WO2004096902A2 - Antimicrobial pre-vulcanized rubber compositions and antimicrobial vuclanized rubber articles - Google Patents
Antimicrobial pre-vulcanized rubber compositions and antimicrobial vuclanized rubber articles Download PDFInfo
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- WO2004096902A2 WO2004096902A2 PCT/US2004/009580 US2004009580W WO2004096902A2 WO 2004096902 A2 WO2004096902 A2 WO 2004096902A2 US 2004009580 W US2004009580 W US 2004009580W WO 2004096902 A2 WO2004096902 A2 WO 2004096902A2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/015—Biocides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
Definitions
- This invention relates to certain non-silicone vulcanized rubber articles made from at least a majority by weight of non-silicone rubber that includes silver-based compounds to provide highly desirable long-term antimicrobial characteristics within the cured rubber articles.
- Such articles are in either solid or blown (foam or sponge) state (or combinations of both in multilayered forms) and can be utilized in a variety of different applications.
- this invention encompasses the presence of different non-sulfur-based curing systems and agents, such as bisphenol and peroxide, as examples, that permit vulcanization and do not irreversibly bind silver ions thereto, thereby resulting in long-term antimicrobial performance of the ultimate rubber article itself.
- the rubber articles may also comprise fillers and may also include plasticizers to provide desired characteristics of dimensional stability, stiffness, flexural modulus, tensile strength, abrasion resistance, elongation, and the like, for the ultimate rubber article, while simultaneously enhancing the control of antimicrobial efficacy of the rubber article as well.
- This invention also encompasses a simple method of producing such an antimicrobial non-silicone vulcanized rubber article.
- this invention provides certain non-silicone pre- vulcanized raw rubber formulations made from at least a majority by weight of non-silicone rubber that includes silver-based components to provide highly desirable long-term antimicrobial characteristics within the ultimate cured non-silicone rubber articles made therefrom.
- Escherichia coli being found within undercooked beef in fast food restaurants; Salmonella enteritidis contamination causing sicknesses from undercooked and unwashed poultry food products; and illnesses and skin infections attributed to Staphylococcus aureus, Klebsiella pneumoniae, yeast (Candida albicans), and other unicellular organisms.
- manufacturers have begun introducing antimicrobial agents within various everyday products and articles. For instance, certain brands of cutting boards, shoe soles, shoe inserts, medical devices and implements, liquid soaps, etc., all contain antimicrobial compounds. The most popular antimicrobial for such articles is triclosan.
- Antimicrobial rubber formulations are certainly highly desired for the production of vulcanized rubber articles and compositions to provide not only antibacterial benefits, but also antifungal, antimildew, antistaining, and odor control properties.
- Rubber articles are utilized in many different applications, from automobiles (hoses, tires, bumpers, etc.), to household items (toys, sink washers, gaskets, appliances, floor mats, door mats, carpeted rubber mats, gloves, and the like), and other areas in which bacterial growth is a potential problem.
- Unfortunately such a highly desired antimicrobial rubber formulation and/or vulcanized article containing silver- based antimicrobial agents has heretofore not been provided by the pertinent prior art.
- the closest art includes Japanese Patent Application 1997-342076 which discloses the production of unvulcanized rubber formulations and articles exhibiting antibacterial properties due to the presence of silver complexes. Such formulations are formed through high temperature kneading in an oxygen-free atmosphere and are used as parts in a water disinfection system. Again, no vulcanized rubber is taught or obtained within or through this disclosure.
- the vulcanization step must include a sulfur curing agent to effectuate the final vulcanized arrangement of the subject rubber.
- sulfur curing agents have a remarkably deleterious effect on certain silver-based antimicrobials such that the sulfur reacts with the silver ion to from silver sulfide, thereby rendering it ineffective as a bactericide.
- the utilization of such specific rubber band formulations for and within large-scale antimicrobial articles is basically unworkable.
- an object of this invention to provide an antimicrobial vulcanized substantially non-silicone rubber article exhibiting sufficient antimicrobial activity and structural integrity to withstand repeated use without losing an appreciable level of either antimicrobial power or modulus strength.
- Another object of the invention is to provide an antimicrobial vulcanized substantially non-silicone rubber article comprising silver-based antimicrobial compounds which include curing agents that do not deleteriously affect the antimicrobial activity of the finished vulcanized article (and thus is essentially free from sulfur-based curing agents and accelerators).
- a further object of this invention is to provide an antimicrobial substantially non- silicone pre- vulcanized raw rubber formulation that ultimately provides a vulcanized non- silicone rubber article of sufficient antimicrobial activity and structural integrity to withstand repeated use without losing an appreciable level of either antimicrobial efficiency or modulus strength.
- Another object of this invention is to ultimately provide an antimicrobial non- silicone pre- vulcanized rubber formulation comprising silver-based antimicrobial compounds which include curing agents and curing accelerators which do not deleteriously effect the antimicrobial activity of the ultimate vulcanized non-silicone rubber article (and thus is essentially free from sulfur-based curing agents and accelerators).
- dimensionally stable is intended to encompass a vulcanized rubber article that is structurally able to be handled without disintegrating into smaller portions.
- the article must exhibit some degree of structural integrity and, being a rubber, a certain degree of fiexural modulus.
- non-sulfur curing agents and most preferably peroxide and/or bisphenol curing agents
- silver-based antimicrobial agents within pre- vulcanized non-silicone rubber formulations to form effectively antimicrobial vulcanized rubber articles.
- fillers and oils are generally, although not necessarily, required to provide both fiexural modulus and structural integrity to vulcanized rubber articles.
- the rubber component alone generally does not exhibit proper dimensional stability without such additives.
- the presence of such additives may also provide the ability to control silver-ion release at the target article surface.
- fillers as silica and such oils as paraffinic oil (as some examples), act in such a way as to draw moisture into the article which then transports silver ions from within the article to the surface, hi such a situation, then, the rubber article may exhibit enhanced silver release resulting in higher log kill rates for certain bacteria due to the presence of larger amounts of available surface silver ions.
- hydrophobic fillers such as pigments (for example, carbon black) and calcium carbonate appear to work in the opposite manner by keeping water out of the target article and prevent silver-ion migration to the article surface.
- pigments for example, carbon black
- calcium carbonate appear to work in the opposite manner by keeping water out of the target article and prevent silver-ion migration to the article surface.
- the reduction of such silver-ion availability decreases the antibacterial efficacy of the rubber article.
- the actual antibacterial efficacy of the entire rubber article can be controlled through the presence of certain amounts of such generally required fillers and oils (some hydrophilic antistatic agents also appear to act in the same manner as silica as well).
- the term rubber is intended to cover any standard rubber which must be vulcanized to provide a dimensionally stable rubber article.
- the specific types of rubber are listed below and have been utilized previously within the rubber industry for a variety of applications and are generally well known and taught throughout the prior art.
- the inventive rubber formulations and cured articles may also possess a chemical plasticizer which aids in the breakdown period of the elastomer during compounding and processing (and provides fiexural modulus properties to the finished article) as well as fillers required for reinforcement (e.g. calcium carbonate, carbon black, silica, and clays).
- a blowing agent may be added to the inventive formulation.
- the rubber component or components of the inventive rubber formulation and cured article is therefore selected from the group consisting of nitrile rubber [such as acrylomtrile- butadiene rubber (NBR)], styrene-butadiene rubber (SBR), natural rubber, chloroprene rubber, polychloroprene rubber, ethylene propylene rubber, ethylene propylene diene monomer (EPDM) rubber, fluoroelastomer rubber, polyurethane rubber, butyl rubber, halogenated butyl rubber [such as chlorobutyl rubber and bromobutyl rubber], isoprene rubber, epichlorohydrin rubber, polyacrylate rubber, chlorinated polyethylene rubber, hydrogenated NBR, carboxylated NBR, polybutadiene rubber, and the like.
- nitrile rubber such as acrylomtrile- butadiene rubber (NBR)]
- SBR styrene-butadiene rubber
- natural rubber such as acrylom
- nitrile rubber such as acrylonitrile-butadiene rubber (NBR)], styrene-butadiene rubber (SBR), natural rubber, chloroprene rubber, polychloroprene rubber, ethylene propylene rubber, ethylene propylene diene monomer (EPDM) rubber, fluoroelastomer rubber, polyurethane rubber, butyl rubber, butyl rubber, halogenated butyl rubber [such as chlorobutyl rubber and bromobutyl rubber], isoprene rubber, epichlorohydrin rubber, polyacrylate rubber, chlorinated polyethylene rubber, hydrogenated NBR, carboxylated NBR, polybutadiene rubber, and the like.
- NBR acrylonitrile-butadiene rubber
- SBR styrene-butadiene rubber
- EPDM ethylene propylene diene monomer
- fluoroelastomer rubber polyurethane rubber
- butyl rubber butyl rubber
- fluoroelastomer rubber is intended to cover any standard rubber which possesses at least a majority by weight of fluoroelastomer rubber and which must be vulcanized to provide a dimensionally stable rubber article.
- Fluoroelastomer rubber is generically referred to as FKM polymer according to the nomenclature noted in ASTM D1418 and is often classified by its fluorine content.
- FKM polymer a fluorine content of 66%, 68%, and 70%, although many specialty grades are now available with fluorine content in a range of between about 60%o and about 75%.
- epichlorohydrin rubber is intended to cover any standard rubber which possesses at least a majority by weight of epichlorohydrin rubber and which must be vulcanized to provide a dimensionally stable rubber article.
- polybutadiene rubber is intended to cover any standard rubber which possesses at least a majority by weight of polybutadiene rubber and which must be vulcanized to provide a dimensionally stable rubber article.
- polychloroprene rubber is intended to cover any standard rubber which possesses at least a majority by weight of polychloroprene rubber and which must be vulcanized to provide a dimensionally stable rubber article.
- styrene butadiene rubber is intended to cover any standard rubber which possesses at least a majority by weight of styrene butadiene rubber and which must be vulcanized to provide a dimensionally stable rubber article.
- silicone rubber is discouraged within the inventive formulation, there remains the possibility of adding certain low amounts of such specific unvulcanized rubber components without adversely affecting the overall antimicrobial rubber formulation itself.
- up to 25% by total weight of the formulation may be silicone rubber; however, the vast majority of the rubber formulation must be non-silicone rubber.
- the non-silicone rubber portion must not possess an appreciable amount of sulfur-based curing agent or residue (in the finished article) and thus must be vulcanized through curing with primarily non-sulfur-based compounds (such as resins, bisphenols, peroxides, and/or metal oxides, for example).
- the rubber component is present in an amount of from about 10 to about 1,000 parts of the entire composition, more preferably from about 50 to about 500 parts, and most preferably from about 70 to about 200 parts of the entire composition.
- the rubber constitutes from about 25 to about
- the remainder comprises additives such as fillers, oils, curing agents, the desired antimicrobial agents, optional blowing agents, and the like (as discussed more thoroughly below).
- vulcanization or other processing of these non-silicone rubbers be performed in an environment that is inexpensive to provide and should be undertaken in an oxygen-rich atmosphere (as opposed to an anaerobic environment which is generally difficult to provide).
- these non-silicone rubbers have been utilized previously within the rubber industry for a variety of applications and are generally well known and taught throughout the prior art.
- Such inventive rubber articles may also possess a chemical plasticizer which aids in the breakdown period of the elastomer during compounding and processing (and provides fiexural modulus properties to the finished article) as well as fillers required for reinforcement (e.g. calcium carbonate, carbon black, magnesium oxide, calcium hydroxide, silica, and clays).
- a blowing agent may be added to the inventive formulation.
- the antimicrobial agent of the inventive raw rubber formulation maybe of any standard silver-based compounds.
- Such compounds in contrast with organic types, such as triclosan, for example, do not exhibit low thermal stability and remain within the target matrix or substrate at different temperatures.
- Such an antimicrobial is more easily controlled, as discussed above, for surface release as desired.
- Such agents include, without limitation, silver salts, silver oxides, elemental silver, and, most preferably, ion exchange, glass, and/or zeolite compounds.
- silver-based ion exchange compounds for this purpose due to the low levels of discoloration and enhanced durability in the final product provided by such compounds, the efficacy provided to the final formulation with such a compound, and the ease of manufacture permitted with such specific compounds.
- the antimicrobial agent of this invention maybe any type which imparts the desired log kill rates to Staphylococcus aureus, Klebsiella pneumoniae, Escherichia coli, and Pseudomonas aeruginosa, as merely representative organisms.
- such antimicrobial compounds must be able to withstand elevated processing temperatures for successful incorporation within the target non-sulfur (bisphenol and/or peroxide," for example) cured rubber articles.
- antimicrobial agents comprise, preferably, silver- containing ion exchange, glass, and/or zeolite compounds. Most preferably, such a compound is a silver-based ion-exchange compound and particularly does not include any added organic bactericide compounds (thereby not permitting a release of volatile organic compounds into the atmosphere during processing at high temperatures, etc.).
- the preferred silver-based ion exchange material is an antimicrobial silver zirconium phosphate available from Milliken & Company, under the trade name ALPHASAN®. Such compounds are available in different silver ion concentrations as well as mixtures with zinc oxide. Thus, different compounds of from about 0.01 to 15%) of silver ion concentration, more preferably from about 3 to about 10%, and most preferably amounts of about 10% by total amount of components (e.g. of the total amount of silver ions and zirconium phosphate) are possible.
- Other potentially preferred silver-containing solid inorganic antimicrobials in this invention are silver-substituted zeolite available from Sinanen under the tradename
- ZEOMIC® or a silver-substituted glass available from Ishizuka Glass under the tradename IONPURE®, which may be utilized either in addition to or as a substitute for the preferred species.
- Other possible compounds are silver-based materials such as MICROFREE®, available from DuPont, as well as JMAC®, available from Johnson Mathey.
- such an antimicrobial compound is added to a rubber formulation in an • amount of from about 0.1 to 10% by total weight of the particular total rubber formulation, preferably from about 0.1 to about 5%, more preferably from about 0.1 to about 2%, and most preferably about 2%>.
- silver-based inorganic antimicrobial materials these particular antimicrobial rubber articles are shown to be particularly suitable for the desired high levels of efficacy and durability required of such articles. It has been found that certain silver-based ion exchange compounds, such as ALPHASAN® brand antimicrobials available from Milliken & Company, (U.S. Patent 5926238, U.S. Patent 5441717, U.S. Patent 5698229 to Toagosei Chemical Industry Inc.), exhibit spectacular bio-efficacy. After a period of time, alternative antimicrobial compounds (e.g.
- triclosan, microchek, OBPA, Zn-omadine initially suffer from decomposition under the high processing temperatures, which is followed by depletion of the biocide through leaching into the surrounding environment and finally through depleted bactericidal activity.
- silver-containing ion exchange, glass, and or zeolite compounds do not suffer from these shortcomings.
- Such antimicrobial agents exhibit high temperature stability (>1000°C), do not leach into the environment and provide substantial amounts of the oligodynamic silver ion to provide for the desired extensive durability.
- silver elution values quantity of silver ions released at the surface of the article
- antimicrobial efficacy against certain organisms For example, silver elution values greater than about 1.5 ng/cm 2 silver generally result in the maximum log kill reduction against Klebsiella pneumoniae and Staphylococcus aureus. Accordingly, it is generally desirable that the inventive antimicrobial articles should exhibit an acceptable log kill rate after 24 hours for S. aureus when tested in accordance with the ATCC Test Method 6538 and for K. pneumoniae when tested in accordance with ATCC Test Method 4352. Such an acceptable level log kill rate is tested for S. aureus or K.
- log kill rate baseline increases are at least 0.3 and 0.3, respectively for S. aureus and K. pneumoniae; more preferably these log kill rates are 0.5 and 0.5, respectively; and most preferably these are 1.0 and 1.0, respectively.
- high end of such log kill rates are much higher than the baseline, on the magnitude of 5.0 (99.999%o kill rate). Any rate in between is thus, of course, acceptable as well.
- log kill rates which are negative in number are also acceptable for this invention as long as such measurements are better than that recorded for correlated non- treated rubber articles, hi such an instance, the antimicrobial material present within the rubber article at least exhibits a hindrance to microbe growth. Furthermore, such rubber articles should exhibit log kill rates of the same degree for other types of bacteria, such as,
- the finished inventive articles will provide antifungal benefits as well as antibacterial characteristics.
- Such versatility is rare among antibacterial compounds; however, without intending to be limited to any particular scientific theory, it appears that the silver ions, and particularly the silver ions present at the article surface in great abundance, provide excellent antifungal properties.
- this inventive rubber formulation should provide fungal kill durability of at least 15 sequential days for such organisms as Aspergillus niger and possibly for mixtures of fungi including ⁇ , niger ATCC 6275, Paecilomyces variotii ATCC 18502, and Trichoderma virens ATCC 9645, when tested according to Test Method ISO 846.
- other compounds may be incorporated within the target pre- vulcanized rubber formulation (and subsequent article), such as zinc oxide, as one example.
- inventive rubber articles listed above are available without such sulfur-based curing agents in any appreciable amounts; most importantly, with the introduction of certain additives, the structural integrity and/or fiexural modulus of the rubber formulation is improved to an acceptable level, and the efficacy of the antimicrobial components can be controlled simultaneously.
- the curing agent present within the raw rubber formulation to be vulcanized to form the inventive article must be at least a majority, and preferably at least about 75% by weight of a non-sulfur-based curing agent.
- a non-sulfur-based curing agent such as, for example and without limitation, bisphenols, peroxides, and other oxide curing systems.
- Peroxides include, for example, organic peroxides such as dicumyl peroxide, 2,5-bis(t- butylperoxy)-2,5-dimethylhexane, di-(t-butyl- ⁇ eroxy-isopropyl) benzene, di-(t-butyl-peroxy- trimethyl)-cyclohexane, and the like, as well as inorganic peroxides.
- Oxides include, for example, zinc oxide, and the like.
- curing agents should generally be present in amount of from about 0.5 to about 100 parts per hundred parts of rubber (pphr), more preferably from about 1 to about 50 pphr, and most preferably from about 1 to about 10 pphr, all either as one curing agent alone, or as the combination of any number of different types of curing agents.
- additives present within the inventive vulcanized rubber article may include any of the aforementioned silver ion release control additives, accelerators, accelerator activators, antidegradants, softeners, abrasives, colorants, flame retardants, homogenizing agents, internal lubricants, and deodorants. Such components should be present, if at all, in rather low amounts, of from about 0.1 to about 50 pphr.
- a substantial increase in the antibacterial and antifungal efficacy may be provided upon washing the finished inventive article. Abrading the surface of such an article may permit increases in such characteristics due to an increase in Ag+ release; however, industrial laundering of certain rubber products (mats, and the like) may provide improved antimicrobial, antifungal, etc., efficacy through a simple washing, i fact, such an increase may steadily improve with greater numbers of consistent washes such that a rubber article, as first vulcanized, may exhibit lower overall antibacterial and antifungal activity than one that has been washed one, two, three, and up to at least 20 times (in a standard industrial rotary washing machine).
- Such a surprising benefit may permit utilization of such rubber articles as floor coverings (mats, as one example, such-as those with carpeted portions or those which are rubber alone; particularly foamed rubber mats for antifatigue properties and reduced specific gravity so as to reduce the chances of machinery damage during such industrial rotary launderings and dryings), and other articles which can be easily washed within standard laundry machines.
- floor coverings such-as those with carpeted portions or those which are rubber alone; particularly foamed rubber mats for antifatigue properties and reduced specific gravity so as to reduce the chances of machinery damage during such industrial rotary launderings and dryings
- the inventive article produced from the inventive raw rubber formulation exhibits an even dispersion of antimicrobial particles throughout the entire rubber article.
- Such an even dispersion of the biocide throughout the rubber article thus provides a reservoir of fresh crystallites containing the biocidal metallic ion.
- antimicrobial particles containing untapped silver ions become available.
- the preferred non-sulfur cured rubber articles of this invention containing the antimicrobial agent can be processed into rubber articles which exhibit excellent antimicrobial qualities as well as antimicrobial efficiency throughout the rubber article's lifetime.
- rubber articles encompassed within this invention include, but are not limited to hard rubber mats, static dissipative rubber mats, anti-fatigue rubber mats, rubber mats which include a face fiber, rubber link mats, rubber seals and gaskets, rubber medical goods, rubber gloves, rubber medical devices, rubber conveyor belts, rubber belts and rubber wheels used in food processing, rubber clothing, rubber shoes, rubber boots, rubber tubing, and rubber automotive fuel hoses.
- inventive formulations may also be incorporated into a multilayered rubber article in which the antimicrobial agent can be incorporated into any surface layer and still provide the desired antimicrobial efficiency.
- multilayered rubber articles wherein at least one of such rubber layers exhibit the desired antimicrobial activity and thus is made from an inventive non-sulfur cured, non-silicone containing rubber article.
- Such layered articles may be adhered together through co-vulcanization, gluing, and the like.
- layers of other types of materials may be placed between the rubber layers as well to provide, as one non-limiting property, better structural stability to the desired multilayered article.
- Fluoroelastomer Rubber (Dai-el G751 from Daikin Industries, Ltd.)* 100 parts N990 Black (CABOT carbon black filler) 20 pphr Magnesium oxide 3 pphr Calcium hydroxide 6 pphr
- Antimicrobial (ALPHASAN® RC2000 from Milliken & Company) 2% by weight *Bisphenol added prior to compounding.
- Fluoroelastomer Rubber (Dai-el G902 from Daikin Industries, Ltd.) 100 parts N990 Black (CABOT carbon black filler) 20 pphr di-(tert-butyl-peroxy-isopropyl)benzene (14/40 from AKM) 2 pphr di-(tert-butyl-peroxy-trimethyl)cyclohexane (29/40 from AKM) 2 pphr
- FEF N550 (CABOT carbon black filler) 50 pphr
- DIDP Di-isodecyl phthalate
- Aflux 54 penentaerythritol tetrastearate process aid from Rhein-chemie 2 pphr
- Stearic Acid available from AKM 0.25 pphr Antimicrobial (ALPHASAN® RC2000 from Milliken & Company) 2% by weight
- Zinc Oxide Active available from Bayer 5 pphr
- SBR 1502 Styrene Butadiene Rubber 100 parts Mistron Vapour (magnesium silicate filler from Luzanac) 25 pphr FEF N550 (Cabot carbon black filler) 25 pphr Brisol 300 (available from AKM) 20 pphr Zinc Oxide Active (available from Bayer) 5 pphr
- Aflux 54 (pentaerythritol tetrastearate process aid from Rhein-chemie) 2 pphr di-(tert-butyl-peroxy-isopropyl)benzene (14/40 from AKM) 2 pphr di-(tert-butyl-peroxy-trimethyl)cyclohexane (29/40 from AKM) 2 pphr CPL (antioxidant available from AKM) 1 pphr Stearic Acid (available from AKM) 0.5 pphr
- Antimicrobial (ALPHASAN® RC2000 from Milliken & Company) 5%> by weight
- the compounding of ingredients within each formulation can be carried out in an open mill, an internal mixer, or an extruder where intensive mixing within the polymer matrix of each component will take place.
- the control of temperature rise, due to high shear incorporation of the ingredients, is crucial to ensure that pre- vulcanization (scorch) does not take place during processing.
- a maximum temperature of 120°C is reached on single stage (pass) mixing through an internal mixer.
- the compounds can be further processed after mixing into specific forms to allow adequate presentation for manufacturing into products. This could be calendering, extrusion, granulation/pelletization, strip form, fabrication and preforming into specific shaped blanks.
- the vulcanization of the compounds can be in the form of molding (compression, transfer, injection), continuous extrusion (LCM, UHF[where pe ⁇ nissible], autoclave and hot air), and coatings.
- the vulcanization (cure) temperatures can range from 150°C to 250°C. In this specific situation, the rubber articles were calendared into rough mat structures and then subjected to vulcanization under high temperature and pressure.
- Silver-ion extraction (or, silver elution) values were determined for the inventive rubber article.
- the rubber article was immersed in an aqueous salt extraction solution (sodium phosphate) for 24 hours; the extract was then analyzed by inductively coupled plasma measurements for a measurement of available silver removed from the article surface.
- Base Formulation 1 exhibited 1.049 ppb/cm 2 and 16.570 ng/cm 2 surface available Ag+ ions.
- the inventive article exhibited controlled release of silver ions.
- silver elution at a rate of greater than 1.5 ng/cm 2 is believed to provide maximum log kill reduction after 24 hours for S. aureus when tested in accordance with ATCC Test Method 6538 and for K. pneumoniae when tested in accordance with ATCC Test Method 4352. Accordingly, it is believed that the silver elution results shown above provide highly desirable long-term antimicrobial characteristics within the cured rubber article.
- Rubber Formulation 3 Epichlorohydrin 2.98 3.52 Rubber Formulation 4 Polybutadiene 2.98 3.04 Rubber Formulation 5 Polychloroprene 2.58 3.52 Max. Log Kill 2.98 3.52
- inventive formulations provided inventive vulcanized rubber articles that exhibited improved antimicrobial activity over the same formulations without any antimicrobial compounds present.
- the epichlorohydrin and polybutadiene rubber articles reached maximum log kill reduction for S. aureus, while the epichlorohydrin and polychloroprene reached maximum log kill reduction for K. pneumoniae.
- inventive articles with Formulations 3 and 4 above were also tested for silver ion elution at the articles' surface both before and after exposure of the articles to repeated standard industrial wash cycles (35 lb. loads).
- the target articles were immersed in an aqueous salt extraction solution (sodium phosphate) for 24 hours; the extract was then analyzed by inductively coupled plasma measurements for a measurement of available silver removed from the articles' surface. The results are as follows:
- the inventive formulation provided an inventive vulcanized rubber article that exhibited improved antimicrobial activity over the same formulation without any antimicrobial compounds present.
- the SBR article achieved maximum log kill reduction for both S. aureus and K. pneumoniae.
- the inventive article was also tested for silver ion elution at the article surface both before and after exposure of the article to repeated standard industrial wash cycles (35 lb. loads).
- the target article was immersed in an aqueous salt extraction solution (sodium phosphate) for 24 hours; the extract was then analyzed by inductively i coupled plasma measurements for a measurement of available silver removed from the article surface. The results are as follows:
- Formulation 6 SBR 20 wash 1.571
- the amount of available silver ions increased dramatically not just from the article's finished state, but also up to (and beyond) twenty standard washes.
- Such an unexpected benefit thus provides the user with an antimicrobial structure, such as a mat, that actually increases its antimicrobial efficacy during use.
Abstract
Description
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006509435A JP2006524740A (en) | 2003-04-25 | 2004-03-26 | Antibacterial unvulcanized rubber composition and antibacterial vulcanized rubber article |
EP04760221A EP1618144A4 (en) | 2003-04-25 | 2004-03-26 | Antimicrobial pre-vulcanized rubber compositions and antimicrobial vuclanized rubber articles |
BRPI0409713-0A BRPI0409713A (en) | 2003-04-25 | 2004-03-26 | antimicrobial pre-vulcanized rubber compositions and antimicrobial vulcanized rubber articles |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/423,204 US6943205B2 (en) | 2003-04-25 | 2003-04-25 | Antimicrobial articles and compositions made from styrene butadiene rubber |
US10/423,204 | 2003-04-25 | ||
US10/424,024 | 2003-04-25 | ||
US10/424,024 US7060739B2 (en) | 2003-04-25 | 2003-04-25 | Antimicrobial fluoroelastomer rubber articles and compositions |
US10/424,112 US6852782B2 (en) | 2003-04-25 | 2003-04-25 | Antimicrobial articles and compositions made from non-silicone vulcanized rubber |
US10/424,112 | 2003-04-25 |
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WO2004096902A2 true WO2004096902A2 (en) | 2004-11-11 |
WO2004096902A3 WO2004096902A3 (en) | 2005-10-06 |
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PCT/US2004/009580 WO2004096902A2 (en) | 2003-04-25 | 2004-03-26 | Antimicrobial pre-vulcanized rubber compositions and antimicrobial vuclanized rubber articles |
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EP (1) | EP1618144A4 (en) |
JP (1) | JP2006524740A (en) |
BR (1) | BRPI0409713A (en) |
WO (1) | WO2004096902A2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101052303B (en) * | 2004-06-25 | 2013-08-21 | 美国杜邦泰津胶片合伙人有限公司 | Antimicrobial polymer film |
CN111944215A (en) * | 2020-09-09 | 2020-11-17 | 河北九度橡胶科技有限公司 | Rubber antibacterial chopping board and preparation method thereof |
CN112063062A (en) * | 2020-08-07 | 2020-12-11 | 山东玲珑轮胎股份有限公司 | Antibacterial rubber composition and tire |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103339199B (en) * | 2011-02-07 | 2016-08-10 | 大曹株式会社 | Motion dress material compositions and foaming body thereof |
DE102012206968A1 (en) * | 2012-04-26 | 2013-10-31 | Wacker Chemie Ag | Silicone composition with protection against harmful substances |
KR101267830B1 (en) * | 2012-11-23 | 2013-05-27 | 국방과학연구소 | Elastomer composition |
JP6989251B2 (en) * | 2015-11-10 | 2022-01-05 | エア・ウォーター株式会社 | Rubber compositions for beverage or liquid food components, beverage or liquid food components, drinking water dispensers, and beverage or liquid food manufacturing equipment. |
KR101861653B1 (en) * | 2016-10-31 | 2018-05-28 | 주식회사 케이비엘러먼트 | Composition for Glass Contacting O-Ring Having Excellent Electrostatic Quality and Manufacturing Method of Glass Contacting O-Ring Using the Same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4677143A (en) * | 1984-10-01 | 1987-06-30 | Baxter Travenol Laboratories, Inc. | Antimicrobial compositions |
CN1303142C (en) * | 2001-03-23 | 2007-03-07 | 美利肯公司 | Antimicrobial rubber compositions |
US6448306B1 (en) * | 2001-03-23 | 2002-09-10 | Milliken & Company | Antimicrobial articles made from nitrile or natural rubber |
US6455610B1 (en) * | 2001-03-23 | 2002-09-24 | Milliken & Company | Antimicrobial pre-vulcanized rubber compositions |
-
2004
- 2004-03-26 WO PCT/US2004/009580 patent/WO2004096902A2/en active Application Filing
- 2004-03-26 EP EP04760221A patent/EP1618144A4/en not_active Withdrawn
- 2004-03-26 JP JP2006509435A patent/JP2006524740A/en not_active Withdrawn
- 2004-03-26 BR BRPI0409713-0A patent/BRPI0409713A/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
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See references of EP1618144A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101052303B (en) * | 2004-06-25 | 2013-08-21 | 美国杜邦泰津胶片合伙人有限公司 | Antimicrobial polymer film |
CN112063062A (en) * | 2020-08-07 | 2020-12-11 | 山东玲珑轮胎股份有限公司 | Antibacterial rubber composition and tire |
CN111944215A (en) * | 2020-09-09 | 2020-11-17 | 河北九度橡胶科技有限公司 | Rubber antibacterial chopping board and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
EP1618144A2 (en) | 2006-01-25 |
EP1618144A4 (en) | 2007-02-21 |
BRPI0409713A (en) | 2006-05-02 |
JP2006524740A (en) | 2006-11-02 |
WO2004096902A3 (en) | 2005-10-06 |
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