well as to be trapped within the rubber matrix). The biocide molecules not adsorbed in the pores will be leached out in the non-solvent leaving the biocide adsorbed on the pore surfaces. Any solvent or non-solvent remaining in the films can be removed by drying and annealing. (3) Precipitation of the biocide within the rubber matrix. This method is applied to non-porous urethane films. The same procedures as in 1A and 1B are used except that the methods for producing the pores, described in the Gilding patents do not apply. Instead, the films are simply manufactured from the solution using common film forming procedures: dip coating, spraying, spinning, etc. In case of the prefabricated films the diffusion of the swelling agent plus the biocide can be increased by stretching the rubber film biaxially. The extraction of the solvent / swelling agent is carried out by drying and annealing. A non-solvent bath saturated with bioside can also be used as in (1) but drying is preferred. As the concentration of the solvent / swelling agent in the rubber decreases, the biocide will precipitate outwardly forming phase-separated regions within the rubber matrix. (4) Chemical link of the biocide to functional groups in the polyurethane chains. This method applies to both porous and non-porous films. Polyurethanes have the advantage that the urethane and urea bonds in the chains are relatively reactive. In addition, the rubber can easily be formulated to have excess amine, -OH or isocyanate groups at chain ends or branch points, by simply deviating slightly from the stoichiometric proportions of 1: 1 isocyanate: amine or isocyanate groups: -OH groups . The biocide molecules can then be chemically linked to said groups. It is important that such a link is carried out in such a way that the biocidal activity of these molecules is not compromised. Said binding reactions can be carried out (1) before the manufacture of the film, while the polyurethane or urethane prepolymer is in solution (after the addition of the entrainer or curing agent), or (2) after the movie making. In the first case, the biocide binding reaction would take place with the polyurethane in solution. In the second case, the biocide binding reaction would take place in the swollen rubber network. In both cases, the solvent or swelling agents must remain inert during the binding reaction. After the reaction, the solvent or swelling agent is removed as described in sections (1) or (3). Although the biocide is chemically bonded to the polyurethane chains, it will continue to separate in phases in the rubber matrix, but on a much finer scale than with the method described in section (3). The need to use solvents or swelling agent can be avoided by using water-based synthetic materials. (5) Sealing of the film surfaces. For all the above methods, it is very convenient to apply a final coating to seal the surfaces of the film to prevent leaching of the biocide during use or storage. Said coating can be applied by a final immersion in a low viscosity polyurethane solution (low percentage solid), or by plasma or vapor deposition of a thin elastic polymer film.

Mixture of gentian violet with latex In accordance with one aspect of the invention, gentian violet is mixed with liquid latex before membrane formation by immersion or spraying techniques. A wide variety of different concentrations can be used, but a 1.5% by weight solution of gentian violet is preferred. The applicant has found that in addition to the biocidal properties, the addition of gentian violet by mixing produces two unexpected results. Gentian violet seems to bind protein molecules in latex, which results in two important benefits. First, this produces an anti-aging or anti-oxidation effect that lengthens the shelf life and increases tear resistance. Second, it seems to minimize allergic reactions in allergic or latex-sensitive users. Other biocides that bind proteins that can be used instead of or in combination with gentian violet.

Reinforcement with microfibers The present invention also contemplates a membrane reinforcement by the addition of micro fibers during the production process. Microfibers such as aramid, Kevlar, glass fibers, natural fibers, nylon, and graphite can be mixed directly with latex or polymer membrane materials either before, during, or after application. Said fiber reinforcement can be used in relation to a single layer membrane, or in one or more layers of a multi-layer membrane. The fiber reinforcement can also be carried out by adding one or more layers of preformed sheet in a multi-layer membrane. Reinforcement may also be employed by incorporating a monofilament, similar to fishing line, into or between one or more layers, or winding the monofilament in a predetermined pattern around or between one or more layers. Fish-like particles or small discs can also be used to increase the resistance and resistance to penetration of the membranes. Said flakes or disks can be incorporated in or disposed between one or more layers of a single layer or multiple layer membrane. The flakes or discs could also include magnetic properties so that they could be oriented in a predetermined manner by application of an electromagnetic or magnetic field during membrane formation.

List of biocides that applicants believe are suitable for use in connection with the invention described Taken from a book entitled Cosmetic Ingredients Dictionary of the CTFA, third edition. 1982, published by The Cosmetic. Toiletry and Fragrance Association. Inc., Washington, D.C. BLUE HC NO. 1 N4, N4-Bls (2-Hydroxyethyl) -N1-Methyl-2-Nitro-p-phenylenediamine BLUE HC NO. 2 N1, N4, N4- (2-Hydroxyethyl) -2-Nitro-p-phenylenediamine BLUE HC NO. 3 Cibalan blue FBL BLUE HC NO. 4 BLUE HC NO. 5 CAFE HC NO. 1 Cafe de Capracilo 2R ORANGE HC NO. 1 2-Nitro-4-Hydroxydiphenylamine RED HC NO. 1 4-Amino-2-Nitrodiphenylamine RED HC NO. 3 N1- (2-Hydroxyethyl) -2-Nitro-p-phenylenediamine RED HC NO. 6 YELLOW HC NO. 2 N- (2-Hydroxyethyl) -2-N -troaniline YELLOW HC NO. 3 N1-Tris (Hydroxymethyl) -Methyl-4-Nitro-o-phenylenediamine AMRILLO HC NO. 5 N1- (2-Hydroxyethyl) -4-Nitro-o-Phenylenediamine NONOXINOL-2 Polyoxyethylene nonylphenol ether NONOXINOL-4, -8 NONOXINOL-9 IODINE NONOXINOL-12 IODINE RED PIGMENT 57 RED PIGMENT 57: 1 RED PIGMENT 63: 1 RED PIGMENT 64: 1 RED PIGMENT 112 VIOLET PIGMENT 19 PIGMENT YELLOW 1 PIGMENT YELLOW 3 PIGMENT YELLOW12 PIGMENT YELLOW 13 PIGMENT YELLOW 73 QUINOLINE QUINOLINE SALTS TERPENE TERPINEOL COLORANTS VAT XANTENO BLACK ACID 58 Gray of Irgalan B1 BLACK ACID 107 Black of Lanamide B1 BLACK ACID 131 Nigrosine AMMONIUM SALT OF BLUE ACID 9 BLUE ACID 62 ACID COFFEE 46 ACID COFFEE 48 COLORANCIES ACID ACID GREEN ACID ACID 25 ORANGE ORANGE 7 ACID ORANGE 24 RED ACID 33 RED ACID 35 RED ACID 51 RED ACID 52 RED ACID 87 RED ACID 92 RED ACID 95 VIOLET ACID 43 YELLOW ACID 1 YELLOW ACID 3 YELLOW ACID 23 ACID YELLOW 73 ACID YELLOW SODIUM SALT 73 BLUE ALUMINUM DOLL D & C NO. 1 Gloss blue lacquer BLUE ALUMINUM LACQUER D & C NO. 2 Acid blue 74, Indigetin 1A, Carmine indigo BLUE D & C NO. 4 Acid blue 9 (ammonium salt) BLUE D & C NO. 6 indigo CAFE D & C 1 Resorcina coffee, Capracilo coffee GREEN D & C NO. 3 Aluminum Lacquer. Green Food 3 GREEN D & C NO. 5 Green Acid 25 GREEN ACID D & C NO. 6 Solvent Green 3 GREEN D & C NO. 8 Solvent Green 7 ORANGE D & C NO. 4 Orange Acid 7 ORANGE D & C NO. 5 Orange Acid 11, Red Solvent 72. Dibromofluorescein ORANGE ALUMINUM LACQUER D & C NO. 5 Orange Dawn. Orange Manchú ORANGE ZIRCONIA LACQUER D & C NO. 5 Small Orange. Orange Dawn. Acid Red 26. Ponceau R. ORANGE D & amp;; C NO. 10 Solvent 73. Dilodofluorescein ORANGE ALUMINUM LACQUER D & C NO. 10 Red Solvent 73. Erythrosin G. ORANGE D & C NO. 11 ORANGE D & C NO. 17 ORANGE LACQUER D & C NO. 17 RED ALUMINUM LACQUER D & C NO. 2 RED ALUMINUM LACQUER D & C NO. 3 RED ALUMINUM LACQUER D & C NO. 4 RED D & C NO. 6 Litol Rubin B RED ALUMINUM LACQUER D & C NO. 6 RED BARRY LACQUER D & C NO. 6 RED CALCIUM LACQUER D & C NO. 7 RED ZIRCONIA LACQUER D & C NO. 7 RED D & C NO. 8 RED BARRY LACQUER D & C NO. 8 RED SODIUM LACQUER D & C NO. 8 RED D & C NO. 9 RED BARRY LACQUER D & C NO. LACQUER OF STRONCIO - ZIRCONIO DE ROJO D & C NO. 9 RED D & C NO. 10 RED D & C NO. 17 RED D & C NO. 19 Magenta of Rhodamine B RED BARRY LACQUER D & C NO. 19 Magenta of Rhodamine B LACQUER OF ZIRCONIUM OF RED D & C NO. 19 RED D & C NO. 21 RED ALUMINUM LACQUER D & C NO. 21 RED ZIRCONIA LACQUER D & C NO. 21 RED D & C NO. 22 Eosina YS RED D & C NO. 27 RED ALUMINUM LACQUER D & C NO. 27 Terabromo-Teracloro-Fluorescein Lacquer RED DIA BARITO LACQUER C NO. 27 ZIRCONIUM LACQUER OF RED D & C NO. 27 RED D & C NO. 28 Floxin B RED D & C NO. 30 RED ALUMINUM LACQUER D & C NO. 30 CALCIUM LACQUER OF RED D & C NO. 30 RED D & C NO. 31 RED CALCIUM LACQUER D & C NO. 31 RED D & C NO. 33 RED D & C NO. 34 RED CALCIUM LACQUER D & C NO. 34 RED D & C NO. 36 DARK RED BARILE LACQUER C NO. 36 RED LACQUER D & C NO. 36 For Chlorinated Lacquer. Orange Tange ZIRCONIUM LACQUER OF RED D & C NO. 36 RED D & C NO. 37 Rodamide Stearate B RED CALCIUM LACQUER D & C NO. 37 Rhodamine stearate solvent B RED D & C NO. 39 RED D & C NO. 40 YELLOW ALUMINUM LACQUER D & C NO. 5 ZIRCONIO LACQUER OF YELLOW D & C NO. 5 YELLOW ALUMINUM LACQUER D & C NO. 6 YELLOW D & C NO. 7 YELLOW D & C NO. 8 Uranine, Sodium Fluorescein, Naphthol Yellow S YELLOW D &C NO. 10 YELLOW ALUMINUM LACQUER D &C NO. 10 YELLOW D &C NO. 11 VIOLET EXT. D &C NO.2 YELLOW EXT. D &C NO. 7 YELLOW ALUMINUM LACQUER EXT. D &C NO. 7 RED FD &C NO. 20 RED FD &C NO. 22 RED FD &C NO. 40 YELLOW FD &C NO. 5 YELLOW ALUMINUM LACQUER FD &C NO. 5 YELLOW FD &C NO. 6 YELLOW ALUMINUM LACQUER FD &C NO. 6 SOLVENT RED 48 SOLVENT RED 49: 1 SOLVENT RED 72 SOLVENT RED 73 SOLVENT VIOLET 13 SOLVENT YELLOW 13 TARTRAZINE Taken from the "Federal Register" vol. 43, no. 4 - Friday, January 26, 1978.

Antimicrobial soaps Cloflucarban Para-chloro-mein-xilenof Povidone-iodine complex 1.5% Phenol or less aqueous / alcoholic Triclosan triclocarbon Handwashing solution for health care workers Benzalkonium chloride Benzathonium chloride Cloflucarban Hexyl-ional Iodine in complex with alkylaryloxy polyethylene glycol ester Methylbenzathonium chloride Nonylphenoxypoly (ethyleneoxy) ethanol-iodine Para-chloro-meta-xyleneol Complex of povidena-iodine 1.5% Phenol or less aqueous / alcoholic Complex poloxamer-iodine Triclocarban Complex of undecylium-iodine chloride Preoperative preparation for the patient's skin Benzalkonium chloride Benzathonium chloride Hexylresorcinol Iodine in complex with alkylaryl oxypolyethylene glycol ester Methylbenzathonium chloride Nonylphenoxypoly (ethyleneoxy) ethanoylline Para-chloro-meta-xyleneol 1.5% Phenol or less aqueous / alcoholic Poloxamer-iodine complex Povidine-iodine complex Undecylium-iodine chloride complex Skin Antiseptic Benzalkonium Chloride Benzathonium Chloride 10 Hexylresorcinol Iodine in complex with alkylaryl oxypolyethylene glycol ester iodine dye Methylbenzathonium chloride Nonylphenoxypoly (ethyleneoxy) ethanoliodine 15 Para-chloro-meta-xyleneol 1.5% Phenol or less aqueous / alcoholic Poloxamer complex -iodo Complex of povidena-iodine Triclosan 20 Triple colorant Complex of undecoil-iodine chloride Cleaner for wounds on the skin Cloflucarban Iodine in complex with alkylaryl ester polyethylene glycol iodine tincture Nonylphenoxypoly (ethyleneoxy) ethanoliodine Para-chloro-meta-xylenol Phenol 1.5 % or less watery / alcoholic Poloxamer-iodine complex Povidine-iodine complex 10 Triclocarban Triclosan Undecylium-iodine chloride complex Skin Wound Protector 15 Benzalkonium Chloride Benzathonium Chloride Hexylresorcinol Iodine in complex with alkylaryl oxypolyethylene glycol ester iodine dye 20 Methylbenzathonium chloride Nonylphenoxypoly (ethyleneoxy) ethanoliodine Para-chloro-meta-xyleneol

Claims (29)

NOVELTY OF THE INVENTION CLAIMS

1. - A method for making a multilayer latex membrane that includes at least two discrete layers, comprising the steps of: (a) depositing a first latex layer in a former; (b) treating at least a portion of said first layer with a separating agent; (c) treating at least a portion of said first layer with an effective material such as a latex coagulant; (d) depositing on at least a portion of said first layer on said former a second layer of latex, said separating agent effective to substantially prevent melting of the first and second layers on at least a portion of said membrane; and (e) fixing or curing said first and second layers.

2. The method according to claim 1, further comprising the step of treating at least a portion of said first latex layer with a biocide before step (d).

3. The method according to claim 2, further characterized in that said biocide is mixed with said coagulant.

4. The method according to claim 2, further characterized in that said biocide is mixed with said release agent.

5. - The method according to claim 2, further characterized in that said biocide comprises gentian violet.

6. The method according to claim 2, further characterized in that said biocide comprises Nonoxynol 9.

7. The method according to claim 2, further characterized in that said biocide comprises chlorhexidine.

8. The method according to claim 2, further characterized in that said separating agent deposited in step (b) is not in contact with a circumferentially extending zone in said first layer so that said first and second layers are fused together in said zone.

9. The method according to claim 8, further characterized in that said membrane comprises a glove.

10. The method according to claim 8, further characterized in that said membrane comprises a condom.

11. The method according to claim 1, further characterized in that said membrane comprises a glove.

12. The method according to claim 1, further characterized in that said membrane comprises a condom.

13. The method according to claim 1, further comprising the step of depositing a substance on at least a portion of said first layer in said former prior to step (d), further characterized in that said substance is selected from the group consisting of lubricants, sealants, biocides, indicators, spermicides, antiseptics, gels, hydrogels, pituitous substances, cleaning agents, surfactants, detergents, abrasives, coating agents, cleaning agents by rubbing, fibers, objects that increase sensitivity to touch, flakes, discs and other materials to inhibit the penetration of needles and other pointed objects, and sheet forming agents, such that said substance is contained substantially between the first latex layer and the second latex layer.

14. The method according to claim 1, further comprising the step of depositing at least one additional layer on at least a portion of said second layer.

15. The method according to claim 1, further characterized in that said separating agent comprises zinc stearate.

16. A method for forming a multilayer membrane that includes at least two discrete layers, comprising the steps of: (a) depositing in a former a material selected from the group consisting of liquid polymers and polymers dissolved in a solvent for form a first layer; (b) treating at least a portion of said first layer with a surfactant; (c) depositing on at least a portion of said first layer in the former a material selected from the group consisting of liquid polymers and polymers dissolved in a solvent to form a second layer, said surfactant is effective to substantially prevent melting at least a portion of said first and second layers; and (d) fixing or curing said first and second layers.

17. The method according to claim 16, further comprising the step of treating at least a portion of said first layer with a biocide before step (c).

18. The method according to claim 17, further characterized in that said biocide is mixed with said surfactant.

19. The method according to claim 17, further characterized in that said biocide comprises gentian violet.

20. The method according to claim 17, further characterized in that said biocide comprises Nonoxynol 9.

21. The method according to claim 17, further characterized in that said biocide comprises chlorhexidine.

22. The method according to claim 16, further characterized in that said surfactant deposited in step (b) is not in contact with a circumferentially extending zone in said first layer such that said first and second layers are melted together in that area.

23. The method according to claim 16, further characterized in that said membrane comprises a glove.

24. The method according to claim 16, further characterized in that said membrane comprises a condom.

25. - The method according to claim 17, further characterized in that said membrane comprises a glove.

26. The method according to claim 17, further characterized in that said membrane comprises a condom.

27. The method according to claim 16, further comprising the step of depositing a substance on at least a portion of said first layer in said former before step (c), further characterized in that said substance is selected from the group consisting of lubricants, sealants, biocides, indicators, spermicides, antiseptics, gels, hydrogels, pituitous substances, cleaning agents, surfactants, detergents, abrasives, flakes, discs and other materials to inhibit the penetration of needles and other sharp objects, agents of coating, cleaning agents by rubbing, fibers, objects that increase sensitivity to touch, and sheet forming agents, so that said substance is contained substantially between the first and second layers of latex.

28. The method according to claim 16, further comprising the step of depositing at least one additional layer on at least a portion of said second layer.

29. A method for making a multilayer latex membrane that includes at least two discrete layers, comprising the steps of: (a) depositing in a former a first layer of latex; (b) treating at least a portion of said first layer with a separating agent; (c) depositing on at least a portion of said first layer in said former a second layer of latex, said separating agent effective to substantially prevent melting of the first and second layers in at least a portion of said membrane; and (d) fixing or curing said first and second layers.