WO2009061311A1 - Methods and compositions for reducing the protein content and odor of latex articles - Google Patents

Methods and compositions for reducing the protein content and odor of latex articles Download PDF

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Publication number
WO2009061311A1
WO2009061311A1 PCT/US2007/083658 US2007083658W WO2009061311A1 WO 2009061311 A1 WO2009061311 A1 WO 2009061311A1 US 2007083658 W US2007083658 W US 2007083658W WO 2009061311 A1 WO2009061311 A1 WO 2009061311A1
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Prior art keywords
leach
latex
potentiator
bath
surfactant
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PCT/US2007/083658
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French (fr)
Inventor
Rick L. Tabor
William L. Howe
Laura L. Whitlock
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Stepan Company
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Priority to PCT/US2007/083658 priority Critical patent/WO2009061311A1/en
Publication of WO2009061311A1 publication Critical patent/WO2009061311A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08CTREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C3/00Treatment of coagulated rubber
    • C08C3/02Purification

Definitions

  • the presently described technology relates generally to methods and compositions for reducing and/or neutralizing the protein content and/or odor of latex articles by combining a surfactant with a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof.
  • Natural rubber latex is used for a variety of applications, including exam gloves, surgical gloves, catheters, tubing and condoms. Due to concerns about AIDS and other blood and fluid borne diseases, the market for rubber articles has experienced high growth in recent years. Natural rubber is obtained in latex form from the milky sap (latex) of the tree Hevea Brasiliensis. The natural rubber latex products industry is presently in the midst of a paradigm shift, because the endogenous proteins in inexpensive NRL cause allergic reactions in about 8% of the population, including itching or burning skin, rashes, asthma and even anaphylactic shock in both medical professionals and their patients (Annals of Emergency Medicine 2002; 40:411-419).
  • chlorination of some natural rubber latex product may undesirably change the physical properties of the product.
  • some natural rubber latex product such as medical gloves
  • the application may result in the gloves having dark discoloration and poor physical properties (such as low tensile strength and poor elongation), particularly after high temperature ageing at 100° C for 22 hours. Therefore, there is a need for methods and compositions that can reduce protein content of a natural rubber latex product with reduced levels of chlorinating agents.
  • latices are also used to prepare dip- manufactured articles such as gloves, condoms, balloons, catheters, medical devices and finger cots.
  • These latices include, for example, nitrile rubber, polyisoprene, polyurethane, ethylene copolymers, styrene copolymers, butadiene copolymers, emulsion manufactured polymers, dispersion manufactured polymers, silicone rubber, alpha olefin copolymers, mixtures thereof, and composites thereof.
  • undesirable odors may originate from dip manufactured products prepared from these types of latices as well as from natural rubber latices.
  • the compositions and methods of the presently described technology are capable of removing odors from dip manufactured goods prepared from these types of latices as well as from natural rubber latex based, dip manufactured products.
  • compositions of the present technology may also be used in postprocessing (e.g., post-washing) of many of these articles. It is contemplated that the compositions of the present technology can be useful at removing undesirable odors, vulcanization residues and protein from the articles produced by these processes.
  • the presently described technology relates generally to methods and compositions for reducing the protein content and/or undesirable odor, especially the allergenic protein content of latex articles, e.g., natural rubber latex articles.
  • the presently described technology provides methods to reduce the protein content and/or odor of latex articles by introducing compositions comprising a surfactant component combined with a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof, into one or more stages of the manufacture of an article made of latex, or alternatively during the post laundering or washing treatment of the article.
  • the methods and compositions of the presently described technology are particularly applicable to, but not limited to, natural rubber latex articles that are made through a dipping process.
  • Many latex articles are made using multi-staged dipping processes that may include holding the latex in a tank; dipping a former into one or more latex dipping tanks so that the former is covered with the latex to make an article in the shape of the former; heating the latex covered former so that the latex film may dry into a pre-cured film; passing the formers through pre- vulcanization leaching tanks (may be referred to as "pre-leach” tanks or baths) to remove excess chemical residue and latex protein with hot water; passing the former through a vulcanization stage; passing the former through a post-vulcanization leaching tank (may be referred to a "post-leach” tank or bath) to remove more latex protein and chemical residue; removal of the formed article from the former; laundering the formed articles in a washing step; drying the formed articles; and optionally, packaging them for shipment.
  • pre- vulcanization leaching tanks may be referred to as "pre-leach” tanks or baths
  • pre-leach post-vulcanization le
  • a composition comprising a surfactant component and a low level of a potentiator can be added into one or more of the leach baths of the dip manufacturing process.
  • the composition comprising the surfactant and the potentiator may be employed in the latex holding tank, the dipping tanks, any of the leaching tanks, the vulcanization stage, the laundering stage or any combination of these stages.
  • the composition may also be employed in the final drying stage by introduction as a vapor or aerosol, for example, via the use of dryer sheets coated with the composition.
  • the composition may also be employed in a post-washing step for products manufactured from natural rubber latex as well as other types of latices.
  • the surfactant component in the composition of the presently described technology comprises at least one surfactant.
  • Suitable surfactants are preferably molecules that have the property of increasing the aqueous solubility or creating emulsions of a variety of otherwise insoluble or only slightly water-soluble organic compounds.
  • the surfactant of the presently described technology can be a chemical substance which includes a hydrophobic organic group chemically bonded to one or more hydrophilic groups.
  • the hydrophobic organic group can be aliphatic, aromatic, polynuclear aromatic, or combinations thereof.
  • One preferred attribute of the surfactant is that it be essentially non-foaming or very low-foaming during conditions experienced in the leach baths for NRL dip manufacturing.
  • the potentiator in the composition of the presently described technology comprises a chlorinating agent, a non-chlorinating salt, or a combination thereof.
  • Suitable chlorinating agents include, for example, metal salts of hypochlorite, chlorine, trichloro-s-triazinetrione, dichloro-s- triazinetrione, and combinations thereof. More specific examples include, but are not limited to, sodium hypochlorite, sodium dichloro-triazinetrione, hypochlorous acid, and combinations thereof.
  • a non-chlorinating salt may be used instead of, or in combination with, a chlorinating agent in the composition of the presently described technology.
  • Suitable non-chlorinating salts include, for example, water-soluble metal or ammonium salts of sulfates, carbonates, chlorides, chlorates, chlorites, phosphates, sulfites, bisulfites, bicarbonates, citrates, acetates, borates, lactates, nitrates, phosphites, silicates, and combinations thereof. It is understood that many salts occur with waters of hydration. In these instances, the waters of hydration are not considered towards actives content in leach bath compositions.
  • the presently described technology provides a method for reducing the protein content and/or odor of a manufactured latex (e.g., natural rubber latex) article.
  • the method exposes a formed article to one or more leach baths, wherein at least one of the leach baths comprises: (1) a surfactant component comprising at least one chemical substance that includes at least one hydrophobic organic group chemically bonded to at least one hydrophilic group; and (2) a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof.
  • the surfactant component is present in an amount sufficient to provide about 1.0% or less surfactant actives
  • the potentiator is present in an amount sufficient to provide about 0.06% or less actives, both based on the total weight of the at least one leach bath.
  • the surfactant component is present in an amount sufficient to provide about 0.5% by weight or less surfactant actives
  • the potentiator is present in an amount sufficient to provide about 0.005% by weight or less actives, in the at least one leach bath.
  • the present technology provides a method for reducing the protein content and/or odor of a manufactured natural rubber latex article comprising the steps of exposing the article to a combination of baths comprising any sequential combination selected from the following treatments:
  • a leach batch comprising a surfactant component comprising at least one chemical substance that includes at least one hydrophobic organic group chemically bonded to at least one hydrophilic group; and a potentiator comprising a chlorinating agent, a non-chlorinating salt or a combination thereof.
  • the surfactant component is present in an amount sufficient to provide about 0.5% or less surfactant actives
  • the potentiator is present in an amount sufficient to provide about 0.005% or less actives, both based on the total weight of the leach batch.
  • the steps of exposing the article to a combination of baths in the above method comprise:
  • the temperatures of the first clean water bath, the leach bath, and the second clean water bath are about 70° C or lower and preferably are about 60° C or lower.
  • the present technology provides a method for treating latex articles so as to reduce their protein content and/or odor, comprising the steps of:
  • the present technology provides a concentrate composition comprising:
  • a surfactant component comprising at least one chemical substance that includes at least one hydrophobic organic group chemically bonded to at least one hydrophilic group
  • a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof.
  • the concentrate composition can be used to treat latices or latex articles to reduce the protein content and/or odor in them.
  • the surfactant component is present in an amount sufficient to provide from about 21% to about 80% surfactant actives, and the potentiator is present in an amount sufficient to provide from about 0.2% to about 15% actives, both based on the total weight of the concentrate composition.
  • compositions of the presently described technology may be used during the manufacture of or in washing treatments for latex articles that have been manufactured by methods other than dip manufacturing.
  • articles include, but are not limited to, mattresses, foams, pillows, cushions, area rugs, continuously manufactured carpets, bathroom rugs, outdoor recycled tire mats, drapes, tarpolins, textile inserts or composites, bra padding, clothing padding, bandages, threads, elastic textiles, athletic support wrap, veterinarian support wrap, coated textile gloves, coated textile articles, and composites of textiles and latex coatings.
  • the protein and/or odor reducing methods and compositions of the presently described technology have one or more of the following advantages: protein reductions of up to 90% or more; reduction of undesirable odors, applicable for use with on-line polymer coating technology and processing; effectiveness with post laundering processes; energy cost savings via reduced leach bath temperatures; applicability to condoms, catheters, balloons, foam, membranes, films, coatings gloves, area rugs, bra and clothing padding, mattresses, pillows, cushions, and other latex products or applications; no or substantially no change in physical properties of the products; biodegradable active components, which are compatible with waste water treatment; simplicity to implement; minimal change to conventional glove manufacturing lines; and minimal or no additional capital investment.
  • At least one method of the presently described technology includes the step of exposing latex such as natural rubber latex (NRL) or a latex article to a composition comprising a surfactant component and a potentiator.
  • latex such as natural rubber latex (NRL) or a latex article
  • a composition comprising a surfactant component and a potentiator.
  • This exposure can reduce and/or neutralize the protein content, including allergenic protein content of the resulting latex articles.
  • This exposure may also reduce and/or neutralize the undesirable odor of the resulting latex articles.
  • a surfactant component refers generally to all surfactants in a composition
  • a “potentiator” refers generally to all chlorinating compounds and/or non-chlorinating salts in a composition. If two or more surfactants are used, they can be added together or at different times. If two or more chlorinating compounds and/or non- chlorinating salts are used, they can also be added together or at different times.
  • formers can be provided in the shape of a desired article, such as in the shape of a hand for making latex exam or surgical gloves, for example. These formers may be first washed in hot water to clean the formers. The formers can then be dipped into a coagulant tank that contains an aqueous solution of calcium nitrate, for example. The formers may then be dipped in a tank holding latex where the calcium on the surface of the former coagulates a thin layer of gel onto the former. The formers can then be passed through an oven where the coagulated latex dries into a pre-cured film.
  • the formers can then be passed through pre- vulcanization leaching tanks to remove excess chemical residue and latex protein with hot water.
  • pre-leach tanks Any number of pre- vulcanization leaching tanks (pre-leach tanks) may be used.
  • a typical arrangement includes three long pre-vulcanization leaching tanks instead of just a single leaching tank, because multiple leaching tanks ensure the maximum removal of latex protein and chemical residue from the latex gel film on the formers.
  • the extraction of the latex proteins and chemical residues is further enhanced by employing hot water, counter-flowing continuously against the formers as they pass through the pre-vulcanization leaching tanks.
  • the next step involves, in general, passing the formers into the vulcanization oven to be heated to remove moisture from the latex gel and harden the latex gel.
  • the formers may then be passed through a post-vulcanization leaching tank (post-leach tank) to remove more latex protein and chemical residue.
  • post-vulcanization leaching tank is considered by some familiar with the field of the present technology to be the most important step in removing excess latex protein from the formed latex articles.
  • the formers may then be passed into another oven for further drying.
  • the formers may then be passed into another tank containing, for example, wet cornstarch powder and water (as a donning or anti- tacking aide).
  • the articles may be stripped from the formers either by hand one at a time or by an automatic air ejection machine.
  • the articles may then be placed into tumble dryers for the final vulcanization process.
  • the method of the presently described technology involves the step of exposing the latex or latex articles with a composition comprising a surfactant component and a potentiator in an amount sufficient to effectively reduce and/or neutralize the allergenic protein content of the latex articles.
  • a composition comprising a surfactant component and a potentiator in an amount sufficient to effectively reduce and/or neutralize the allergenic protein content of the latex articles.
  • the composition of the present technology can be added into one or more of the leach baths of the dip manufacturing process.
  • the surfactant component in the protein reducing composition of the present technology comprises one or more surfactants that have the property of increasing the aqueous solubility or creating emulsions of a variety of otherwise insoluble or only slightly water-soluble organic compounds.
  • the surfactant of the present technology is a chemical substance that includes a hydrophobic organic group chemically bonded to one or more hydrophilic groups.
  • the hydrophobic organic group can be aliphatic, aromatic, polynuclear aromatic, or a combination thereof.
  • one preferred attribute of the surfactant is that the surfactant be essentially non-foaming or very low- foaming during conditions experienced in the leach baths during NRL dip manufacturing.
  • Another preferred attribute of the surfactant is that if any trace residues of the surfactant remain on the final resultant, dried article, the residues of surfactant have low or negligible skin irritation. This is because many of the articles prepared by dip manufacturing are for skin contact applications.
  • a further preferred property of the surfactant is that the surfactant has some degree of protein removal efficacy even in the absence of the potentiator.
  • a still another preferred property of the surfactant is that the surfactant be biodegradable to the extent that it is compatible with an industrial or municipal water treatment facility that treats the effluent of the leach water baths with little or no detrimental effects on these water treatment processes.
  • very low-foaming or "essentially non-foaming," when used to describe a leach bath or surfactant in a leach bath of the present technology, means that the leach bath allows for viewing of the liquid contents of the leach bath and does not transfer quantities of foam to the articles which are being dip manufactured so as to create defects.
  • foaming is an acceptable characteristic, however, since foaming does not create defects in the existing manufactured products or cause undesirable manufacturing problems at this point in the overall production process.
  • the hydrophilic group of the surfactant can be, for example, carboxylate, phosphate, sulfate, sulfonate, succinate, sulfosuccinate, or a combination thereof, in the form of a water-soluble salt.
  • the counterion of the hydrophilic group may be sodium, potassium, magnesium, aluminum, ammonium, mono-, di-, or tri-alkyl ammonium, mono-, di-, or tri-hydroxy alkyl ammonium, a combination thereof, or any other cationic counterion which provides water solubility in the final surfactant.
  • the hydrophilic group of the surfactant may be a polyalkoxylate.
  • it can be a polyalkoxylate comprising two or greater ethoxylate groups.
  • the polyalkoxylate may further comprise 40% or less propoxylate or butoxylate groups.
  • the hydrophilic group of the surfactant may also be polyglycerols, sugars, and glycosides or polyglycosides.
  • the hydrophilic group of the surfactant may be quaternary amines, tertiary ammonium salts, secondary ammonium salts, primary ammonium salts, ammonium salts, sulfobetaines, betaines, pyridinium salts, nitrogen- containing heterocyclic amine salts, amino carboxylates, amine oxides, amides, nitrogen-containing heterocyclic amides, polyvinyl pyrrolidone, and combinations thereof.
  • Preferred surfactant compounds for use in the practice of some embodiments of the present technology are amine oxides. At least some amine oxides are effective at removing a variety of different types of soils and stains from surfaces.
  • surfactants include phosphates, sulfates, sulfonates, betaines, sulfobetaines, and nonionic surfactants.
  • the composition of the presently described technology further comprises a potentiator.
  • the potentiator comprises a chlorinating agent, a non-chlorinating salt, or a combination thereof.
  • the potentiator is present in at least some compositions of the presently described technology in a substantially lower level as compared to the surfactant component.
  • the active concentration of the surfactant component is at least 10 times, alternatively at least 50 times, alternatively at least 100 times of the active concentration of the potentiator.
  • the potentiator in the compositions of the present technology may comprise one or more chlorinating compounds.
  • Suitable chlorinating compounds include, but are not limited to, metal salts of hypochlorite, chlorine, trichloro-s-triazinetrione, dichloro-s-triazinetrione, and combinations thereof.
  • More specific examples include sodium dichloro-s-triazinetrione, sodium hypochlorite, potassium hypochlorite, lithium hypochlorite, calcium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, potassium trichlorocyanurate, sodium trichlorocyanurate, trichlorocyanuric acid, dichlorocyanuric acid, potassium dichlorocyanurate, sodium dichlorocyanurate, N-chlorinated succinimide, N- chlorinated malonimide, N-chlorinated phthalimide, N-chlorinated naphthalimide, dichlorodimethylhydantoin, N-chlorosulfamide, chloramine, hypochlorous acid and combinations thereof.
  • preferred chlorinating agents include sodium hypochlorite, hypochlorous acid, and combinations thereof.
  • the potentiator in the compositions of the present technology may comprise one or more non-chlorinating salts.
  • Suitable non-chlorinating salts include, but are not limited to, water-soluble metal or ammonium salts of sulfates, carbonates, chlorides, chlorates, chlorites, phosphates, sulfites, bisulfites, bicarbonates, perborates, percarbonates, citrates, acetates, borates, lactates, nitrates, phosphites, and silicates. It is understood that many salts occur with waters of hydration. In these instances, the waters of hydration are not considered towards actives content in leach bath compositions.
  • the composition of the present technology is a concentrate composition.
  • the concentrate composition preferably (1) contains the surfactant component in an amount sufficient to provide from about 15% to about 80%, alternatively from about 17% to about 50%, surfactant actives in the concentrate composition, most preferably from about 20 to about 45% surfactant actives, and (2) contains the potentiator in an amount sufficient to provide from about 0.5% to about 15%, alternatively from about 1% to about 5%, most preferably from about 1.5% to about 5% actives in the concentrate composition, all based on the total weight of the concentrate composition.
  • Suitable solvents such as water, alcohol, and mixtures thereof, can be used as the delivery vehicle of the concentrate composition. Examples of alcohols that may be used include ethanol, isopropanol, methanol, diethylene glycol, propylene glycol, butanol, and mixtures thereof.
  • the concentrate composition can be diluted in water or added to a dip manufacturing leach bath to form an application solution.
  • the concentrate composition can further comprise a chlorine or hypochlorite stabilizing agent as known by those familiar with the field of hypochlorite- containing formulations.
  • stabilizing agents include sodium hydroxide, potassium hydroxide, silicates, and the like.
  • compositions of the present technology can contain one or more other additives such as, for example, pH controllers, buffers, emulsifiers, viscosity modifiers, inorganic salts, waxes, alcohols, and preservatives.
  • additives such as, for example, pH controllers, buffers, emulsifiers, viscosity modifiers, inorganic salts, waxes, alcohols, and preservatives.
  • the composition of the present technology may be employed in any of several steps in the making of the at least one latex article to reduce the odor and/or protein content in the resulting latex article.
  • the compositions of the presently described technology may be employed in the latex holding tank, the dipping tanks, any of the leaching tanks, the vulcanization stage, the laundering stage or any combination of these processing stages.
  • the compositions should be present in an amount sufficient to effectively reduce and/or neutralize the allergenic protein content and/or odor of the latex such as natural rubber latex articles.
  • the surfactant component of the composition of the present technology when applied, will provide about 1.5% or less, alternatively from about 0.01% to about 1.0%, alternatively from about 0.02% to about 0.5%, surfactant actives in the leach bath; the potentiator will provide about 0.1% or less, alternatively about 0.06% or less, alternatively from about 0.0001% to about 0.01%, actives in the leach bath, all based on the total weight of the leach bath.
  • water and other solvents such as alcohol and combinations thereof, may be used as delivery vehicles for the compositions for use in accordance with the presently described technology.
  • alcohols examples include ethanol, isopropanol, methanol, diethylene glycol, propylene glycol, butanol, and mixtures thereof.
  • water alone is preferred in at least some embodiments to avoid the use of volatile organic compounds.
  • the methods and compositions of the presently described technology have been found to possess one or more of the following additional advantages: protein reductions of up to 90% or more; reduction of undesirable odors, applicability for use with on-line polymer coating technology and processing; effectiveness with post laundering processes; applicability to condoms, catheters, balloons, foam, membranes, films, coatings gloves, area rugs, bra and clothing padding, mattresses, pillows, cushions, and other latex products; no or substantially no change in physical properties of glove or other latex products; biodegradability of active components, which are compatible with conventional waste water treatment; simplicity to implement; minimal change to glove manufacturing lines; and minimal or no additional capital investment.
  • Ammonyx® LO is a surfactant containing 30% lauryl amine oxide actives in water, available from Stepan Company in Northfield, Illinois. This product was used as a source of lauryl amine oxide surfactant in some examples below.
  • Cedaphos® FA-600 is a surfactant containing 99% alkyl ethoxylate phosphate actives in water, available from Stepan Company in Northfield, Illinois. This product was used as a source of alkyl ethoxylated phosphate surfactant in some examples below.
  • the coagulant used in the examples was "20% Calcium Nitrate WCS + R", available from Killian Latex in Akron, Ohio.
  • the natural rubber latex compound used in the examples was Compound 473-11/58% TSC, available from Killian Latex in Akron, Ohio.
  • the guayule rubber latex compound used in the examples was obtained from Yulex Corporation of Maricopa, Arizona, and contained 38% total solids.
  • neoprene (polychloroprene) rubber latex compound used in the examples was obtained from Polytech Synergies of Canal Fulton, Ohio, and contained 38% total solids.
  • Defoamer FreesilTM 80 was used as needed in both latex and coagulant baths for random antifoaming needs. This product was obtained from Crusader Chemical Co., Inc., Baltimore, MD.
  • a computer controlled DiplomatTM 3 axis dipping system (DipTech Systems, Akron, Ohio) was used to control the dip times, mold rotation and dip rates of medium size porcelain ceramic exam glove molds, supplied by General Porcelain Co., Parkersburg, West Virginia.
  • a coagulant bath was heated using a thermostated immersion heater to a temperature of about 50 0 C to about 55 0 C.
  • the natural rubber latex compound bath was used at an ambient temperature of about 23 0 C.
  • the natural rubber latex bath was continuously stirred by variable speed air mixer, except during actual dipping of the forms into the latex.
  • the coagulant bath was manually stirred with a paddle approximately one minute before each dipping cycle.
  • the molds were then dipped into a circulated bath of deionized Akron, Ohio municipal drinking water held by an immersion heater at a temperature of about 38° C or another selected temperature.
  • a second bath contained the same water, but also included a composition of the presently described technology or in the case of comparative examples, water alone.
  • dipping occurred in a variety of combinations of these two baths; the combined dip time for this step totaled anywhere from, for example, approximately 30 seconds to approximately 45 seconds.
  • removal of the molds from the last bath of this dipping step was followed by a 10 second time period during which excess water was allowed to drip off of the gloves and molds.
  • the leach baths used for pre-cure leach dip may be referred to as pre-leach baths.
  • the molds holding the latex gloves were dipped into a post-cure leach bath containing process water held by an immersion heater to a temperature of about 38 0 C or another selected temperature.
  • a post-cure leach bath containing process water held by an immersion heater to a temperature of about 38 0 C or another selected temperature.
  • the combined dip time for this step usually totaled approximately 30 to approximately 45 seconds, but can be another selected period of time.
  • removal of the molds from the last bath of this dipping step was followed by a 10 second time period during which excess water was allowed to drip off of the gloves and molds.
  • the leach baths used for post-cure leach dip may be referred to as post-leach baths.
  • the gloves on their molds were further dried in a convection oven held at about 80° C for approximately two minutes, removed from the oven and allowed to cool for approximately two minutes.
  • Talcum powder was applied by hand to the surface of the resulting gloves to provide a non-tacking surface, and the gloves were then stripped from the mold while at the same time turning them inside out.
  • An attendant wore thin film, disposable nitrile gloves while de-molding each individual glove, to avoid direct human contact with the finished product.
  • ProSlip is comprised of an acrylic based emulsion (25 wt%), a silicone based emulsion (5 wt%), a surfactant (0.1 wt%), and water (69.9 wt%).
  • the process of preparing polymer coated gloves remains the same as the Latex Glove Dip Manufacturing Procedure until the oven dry and curing step described above. After forming beads on the gloves, the gloves on their molds were cured for approximately three minutes at about 100° C. The molds were removed from the oven and dipped into ProSlip at 3% strength in water at ambient temperature. The gloves are then cured at about 100° C for approximately 10 minutes, and at about 110° C for approximately two minutes. Post-cure leaching scheme was the same as that described above.
  • Post laundering was conducted using non-treated latex gloves prepared using leach water of about 40 0 C or another selected temperature that contained, for example, selected treatment agents or no treatment agents.
  • Four gloves were washed in a laundering solution of either (1) a composition of the present technology containing, for example, 0.1% lauryl amine oxide and 0.0023% sodium hypochlorite in deionized water, or (2) deionized water alone.
  • Gentle agitation using a stainless steel rod was conducted during the post laundering time of approximately 90 seconds (1.5 minutes) or another selected time X.
  • the lauryl amine oxide/hypochlorite laundering step was followed by approximately 90 seconds (1.5 minutes) or another selected time X of a rinse with deionized water.
  • the control (deionized water alone) was simply approximately 3.0 minutes or another selected time 2X of gentle agitation of four latex gloves using a stainless steel rod.
  • Protein content was tested by the Total Protein Method. According to this method, chemoassay protein content was measured using Modified Lowry Assay (ASTM D5712-95), using four 2-fold serial dilutions in duplicate. Antigenic Protein content was measured using ELISA Inhibition Assay (ASTM D6499-03), using seven 2-fold serial dilutions in duplicate. All protein content measurements were conducted by LEAP Testing Service of Sayre, Pennsylvania.
  • Extractions were performed for approximately two (2) hours with constant agitation at 25° C +/1.5° C in 100 mM phosphate buffered saline (pH 7.4). The extraction ratio used was about 5 to 1. Extracts were centrifuged to remove particulates, then assayed.
  • Leach Bath Treatment Concentrate #1 was prepared by the following procedure: Ammonyx® LO (800 g) was added to a 1000 ml beaker. The initial pH of about 7.7 was adjusted to about 12.2 using a 50% sodium hydroxide solution. About 184 g of a sodium hypochlorite solution (10-13% NaOCl) were added to the Ammonyx® LO mixture with stirring. The pH was measured again, this time providing a reading of about 11.8. It was readjusted dropwise with the 50% sodium hydroxide solution to a value of about 12.2.
  • This concentrate (0.38 parts) was diluted with deionized water (99.62 parts) to form a leach bath containing about 0.1% lauryl amine oxide actives and 0.001% nominal sodium hypochlorite actives (i.e., chlorine actives).
  • Leach Bath Treatment Concentrate #2 was prepared by the following procedure: Cedaphos® FA600 (240 g) was added to a 1000 ml beaker along with 560 g of deionized water. The initial pH of the mixture was about 1.5, which was adjusted to about 12.4 using a 50% sodium hydroxide solution. The solution exothermed to about 52° C during this neutralization, and was allowed to cool to about 26° C. About 184 g of the sodium hypochlorite solution (10-13% NaOCl) were added to the surfactant solution with stirring. The pH was measured again, this time providing a reading of about 12.6.
  • This concentrate (0.38 parts) was diluted with deionized water (99.62 parts) to form a leach bath containing about 0.1% alkyl ethoxylate phosphate actives and about 0.001% nominal sodium hypochlorite actives (i.e., chlorine actives).
  • This leach bath yielded a reduced protein content of 105 micrograms/ g of glove, when compared to the control (water alone) sample, which had a protein content of 108 micrograms/ g of glove.
  • Example 3 Study of a leach bath of the present technology
  • a leach bath of the present technology (Type 1, prepared from Leach Bath Treatment Concentrate #1) containing 0.1% lauryl amine oxide actives and 0.0023% sodium hypochlorite actives (0.001% by weight chlorine actives) was compared to leach baths containing untreated water (Comparative Type A), and a leach bath containing 0.5% lauryl amine oxide actives alone in water (Comparative Type B).
  • the total protein contents of natural rubber latex gloves prepared by the Latex Glove Dip Manufacturing Procedure were tested by the Total Protein Method.
  • Type 1 leach bath of the present application achieves a 74% further reduction of protein content as compared to Comparative Type A leach bath which used a clean water bath only.
  • the results also show that with the addition of 0.0023% by weight sodium hypochlorite (0.001% chorine actives), only 0.10% by weight of the lauryl amine oxide surfactant actives was needed to achieve a comparable protein reduction to that achieved by Comparative Type B leach bath that contained five times the weight percentage of lauryl amine oxide surfactant actives.
  • Example 4 Comparative study of a series of leach baths of the present technology
  • Types 2-5) a series of leach baths of the present technology (Types 2-5) were studied in comparison to two comparative leach baths (Comparative Types C and D).
  • Each leach bath of Types 2-5 contain 0.1% lauryl amine oxide actives and 0.0023% sodium hypochlorite actives (0.001% by weight chlorine) held at a temperature of about 40° C.
  • Comparative Type C was a bath of clean water at about 40° C
  • Comparative Type D was a bath of clean water at about 60° C.
  • Five natural rubber latex gloves were prepared using leach baths of Comparative Types C and D and leach baths of Types 2-4 of the present technology at the temperature and location indicated in Table 2 below using the Latex Glove Dip Manufacturing Procedure.
  • Type 5 leach bath of the present technology demonstrates how the technology may be used to treat a Polymer Coated Glove (preparation described above) in a post laundering step. The results of the total protein content analysis are summarized in Table 2 below.
  • Example 6 Comparative study of a series of leach baths of the present technology
  • the middle leach water bath composition indicates the composition of the leach bath of the present technology used between two water-only baths.
  • the pre- and post-leach time profiles indicate the time for the water-only bath, the middle treatment bath, and the second water only bath.
  • a Pre- or Post-Leach Time Profile of "10/10/10" indicates 10 seconds of water only, followed by 10 seconds of the middle treatment bath, followed by 10 seconds of water- only leaching prior to or after the vulcanization oven step. In the instances where water alone was used, there was only one leach bath for both pre-leach and post-leach with the indicated time.
  • a new set (five types) of natural rubber (NR) latex gloves were prepared using a protocol similar to that observed for the gloves prepared as recorded in Table 4.
  • the five types of leach baths used are Types 20-23 of the present technology and Comparative Type K.
  • the key difference between these gloves and the gloves in Table 4 is that the gloves described in Table 5 utilize a total post leach time of 120 seconds in order to better simulate the post leach times used on an exam glove manufacturing line.
  • two gloves from each type were placed into a 6 ounce, wide mouth, glass bottle with a metal lid and sealed until tested.
  • Eleven odor panelists were asked to come separately with a test administrator into an office for the odor test.
  • each panelist was permitted into the office at a time in the office to avoid the possibility of information being shared between the panelists. The same panelist was not allowed to perform odor testing twice within one hour of a previous odor test in order to allow their noses a time for full recovery. Each panelist was asked to rank the samples in order of odor intensity. [0090] To reduce the complexity of the sensory test and provide a clear comparison between the five test samples, each set of test samples was limited to five in number. The results were recorded as five (5) for most intense, and one (1) for least intense. The data for each set were treated by subtracting one (1) from each individual odor intensity value to set zero as the odor intensity threshold. Eleven panelists were used and the highest deviation panelist data was discarded.
  • Example 8 Odor panel testing of neoprene and guayule exam gloves
  • a set (four types) of natural rubber (NR) latex gloves were prepared using the same protocol described in Example 7 by leach baths of Types 27-29 of the present technology and Comparative Type N. Odor panel testing of these gloves was conducted in the same manner as that described in Example 7.
  • a pair of Fisher Scientific latex gloves were included in this experiment to benchmark the results of the present technology to leading commercial product. The results are recorded in Table 7 below.
  • This experiment clearly indicates that the leach bath compositions of the present technology containing different potentiators (NaOCl, MgSO 4 , and Na 2 SO 4 ) reduce the odor intensity of natural rubber latex gloves versus a water only control.
  • the benchmark Fisher scientific gloves were low in odor intensity versus the gloves produced by DipTech Systems in the present experiment.
  • leach bath Type 30 was studied against a comparative leach bath (Comparative Type P) to evaluate the extent of protein content reduction by the leach bath of the present technology.
  • the latex articles tested in this experiment were natural rubber (NR) latex gloves.
  • Leach bath Type 30 contained 0.1% lauryl amine oxide and 0.0023% sodium hypochlorite.
  • the leach water temperature and pre/post-leach time profiles are shown in Table 8 below.
  • Chemoassay protein content was measured using Modified Lowry Assay (ASTM D5712- 95), and antigenic protein content was measured using ELISA Inhibition Assay (ASTM D6499-03). The results of the protein content analysis are summarized in Table 8.
  • Cohesive bandages from Andover Healthcare, Inc., Salisbury, MA, and 3M, St. Paul, MN were tested in this experiment. Both types of cohesive bandages were made from natural rubber (NR) latices. Leach baths Type 31 and Comparative Type Q were used to treat the Andover type cohesive bandages, and leach baths Type 32 and Comparative Type R were used to treat the 3M type cohesive bandages. The composition, leach water temperature, and post wash time of each type of leach bath are shown in Table 9 below.
  • each bandage was washed in one liter of wash treatment (i.e., leach bath) at about 40° C for approximately 30 seconds with gentle agitation using a stainless steel stirring rod, followed by approximately 30 seconds of similarly agitated rinse in a plain water bath held at about 40° C.
  • the comparative wash treatments were identical, except that plain water was used for the entire treatment.
  • the cohesive bandages were then allowed to air dry for 48 hours prior to testing for protein content.
  • NR latex condoms Two types of natural rubber (NR) latex condoms were prepared using a leach bath of
  • Type 33 of the present technology and Comparative Type S.
  • a procedure similar to the Latex Glove Manufacturing Procedure was used with a difference that the condoms were not treated by pre-leach baths, and were treated by post-leach baths only.
  • composition, leach water temperature, and post-leach time profile of each type of leach bath are shown in Table 10 below.
  • “15/30/15” means 15 seconds of water treatment, followed by 30 seconds of Type 32 leach bath treatment, followed by 15 seconds of water treatment.
  • Chemoassay protein content was measured using Modified Lowry Assay (ASTM D5712-95), and the results are summarized in Table 10.

Abstract

Provided are methods and compositions for reducing the protein content and/or undesirable odor of latex articles. The methods reduce the odor and/or protein content of latex articles by introducing compositions comprising a surfactant component and a potentiator into one or more stages of the manufacture of an article made of latex, or alternatively during the post laundering or washing treatment of the article. The potentiator comprises a chlorinating agent, a non-chlorinating salt, or a combination thereof. The methods and compositions are particularly applicable to natural rubber latex articles, especially those made through a dipping process.

Description

METHODS AND COMPOSITIONS FOR REDUCING THE PROTEIN CONTENT AND ODOR
OF LATEX ARTICLES
BACKGROUND OF THE INVENTION
[0001] The presently described technology relates generally to methods and compositions for reducing and/or neutralizing the protein content and/or odor of latex articles by combining a surfactant with a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof.
[0002] Natural rubber latex (NRL) is used for a variety of applications, including exam gloves, surgical gloves, catheters, tubing and condoms. Due to concerns about AIDS and other blood and fluid borne diseases, the market for rubber articles has experienced high growth in recent years. Natural rubber is obtained in latex form from the milky sap (latex) of the tree Hevea Brasiliensis. The natural rubber latex products industry is presently in the midst of a paradigm shift, because the endogenous proteins in inexpensive NRL cause allergic reactions in about 8% of the population, including itching or burning skin, rashes, asthma and even anaphylactic shock in both medical professionals and their patients (Annals of Emergency Medicine 2002; 40:411-419). Exam gloves are being developed from much more expensive synthetic polymers in order to avoid this problem, but these polymers, thus far, are deficient with respect to their tensile, elongation and "comfort" properties. Natural rubber elongates to between 4-900% at very low strain, and then stress crystallizes natural rubber to provide high ultimate tensile strength. This property of natural rubber is difficult to achieve using synthetic polymers, and allows for a high degree of comfort in gloves or other articles made from natural rubber.
[0003] Efforts to eliminate the endogenous proteins of natural rubber latex have included chlorination of latex articles and treatment with enzymes to cleave the proteins to lower, less allergenically active, molecular weights. Additionally, salt solutions such as sodium chloride have been used to provide reduction of protein in NRL articles. These approaches have allowed for reduction of the protein content of current latex products, but they have not eliminated the protein problem, and/or have inherent problems of their own. (For further background see: U.S. Pat. No. 5,777,004: "Method of neutralizing protein allergens in natural rubber latex product formed thereby"; U.S. Pat. No. 5,563,241: "Methods to remove proteins from natural rubber latex", and U.S. Pat. No. 6,790,933 B2: "Low Protein Natural Latex Articles".)
[0004] As an example of the problems inherent to the aforementioned protein reduction approaches, the usual concentrations of chlorine utilized for on-line chlorination or sodium chloride treatment of dip manufactured latex articles can cause corrosion of the materials used to construct leach water tanks (e.g., stainless steel). This corrosion issue forces manufacturers to replace their leach tanks with more expensive, potentially less durable, chlorine-resistant materials such as specially engineered plastics. Therefore, there is a need for protein reducing methods and compositions that can avoid or reduce corrosion in leach water tank construction materials.
[0005] Moreover, chlorination of some natural rubber latex product, such as medical gloves, may undesirably change the physical properties of the product. For example, when chlorination is applied to medical gloves where their thickness is approximately 0.2 mm and below, the application may result in the gloves having dark discoloration and poor physical properties (such as low tensile strength and poor elongation), particularly after high temperature ageing at 100° C for 22 hours. Therefore, there is a need for methods and compositions that can reduce protein content of a natural rubber latex product with reduced levels of chlorinating agents.
[0006] Besides natural rubber latex, other types of latices are also used to prepare dip- manufactured articles such as gloves, condoms, balloons, catheters, medical devices and finger cots. These latices include, for example, nitrile rubber, polyisoprene, polyurethane, ethylene copolymers, styrene copolymers, butadiene copolymers, emulsion manufactured polymers, dispersion manufactured polymers, silicone rubber, alpha olefin copolymers, mixtures thereof, and composites thereof. It is well known that undesirable odors may originate from dip manufactured products prepared from these types of latices as well as from natural rubber latices. The compositions and methods of the presently described technology are capable of removing odors from dip manufactured goods prepared from these types of latices as well as from natural rubber latex based, dip manufactured products.
[0007] Additionally, other manufacturing processes that utilize natural rubber latex or other types of latices can also benefit from the presently described technology. These processes utilize various combinations of methods selected from coagulation, foaming, coating, vulcanization and drying to produce latex foams, carpet backings, bandages, elastomeric fibers, textiles, athletic wraps, thread, and various other products. The compositions of the present technology may also be used in postprocessing (e.g., post-washing) of many of these articles. It is contemplated that the compositions of the present technology can be useful at removing undesirable odors, vulcanization residues and protein from the articles produced by these processes.
BRIEF SUMMARY OF THE INVENTION
[0008] The presently described technology relates generally to methods and compositions for reducing the protein content and/or undesirable odor, especially the allergenic protein content of latex articles, e.g., natural rubber latex articles. In particular, the presently described technology provides methods to reduce the protein content and/or odor of latex articles by introducing compositions comprising a surfactant component combined with a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof, into one or more stages of the manufacture of an article made of latex, or alternatively during the post laundering or washing treatment of the article. The methods and compositions of the presently described technology are particularly applicable to, but not limited to, natural rubber latex articles that are made through a dipping process.
[0009] Many latex articles are made using multi-staged dipping processes that may include holding the latex in a tank; dipping a former into one or more latex dipping tanks so that the former is covered with the latex to make an article in the shape of the former; heating the latex covered former so that the latex film may dry into a pre-cured film; passing the formers through pre- vulcanization leaching tanks (may be referred to as "pre-leach" tanks or baths) to remove excess chemical residue and latex protein with hot water; passing the former through a vulcanization stage; passing the former through a post-vulcanization leaching tank (may be referred to a "post-leach" tank or bath) to remove more latex protein and chemical residue; removal of the formed article from the former; laundering the formed articles in a washing step; drying the formed articles; and optionally, packaging them for shipment.
[0010] In accordance with at least some embodiments of the presently described technology, a composition comprising a surfactant component and a low level of a potentiator can be added into one or more of the leach baths of the dip manufacturing process. For example, the composition comprising the surfactant and the potentiator may be employed in the latex holding tank, the dipping tanks, any of the leaching tanks, the vulcanization stage, the laundering stage or any combination of these stages. The composition may also be employed in the final drying stage by introduction as a vapor or aerosol, for example, via the use of dryer sheets coated with the composition. The composition may also be employed in a post-washing step for products manufactured from natural rubber latex as well as other types of latices.
[0011] The surfactant component in the composition of the presently described technology comprises at least one surfactant. Suitable surfactants are preferably molecules that have the property of increasing the aqueous solubility or creating emulsions of a variety of otherwise insoluble or only slightly water-soluble organic compounds. More specifically, the surfactant of the presently described technology can be a chemical substance which includes a hydrophobic organic group chemically bonded to one or more hydrophilic groups. The hydrophobic organic group can be aliphatic, aromatic, polynuclear aromatic, or combinations thereof. One preferred attribute of the surfactant is that it be essentially non-foaming or very low-foaming during conditions experienced in the leach baths for NRL dip manufacturing.
[0012] The potentiator in the composition of the presently described technology comprises a chlorinating agent, a non-chlorinating salt, or a combination thereof. Suitable chlorinating agents include, for example, metal salts of hypochlorite, chlorine, trichloro-s-triazinetrione, dichloro-s- triazinetrione, and combinations thereof. More specific examples include, but are not limited to, sodium hypochlorite, sodium dichloro-triazinetrione, hypochlorous acid, and combinations thereof.
[0013] A non-chlorinating salt may be used instead of, or in combination with, a chlorinating agent in the composition of the presently described technology. Suitable non-chlorinating salts include, for example, water-soluble metal or ammonium salts of sulfates, carbonates, chlorides, chlorates, chlorites, phosphates, sulfites, bisulfites, bicarbonates, citrates, acetates, borates, lactates, nitrates, phosphites, silicates, and combinations thereof. It is understood that many salts occur with waters of hydration. In these instances, the waters of hydration are not considered towards actives content in leach bath compositions.
[0014] In one aspect, the presently described technology provides a method for reducing the protein content and/or odor of a manufactured latex (e.g., natural rubber latex) article. The method exposes a formed article to one or more leach baths, wherein at least one of the leach baths comprises: (1) a surfactant component comprising at least one chemical substance that includes at least one hydrophobic organic group chemically bonded to at least one hydrophilic group; and (2) a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof. Preferably, the surfactant component is present in an amount sufficient to provide about 1.0% or less surfactant actives, and the potentiator is present in an amount sufficient to provide about 0.06% or less actives, both based on the total weight of the at least one leach bath.
[0015] In some preferred embodiments, the surfactant component is present in an amount sufficient to provide about 0.5% by weight or less surfactant actives, and the potentiator is present in an amount sufficient to provide about 0.005% by weight or less actives, in the at least one leach bath.
[0016] In another aspect, the present technology provides a method for reducing the protein content and/or odor of a manufactured natural rubber latex article comprising the steps of exposing the article to a combination of baths comprising any sequential combination selected from the following treatments:
(1) a clean water bath; and
(2) a leach batch comprising a surfactant component comprising at least one chemical substance that includes at least one hydrophobic organic group chemically bonded to at least one hydrophilic group; and a potentiator comprising a chlorinating agent, a non-chlorinating salt or a combination thereof. Preferably, the surfactant component is present in an amount sufficient to provide about 0.5% or less surfactant actives, and the potentiator is present in an amount sufficient to provide about 0.005% or less actives, both based on the total weight of the leach batch.
[0017] In some preferred embodiments, the steps of exposing the article to a combination of baths in the above method comprise:
(1) exposing the article to a first clean water bath;
(2) exposing the article to the leach batch as described above; and then
(3) exposing the article to a second clean water bath.
Also, the temperatures of the first clean water bath, the leach bath, and the second clean water bath are about 70° C or lower and preferably are about 60° C or lower.
[0018] In a further aspect, the present technology provides a method for treating latex articles so as to reduce their protein content and/or odor, comprising the steps of:
(1) providing a natural rubber latex article;
(2) providing a composition comprising a surfactant component and a potentiator, wherein the weight concentration of the potentiator is substantially lower than that of the surfactant component; and
(3) exposing the natural rubber latex article to the protein reducing composition.
[0019] In yet another aspect, the present technology provides a concentrate composition comprising:
(1) a surfactant component comprising at least one chemical substance that includes at least one hydrophobic organic group chemically bonded to at least one hydrophilic group; and
(2) a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof.
[0020] The concentrate composition can be used to treat latices or latex articles to reduce the protein content and/or odor in them. Preferably, the surfactant component is present in an amount sufficient to provide from about 21% to about 80% surfactant actives, and the potentiator is present in an amount sufficient to provide from about 0.2% to about 15% actives, both based on the total weight of the concentrate composition.
[0021] In yet another aspect, the compositions of the presently described technology may be used during the manufacture of or in washing treatments for latex articles that have been manufactured by methods other than dip manufacturing. Examples of such articles include, but are not limited to, mattresses, foams, pillows, cushions, area rugs, continuously manufactured carpets, bathroom rugs, outdoor recycled tire mats, drapes, tarpolins, textile inserts or composites, bra padding, clothing padding, bandages, threads, elastic textiles, athletic support wrap, veterinarian support wrap, coated textile gloves, coated textile articles, and composites of textiles and latex coatings.
[0022] The protein and/or odor reducing methods and compositions of the presently described technology have one or more of the following advantages: protein reductions of up to 90% or more; reduction of undesirable odors, applicable for use with on-line polymer coating technology and processing; effectiveness with post laundering processes; energy cost savings via reduced leach bath temperatures; applicability to condoms, catheters, balloons, foam, membranes, films, coatings gloves, area rugs, bra and clothing padding, mattresses, pillows, cushions, and other latex products or applications; no or substantially no change in physical properties of the products; biodegradable active components, which are compatible with waste water treatment; simplicity to implement; minimal change to conventional glove manufacturing lines; and minimal or no additional capital investment.
DETAILED DESCRIPTION OF THE INVENTION
[0023] At least one method of the presently described technology includes the step of exposing latex such as natural rubber latex (NRL) or a latex article to a composition comprising a surfactant component and a potentiator. This exposure can reduce and/or neutralize the protein content, including allergenic protein content of the resulting latex articles. This exposure may also reduce and/or neutralize the undesirable odor of the resulting latex articles.
[0024] As used in the presently described technology, a "surfactant component" refers generally to all surfactants in a composition, and a "potentiator" refers generally to all chlorinating compounds and/or non-chlorinating salts in a composition. If two or more surfactants are used, they can be added together or at different times. If two or more chlorinating compounds and/or non- chlorinating salts are used, they can also be added together or at different times.
[0025] One typical method of making latex articles is a dipping process. In accordance with the dipping process, formers can be provided in the shape of a desired article, such as in the shape of a hand for making latex exam or surgical gloves, for example. These formers may be first washed in hot water to clean the formers. The formers can then be dipped into a coagulant tank that contains an aqueous solution of calcium nitrate, for example. The formers may then be dipped in a tank holding latex where the calcium on the surface of the former coagulates a thin layer of gel onto the former. The formers can then be passed through an oven where the coagulated latex dries into a pre-cured film. [0026] The formers can then be passed through pre- vulcanization leaching tanks to remove excess chemical residue and latex protein with hot water. Any number of pre- vulcanization leaching tanks (pre-leach tanks) may be used. A typical arrangement includes three long pre-vulcanization leaching tanks instead of just a single leaching tank, because multiple leaching tanks ensure the maximum removal of latex protein and chemical residue from the latex gel film on the formers. The extraction of the latex proteins and chemical residues is further enhanced by employing hot water, counter-flowing continuously against the formers as they pass through the pre-vulcanization leaching tanks.
[0027] The next step involves, in general, passing the formers into the vulcanization oven to be heated to remove moisture from the latex gel and harden the latex gel. The formers may then be passed through a post-vulcanization leaching tank (post-leach tank) to remove more latex protein and chemical residue. The post- vulcanization leaching tank is considered by some familiar with the field of the present technology to be the most important step in removing excess latex protein from the formed latex articles.
[0028] The formers may then be passed into another oven for further drying. The formers may then be passed into another tank containing, for example, wet cornstarch powder and water (as a donning or anti- tacking aide). After another drying oven, the articles may be stripped from the formers either by hand one at a time or by an automatic air ejection machine. The articles may then be placed into tumble dryers for the final vulcanization process.
[0029] In accordance with some embodiments, the method of the presently described technology involves the step of exposing the latex or latex articles with a composition comprising a surfactant component and a potentiator in an amount sufficient to effectively reduce and/or neutralize the allergenic protein content of the latex articles. For example, the composition of the present technology can be added into one or more of the leach baths of the dip manufacturing process.
[0030] The surfactant component in the protein reducing composition of the present technology comprises one or more surfactants that have the property of increasing the aqueous solubility or creating emulsions of a variety of otherwise insoluble or only slightly water-soluble organic compounds. Preferably, the surfactant of the present technology is a chemical substance that includes a hydrophobic organic group chemically bonded to one or more hydrophilic groups. The hydrophobic organic group can be aliphatic, aromatic, polynuclear aromatic, or a combination thereof.
[0031] When the compositions of the presently described technology are used in leach baths, one preferred attribute of the surfactant is that the surfactant be essentially non-foaming or very low- foaming during conditions experienced in the leach baths during NRL dip manufacturing. Another preferred attribute of the surfactant is that if any trace residues of the surfactant remain on the final resultant, dried article, the residues of surfactant have low or negligible skin irritation. This is because many of the articles prepared by dip manufacturing are for skin contact applications. A further preferred property of the surfactant is that the surfactant has some degree of protein removal efficacy even in the absence of the potentiator. A still another preferred property of the surfactant is that the surfactant be biodegradable to the extent that it is compatible with an industrial or municipal water treatment facility that treats the effluent of the leach water baths with little or no detrimental effects on these water treatment processes.
[0032] The term "very low-foaming" or "essentially non-foaming," when used to describe a leach bath or surfactant in a leach bath of the present technology, means that the leach bath allows for viewing of the liquid contents of the leach bath and does not transfer quantities of foam to the articles which are being dip manufactured so as to create defects. When the compositions of the presently described technology are used for post-laundering of latex products, foaming is an acceptable characteristic, however, since foaming does not create defects in the existing manufactured products or cause undesirable manufacturing problems at this point in the overall production process.
[0033] The hydrophilic group of the surfactant can be, for example, carboxylate, phosphate, sulfate, sulfonate, succinate, sulfosuccinate, or a combination thereof, in the form of a water-soluble salt. The counterion of the hydrophilic group may be sodium, potassium, magnesium, aluminum, ammonium, mono-, di-, or tri-alkyl ammonium, mono-, di-, or tri-hydroxy alkyl ammonium, a combination thereof, or any other cationic counterion which provides water solubility in the final surfactant.
[0034] According to some embodiments of the present technology, the hydrophilic group of the surfactant may be a polyalkoxylate. For example, it can be a polyalkoxylate comprising two or greater ethoxylate groups. For another example, when the polyalkoxylate contains greater than 2 ethoxylate units, the polyalkoxylate may further comprise 40% or less propoxylate or butoxylate groups.
[0035] According to some embodiments of the present technology, the hydrophilic group of the surfactant may also be polyglycerols, sugars, and glycosides or polyglycosides.
[0036] According to at least some embodiments of the present technology, the hydrophilic group of the surfactant may be quaternary amines, tertiary ammonium salts, secondary ammonium salts, primary ammonium salts, ammonium salts, sulfobetaines, betaines, pyridinium salts, nitrogen- containing heterocyclic amine salts, amino carboxylates, amine oxides, amides, nitrogen-containing heterocyclic amides, polyvinyl pyrrolidone, and combinations thereof.
[0037] Preferred surfactant compounds for use in the practice of some embodiments of the present technology are amine oxides. At least some amine oxides are effective at removing a variety of different types of soils and stains from surfaces.
[0038] Other preferred surfactants include phosphates, sulfates, sulfonates, betaines, sulfobetaines, and nonionic surfactants.
[0039] Other surfactants with hydrophilic groups as those identified above also have a similar ability to provide cleaning of soiled surfaces, and it is believed that they too would provide the same or similar benefits to latex articles.
[0040] The composition of the presently described technology further comprises a potentiator. The potentiator comprises a chlorinating agent, a non-chlorinating salt, or a combination thereof. The potentiator is present in at least some compositions of the presently described technology in a substantially lower level as compared to the surfactant component. For example, in some compositions of the presently described technology, the active concentration of the surfactant component is at least 10 times, alternatively at least 50 times, alternatively at least 100 times of the active concentration of the potentiator.
[0041] The potentiator in the compositions of the present technology may comprise one or more chlorinating compounds. Suitable chlorinating compounds include, but are not limited to, metal salts of hypochlorite, chlorine, trichloro-s-triazinetrione, dichloro-s-triazinetrione, and combinations thereof. More specific examples include sodium dichloro-s-triazinetrione, sodium hypochlorite, potassium hypochlorite, lithium hypochlorite, calcium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, potassium trichlorocyanurate, sodium trichlorocyanurate, trichlorocyanuric acid, dichlorocyanuric acid, potassium dichlorocyanurate, sodium dichlorocyanurate, N-chlorinated succinimide, N- chlorinated malonimide, N-chlorinated phthalimide, N-chlorinated naphthalimide, dichlorodimethylhydantoin, N-chlorosulfamide, chloramine, hypochlorous acid and combinations thereof. Examples of preferred chlorinating agents include sodium hypochlorite, hypochlorous acid, and combinations thereof.
[0042] The potentiator in the compositions of the present technology may comprise one or more non-chlorinating salts. Suitable non-chlorinating salts include, but are not limited to, water-soluble metal or ammonium salts of sulfates, carbonates, chlorides, chlorates, chlorites, phosphates, sulfites, bisulfites, bicarbonates, perborates, percarbonates, citrates, acetates, borates, lactates, nitrates, phosphites, and silicates. It is understood that many salts occur with waters of hydration. In these instances, the waters of hydration are not considered towards actives content in leach bath compositions.
[0043] In accordance with some embodiments, the composition of the present technology is a concentrate composition. The concentrate composition preferably (1) contains the surfactant component in an amount sufficient to provide from about 15% to about 80%, alternatively from about 17% to about 50%, surfactant actives in the concentrate composition, most preferably from about 20 to about 45% surfactant actives, and (2) contains the potentiator in an amount sufficient to provide from about 0.5% to about 15%, alternatively from about 1% to about 5%, most preferably from about 1.5% to about 5% actives in the concentrate composition, all based on the total weight of the concentrate composition. Suitable solvents such as water, alcohol, and mixtures thereof, can be used as the delivery vehicle of the concentrate composition. Examples of alcohols that may be used include ethanol, isopropanol, methanol, diethylene glycol, propylene glycol, butanol, and mixtures thereof.
[0044] However, at least in some embodiments, water alone is preferred. The concentrate composition can be diluted in water or added to a dip manufacturing leach bath to form an application solution. In some embodiments, the concentrate composition can further comprise a chlorine or hypochlorite stabilizing agent as known by those familiar with the field of hypochlorite- containing formulations. Examples of stabilizing agents include sodium hydroxide, potassium hydroxide, silicates, and the like.
[0045] It is anticipated that the compositions of the present technology can contain one or more other additives such as, for example, pH controllers, buffers, emulsifiers, viscosity modifiers, inorganic salts, waxes, alcohols, and preservatives.
[0046] As noted above, the composition of the present technology may be employed in any of several steps in the making of the at least one latex article to reduce the odor and/or protein content in the resulting latex article. For example, the compositions of the presently described technology may be employed in the latex holding tank, the dipping tanks, any of the leaching tanks, the vulcanization stage, the laundering stage or any combination of these processing stages. The compositions should be present in an amount sufficient to effectively reduce and/or neutralize the allergenic protein content and/or odor of the latex such as natural rubber latex articles. Preferably, when applied, the surfactant component of the composition of the present technology will provide about 1.5% or less, alternatively from about 0.01% to about 1.0%, alternatively from about 0.02% to about 0.5%, surfactant actives in the leach bath; the potentiator will provide about 0.1% or less, alternatively about 0.06% or less, alternatively from about 0.0001% to about 0.01%, actives in the leach bath, all based on the total weight of the leach bath.
[0047] Those skilled in the art will understand that water and other solvents such as alcohol and combinations thereof, may be used as delivery vehicles for the compositions for use in accordance with the presently described technology. Examples of alcohols that may be used include ethanol, isopropanol, methanol, diethylene glycol, propylene glycol, butanol, and mixtures thereof. However, water alone is preferred in at least some embodiments to avoid the use of volatile organic compounds.
[0048] It has been surprisingly found that with the addition of a very low level of potentiator (e.g., 0.001% by weight actives), a much lower (e.g., five times lower) concentration of surfactant actives is needed to achieve the same level of protein reduction than when the surfactant component is used alone. It has also been surprisingly found that the composition of the present technology at a low application concentration (e.g., 0.1% by weight surfactant actives and 0.001% by weight actives) can achieve excellent (e.g., 90% or more) protein reduction level at a much lower leach bath temperature (e.g., 40 0C or lower) as compared to a simple water bath absent of any content of the presently described technology. This temperature reduction can provide substantial savings on energy costs.
[0049] Further, the methods and compositions of the presently described technology have been found to possess one or more of the following additional advantages: protein reductions of up to 90% or more; reduction of undesirable odors, applicability for use with on-line polymer coating technology and processing; effectiveness with post laundering processes; applicability to condoms, catheters, balloons, foam, membranes, films, coatings gloves, area rugs, bra and clothing padding, mattresses, pillows, cushions, and other latex products; no or substantially no change in physical properties of glove or other latex products; biodegradability of active components, which are compatible with conventional waste water treatment; simplicity to implement; minimal change to glove manufacturing lines; and minimal or no additional capital investment.
[0050] The presently described technology and its advantages will be better understood by reference to the following examples. These examples are provided to describe specific embodiments of the present technology. By providing these specific examples, the applicants do not limit the scope and spirit of the present technology. It will be understood by those skilled in the art that the full scope of the presently described technology encompasses the subject matter defined by the claims appending this specification, and any alterations, modifications, or equivalents of those claims. Description of Materials:
[0051] Ammonyx® LO is a surfactant containing 30% lauryl amine oxide actives in water, available from Stepan Company in Northfield, Illinois. This product was used as a source of lauryl amine oxide surfactant in some examples below.
[0052] Cedaphos® FA-600 is a surfactant containing 99% alkyl ethoxylate phosphate actives in water, available from Stepan Company in Northfield, Illinois. This product was used as a source of alkyl ethoxylated phosphate surfactant in some examples below.
[0053] The coagulant used in the examples was "20% Calcium Nitrate WCS + R", available from Killian Latex in Akron, Ohio.
[0054] The natural rubber latex compound used in the examples was Compound 473-11/58% TSC, available from Killian Latex in Akron, Ohio.
[0055] The guayule rubber latex compound used in the examples was obtained from Yulex Corporation of Maricopa, Arizona, and contained 38% total solids.
[0056] The neoprene (polychloroprene) rubber latex compound used in the examples was obtained from Polytech Synergies of Canal Fulton, Ohio, and contained 38% total solids.
[0057] Water used in all leach bath experiments was deionized municipal drinking water. All leach water was replaced with fresh water upon introduction of each new composition for testing.
[0058] Defoamer Freesil™ 80 was used as needed in both latex and coagulant baths for random antifoaming needs. This product was obtained from Crusader Chemical Co., Inc., Baltimore, MD.
Procedures and Test Methods:
1. Latex Glove Dip Manufacturing Procedure
[0059] A computer controlled Diplomat™ 3 axis dipping system (DipTech Systems, Akron, Ohio) was used to control the dip times, mold rotation and dip rates of medium size porcelain ceramic exam glove molds, supplied by General Porcelain Co., Parkersburg, West Virginia. A coagulant bath was heated using a thermostated immersion heater to a temperature of about 50 0C to about 55 0C. The natural rubber latex compound bath was used at an ambient temperature of about 23 0C. The natural rubber latex bath was continuously stirred by variable speed air mixer, except during actual dipping of the forms into the latex. The coagulant bath was manually stirred with a paddle approximately one minute before each dipping cycle.
[0060] Ceramic molds were hand cleaned with warm city water and a towel, usually once per day, to remove residual ingredients occurring from glove manufacturing iterations. Coagulant Dip:
[0061] Two to four ceramic molds were fixed to the robotic attachment points of the Diplomat™ 3 axis dipping system. The glove molds were lowered into the coagulant bath (fingertips pointed downward) at a speed of one inch per second and allowed to dwell in the bath for 1 second. The molds were then automatically removed from the bath at a speed of 1 inch per second, and rotated from about 70 to 90 degrees angle in mid-air with forms spinning axially, for approximately 90 seconds, while a conventional hair drier was utilized to dry the coagulant onto the surface of the ceramic molds.
Natural Rubber Latex Dip:
[0062] After drying the molds, they were dipped into the natural rubber latex compound, and allowed to remain in the bath for approximately two seconds, whereupon they were removed, and allowed to rotate from about 70 to 90 degrees for approximately 30 seconds. The molds were then allowed to air dry for approximately 60 seconds to allow the latex to form a gel.
Pre-Cure Leach Dip:
[0063] The molds were then dipped into a circulated bath of deionized Akron, Ohio municipal drinking water held by an immersion heater at a temperature of about 38° C or another selected temperature. A second bath contained the same water, but also included a composition of the presently described technology or in the case of comparative examples, water alone. Depending on the experiment being conducted, dipping occurred in a variety of combinations of these two baths; the combined dip time for this step totaled anywhere from, for example, approximately 30 seconds to approximately 45 seconds. In each case, removal of the molds from the last bath of this dipping step was followed by a 10 second time period during which excess water was allowed to drip off of the gloves and molds. The leach baths used for pre-cure leach dip may be referred to as pre-leach baths.
Oven Drying and Curing:
[0064] The molds were then oven dried for approximately 2.0 minutes at about 80 0C in a convection oven to further remove excess water. Immediately upon removing the gloves from the oven, approximately 0.5 inches of the upper cuff area of each latex gloves was rolled into a bead by hand. After forming the beads on the gloves, the molds were placed into a convection oven held at about 100 0C for approximately 13 minutes, and then into a convection oven held at about 110 0C for another two minutes. Post-Cure Leach Dip:
[0065] Upon removal from the final cure oven, the molds holding the latex gloves were dipped into a post-cure leach bath containing process water held by an immersion heater to a temperature of about 38 0C or another selected temperature. Depending on the experiment being conducted, dipping occurred in a variety of combinations of these two baths; the combined dip time for this step usually totaled approximately 30 to approximately 45 seconds, but can be another selected period of time. In each case, removal of the molds from the last bath of this dipping step was followed by a 10 second time period during which excess water was allowed to drip off of the gloves and molds. The leach baths used for post-cure leach dip may be referred to as post-leach baths.
Drying and Stripping:
[0066] The gloves on their molds were further dried in a convection oven held at about 80° C for approximately two minutes, removed from the oven and allowed to cool for approximately two minutes. Talcum powder was applied by hand to the surface of the resulting gloves to provide a non-tacking surface, and the gloves were then stripped from the mold while at the same time turning them inside out. An attendant wore thin film, disposable nitrile gloves while de-molding each individual glove, to avoid direct human contact with the finished product.
2. Preparation of Polymer Coated Gloves
[0067] Polymer coated gloves tested in the presently described technology were coated with an acrylic based coating, which was composition ProSlip supplied by Polytech Synergies of Canal Fulton, Ohio.
[0068] ProSlip is comprised of an acrylic based emulsion (25 wt%), a silicone based emulsion (5 wt%), a surfactant (0.1 wt%), and water (69.9 wt%). The process of preparing polymer coated gloves remains the same as the Latex Glove Dip Manufacturing Procedure until the oven dry and curing step described above. After forming beads on the gloves, the gloves on their molds were cured for approximately three minutes at about 100° C. The molds were removed from the oven and dipped into ProSlip at 3% strength in water at ambient temperature. The gloves are then cured at about 100° C for approximately 10 minutes, and at about 110° C for approximately two minutes. Post-cure leaching scheme was the same as that described above.
3. Post Laundering Procedure
[0069] Post laundering was conducted using non-treated latex gloves prepared using leach water of about 40 0C or another selected temperature that contained, for example, selected treatment agents or no treatment agents. Four gloves were washed in a laundering solution of either (1) a composition of the present technology containing, for example, 0.1% lauryl amine oxide and 0.0023% sodium hypochlorite in deionized water, or (2) deionized water alone. Gentle agitation using a stainless steel rod was conducted during the post laundering time of approximately 90 seconds (1.5 minutes) or another selected time X. The lauryl amine oxide/hypochlorite laundering step was followed by approximately 90 seconds (1.5 minutes) or another selected time X of a rinse with deionized water. The control (deionized water alone) was simply approximately 3.0 minutes or another selected time 2X of gentle agitation of four latex gloves using a stainless steel rod.
4. Protein Content Testing Total Protein Method:
[0070] Protein content was tested by the Total Protein Method. According to this method, chemoassay protein content was measured using Modified Lowry Assay (ASTM D5712-95), using four 2-fold serial dilutions in duplicate. Antigenic Protein content was measured using ELISA Inhibition Assay (ASTM D6499-03), using seven 2-fold serial dilutions in duplicate. All protein content measurements were conducted by LEAP Testing Service of Sayre, Pennsylvania.
[0071] Four protein testing samples were weighed and measured after which the samples were cut to allow buffer contact with all surfaces. Extractions were performed for approximately two (2) hours with constant agitation at 25° C +/1.5° C in 100 mM phosphate buffered saline (pH 7.4). The extraction ratio used was about 5 to 1. Extracts were centrifuged to remove particulates, then assayed.
Example 1: Preparation of Leach Bath Treatment Concentrate #1
[0072] Leach Bath Treatment Concentrate #1 was prepared by the following procedure: Ammonyx® LO (800 g) was added to a 1000 ml beaker. The initial pH of about 7.7 was adjusted to about 12.2 using a 50% sodium hydroxide solution. About 184 g of a sodium hypochlorite solution (10-13% NaOCl) were added to the Ammonyx® LO mixture with stirring. The pH was measured again, this time providing a reading of about 11.8. It was readjusted dropwise with the 50% sodium hydroxide solution to a value of about 12.2.
[0073] This concentrate (0.38 parts) was diluted with deionized water (99.62 parts) to form a leach bath containing about 0.1% lauryl amine oxide actives and 0.001% nominal sodium hypochlorite actives (i.e., chlorine actives).
Example 2: Preparation of Leach Bath Treatment Concentrate #2
[0074] Leach Bath Treatment Concentrate #2 was prepared by the following procedure: Cedaphos® FA600 (240 g) was added to a 1000 ml beaker along with 560 g of deionized water. The initial pH of the mixture was about 1.5, which was adjusted to about 12.4 using a 50% sodium hydroxide solution. The solution exothermed to about 52° C during this neutralization, and was allowed to cool to about 26° C. About 184 g of the sodium hypochlorite solution (10-13% NaOCl) were added to the surfactant solution with stirring. The pH was measured again, this time providing a reading of about 12.6.
[0075] This concentrate (0.38 parts) was diluted with deionized water (99.62 parts) to form a leach bath containing about 0.1% alkyl ethoxylate phosphate actives and about 0.001% nominal sodium hypochlorite actives (i.e., chlorine actives). This leach bath yielded a reduced protein content of 105 micrograms/ g of glove, when compared to the control (water alone) sample, which had a protein content of 108 micrograms/ g of glove.
Example 3: Study of a leach bath of the present technology
[0076] In this example, a leach bath of the present technology (Type 1, prepared from Leach Bath Treatment Concentrate #1) containing 0.1% lauryl amine oxide actives and 0.0023% sodium hypochlorite actives (0.001% by weight chlorine actives) was compared to leach baths containing untreated water (Comparative Type A), and a leach bath containing 0.5% lauryl amine oxide actives alone in water (Comparative Type B). The total protein contents of natural rubber latex gloves prepared by the Latex Glove Dip Manufacturing Procedure were tested by the Total Protein Method.
[0077] In this example, when Type 1 leach bath was used, lauryl amine oxide actives and chlorine actives were present in both the pre-cure leach dip and post-cure leach dip treatment locations. The results are shown in Table 1 below. In the table, "Pre/Post" means that the NLR glove was treated by the leach bath during both pre-cure leach dip and post-cure leach dip; "None" means that water was used in lieu of surfactant or surfactant composition. A Pre- or Post-Leach Time Profile of "15/15/15" indicates 15 seconds of water only treatment, followed by 15 seconds of treatment by the leach bath of Comparative Type B or Type 1, followed by 15 seconds of water-only leaching prior to or after the vulcanization oven step. In the instance where water alone, i.e., Comparative Type A was used, there was only one leach bath for both pre-leach and post-leach with the indicated time.
Table 1
Figure imgf000017_0001
[0078] The results show that Type 1 leach bath of the present application achieves a 74% further reduction of protein content as compared to Comparative Type A leach bath which used a clean water bath only. The results also show that with the addition of 0.0023% by weight sodium hypochlorite (0.001% chorine actives), only 0.10% by weight of the lauryl amine oxide surfactant actives was needed to achieve a comparable protein reduction to that achieved by Comparative Type B leach bath that contained five times the weight percentage of lauryl amine oxide surfactant actives.
Example 4: Comparative study of a series of leach baths of the present technology
[0079] In this experiment, a series of leach baths of the present technology (Types 2-5) were studied in comparison to two comparative leach baths (Comparative Types C and D). Each leach bath of Types 2-5 contain 0.1% lauryl amine oxide actives and 0.0023% sodium hypochlorite actives (0.001% by weight chlorine) held at a temperature of about 40° C. Comparative Type C was a bath of clean water at about 40° C, and Comparative Type D was a bath of clean water at about 60° C. Five natural rubber latex gloves were prepared using leach baths of Comparative Types C and D and leach baths of Types 2-4 of the present technology at the temperature and location indicated in Table 2 below using the Latex Glove Dip Manufacturing Procedure. Type 5 leach bath of the present technology demonstrates how the technology may be used to treat a Polymer Coated Glove (preparation described above) in a post laundering step. The results of the total protein content analysis are summarized in Table 2 below.
Table 2
Figure imgf000018_0001
[0080] The results show that 40 0C leach baths containing the composition of the present technology can reduce protein content to a much greater extent than a 60 0C clean water leach bath. The results also demonstrate a very large reduction in protein content using very low levels of surfactant and chlorine actives versus water alone. Example 5: Comparative study of leach baths with and without a non-chlorinating salt
[0081] In this experiment, a series of leach baths of the present technology (Types 6-8) were studied together with two comparative leach baths (Comparative Types E and F). Each of leach baths of Types 6-8, and Comparative Type F contain 0.1% lauryl amine oxide actives, sodium hypochlorite, sodium chloride, and sodium hydroxide at the actives levels indicated in Table 3, and were held at a temperature of about 40° C. Comparative Type E was a bath of clean water at 40° C. Five natural rubber latex gloves were prepared using each of the five leach baths as indicated in Table 3 below using the Latex Glove Dip Manufacturing Procedure. The results of the total protein content analysis are summarized in Table 3.
Table 3
Figure imgf000019_0001
[0082] These results indicate that the use of leach bath compositions of the present invention provide enhanced protein removal versus water alone. Additionally, it appears that the use of sodium hydroxide, which is a hypochlorite stabilizing agent, as potentiators did not yield improved protein reduction.
Example 6: Comparative study of a series of leach baths of the present technology
[0083] In this experiment, a series of leach baths of the present technology (Types 9-19) were studied in comparison to comparative leach baths (Comparative Types G through J). The gloves were manufactured using the Latex Glove Dip Manufacturing Procedure, with the leach bath temperatures, and pre-leach and post leach profile times indicated. All of the latexes were natural rubber latex. The three potentiators used in the compositions of the present technology are NaOCl, Na2SO4 and MgSO4.
[0084] The middle leach water bath composition indicates the composition of the leach bath of the present technology used between two water-only baths. The pre- and post-leach time profiles indicate the time for the water-only bath, the middle treatment bath, and the second water only bath. For example, in Table 4, a Pre- or Post-Leach Time Profile of "10/10/10" indicates 10 seconds of water only, followed by 10 seconds of the middle treatment bath, followed by 10 seconds of water- only leaching prior to or after the vulcanization oven step. In the instances where water alone was used, there was only one leach bath for both pre-leach and post-leach with the indicated time.
[0085] The results of the total protein content analysis are summarized in Table 4 below.
Table 4
Figure imgf000020_0001
[0086] These results indicate that the use of leach bath compositions of the present technology containing both a surfactant and a potentiator provide enhanced protein removal versus water alone at both about 40° C and about 60° C using low actives content in the leach bath compositions. The results also show that the same type of leach bath at 60° C reduces more protein versus when at 40° C. The results further show that higher active concentrations of the compositions of the present technology do not appear to necessarily reduce protein content more than lower concentrations, and longer wash and rinse times do not seem to assist in protein reduction either.
[0087] Surprisingly, the results show that the use of prior art leach batch technology (Comparative Type I and J) actually caused an increase in the protein content versus the use of water alone. Example 7. Odor panel testing of natural rubber latex exam gloves using different concentrations of actives
[0088] A new set (five types) of natural rubber (NR) latex gloves were prepared using a protocol similar to that observed for the gloves prepared as recorded in Table 4. The five types of leach baths used are Types 20-23 of the present technology and Comparative Type K. The key difference between these gloves and the gloves in Table 4 is that the gloves described in Table 5 utilize a total post leach time of 120 seconds in order to better simulate the post leach times used on an exam glove manufacturing line. Immediately after drying was completed, two gloves from each type were placed into a 6 ounce, wide mouth, glass bottle with a metal lid and sealed until tested. [0089] Eleven odor panelists were asked to come separately with a test administrator into an office for the odor test. Only one panelist was permitted into the office at a time in the office to avoid the possibility of information being shared between the panelists. The same panelist was not allowed to perform odor testing twice within one hour of a previous odor test in order to allow their noses a time for full recovery. Each panelist was asked to rank the samples in order of odor intensity. [0090] To reduce the complexity of the sensory test and provide a clear comparison between the five test samples, each set of test samples was limited to five in number. The results were recorded as five (5) for most intense, and one (1) for least intense. The data for each set were treated by subtracting one (1) from each individual odor intensity value to set zero as the odor intensity threshold. Eleven panelists were used and the highest deviation panelist data was discarded. The resulting ten data were then summed for each sample to provide an odor intensity value. Note that odor intensity values cannot be compared between different sets of odor intensity test data, because the data was generated from rankings within a particular set of five samples. The results are recorded in Table 5 below.
Table 5
Figure imgf000021_0001
[0091] This experiment clearly indicates that the leach bath compositions of the present technology reduce the odor intensity of natural rubber latex gloves at several use levels both at 40° C and 60° C versus a 40° C water only control.
Example 8. Odor panel testing of neoprene and guayule exam gloves
[0092] Two types of neoprene and three types of guayule gloves were prepared using the same protocol described in Example 7 by leach baths of Types 24-26 of the present technology and Comparative Types L and M. Odor panel testing of these gloves was conducted in the same manner as that described in Example 7. The results are recorded in Table 6 below.
Table 6
Figure imgf000022_0001
[0093] This experiment clearly indicates that the leach bath compositions of the present technology reduce the odor intensity of guayule latex gloves at several use levels versus a water only control. The neoprene control gloves had very low odor intensity, and did not need help of the composition of the present technology to decrease odor intensity.
Example 9. Odor panel testing of natural rubber latex exam gloves
[0094] A set (four types) of natural rubber (NR) latex gloves were prepared using the same protocol described in Example 7 by leach baths of Types 27-29 of the present technology and Comparative Type N. Odor panel testing of these gloves was conducted in the same manner as that described in Example 7. A pair of Fisher Scientific latex gloves were included in this experiment to benchmark the results of the present technology to leading commercial product. The results are recorded in Table 7 below. [0095] This experiment clearly indicates that the leach bath compositions of the present technology containing different potentiators (NaOCl, MgSO4, and Na2SO4) reduce the odor intensity of natural rubber latex gloves versus a water only control. The benchmark Fisher scientific gloves were low in odor intensity versus the gloves produced by DipTech Systems in the present experiment.
Table 7
Figure imgf000023_0001
Example 10. Protein reduction in natural rubber latex gloves
[0096] In this experiment, leach bath Type 30 was studied against a comparative leach bath (Comparative Type P) to evaluate the extent of protein content reduction by the leach bath of the present technology. The latex articles tested in this experiment were natural rubber (NR) latex gloves. Leach bath Type 30 contained 0.1% lauryl amine oxide and 0.0023% sodium hypochlorite. The leach water temperature and pre/post-leach time profiles are shown in Table 8 below. [0097] Chemoassay protein content was measured using Modified Lowry Assay (ASTM D5712- 95), and antigenic protein content was measured using ELISA Inhibition Assay (ASTM D6499-03). The results of the protein content analysis are summarized in Table 8.
Table 8
Figure imgf000023_0002
[0098] This experiment clearly indicates that the leach bath compositions of the present technology can significantly reduce the protein content as measured by immunoassay of natural rubber latex gloves (by up to 90% in this experiment) versus a 40° C water only control leach bath.
Example 11. Protein reduction in cohesive bandages
[0099] Cohesive bandages from Andover Healthcare, Inc., Salisbury, MA, and 3M, St. Paul, MN were tested in this experiment. Both types of cohesive bandages were made from natural rubber (NR) latices. Leach baths Type 31 and Comparative Type Q were used to treat the Andover type cohesive bandages, and leach baths Type 32 and Comparative Type R were used to treat the 3M type cohesive bandages. The composition, leach water temperature, and post wash time of each type of leach bath are shown in Table 9 below.
[00100] In the case of wash treatments using leach bath Type 31 or 32, each bandage was washed in one liter of wash treatment (i.e., leach bath) at about 40° C for approximately 30 seconds with gentle agitation using a stainless steel stirring rod, followed by approximately 30 seconds of similarly agitated rinse in a plain water bath held at about 40° C. The comparative wash treatments were identical, except that plain water was used for the entire treatment. The cohesive bandages were then allowed to air dry for 48 hours prior to testing for protein content.
[00101] Chemoassay protein content was measured using Modified Lowry Assay (ASTM
D5712-95), and the results are summarized in Table 9.
Table 9
Figure imgf000024_0001
[00102] This experiment clearly indicates that the wash water treatment compositions of the present technology can significantly reduce (by up to 89% in this experiment) the protein content on cohesive bandages via a simple post wash treatment. Example 12. Protein reduction in natural rubber latex condoms
[00103] Two types of natural rubber (NR) latex condoms were prepared using a leach bath of
Type 33 of the present technology and Comparative Type S. A procedure similar to the Latex Glove Manufacturing Procedure was used with a difference that the condoms were not treated by pre-leach baths, and were treated by post-leach baths only.
[00104] The composition, leach water temperature, and post-leach time profile of each type of leach bath are shown in Table 10 below. "15/30/15" means 15 seconds of water treatment, followed by 30 seconds of Type 32 leach bath treatment, followed by 15 seconds of water treatment. Chemoassay protein content was measured using Modified Lowry Assay (ASTM D5712-95), and the results are summarized in Table 10.
Table 10
Figure imgf000025_0001
[00105] The results show significant (about 88% in this experiment) reduction of chemoassay protein content on the natural rubber condom when a leach bath of the present technology was utilized.
[00106] The present technology is now described in such full, clear, concise and exact terms as to enable any person skilled in the art to which it pertains, to practice the same. It is to be understood that the foregoing describes preferred embodiments of the invention and that modifications may be made therein without departing from the spirit or scope of the present technology as set forth in the appended claims.

Claims

1. A method for reducing the protein content, odor, or both of a manufactured latex article comprising the steps of: forming a latex article by coagulation or drying of a latex into a desired shape or coating; and exposing the formed latex article to one or more leach baths or washing treatments, wherein at least one of the leach baths or washing treatments comprises: a surfactant component comprising at least one surfactant that includes at least one hydrophobic organic group chemically bonded to at least one hydrophilic group; and a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof, wherein the surfactant component is present in an amount sufficient to provide about 1.0% or less surfactant actives based on the total weight of the at least one leach bath or washing treatment, and the potentiator is present in an amount sufficient to provide about 0.06% or less actives based on the total weight of the at least one leach bath or washing treatment.
2. The method of claim 1, wherein the at least one hydrophilic group is a carboxylate, phosphate, sulfate, sulfonate, succinate, sulfosuccinate, betaine, sulfobetaine or a combination thereof, in the form of a water-soluble salt.
3. The method of claim 2, wherein the counterion of the hydrophilic group is selected from the group consisting of sodium, potassium, magnesium, aluminum, ammonium, mono-, di-, or tri-alkyl ammoniums, mono-, di-, or tri-hydroxy alkyl ammoniums, and combinations thereof.
4. The method of claim 1, wherein the at least one hydrophilic group is selected from the group consisting of polyalkoxylates comprising two or more ethoxylate groups, polyglycerols, sugars, glycosides, polyglycosides, and mixtures thereof.
5. The method of claim 4, wherein the at least one hydrophilic group comprises a polyalkoxylate that further comprises 40% or less propoxylate groups.
6. The method of claim 1, wherein the at least one hydrophilic group is selected from the group consisting of quaternary amines, tertiary ammonium salts, secondary ammonium salts, primary ammonium salts, ammonium salts, sulfobetaines, betaines, pyridinium salts, nitrogen- containing heterocyclic amine salts, amino carboxylates, amine oxides, amides, nitrogen-containing heterocyclic amides, polyvinyl pyrrolidone, and combinations thereof.
7. The method of claim 1 , wherein the at least one hydrophilic group is dimethyl amine oxide.
8. The method of claim 1, wherein the potentiator comprises at least one chlorinating compound selected from the group consisting of metal salts of hypochlorite, hypochlorous acid, chlorine, trichloro-s-triazinetrione, dichloro-s-triazinetrione, and combinations thereof.
9. The method of claim 1, wherein the potentiator comprises sodium hypochlorite, hypochlorous acid, or a combination thereof.
10. The method of claim 1, wherein the potentiator comprises a non-chlorinating salt selected from the group consisting of water-soluble metal or ammonium salts of sulfates, carbonates, chlorides, chlorates, chlorites, phosphates, sulfites, bisulfites, bicarbonates, perborates, percarbonates, citrates, acetates, borates, lactates, nitrates, phosphites, silicates, and combinations thereof.
11. The method of claim 1, wherein the surfactant component is essentially non- foaming or very low-foaming in the at least one leach bath or washing treatment.
12. The method of claim 11, wherein the surfactant component is present in an amount sufficient to provide about 0.5% by weight or less surfactant actives, and the potentiator component is present in an amount sufficient to provide about 0.005% by weight or less potentiator actives, in the at least one leach bath or washing treatment.
13. A method for reducing the protein content, odor, or both of a latex article comprising the step of exposing the article to a combination of leach baths or washing treatments comprising any sequential combination of the following treatments:
at least one untreated leach water bath or washing treatment; and at least one treated leach batch or washing treatment comprising a surfactant component comprising at least one surfactant that includes at least one hydrophobic organic group chemically bonded to at least one hydrophilic group; and a potentiator comprising a chlorinating agent, a non- chlorinating salt or a combination thereof, wherein the surfactant component is present in an amount sufficient to provide about 0.5% or less surfactant actives, and the potentiator is present in an amount sufficient to provide about 0.005% or less of potentiator actives, both based on the total weight of the treated leach batch or washing treatment.
14. The method of claim 13, wherein the step of exposing the article to a combination of leach baths or washing treatments comprises: exposing the article to a first untreated leach water bath or washing treatment; exposing the article to a treated leach bath or washing treatment; and then exposing the article to a second untreated leach water bath or washing treatment.
15. The method of claim 14, wherein the temperatures of the first untreated leach water bath or washing treatment, the treated leach bath or washing treatment, and the second untreated leach water bath or washing treatment are about 60° C or lower.
16. The method of claim 14, wherein the temperatures of the first untreated leach water bath or washing treatment, the treated leach water bath or washing treatment, and the second untreated leach water bath or washing treatment are about 50° C or lower.
17. A method for reducing the odor, protein content or both of latex articles comprising the steps of:
providing a latex article;
providing a composition comprising a surfactant component and a potentiator, wherein the potentiator comprises a chlorinating agent, a non-chlorinating salt or a combination thereof, wherein the active concentration of the potentiator is lower than that of the surfactant component; and
exposing the latex article to the composition, wherein the latex article is produced from a latex.
18. The method of claim 17, wherein the latex is selected from the group consisting of natural rubber latices, nitrile rubber latices, polyisoprenes, polyurethanes, ethylene copolymers, styrene copolymers, butadiene copolymers, silicone rubber latices, emulsion manufactured polymers, dispersion manufactured polymers, alpha olefin copolymers, mixtures thereof, and composites thereof.
19. The method of claim 17, wherein the step of exposing the latex article to the composition comprises washing or leaching the latex article in a treatment solution including the composition.
20. The method of claim 19, wherein the surfactant component is present in an amount sufficient to provide about 0.5% or less surfactant actives in the treatment solution based on the total weight of the treatment solution, and the potentiator is present in an amount sufficient to provide about 0.005% or less actives in the treatment solution based on the total weight of the treatment solution.
21. A latex article produced by the method of claim 17.
22. The latex article of claim 21, wherein the latex article is polymer coated.
23. A concentrate composition for reducing the odor, protein content, or both of latices or latex articles, comprising: a surfactant component comprising at least one surfactant that includes at least one hydrophobic organic group chemically bonded to at least one hydrophilic group; and a potentiator comprising a chlorinating agent, a non-chlorinating salt, or a combination thereof, wherein the surfactant component is present in an amount sufficient to provide from about 21% to about 80% surfactant actives, and the potentiator is present in an amount sufficient to provide from about 0.5% to about 15% potentiator actives, both based on the total weight of the concentrate composition.
24. The concentrate composition of claim 23, further comprising water, an alcohol, or a mixture thereof.
25. The concentrate composition of claim 23, further comprising a chlorine or hypochlorite or hypochlorous acid stabilizing agent.
26. The concentrate composition of claim 23 , wherein the at least one hydrophilic group is a carboxylate, phosphate, sulfate, sulfonate, succinate, sulfosuccinate, betaine, sulfobetaine or a combination thereof, in the form of a water-soluble salt.
27. The concentrate composition of claim 26, wherein the counterion of the hydrophilic group is selected from the group consisting of sodium, potassium, magnesium, aluminum, ammonium, mono-, di-, or tri-alkyl ammoniums, mono-, di-, or tri-hydroxy alkyl ammoniums, and combinations thereof.
28. The concentrate composition of claim 23, wherein the at least one hydrophilic group is selected from the group consisting of polyalkoxylates comprising two or more ethoxylate groups, polyglycerols, sugars, glycosides, polyglycosides, and mixtures thereof.
29. The concentrate composition of claim 28, wherein the at least one hydrophilic group comprises a polyalkoxylate that further comprises 40% or less propoxylate groups.
30. The concentrate composition of claim 23, wherein the at least one hydrophilic group is selected from the group consisting of quaternary amines, tertiary ammonium salts, secondary ammonium salts, primary ammonium salts, ammonium salts, sulfobetaines, betaines, pyridinium salts, nitrogen-containing heterocyclic amine salts, amino carboxylates, amine oxides, amides, nitrogen-containing heterocyclic amides, polyvinyl pyrrolidone, and combinations thereof.
31. The concentrate composition of claim 23, wherein the at least one hydrophilic group is dimethyl amine oxide.
32. The concentrate composition of claim 23, wherein the potentiator comprises at least one chlorinating compound selected from the group consisting of metal salts of hypochlorite, hypochlorous acid, chlorine, trichloro-s-triazinetrione, dichloro-s-triazinetrione, and combinations thereof.
33. The method of claim 23, wherein the potentiator comprises at least one hydrates or anhydrous compound selected from the group consisting of, sodium chloride, potassium chloride, sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, hypochlorous acid, sodium sulfate, magnesium sulfate, aluminum potassium sulfate, aluminum sulfate, sodium carbonate, sodium bicarbonate, zinc sulfate, sodium chlorate, sodium silicate, sodium perborate, sodium percarbonate, hydrogen peroxide and combinations thereof.
34. A manufacturing leach bath or washing treatment formed by diluting the concentrate composition of claim 23 in water.
35. The manufacturing leach bath of claim 34, wherein the surfactant component is present in an amount sufficient to provide about 0.5% by weight or less surfactant actives based on the total weight of the leach bath or washing treatment, and the potentiator is present in an amount sufficient to provide about 0.005% by weight or less potentiator actives based on the total weight of the leach bath or washing treatment.
36. The latex article produced by the method of claim 1.
37. The latex article produced by the method of claim 13.
38. The method of claim 23, wherein the potentiator comprises at least one non- chlorinating salt selected from the group consisting of water-soluble metal or ammonium salts of sulfates, carbonates, chlorides, chlorates, chlorites, phosphates, sulfites, bisulfites, bicarbonates, perborates, percarbonates, citrates, acetates, borates, lactates, nitrates, phosphites, silicates, and combinations thereof.
PCT/US2007/083658 2007-11-05 2007-11-05 Methods and compositions for reducing the protein content and odor of latex articles WO2009061311A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637565A (en) * 1964-11-30 1972-01-25 Dow Chemical Co Latex compositions having improved adhesion
US4575476A (en) * 1982-09-03 1986-03-11 Howard I. Podell Dipped rubber article
US5972875A (en) * 1997-04-23 1999-10-26 Crutcher; Terry Low-foaming amine oxide surfactant concentrate and method of manufacture
US6828387B2 (en) * 2001-03-12 2004-12-07 Allegiance Corporation Polyisoprene articles and process for making the same
US20070231247A1 (en) * 2004-03-23 2007-10-04 Bromberg Steven E Method for Diluting Hypochlorite

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637565A (en) * 1964-11-30 1972-01-25 Dow Chemical Co Latex compositions having improved adhesion
US4575476A (en) * 1982-09-03 1986-03-11 Howard I. Podell Dipped rubber article
US5972875A (en) * 1997-04-23 1999-10-26 Crutcher; Terry Low-foaming amine oxide surfactant concentrate and method of manufacture
US6828387B2 (en) * 2001-03-12 2004-12-07 Allegiance Corporation Polyisoprene articles and process for making the same
US20070231247A1 (en) * 2004-03-23 2007-10-04 Bromberg Steven E Method for Diluting Hypochlorite

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