Note: Descriptions are shown in the official language in which they were submitted.
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POLYMERS CONTAINING HEAT LABILE COMPONENTS ADSORBED ON
POLYMERIC CARRIERS AND METHODS FOR THEIR PREPARATION
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No.
61/508,354, filed July 15,
2011, U.S. Provisional Application No. 61/537,270, filed September 21, 2011,
and U.S.
Provisional Application No. 61/537,272, filed September 21, 2011, and
incorporates all by
reference herein, in their entirety.
BACKGROUND
The present invention relates to a polymer composition including a heat labile
component
where the composition exhibits properties derived from the heat labile
component after the
composition has been processed at a temperature above the heat labile
component's
transformation temperature, The heat labile component's transformation
temperature is a
temperature at which the component is normally transformed by inactivation,
volatilization,
decomposition, chemical reaction, and combinations thereof The compositions
provided are
prepared by a method which avoids transformation of the heat labile component
when
composition containing the component is processed at elevated temperatures
above the
component's transformation temperature.
The inclusion of a heat labile component such as, for example, a biocide into
a polymer
composition can offer important properties to the resulting polymer
composition, provided
transformation (decomposition) can be avoided. Such polymer/biocide
compositions can be
more resistant to biological degradation and provide surfaces that don't
support the growth of a
range of organisms and/or viruses and which can kill identified organisms
(including bacteria,
fungi, algae, viruses, and the like) which contact the surface. Such
polymer/biocide
compositions find particular uses in medical and related fields in which a
need exists to create
surfaces, equipment, and polymeric fabrics capable of: resisting the
colonization of
microorganisms, killing microorganisms upon contact, and/or providing a
barrier to
microorganisms. Unlike topical applications of biocides which typically
provide a concentration
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gradient across the applied surface leading to resistant strains, a polymer
having a uniform
distribution of a biocide, provides a surface lacking such a concentration
gradient and at proper
levels minimizes the formation of resistant strains. In addition, the biocidal
properties provided
by the polymer/biocide composition are not dependent on whether a surface
disinfectant was or
was not applied according to established procedures. Further, the bulk of the
polymer
composition provides an ongoing reservoir of biocide for continued effect. The
ability to
provide and maintain such substantially sterile surfaces and minimize the
formation of resistant
strains of microorganisms is particularly important in today's hospital
environment and in related
fields.
Most polymers used to prepare surfaces associated with structures, articles,
containers,
devices, and fabrics (both woven and nonwoven) pass through a molten state at
relatively high
temperatures during processing. Depending on the polymer, such processing
temperatures
typically range from about 180 C to about 550 C. For a heat labile component
such as a
biocide to be successfully incorporated into such a polymer composition
utilizing these standard
methods, it must typically have sufficient thermal stability to survive any
necessary processing at
the elevated temperatures. Currently only a limited number of inorganic
biocides have been
successfully incorporated to provide polymers that exhibit some level of
biocidal activity
utilizing common manufacturing practices. Decomposition while processing a
melt phase of the
polymer biocide has typically inactivated organic biocides included in the
combination.
What is needed is a range of polymer/heat labile component compositions which
can be
engineered in a variety of forms utilizing substantially standard
manufacturing techniques and
which can include one or more heat labile components, such as for example,
biocides selected to
fulfill a specific need, without regard to whether or not the biocide is
provided sufficient thermal
stability to survive the necessary polymer processing. Further, methods are
needed for
producing such polymer/heat labile component compositions, wherein the heat
labile
component's necessary properties are maintained following one or several
thermal processing
steps. The current disclosure addresses these needs.
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SUMMARY
In its broadest form, the present disclosure provides for solid materials
formed from a
molten or liquid state and containing a heat labile component initially
adsorbed in a carrier
particle that alone and unassociated with the carrier particle would not be
capable of surviving
the conditions of the molten or liquid state. Although not required, the
molten or liquid states
typically occur at elevated temperatures. Failure of the component alone to
survive can result
from inactivation, decomposition, volatilization, chemical reaction and the
like. In its broadest
form, the present disclosure also provides a method for preparing the carrier
loaded component
and for incorporating the component/carrier combination into the molten
material, mixing the
combination, and solidifying the molten mixture to provide a substantially
homogeneous solid
containing the component, substantially unchanged. Polymers have proven
particularly useful as
solid materials capable of forming molten forms for this application.
A narrower perspective of the present disclosure provides for a
polymer/biocide
composition (a "biocidal polymer") exhibiting antimicrobial properties wherein
the composition
was formed and/or processed at temperatures above the biocide's transformation
or
decomposition temperature, without substantial decomposition of the biocide.
Further, methods
are provided for preparing the polymer/biocide compositions.
In the discussions which follow, the focus will be on biocides as examples of
heat labile
components. However, it is understood that except for the nature of the
properties exhibited, the
concepts described for heat labile biocides relate to other heat labile
components.
A first aspect of the present disclosure includes a composition comprising a
polymer
having a continuous solid phase and a heat labile component/carrier
combination. The polymer
has a melting temperature, the heat labile component has a transformation
temperature, the
polymer's melting temperature is greater than the heat labile component's
transformation
temperature, and the heat labile component/carrier combination is distributed
throughout the
polymer's continuous phase. One example includes a biocidal polymer comprising
a
homogeneous solid including a polymer having a melting temperature and a heat
labile biocide
adsorbed on a carrier and having a transformation or decomposition temperature
where the
polymers melting temperature is greater than the biocide's transformation or
decomposition
temperature. The carrier is typically a porous material which remains solid at
the processing
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temperature upon which a sufficient amount of heat labile biocide can be
adsorbed. In the
polymer/biocide composition, the biocide is typically distributed throughout
the polymer
including its surface, but is not limited to placement on its surface.
Although some polymers can have melting temperatures as low as 100 C,
preferred
polymers typically have a melting temperature or a glass transition
temperature (ranging from
about 180 C to about 550 C) above which the polymer forms a viscous liquid
to which a
biocide/carrier combination can be added and mixed during processing. Such
mixing provides
for a generally uniform distribution of the various components within the mix
and any
subsequent article derived from the mix. Such polymers can include, but are
not limited to
organic polymers, inorganic polymers, copolymers including mixed
organic/inorganic polymers,
linear polymers, branched polymers, star polymers, and mixtures thereof.
Depending on the
biocide concentration, cooling and solidification of the resulting
polymer/biocide composition
can provide a product ranging from a concentrate (a "masterbatch") for
subsequent incorporation
into additional polymer to a finished article. Such masterbatch materials can
be based on a
single polymer or on a polymer blend.
Suitable masterbatch combinations of a carrier/heat labile component and a
second
material can be a solid or a liquid. Such masterbatch combinations allow
incorporation of the
carrier/heat labile component into polymers during current manufacturing
processes along with
other solids, liquids, and/or combinations thereof One such masterbatch
embodiment involves a
carrier/heat labile component incorporated into a polymer or polymer blend to
provide a solid
form, such as for example, a pellet or a powder form. Masterbatch materials
can similarly
involve a suspension or dispersion of the carrier/heat labile material in a
liquid suitable for
incorporation into a finished polymer material or article during manufacture.
The liquid
masterbatch formulation provides material handling advantages such as improved
metering
capabilities. Suitable liquid phase materials for the carrier dispersions or
suspensions include,
but are not limited to mineral oil, soybean oil, castor oil, linseed oil,
alkyl phthalates, citric acid
esters, and the like. Additional polymer additives can be included in the
liquid masterbatch
formulation such as colorants, plasticizers, UV stabilizers, and the like. As
illustrated in the
Examples, the carrier/heat labile component loading in such masterbatch
materials is typically
higher than intended in a finished product to account for dilution when
combined with a bulk
polymer.
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Preferred biocides include, but are not limited to bacteriocides, fungicides,
algicides,
miticides, viruscides, insecticides, herbicides rodenticides, animal and
insect repellants, and the
like, which suffer some level of decomposition, inactivation, and/or
volatilization at the
temperatures required to incorporate the biocide into the polymer/biocide
composition, and/or
which offer some advantage to the resulting polymer/biocide combination. In
other words, the
heat labile biocide is inactivated, decomposes or vaporizes upon exposure to
the elevated
temperatures and/or processing conditions if not adsorbed on a carrier. For
biocide mixtures, at
least one of the biocide components is typically heat labile. One kind of
suitable biocide
includes biocides containing a quaternary amine group that accounts for some
level of the
compound's biocidal activity.
Suitable heat carriers are generally insoluble in the polymer's liquid phase,
do not melt,
or otherwise cease the function of a carrier during processing, and have a
relatively high internal
surface area. Carriers are porous and have an internal surface area to allow
the adsorption of
necessary levels of the biocide. The biocide can be adsorbed on the carrier by
contacting the
carrier with a liquid form of the biocide. If the biocide is a liquid at a
temperature below its
transition or decomposition temperature it can be used directly in its liquid
form. If the biocide
is a solid at the necessary processing temperatures, it can be dispersed or
dissolved in a solvent,
prior to adsorption onto the carrier. Any remaining solvent or dispersant can
be removed or
evaporated to provide a flowable carrier containing the biocide, for
subsequent incorporation into
a polymer. Solvents such as the lower boiling alcohols, for example, can be
left on the
carrier/biocide combination and volatilized upon contact with the molten
polymer. For a carrier
to be loaded with a dispersion of the biocide, the biocide's particle size
should be smaller than
the carrier's pores being entered. The term "transformation temperature"
generally refers to a
temperature at which a heat labile component is transformed by inactivation
volatilization,
decomposition, chemical reaction, and combinations thereof The term
"decomposition
temperature" generally refers to the temperature at which a substance
chemically decomposes to
provide generally non-specific products.
A further aspect of the present disclosure involves a method for preparing the
polymer/biocide composition described above. The method includes the steps of:
providing a
polymer and a heat labile component/carrier combination, subjecting the
polymer to a processing
temperature for a time sufficient to form a melt, distributing the heat labile
component/carrier
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combination within the melt; and cooling the melt to form a continuous solid
phase containing
the heat labile component, with substantially no transformation of the heat
labile component.
The polymer has a melting temperature, the heat labile component has a
transformation
temperature, the processing temperature is > the polymer's melting temperature
and the heat
A further variation of the method where the heat labile component is a biocide
involves,
(a) providing a mixture including a polymer or polymer phase and a heat labile
component such
20 The time during which the polymer/biocide/carrier combination is
subjected to a
processing temperature should be sufficient to provide a generally uniform
distribution of the
biocide/carrier combination within the polymer melt; allow the resulting
polymer/biocide/carrier
combination to be conformed to and cooled in a desired form; but not so long
that the biocide
ultimately thermally decomposes. Preferred methods utilize a processing time
of 30 minutes or
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the polymer/biocide/carrier to extended periods of time above the biocide's
decomposition
temperature can ultimately result in biocide decomposition. How long the
polymer/biocide/carrier combination can be maintained above the biocide's
decomposition
temperature depends primarily on the polymer selected, the carrier selected,
the selected
polymer's necessary processing temperature, and the biocide's rate of thermal
decomposition or
volatilization at the processing temperature of the selected polymer. Based on
tests conducted
thus far, additional cycles of heating and cooling can be carried out on the
polymer/biocide
combination for similar processing times without resulting loss of activity.
Finally, suitable heat labile components can include materials having a range
of
biological activities (controlling the growth of microorganisms, plants, and
insects), volatiles,
such as fragrances, repellants, pheromones, water and aqueous solutions, and
materials which
react or are inactivated by the exposure to elevated temperatures. In
addition, other materials
which are not heat labile will also likely benefit from the carrier technology
provided. For
example, the incorporation of materials such as plasticizers into carrier
materials utilized in
polymers may slow down the rate at which the plasticizer "blooms" to the
plastic's surface,
increasing its useful life. Additionally, mixtures of materials which are
incompatible when
mixed or otherwise combined can be loaded onto separate carriers and
incorporated into a
polymer to provide homogeneous compositions that could not otherwise be
prepared.
Incompatible components can include heat labile components and/or materials
that would
otherwise be stable at the processing temperatures.
A still further aspect of the current disclosure involves a composition that
includes an
encapsulated form of a heat labile component/carrier combination. Forms of the
composition
including higher levels of heat labile component/carrier combination are
suitable for use as a
masterbatch. Masterbatches can have a liquid or solid form suitable for
incorporation into a
polymer.
Additionally, the biocide or other heat labile component can be modified
and/or extruded
under conditions which result in it being concentrated closer to the extruded
plastic's surface,
thus further enhancing the extruded plastic's biocidal activity. In the
discussions which follow,
examples are provided in which a single heat labile component/carrier
combination is utilized. It
is understood that for some applications a single heat labile
component/carrier may be utilized,
for other applications, multiple heat labile components may be loaded onto a
single carrier, and
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for still other applications, multiple heat labile component/carrier
combinations can be utilized.
Reference to a single combination is intended to also cover these additional
combinations.
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DETAILED DESCRIPTION
For the purposes of promoting an understanding of what is claimed, references
will now
be made to the embodiments illustrated and specific language will be used to
describe the same.
It will nevertheless be understood that no limitation of scope of what is
claimed is thereby
intended, such alterations and further modifications and such further
applications of the
principles thereof as illustrated therein being contemplated as would normally
occur to one
skilled in the art to which the disclosure relates.
Broadly considered, the method disclosed herein, generally involves subjecting
a heat
labile component to a processing step carried out at processing temperatures
above the
component's transformation temperature, a temperature at which the component
will become
subject to inactivation volatilization, decomposition, a chemical reaction, or
combinations
thereof Transformation of the heat labile component is avoided by first
adsorbing the heat labile
component onto a carrier prior to processing and by limiting the processing
time. Suitable
carriers are stable to the processing conditions and have the ability to load
sufficient heat labile
component, necessary for a particular application. The method generally
provides for
combinations including one or more heat labile components that could not
otherwise be
processed without decomposition and or which are incompatible with each other
or other
components. For example, some heat labile biocides are incompatible and can
react, form a
precipitate, a slime, and the like. For such incompatible biocides, a single
heat labile biocide
should be added to a single carrier. Other otherwise incompatible materials
can more readily be
handled and incorporated into the polymer by first being loaded into a
carrier. Combinations of
single biocide/carrier combinations can and have been combined in a masterbach
material and
extruded into polymer sheets without further evidence of incompatibility.
Heat labile components additionally involve materials that are volatile at a
polymer's
processing temperature and unless incorporated into a carrier. Incorporation
of the volatile
component into a carrier prior to incorporation into the polymer prevents
substantial
volatilization during processing. Volatile fragrances loaded into a carrier
have been successfully
incorporated into a range of polymers without decomposition or volatilization.
The resulting
polymer articles were capable of emitting the fragrance over a long period of
time. Attempts to
incorporate the fragrance into a polymer without being loaded into a carrier
resulted in both
volatilization and decomposition. Additionally, volatile materials such as
animal and insect
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repellants can be successfully loaded into polymers without decomposition or
volatilization to
provide combinations capable of repelling animals and/or insects for long
periods of time.
In the discussion which follows, specific compositions and methods will be
described
with regard to one or more heat labile components, such as biocides. It is
understood that other
heat labile materials discussed herein can be utilized similarly to provide a
variety of solids from
a molten phase which contain the other heat labile materials distributed
throughout the solid.
A first aspect of the present disclosure involves a method for the
incorporation of a heat
labile component such as a biocide into a polymer phase at temperatures above
the biocide's
decomposition temperature without substantially decomposing the biocide or
interfering with its
properties. Prior to incorporation, the biocide is adsorbed onto a suitable
carrier. Suitable
carriers are porous materials capable of remaining solid at any necessary
processing
temperatures. Incorporation of the biocide/carrier combination into a polymer
or other molten
mass is carried out in a manner that minimizes the time the biocide/carrier
combination is
subjected to temperatures greater than the biocide's decomposition
temperature. The processing
temperature is typically determined by the properties of the polymer phase and
the nature of the
processing step. Once a processing temperature has been determined,
combinations of
polymer/carrier/biocide can be provided and maintained at that temperature for
varying amounts
of time to determine a maximum processing time.
Polymers:
Based on testing carried out at this time, polymers have had a glass
transition temperature
(or melting temperature) of at least 100 C and more typically ranging from
about 180 C to
about 550 C. At or above these temperatures the preferred polymers form a
viscous liquid to
which a biocide/carrier combination can be added and mixed during initial
processing. Such
polymers include, but are not limited to organic polymers, inorganic polymers,
mixtures of
organic and inorganic polymers, copolymers including mixed organic/inorganic
polymers, linear
polymers, branched polymers, star polymers, and mixtures thereof. A specific
polymer or
polymer combination is typically selected to provide the necessary physical
properties for an
application at an acceptable cost.
Polymers generally suitable for processing according to the current disclosure
include,
but are not limited to:
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1. Polymers of monoolefins and diolefins, for example polypropylene,
polyisobutylene,
polybut-l-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well
as polymers of
cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which
optionally can be
crosslinked), for example high density polyethylene (HDPE), low density
polyethylene (LDPE),
linear low density polyethylene (LLDPE), branched low density polyethylene
(BLDPE) and
medium density polyethylene (MDPE). Polyolefins, i.e. the polymers of
monoolefins
exemplified in the preceding paragraph, preferably polyethylene and
polypropylene, can be
prepared by different, and especially by the following, methods:
a) radical polymerization (normally under high pressure and at elevated
temperature).
b) catalytic polymerization using a catalyst that normally contains one or
more than one
metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
These metals usually have one or more than one ligand, typically oxides,
halides, alcoholates,
esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or
s-coordinated. These
metal complexes may be in the free form or fixed on substrates, typically on
activated
magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These
catalysts may be
soluble or insoluble in the polymerization medium. The catalysts can be used
by themselves in
the polymerization or further activators may be used, typically metal alkyls,
metal hydrides,
metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals
being elements of
groups Ia, ha and/or Ma of the Periodic Table. The activators may be modified
conveniently
with further ester, ether, amine or silyl ether groups. These catalyst systems
are usually termed
Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or
single site
catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of
polypropylene
with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE,
PP/LDPE) and
mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl
monomers, for example ethylene/propylene copolymers, linear low density
polyethylene
(LLDPE) and mixtures thereof with low density polyethylene (LDPE),
propylene/but-l-ene
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copolymers, propylene/isobutylene copolymers, ethylene/but-1 -ene copolymers,
ethylene/hexene
copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers,
ethylene/octene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers,
ethylene/alkyl
acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl
acetate copolymers
and their copolymers with carbon monoxide or
ethylene/acrylic acid copolymers and their salts (ionomers) as well as
terpolymers of
ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or
ethylidene-
norbornene; and mixtures of such copolymers with one another and with polymers
mentioned in
1) above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl
acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EM),
LLDPE/EVA,
LLDPE/EM and alternating or random polyalkylene/carbon monoxide copolymers and
mixtures
thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications
thereof
(e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).
6. Copolymers of styrene or a -methylstyrene with dienes or acrylic
derivatives, for
example styrene/butadiene, styrene/unsaturated ester, styrene/acrylonitrile,
styrene/alkyl
methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
methacrylate,
styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of
high impact strength
of styrene copolymers and another polymer, for example a polyacrylate, a diene
polymer or an
ethylene/propylene/diene terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene.
7. Graft copolymers of styrene or a -methylstyrene, for example styrene on
polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile
copolymers;
styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,
acrylonitrile and
methyl methacrylate on polybutadiene; styrene and maleic anhydride on
polybutadiene; styrene,
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acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and
maleimide on
polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene;
styrene and
acrylonitrile on ethylene/propylene/diene terpolymers; styrene and
acrylonitrile on polyalkyl
acrylates or polyalkyl methacrylates, styrene and acrylonitrile on
acrylate/butadiene copolymers,
as well as mixtures thereof with the copolymers listed under 6), for example
the copolymer
mixtures known as ABS, SAN, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers,
chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and
chlorinated ethylene,
epichlorohydrin homo- and copolymers, especially polymers of halogen-
containing vinyl
compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride,
polyvinylidene fluoride, as well as copolymers thereof such as vinyl
chloride/vinylidene
chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate
copolymers.
9. Polymers derived from a,13-unsaturated acids and derivatives thereof such
as
polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides
and
polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with
other
unsaturated monomers, for example acrylonitrile/butadiene copolymers,
acrylonitrile/alkyl
acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl
halide copolymers
or acrylonitrile/alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and amines or the acyl
derivatives or
acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl
stearate, polyvinyl
benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or
polyallyl melamine; as well
as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols,
polyethylene oxide, polypropylene oxide or copolymers thereof with bis-
glycidyl ethers.
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13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which
contain
ethylene oxide as a comonomer; polyacetals modified with thermoplastic
polyurethanes,
acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides
with
styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or
polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on
the other, as well as
precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids
and/or
from aminocarboxylic acids or the corresponding lactams, for example polyamide
4, polyamide
6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12,
aromatic polyamides
starting from m-xylene diamine and adipic acid; polyamides prepared from
hexamethylenediamine and isophthalic or/and terephthalic acid and with or
without an elastomer
as modifier, for example poly-2,4,4, -trimethylhexamethylene terephthalamide
or poly-m-
phenylene isophthalamide; and also block copolymers of the aforementioned
polyamides with
polyolefins, olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with
polyethers, e.g. with polyethylene glycol, polypropylene glycol or
polytetramethylene glycol; as
well as polyamides or copolyamides modified with EPDM or ABS; and polyamides
condensed
during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from
hydroxycarboxylic
acids or the corresponding lactones, for example polyethylene terephthalate,
polytrimethylene
terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane
terephthalate and
polyhydroxybenzoates, as well as block copolyether esters derived from
hydroxyl-terminated
polyethers; and also polyesters modified with polycarbonates or MBS.
Polyesters and polyester
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copolymers as defined in U.S. Pat. No. 5,807,932 (column 2, line 53),
incorporated herein by
reference.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols,
ureas
and melamines on the other hand, such as phenol/formaldehyde resins,
urea/formaldehyde resins
and melamine/formaldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and
unsaturated
dicarboxylic acids with or without halogen-containing modifications thereof of
low
flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for
example epoxy
acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with
melamine resins,
urea resins, polyisocyanates or epoxy resins.
26. Epoxy resins derived from polyepoxides, for example from bis glycidyl
ethers or
from cycloaliphatic diepoxides.
27. Natural polymers such as cellulose, rubber, gelatin and chemically
modified
homologous derivatives thereof, for example cellulose acetates, cellulose
propionates and
cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well
as rosins and their
derivatives.
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28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM,
Polyamidel-EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA,
PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,
POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP,
PA/PPO.
29. Naturally occurring and synthetic organic materials which are pure
monomeric compounds
or mixtures of such compounds, for example mineral oils, animal and vegetable
fats, oil and
waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates,
adipates, phosphates or
trimellitates) and also mixtures of synthetic esters with mineral oils in any
weight ratios,
typically those used as spinning compositions, as well as aqueous emulsions of
such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or
latices of
carboxylated styrene/butadiene copolymers.
31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for
example, in
U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes described, for
example, in U.S. Pat.
No. 4,355,147.
32. Polyketimines in combination with unsaturated acrylic polyacetoacetate
resins or
with unsaturated acrylic resins. The unsaturated acrylic resins include the
urethane acrylates,
polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups
and the acrylated
melamines. The polyketimines are prepared from polyamines and ketones in the
presence of an
acid catalyst.
33. Radiation curable compositions containing ethylenically unsaturated
monomers or
oligomers and a polyunsaturated aliphatic oligomer.
34. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an
epoxy
functional coetherified high solids melamine resin such as LSE-4103
(Monsanto).
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Resins that do not have a glass transition temperature because of cross-
linking or for other
reasons can be incorporated by mixing with another polymer having a glass
transition
temperature within a necessary temperature range.
The following polymers are particularly suitable for this application:
polyvinylchloride,
thermoplastic elastomers, polyurethanes, high density polyethylene, low
density polyethylene,
silicone polymers, fluorinated polyvinylchloride, polystyrene, styrene-
acrylonitrile resin,
polyethylene terephthalate, rayon, styrene ethylene butadiene styrene rubber,
cellulose acetate
butyrate, polyoxymethylene acetyl polymer, latex polymers, natural and
synthetic rubbers,
epoxide polymers (including powder coats), and polyamide6. Depending on the
biocide
concentration, cooling and solidification of the resulting polymer/biocide
composition can
provide a product ranging from a concentrate (a "masterbatch") for subsequent
incorporation into
additional polymer or a finished article.
The carrier/biocide combination can also be incorporated into thermoset resins
that reach
elevated temperatures while curing. When the carrier/biocide combination is
exposed to the
curing temperatures, the biocide does not undergo transformation and imparts
its biocidal
properties to the cured thermoset resin. Examples of thermoset resins which
can be loaded with
the carrier;/biocide combination include, but are not limited to vinyl
plastisol, polyesters, epoxy
resin, polyurethanes, urea formaldehyde resins, vulcanized rubber, melamine,
polyimide, and
resins derived from various acrylated monomers & oligomers of epoxy, urethane,
arylic, and the
like commonly used to formulate UV curable systems.
The Biocides:
Biocides utilized according to the present disclosure are generally biocides
which have
reduced stability when exposed to required processing conditions at
temperatures above their
decomposition temperature. A majority are biocides which have limited heat
stability that
prevent their incorporation into polymers by standard methods.
Biocides generally suitable for processing according to the current disclosure
include, but
are not limited to: Acetylcarnitine, Acetylcholine, Aclidinium bromide,
Acriflavinium chloride,
Agelasine, Aliquat 336, Ambenonium chloride, Ambutonium bromide, Aminosteroid,
Anilinium
chloride, Atracurium besilate, Benzalkonium chloride, Benzethonium chloride,
Benzilone,
Benzododecinium bromide, Benzoxonium chloride, Benzyltrimethylammonium
fluoride,
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Benzyltrimethylammonium hydroxide, Bephenium hydroxynaphthoate, Berberine,
Betaine,
Bethanechol, Bevonium, Bibenzonium bromide, Bretylium, Bretylium for the
treatment of
ventricular fibrillation, Burgess reagent, Butylscopolamine, Butyrylcholine,
Candocuronium
iodide, Carbachol, Carbethopendecinium bromide, Carnitine, Cefluprenam,
Cetrimonium,
Cetrimonium bromide, Cetrimonium chloride, Cetylpyridinium chloride,
Chelerythrine,
Chlorisondamine, Choline, Choline chloride, Cimetropium bromide, Cisatracurium
besilate,
Citicoline, Clidinium bromide, Clofilium, Cocamidopropyl betaine,
Cocamidopropyl
hydroxysultaine, Complanine, Cyanine, Decamethonium, 3-Dehydrocarnitine,
Demecarium
bromide, Denatonium, Dequalinium, Didecyldimethylammonium chloride,
Dimethyldioctadecylammonium chloride, Dimethylphenylpiperazinium,
Dimethyltubocurarinium chloride, Di0C6, Diphemanil metilsulfate, Diphthamide,
Diquat,
Distigmine, Domiphen bromide, Doxacurium chloride, Echothiophate, Edelfosine,
Edrophonium, Emepronium bromide, Ethidium bromide, Euflavine, Fenpiverinium,
Fentonium,
Gallamine triethiodide, Gantacurium chloride, Glycine betaine aldehyde,
Glycopyrrolate, Guar
hydroxypropyltrimonium chloride, Hemicholinium-3, Hexafluronium bromide,
Hexamethonium,
Hexocyclium, Homatropine, Hydroxyethylpromethazine, Ipratropium bromide,
Isometamidium
chloride, Isopropamide, Jatrorrhizine, Laudexium metilsulfate, Lucigenin,
Mepenzolate,
Methacholine, Methantheline, Methiodide, Methscopolamine, Methylatropine,
Methylscopolamine, Metocurine, Miltefosine, MPP+, Muscarine, Neurine,
Obidoxime,
Otilonium bromide, Oxapium iodide, Oxyphenonium bromide, Palmatine,
Pancuronium
bromide, Pararosaniline, Pentamine, Penthienate, Pentolinium, Perifosine,
Phellodendrine,
Phosphocholine, Pinaverium, Pipecuronium bromide, Pipenzolate, Poldine,
Polyquaternium,
Pralidoxime, Prifinium bromide, Propantheline bromide, Prospidium chloride,
Pyridostigmine,
Pyrvinium, Quaternium-15, Quinapyramine, Rapacuronium, Rhodamine B, Rocuronium
bromide, Safranin, Sanguinarine, Stearalkonium chloride, Succinylmonocholine,
Suxamethonium chloride, Tetra-n-butylammonium bromide, Tetra-n-butylammonium
fluoride,
Tetrabutylammonium hydroxide, Tetrabutylammonium tribromide,
Tetraethylammonium,
Tetraethylammonium bromide, Tetramethylammonium chloride, Tetramethylammonium
hydroxide, Tetramethylammonium pentafluoroxenate, Tetraoctylammonium bromide,
Tetrapropylammonium perruthenate, Thiazinamium metilsulfate, Thioflavin,
Thonzonium
bromide, Tibezonium iodide, Tiemonium iodide, Timepidium bromide, Trazium,
Tridihexethyl,
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Triethylcholine, Trigonelline, Trimethyl ammonium compounds, Trimethylglycine,
Trolamine
salicylate, Trospium chloride, Tubocurarine chloride, Vecuronium bromide.
Preferred heat labile biocides include, but are not limited to, quaternary
amines and
antibiotics. Some specific preferred heat labile biocides include, but are not
limited to, N,N-
didecyl-N-methyl-N-(3-trimethoxysilylpropyl)ammonium chloride, cetyl
pyridinium chloride,
N,N-bis(3-aminopropyl)dodecylamine, N-octyl-N-decyl-N-dimethyl-ammonium
chloride, N-di-
octadecyl-N-dimethyl-ammonium chloride, and N-didecyl-N-dimethyl-ammonium
chloride.
Some specific antibiotics include, but are not limited to amoxicillin,
campicillin,
piperacillin, carbenicillin indanyl, methacillin cephalosporin cefaclor,
streptomycin, tetracycline
and the like. Preferred combinations of biocides generally include at least
one heat labile
biocide, which would not survive incorporation into a specific polymer unless
adsorbed onto a
carrier. Examples of preferred fungicides include iodopropynylbutylcarbamate;
N-
[(trichloromethyl)thio]phthalimide; and chlorothalonil. Examples of preferred
bactericides
include benzisothiazolinone and 5-chloro-2-methyl-4-isothiazolin-3-one. Other
biocides which
can be utilized according to this disclosure include, but are not limited to,
bactericides,
fungicides, algicides, miticides, viruscides, insecticides, acaricides,
herbicides rodenticides,
animal and insect repellants, and the like.
The Carriers:
Suitable carriers are typically porous materials capable of adsorbing the heat
labile
biocide, remaining in a solid form without decomposition during processing in
a molten phase,
and maintaining the biocide in the adsorbed state during processing. Carriers
having a
substantial porosity and a high surface area (mostly internal) are
particularly preferred. A further
useful property for a carrier is a relatively low thermal conductivity.
Finally, for some
applications, carriers which do not alter the color or appearance of the
polymer are particularly
preferred.
Carriers which have been utilized include, but are not limited to, inorganics
such as platy
minerals and polymers. Examples of inorganics include, but are not limited to
fumed and other
forms of silicon including precipitated silicon and vapor deposited silicon;
clay; kaolin; perlite
bentonite; talc; mica; calcium carbonate; titanium dioxide; zinc oxide; iron
oxide; silicon
dioxide; and the like. Mixtures of different carriers can also be utilized.
Polymeric carriers
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should remain solid at elevated temperatures and be capable of loading
sufficient quantities of
biocide either into a pore system or through other means of incorporation.
Suitable polymeric
carriers include, but are not limited to, organic polymeric carriers such as
cross-linked
macroreticular and gel resins, and combinations thereof such as the so-called
plum pudding
polymers. The most preferred organic polymeric carriers include porous
macroreticular resins,
some of which can include other resins within the polymer's structure.
Suitable resins for
imbedding within a macroreticular resin include other macroreticular resins or
gel resins.
Additionally, other porous non-polymeric materials such as minerals can
similarly be
incorporated within the macroreticular resin.
Suitable organic polymeric carriers can include polymers lacking a functional
group, such
as a polystyrene resin, or carriers having a functional group such as a
sulfonic acid included.
Generally, any added functional group should not substantially reduce the
organic polymeric
carrier's thermal stability. A suitable organic polymeric carrier should be
able to load a
sufficient amount of biocide, and survive any processing conditions, and
deliver an effective
amount of the heat labile component such as a biocide upon incorporation into
any subsequent
system. Suitable organic polymeric carriers can be derived from a single
monomer or a
combination of monomers. Combinations of inorganic and organic carriers can be
utilized.
General methods for preparing macroreticular and gel polymers are well known
in the art
utilizing a variety of monomers and monomer combinations. Suitable monomers
for the
preparation of organic polymeric carriers include, but are not limited to
styrene, vinyl pyridines,
ethylvinylbenzenes, vinyltoluenes, vinyl imidazoles, an ethylenically
unsaturated monomers,
such as, for example, acrylic ester monomers including methyl acrylate, ethyl
acrylate, butyl
acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, butyl
methacrylate, lauryl
(meth)acrylate, isobornyl (meth)acrylate, isodecyl (meth)acrylate, oleyl
(meth)acrylate, palmityl
(meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, and
hydroxypropyl
(meth)acrylate; acrylamide or substituted acryl amides; styrene or substituted
styrenes;
butadiene; ethylene; vinyl acetate or other vinyl esters such as vinyl
acetate, vinyl propionate,
vinyl butyrate and vinyl laurate; vinyl ketones, including vinyl methyl
ketone, vinyl ethyl ketone,
vinyl isopropyl ketone, and methyl isopropenyl ketone; vinyl ethers, including
vinyl methyl
ether, vinyl ethyl ether, vinyl propyl ether, and vinyl isobutyl ether; vinyl
monomers, such as, for
example, vinyl chloride, vinylidene chloride, N-vinyl pyrrolidone; amino
monomers, such as, for
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example, N,N'-dimethylamino (meth)acrylate; and acrylonitrile or
methacrylonitrile; and the
monomethacrylates of dialkylene glycols and polyalkylene glycols. Descriptions
for making
porous and macroreticular polymers can be found in U.S. patent No. 7,422,879
(Gebhard et al.)
and U.S. patent No. 7,098,252 (Jiang et al.).
The organic polymeric carriers can contain other organic polymeric particles
and/or other
inorganic carrier particles, such as minerals typically characterized as platy
materials. Minerals
suitable for incorporation into a polymeric carrier include, but are not
limited to fumed and other
forms of silicon including precipitated silicon and vapor deposited silicon;
clay; kaolin; perlite
bentonite; talc; mica; calcium carbonate; titanium dioxide; zinc oxide; iron
oxide; silicon
dioxide; and the like. Mixtures of different carriers can also be utilized.
Selection of Components:
The choice of polymer(s) is generally made to provide an article having
necessary and
desired properties and a cost consistent with its use. The organic polymeric
carriers are typically
selected based on their porosity, surface area, and their ability to load
sufficient biocide, and
ultimate impact on the composition's properties. Porosity and surface area
determine how much
biocide can be loaded onto the organic polymeric carrier and generally reduces
the amount of
organic polymeric carrier required. The selection of biocide primarily depends
on the use of the
polymer/biocide combination. For example, the biocide loading can be tailored
to target specific
microorganisms or specific combinations of microorganisms, depending on the
material's end
use. Combinations of biocides can be utilized including both heat stabile and
heat labile biocides
in order to fulfill specific needs. In addition, combinations of biocides
including bactericides,
viruscides, fungicides, insecticides, herbicides, miticides, rodenticides,
animal and insect
repellants, and the like can be incorporated into a single polymer, depending
on it end use.
Additionally, incompatible materials, whether heat labile or not, can be
loaded into separate
carriers and incorporated into polymers.
The Process:
The carrier/biocide combination has been produced by contacting a carrier with
a liquid
form of the biocide (typically a solution or a suspension), allowing
adsorption onto the organic
polymeric carrier to occur and evaporating any solvent to provide the
carrier/biocide
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combination in the form of a flow-able powder. Carrier loaded biocides
containing as much as
60% biocides have been prepared. Multiple biocides can be loaded onto a single
carrier,
provided the multiple biocides are not incompatible. However, the utilization
of a single
biocide/single carrier combination avoids the issue of biocide incompatibility
and offers
advantages regarding flexibility with regard to the variety of available
formulations.
The carrier/biocide combination has also been produced by encapsulating the
carrier/biocide combination after and/or during the loading process. The
encapsulation process
can occur in parallel with separate carrier/biocide combinations that can then
be combined and
further encapsulated or the encapsulation process can be carried out
sequentially. Parallel
encapsulations have generally provided superior results when working with
otherwise
incompatible biocides. Generally the encapsulating agent is determined based
on the
carrier/biocide combination selected. For carriers involving Si02, Ti02, and
Zn02, N,N-Bis(3-
aminopropyl)dodecylamine has been utilized as an encapsulating agent. The
addition of
Diisobutylphenoxyethoxyethyldimethylbenzyl ammonium chloride monohydrate and
Iron Pure
provides a biocidal effect and additionally assists in maintaining gasses and
volatiles within the
encapsulated carrier/biocide combination. The carrier/biocide combination can
be constructed
with a single encapsulation process, a double encapsulation process or can
involve any number
of encapsulations, depending on the desired properties and the number of
components. Example
8 illustrates the encapsulation method described above.
To develop a method, a processing temperature is established for the
polymer/carrier/biocide combination (or combination containing another heat
labile component)
and a maximum processing time at the processing temperature is established,
before the
processing is carried out. Processing equipment is selected to minimize melt
time for the
polymer/carrier/biocide combination. Conventional equipment for processing
polymers can
generally be used. Based on current work, single or twin thermal screws are
effective for
producing both masterbatch material and finished articles. Standard pellet
extrusion has proven
a useful method for producing masterbatch materials. Finished articles or
intermediate forms of
the polymer can be prepared by the following techniques: injection molding,
roll molding,
rotational molding, extrusion, casting, and the like. Organic polymeric
carrier/biocide loading
into the polymer melt can run at least as high as about 40 wt.%
carrier/biocide. For masterbatch
materials, the carrier/biocide concentration also typically runs as high as
about 40 wt.%.
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Masterbatch materials are polymer/carrier/biocide combinations containing a
high level of
carrier/biocide for subsequent incorporation into a final polymer product
through a subsequent
processing step. Although masterbatch materials can take a variety of forms,
they are typically
provided in pellet form, and standard pellet extrusion has proven a useful
method for producing
masterbatch materials. As noted above, however, masterbach materials can also
involve a liquid
form including the carrier/heat labile component. For finished articles or
intermediate forms,
biocide levels in the range of about 0.25 wt.% to 10 wt.% have proven
effective against
microorganism's tested. However, even higher loadings are contemplated and
will be effective.
Applications Utilizing Biocidal Polymers:
Applications involving the polymer/biocide combination taught herein include,
but are not
limited to a wide range of materials which can be used to form surfaces and
equipment utilized
in the medical and consumer fields including hospital, emergency treatment,
first aid, and the
like. Any product that is or could be prepared from a polymer melt or other
fluid that otherwise
requires processing at an elevated temperature and which would benefit from
the ability to
contain a heat labile component such as a biocide to limit the growth of
microorganisms can be
improved by utilizing the polymer/biocide combinations taught herein. Some
specific examples
of articles include, but are not limited to things we touch such as: counter
tops, furniture
components (e.g. a bed rail, a toilet seat, a shower stall, a sink, etc.),
equipment (e.g. a bed pan, a
door handle, shopping cart handles, a writing instrument, a computer keyboard,
a telephone,
toothbrush components, dental equipment, etc.), surgical equipment (e.g.
clamps, surgeon's
gloves, etc.), wound and hygiene products (e.g. bandages), and clothing (e.g.
doctor's gown,
patient's gown, nurses outer clothing, bedding, etc.). In addition, air
filters constructed from
porous forms of the polymer/biocide combination can minimize the microorganism
content of
the air circulating within a hospital, an office building, a hotel, a home, or
other structure with
central air handling equipment. Breathing masks and related portable air-
filtering systems can
similarly benefit from the use of filters constructed from the polymer/biocide
combinations. In
addition, filters suitable for handling other fluids such as liquids can
similarly be passed through
filters constructed from the polymer/biocide combination to cause reduction in
the
microorganism content of the fluid being treated. Finally, clothing
constructed from fabrics
prepared from the polymer/biocide combination can provide additional
protection for individuals
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exposed to a range of biological hazards or weapons. Many of the articles
above are also
important components in schools, where colds, influenza, and the like
typically spread quickly
through surface contacts and air-born microorganisms. Polymers containing
insecticides can be
utilized to prepare articles such as siding, molding such as baseboards,
carpeting, and the like to
allow the killing of susceptible insects that contact the polymer/insecticide
material. Fabrics
including insecticides/miticides can be provided and incorporated into bedding
supplies to
control the reproduction and spread of organisms such as bed bugs and the
like.
Finally, the present disclosure provides for polymeric materials utilizing the
carrier
technology which can contain components selected from the group consisting of
bactericides,
fungicides, insecticides, rodenticides, volatile fragrances (including animal
and insect repellants),
and the like. Such polymeric materials are particularly suitable for forming a
variety of building
materials, and for manufacturing garbage cans/bags and other equipment
designed to handle
garbage, food wastes, and the like. Articles manufactured from this polymeric
material can mask
odors, minimize bacterial and fungal growth, retard the proliferation of flies
and other harmful
insects, and prevent the proliferation of rodents. The incorporation of animal
repellants in
polymeric materials utilized for garbage handling equipment/articles handling
food products can
also keep pets and wild animals away. This is particularly desirable for
garbage cans/bags
awaiting pickup in unattended locations. Articles manufactured from polymeric
materials
containing combinations of these components can ultimately be recycled without
leaching
substantial amounts of biocides/pesticides into the environment.
Specific Examples:
Example 1: Preparation of Silica loaded with N,N-didecyl-N-methyl-N-(3-
trimethoxysilylpropyl)ammonium chloride:
83 parts by weight of a methanolic solution containing 72% N,N-didecyl-N-
methyl-N-(3-
trimethoxysilylpropyl)ammonium chloride was combined with 40 parts by weight
of fumed
silica (5i02). The moist combination was mixed for about 5 minutes at ambient
temperature in a
high speed mixer at approximately 1200 rpm to provide a flowable powder. More
dilute
solutions of the biocide produces a wet paste, rather than a flowable powder.
The resulting
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methanol wet carrier/quaternary salt can be incorporated into a polymer
directly or dried before
further use.
This method was used to prepare carrier/biocide combinations utilizing silica
and, cetyl
pyridinium chloride, N,N-bis(3-aminopropyl)dodecylamine, N-octyl-N-decyl-N-
dimethyl-
ammonium chloride, N-di-octadecyl-N-dimethyl-ammonium chloride, and N-didecyl-
N-
dimethyl-ammonium chloride. Additionally, the method described above can also
be utilized to
prepare other carrier/biocide combinations utilizing the carriers including
clay; kaolin; perlite
bentonite; talc; mica; calcium carbonate; titanium dioxide; zinc oxide; and
iron oxide.
Although multiple compatible biocides can be loaded into a single carrier,
loading a
single biocide into a single carrier is preferred when a combination of
biocides utilized are
incompatible. The single biocide/single carrier loading also allows greater
flexibility in
formulating a variety of biocide/polymer combinations. Multiple
biocide/carrier combinations
can be added to a single polymer at the masterbatch stage or when incorporated
into a polymer
product.
Example 2: Preparation of Polymer loaded with N,N-didecyl-N-methyl-N-(3-
trimethoxysilylpropyl)ammonium chloride:
(a) Polymer selection and pretreatment: A commercial grade of the
macroreticular
crosslinked styrene/divinylbenzene resin, XADTM 16, available from Rohm and
Haas can be
obtained, rinsed with water, dried, and ground to provide particles ranging
from about 1 to about
100 nm. XAD is a common law trademark belonging to Rohm & Haas Company 100
Independence Mall West, Philadelphia, PA 19106-2399.
(b) Polymer Loading: 83 parts by weight of a methanolic solution containing
72% N,N-
didecyl-N-methyl-N-(3-trimethoxysilylpropyl)ammonium chloride are combined
with 25 parts
by weight of the XADTM 16 polymer pre-treated as described above. The moist
combination is
mixed for about 5 minutes at ambient temperature in a high speed mixer at
approximately 1200
rpm to provide a flow able powder. More dilute solutions of the biocide
produces a wet paste,
rather than a flow able powder. The resulting methanol wet carrier/quaternary
salt can be
incorporated into a polymer directly or dried before further use.
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This method can be used to prepare organic polymeric carrier/biocide
combinations
utilizing an organic polymeric carrier and, cetyl pyridinium chloride, N,N-
bis(3-
aminopropyl)dodecylamine, N-octyl-N-decyl-N-dimethyl-ammonium chloride, N-di-
octadecyl-
N-dimethyl-ammonium chloride, and N-didecyl-N-dimethyl-ammonium chloride.
Other suitable
organic polymeric carriers can include resins, particularly macroreticular
resins derived from
styrene, acrylic acid, alkylacrylates, acrylamides, phenol/formaldehyde
combinations,
vinylpyridines, vinylimidazoles, combinations thereof, and the like. Gel and
macroreticular
resins can be unsubstituted or substituted. Polymers having lower levels of
cross-linking will
typically swell more during loading and are expected to provide greater
carrier capacities than
more heavily crosslinked resins. Preferred macroreticular resins have a
surface area of at least
about 50 m2/gm, more preferred resins have a surface area of at least about
200 m2/gm, and most
preferred resins have a surface area of at least about 500 m2/gm. Commercially
available
macroreticular resins which can serve as carrier particles include, but are
not limited to the
resins, XADTM 2, XADTM 4, XADTM 7, XADTM 16, XADTM 200, XADTM 761, XADTM 1180,
and XADTM 2010.
Although multiple compatible biocides can be loaded into a single carrier,
loading a
single biocide into a single carrier is preferred when a combination of
biocides utilized are
incompatible. The single biocide/single carrier loading also allows greater
flexibility in
formulating a variety of biocide/polymer combinations. Multiple
biocide/carrier combinations
can be added to a single polymer at the masterbatch stage or when incorporated
into a polymer
product.
Example 3: Preparation of Carrier/Polymer masterbatch pellets:
A heated single thermal screw equipped with a port for addition of the carrier
and a port
for removal of methanol vapor was prepared for the thermal extrusion of
polystyrene. Once
molten polystyrene was moving through the extruder, the carrier/quat
combination prepared
above was added to the extruder at a rate to provide a polymer:carrier/biocide
ratio of 60:40, by
weight. Methanol and other volatiles were vented from the venting port. The
extruder was
operated to provide a polymer residence time within the extruder of about 1-2
minutes. The hot
polymer was extruded into water to produce a pencil shaped extrusion product
that was
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subsequently cut into pellets. The resulting wet pellets were separated from
the water, dried, and
sized for subsequent incorporation into polymer articles. Similar masterbatch
pellets were
prepared according to this procedure incorporating the carrier/biocide
combinations including
silica and, cetyl pyridinium chloride, N,N-bis(3-aminopropyl)dodecylamine, N-
octyl-N-decyl-N-
dimethyl-ammonium chloride, N-di-octadecyl-N-dimethyl-ammonium chloride, or N-
didecyl-N-
dimethyl-ammonium chloride.
Example 4: Preparation of Organic Polymeric Carrier/Polymer masterbatch
pellets:
A heated single thermal screw equipped with a port for addition of the carrier
and a port
for removal of methanol vapor is prepared for the thermal extrusion of
polystyrene. Once molten
polystyrene is moving through the extruder, the carrier/quat combination
prepared above is
added to the extruder at a rate to provide a polymer:carrier/biocide ratio of
about 60:40, by
weight. Methanol and other volatiles are vented from the venting port. The
extruder is operated
to provide a polymer residence time within the extruder of about 1-2 minutes.
The hot polymer
is extruded into water to produce a pencil shaped extrusion product that is
subsequently cut into
pellets. The resulting wet pellets are separated from the water, dried, and
sized for subsequent
incorporation into polymer articles. Similar masterbatch pellets can be
prepared according to
this procedure incorporating the carrier/biocide combinations including a
crosslinked
macroreticular resin and, cetyl pyridinium chloride, N,N-bis(3-
aminopropyl)dodecylamine, N-
octyl-N-decyl-N-dimethyl-ammonium chloride, N-di-octadecyl-N-dimethyl-ammonium
chloride, or N-didecyl-N-dimethyl-ammonium chloride.
This procedure can also used to prepare similar masterbatch pellets utilizing
polyvinylchloride, thermoplastic elastomers, polyurethanes, high density
polyethylene, low
density polyethylene, silicone polymers, fluorinated polyvinylchloride,
styrene-acrylonitrile
resin, polyethylene terephthalate, rayon, styrene ethylene butadiene styrene
rubber, cellulose
acetate butyrate, polyoxymethylene acetyl polymer, latex polymers, natural and
synthetic
rubbers, epoxide polymers (including powder coats), and polyamide6.
Masterbatch pellets can
similarly be made using a combination or blend of polymers.
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For polymers that have high melt viscosities, a thermal screw extruder having
good
mixing is important in order to ensure the complete distribution of the
carrier/biocide throughout
the entire melt.
Example 5: Preparation of Articles from masterbatch pellets:
A single screw heated extruder of the type described above for preparing the
master batch
material (prepared either in Example 1 or 2) is used to extrude a sheet form
of the polymer. As
in the method for preparing a master batch material, polystyrene is introduced
into the extruder
to provide a melt by the time material reached the addition port. The master
batch material
prepared above is added through the addition port to provide a ratio of
biocide/polymer of about
0.25 wt.% to 10 wt.%. Residence time within the extruder is controlled between
1 and 2 minutes
to provide polystyrene in a sheet form. Using the same equipment, and
masterbatch pellets
incorporating the other polymers listed or blends thereof, this procedure can
be used to prepare
sheet forms of polyvinylchloride, thermoplastic elastomers, polyurethanes,
high density
polyethylene, low density polyethylene, silicone polymers, fluorinated
polyvinylchloride,
styrene-acrylonitrile resin, polyethylene terephthalate, rayon, styrene
ethylene butadiene styrene
rubber, cellulose acetate butyrate, polyoxymethylene acetyl polymer, latex
polymers, natural and
synthetic rubbers, epoxide polymers (including powder coats), and polyamide6.
All of the
polymers are able to pass through the processing without color formation or
other visible signs of
biocide degradation. Depending on the polymer selected, residence times as
long as 30 minutes
can be utilized without decomposition of the biocide. Finally, the
carrier/biocide combination
formed in Example 1 can also be utilized directly with an appropriate dilution
to prepare polymer
loaded with biocide without utilizing the polymer masterbatch pellet material.
Example 6: Preparation of Polymer loaded with an antibiotic:
About 80 parts of a methanolic suspension containing about 70% wt.% penicillin
is
combined with about 40 parts of the macroreticular polymer processed as
described in Example
1 (a), above. The moist combination is mixed for about 5 minutes at ambient
temperature in a
high speed mixer at approximately 1200 rpm to provide a flow able powder. The
resulting
methanol wet carrier/antibiotic salt can be incorporated into a polymer
directly or dried before
further use.
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This method can be used to prepare further carrier/antibiotic combinations
utilizing silica
and, amoxicillin, campicillin, piperacillin, carbenicillin indanyl,
methacillin cephalosporin
cefaclor, streptomycin, tetracycline and the like. Additionally, the method
described above can
also be utilized to prepare other carrier/biocide combinations involving other
macroreticular
resins derived monomers such as styrene, acrylic acid, alkylacrylates,
acrylamides,
phenol/formaldehyde combinations, vinylpyridines, vinylimidazoles,
combinations thereof, and
the like.
Example 6: The Incorporation of a carrier/antibiotic combination into a
polymer masterbatch and
polymer article:
The procedure described in Example 2 can be utilized to prepare antibiotic
loaded
polymer masterbatch pellets and the procedure described in Example 3 can be
utilized to prepare
antibiotic loaded polymer articles from the masterbatch pellets containing an
antibiotic. Finally,
the carrier/antibiotic combination can also be utilized directly with an
appropriate dilution to
prepare polymer loaded with antibiotic without utilizing the polymer
masterbatch pellet material.
Example 7: Biological Tests:
ASTM E 2180, the standard method for determining the activity of incorporated
antimicrobial agents in polymers or hydrophobic material, is utilized to test
untreated sheets of
polypropylene and sheets of polypropylene containing 1% N,N-didecyl-N-methyl-N-
(3-
trimethoxysilylpropyl)ammonium chloride prepared according to the procedure
described in
Example 3 above. The samples are tested by pipetting a thin layer of
inoculated agar slurry
[Klebsiella Pneumoniae ATCC# 4352, and Staphylococus aureus ATCC# 6538] onto
the
untreated sheets and onto the treated sheets. Testing is carried out in
triplicate. After 24 hours of
contact at 35 C, surviving microorganisms are recovered into neutralizing
broth. Serial
dilutions are made, and bacterial colonies from each dilution series are
counted and recorded.
Percent reduction of bacteria from treated versus untreated samples are
calculated.
The geometric mean of the number of organism recovered from the triplicate
incubation
period control and incubation period treated samples are calculated and the
percent reduction
was determined by the following formula:
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a ¨ b
% reduction = x 100
a
where a = the antilog geometric mean of the number of organisms recovered from
the incubation
period control sample; and
b = the geometric mean of he number of organisms recovered from the incubation
period
treated samples.
Substantial reduction in the level of bacterial growth is obtained for regions
in contact with the
sheets containing the carrier/biocide combination.
The heat labile biocides described above can be similarly incorporated into
the polymers
described herein to provide polymer/biocide combinations which are capable of
retarding the
growth of microorganisms including, but not limited to E. coli, MRSA,
Clostridium difficile,
Aspergillus niger, and H1N1 Influenza A virus.
Example 8
Preparation of MACTTm 3.0, biopolyrner:
(a) Preparation of the Carrier Package: 250 grams of 5i02, 200 grams, 200
grams of an solution
of N Bis(3-aminopropyl) dodecylamine chloride (as a 60% N,N Bis(3-aminopropyl)
dodecylamine chloride) and 40 grams of fumed silica (5i02) were combined and
mixed in a high
speed mixer (about 1200rpm) for about 2 minutes at ambient temperature to
provide a flowable
powder. Sufficient amounts of additional dilute solutions of the N-Bis(3-
aminopropyl)dodecylamine chloride were added to convert the flowable powder
into a wet
paste. The following components were added to the wet paste: 20 grams Ti02, 20
grams of Ion
pure (silver iodide coated onto 5-10 micron glass beads), 30 grams of
DIISOBULYLPHENOXYETHOXY ETHYL DIMETHYL BENZYL AMMONIUM
CHLORIDE MONOHYDRATE, and 200 grams of aqueous N,N Bis(3-aminopropyl)
dodecylamine chloride. The combination was compounded for about 2 minutes at
ambient
temperature at a low mix rate less than 1200 rpm to mix the moist paste and
the resulting paste
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was compressed in a high speed shaker to remove any entrained air.
Additional components, 4.2 grams of N-ALKYL (C14-50%, C12-40%, C16-10%), 0.5
grams of Si02 and 0.5 grams of TiO2 were incorporated into the thick paste as
described above.
Sufficient N,N-Bis(3-aminopropyl)dodecylamine chloride was added to maintain
the material in
the form of a thick paste that was thoroughly mixed. This process was repeated
sequentially
with the addition of biocides 3-29.
The following biocides were all included into the carrier package sequentially
as
described above:
(1) N,N-Bis(3-aminopropyl) dodecylamine chloride,
(2) N-ALKYL (C14-50%, C12-40%, C16-10%)
(3) DIMETHYL BENZYL AMMONIUM CHLORIDE,
(3) 1,3-BIS(HYDROXYMETHYL)-5,
(4) 5-DIMETHYLHYDANTOIN,1-(HYDROXYMETHYL)-5,5-DIMETHYLHYDANTOIN,
(6) 3-I0D0-2-PROPYNYL BUTYL CARBAMATE,
(7) DIDECYL DIMETHYL AMMONIUM CHLORIDE,
(8) N-ALKYL (C14-50%, C12-40%, C16-10%) DIMETHYL BENZYL AMMONIUM
CHLORIDE,
(9) 1,3-DI-(HYDROXYMETHYL)-5,5-DIMETHYLHYDANTOIN,
(10) 3-(HYDROXYMETHYL)-5,5-DIMETHYLHYDANTOIN, 5,5-
DIMETHYLHYDANTOIN,
(11) 5-CHLOR0-2-METHYL-4-ISOTHIAZOLIN-3-ONE,
(12) 2-METHYL-4-ISOTHIAZOLIN-3-ONE,
(13) N-ALKYL (C14-60%,C16.30%, C12-50%, C18-5%) DIMETHYL BENZYL
AMMONIUM CHLORIDE,
(14) N-ALKYL (C12-50%, C14-30%, C16-17%, C18.3%) DIMETHYL BENZYL
AMMONIUM CHLORIDE, DIOCTYL DIMETHYL AMMONIUM CHLORIDE, DIDECYL
DIMETHYL AMMONIUM CHLORIDE,
(15) N,N-DIDECYL-N,N-DIMETHYLAMMONIUM CHLORIDE,
(16) ETHANE-1,2-DIOL, N,N BIS (3-AMINOPROPYL) DODECYLAMINE,
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(17) DIMETHYL BENZYL AMMONIUM CHLORIDE,
(18) OCTYL DECYL DIMETHYL AMMONIUM CHLORIDE,
(19) DIOCTYL DIMETHYL AMMONIUM CHLORIDE,
(20) 1-BROM0-3-CHLOR0-5,5-DIMETHYLHYDANTOIN,
(21) 3-BROM0-1-CHLOR0-5,5-DIMETHYLHYDANTOIN,
(22) 1,3-DIBROM0-5,5-DIMETHYLHYDANTOIN,
(23) BORIC ACID
(24) N-TRICHLOROMETHYLTHIO-4-CYCLOHEXENE-1,2-DICARBOXIMIDE,
(25) N-(TRICHLOROMETHYLIO) PHTHAALIMIDE, CARBAMIC ACID
(26) BUTYL-,3-I0D0-2-PROPYNYLESTER 55406-53-6,
(27) 3-I0D0-2-PROPYNL BUTYL CARBAMATE,
(28) 3-I0D0-2-PROPYNL BUTYL CARBAMATE,
(29) (TETRACHOROISOPHTHALONITRILE)
Sample Preparation:
The general procedure described in Examples 3 and 4 was repeated to provide
polypropylene samples plates for testing. A heated single thermal screw
equipped with a port for
addition of the carrier and an exhaust port for pressure relief was utilized.
Once molten
polypropylene was moving through the extruder, the carrier package prepared
above was added
to the extruder at a rate to provide a polymer/carrier package ratio of 60:40,
by weight. The
extruder was operated to provide a polymer residence time within the extruder
of about 1-2
minutes. The molten polymer was extruded to produce solid in the form of
plates for testing.
Pencil shaped extrusion product was also produced by this method that was
subsequently cooled
and solidified in water and cut into pellets. The resulting wet pellets were
separated from the
water, dried, and sized for subsequent incorporation into polymer articles.
Testing of MACTTm 3.0, biopolymer:
The MACTTm 3.0, biopolymer was prepared according to the procedure described
above and was
evaluated according to the standard testing method (JIS Z 2801) developed for
determining the
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ability of plastics and other antimicrobial surfaces to inhibit the growth of
microorganisms or kill
them, over a designated period of contact.
An Overview of the JIS Z 2801 Test:
A test microorganism is prepared, typically by growth in a liquid culture
medium. A
suspension of test microorganism is standardized by dilution in a nutritive
broth (affording
microorganisms the potential to grow during the test). Both control and test
surfaces are
inoculated with microorganisms, typically in triplicate, and then the
microbial inoculum is
covered with a thin, sterile film or similar cover. By covering the inoculum
it is spread,
evaporation is prevented, and close contact with the antimicrobial surface is
assured. Microbial
concentrations are initially determined at "time zero" by elution followed by
dilution and plating.
Inoculated, covered control and antimicrobial test surfaces are allowed to
incubate undisturbed in
a humid environment for the test period, often 24 hours. Following incubation,
microbial
concentrations are determined. Calculations are carried out to determine the
reduction of
microorganisms relative to initial concentrations and the control surface.
Surface Testing:
The JISZ 2801 Test Method was utilized to test plates of the
polymer/carrier/biocides prepared in
above and designated MACTTm 3Ø Tests conducted according to the JISZ 2801
method
involved: Influenza A (H1N1) virus (ATCC VR-1469); Poliovirus type 1 (ATCC VR-
1562);
Vancomycin Resistant Enterococcus faecalis - VRE (ATCC 51575); Pseudomonas
aeruginosa
(ATCC 15442); Acinetobacter baumannii (ATCC 19606); Clostridium difficile -
spore form (ATCC
43598); Methicillin Resistant Staphylococcus aureus - MRSA (ATCC 33592); and
Aspergillus niger
(ATCC 6275). The results are provided below:
Antiviral Studies:
The following data analysis was utilized in evaluating the effectiveness of
MACTTm 3.0,
samples against viral strains.
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CALCULATION OF TITERS
Viral and cytotoxicity titers will be expressed as -logio of the 50 percent
titration endpoint for
infectivity (TCID50) or cytotoxicity (TCD50), respectively, as calculated by
the method of
Spearman Karber.
(7
Sum of % mortality at each dilution i
- Log of 1st dilution inoculated ¨ __________________ 0.5 x (logarithm of
dilution)
100 , ,
Geometric Mean = Antilog of: Logi Xi + LogioX2 + Logi0X3
3*
(X equals TCID50/0.1 mL of each test or control replicate)
*This value (or number of values for X) may be adjusted depending on the
number of replicates
requested.
Calculation of Log Reduction
Zero Time Virus Control TCID50 ¨ Test Substance TCID50 = Log Reduction and/or
Virus Control TCID50 ¨ Test Substance TCID50 = Log Reduction
Calculation of Percent Reduction
Calculation of Percent Reduction
[
TCID50 test
% Reduction = 1 - ] x 100 and/or
TCID50 zero time virus control
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% Reduction = 1 - [ ________________ TC1D50 test
1 x 100
TCID50 virus control
Anti-Viral Test Results
A) Influenza A (H1N1) virus (ATCC VR-1469)
Under the conditions of this investigation and in the presence of a 1% fetal
bovine
serum organic soil load, MACTTm 3.0, (treated FDA grade plastic), demonstrated
complete
inactivation of Influenza A (H1N1) virus following a 2 hour exposure time at
room
temperature (20.0 C) in a relative humidity of 50%.
The titer of the input virus control (starting titer of the virus) was 7.00
logio. The virus
recovered from the untreated FDA grade plastic following the 2 hour exposure
time (2 hour
virus control) was 7.00 logio, indicating that virus was not lost during the 2
hour exposure
time.
Mean Reduction
MACTTm 3.0, demonstrated a >99.993% mean reduction in viral titer, as compared
to the
titer of the virus control held for the 2 hour exposure time.
The mean log reduction in viral titer was >4.17 logio, as compared to the
titer of the virus
control held for the 2 hour exposure time.
Individual Reduction
Replicate #1 and #3 demonstrated a >99.997% reduction in viral titer, as
compared to the
titer of the virus control held for the 2 hour exposure time.
The log reduction in viral titer was >4.50 logio, as compared to the titer of
the virus
control held for the 2 hour exposure time.
Replicate #2 demonstrated a >99.97% reduction in viral titer, as compared to
the titer of the
virus control held for the 2 hour exposure time.
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The log reduction in viral titer was >3.50 logio, as compared to the titer of
the virus
control held for the 2 hour exposure time.
B) Poliovirus type 1 (ATCC VR-1562)
Results of tests with two samples of MACTTm 3.0, biopolymer, treated FDA grade
plastic,
exposed to Poliovirus type 1 in the presence of a 1% fetal bovine serum
organic soil load at room
temperature (20.0 C) in a relative humidity of 50% for two and five minute
exposure times. All cell
controls were negative for test virus infectivity. The titer of the input
virus control was 8.00 logio.
The titer of the zero time virus control (untreated FDA grade plastic) was
7.50 logio. The titer of the
virus controls (untreated FDA grade plastic) was 7.50 logio for the 2 minute
exposure time and 8.25
logio for the 5 minute exposure time.
Following the 2 minute exposure time, test virus infectivity was detected at
6.50 log10.
Following the 5 minute exposure time, test virus infectivity was detected at
7.25 logio. Test
substance cytotoxicity was observed in the cytotoxicity control at 1.50 logio.
The neutralization
control (non-virucidal level of the test substance) indicates that the test
substance was neutralized at
<1.50 logic).
Under the conditions of this investigation and in the presence of a 1% fetal
bovine serum
organic soil load, MACTTm 3.0, biopolymer, treated FDA grade plastic,
demonstrated a 90.0%
reduction in viral titer following a 2 minute exposure time at room
temperature (20.0 C) in a
relative humidity of 50% to Poliovirus type 1, as compared to the titer of the
virus control held for
the 2 minute exposure time. The log reduction in viral titer was 1.00 logio,
as compared to the
titer of the virus control held for the 2 minute exposure time.
Under the conditions of this investigation and in the presence of a 1% fetal
bovine serum
organic soil load, MACTTm 3.0, biopolymer, treated FDA grade plastic,
demonstrated a 90.0%
reduction in viral titer following a 5 minute exposure time at room
temperature (20.0 C) in a
relative humidity of 50% to Poliovirus type 1, as compared to the titer of the
virus control held for
the 5 minute exposure time. The log reduction in viral titer was 1.00 logio,
as compared to the
titer of the virus control held for the 5 minute exposure time
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Antibacterial Studies:
The following general protocol for data analysis was utilized in evaluating
the effectiveness of
MACTTm 3.0, samples against bacterial strains.
Number of Organisms Present on Carriers
CFU/carrier =
faverage CFU at a given dilution) x (dilution factor) x (volume of neutralizer
in mL)
(volume plated in mL)
Geometric Mean of Number of Organisms Surviving on the Test or Untreated
Carriers
Geometric Mean = Antilog of LogioXi + LogioX2 + ...LogioXN
N
Where: X equals CFU/carrier
N equals number of control carriers
Percent Reduction per Time Point Evaluated
% reduction = [(a - b) / a] x 100
a = Geometric mean of the number of organisms surviving on the untreated
carriers*
at specified exposure time
b = Geometric mean of the number of organisms surviving on the
test carriers at
specified exposure time
Logio Reduction per Time Point Evaluated
Average Logio (CFU/untreated carrier*) ¨ Average Logio (CFU/test carrier)
*Note: Test reductions were determined based on the side-by-side provided
untreated control
results. However, if the untreated material was not available or if the
organism did not survive
on the untreated carriers, the test percent and log reduction calculations may
be calculated using:
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- the To control results which offer a test reduction over time, not taking
into
consideration natural organism die-off.
- the stainless steel control results which offer organism reductions in
the test as
compared to survival on a hard, non-porous surface.
Logio Difference for the Neutralization Confirmation Control
Recovery Log Difference = (Logio NC Numbers Control) ¨ (Logio NC Test Results)
Anti-Bacterial Test Results
C) Vancomycin Resistant Enterococcus faecalis - VRE (ATCC 51575)
MACTTm 3.0, demonstrated a >99.99% (>4.42 Logio) reduction of Vancomycin
Resistant
Enterococcus faecalis - VRE (ATCC 51575) following a 5 minute exposure time as
compared to
an untreated control material (FDA/Poly Pro) when tested in the presence of a
5% fetal bovine
serum organic soil load at 35-37 C with >90% relative humidity.
MACTTm 3.0, Platform, demonstrated a >99.99% (>4.58 Logio) reduction of
Vancomycin Resistant Enterococcus faecalis - VRE (ATCC 51575) following a 1
hour exposure
time as compared to the untreated control material (FDA/Poly Pro) when tested
in the presence
of a 5% fetal bovine serum organic soil load at 35-37 C with >90% relative
humidity.
Under the conditions of this investigation, MACTTm 3.0, Platform, demonstrated
a
>99.99% (>4.42 Logio) reduction of Vancomycin Resistant Enterococcus faecalis -
VRE (ATCC
51575) following a 5 minute exposure time as compared to the untreated control
material
(FDA/Poly Pro) when tested in the presence of a 5% fetal bovine serum organic
soil load at 35-
37 C with >90% relative humidity.
Under the conditions of this investigation, MACTTm 3.0, Platform, demonstrated
a
>99.99% (>4.58 Logio) reduction of Vancomycin Resistant Enterococcus faecalis -
VRE (ATCC
51575) following a 1 hour exposure time as compared to the untreated control
material
(FDA/Poly Pro) when tested in the presence of a 5% fetal bovine serum organic
soil load at 35-
37 C with >90% relative humidity.
D) Pseudomonas aeruginosa (ATCC 15442)
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MACTTm 3.0, biopolymer, demonstrated a >99.99% (>4.82 Logio) reduction of
Pseudomonas aeruginosa (ATCC 15442) following a 5 minute exposure time as
compared to the
untreated control material (FDA/Poly Pro) when tested in the presence of a 5%
fetal bovine
serum organic soil load at 35-37 C with >90% relative humidity.
MACTTm 3.0, biopolymer, demonstrated a >99.99% (>4.63 Logio) reduction of
Pseudomonas aeruginosa (ATCC 15442) following a 1 hour exposure time as
compared to the
untreated control material (FDA/Poly Pro) when tested in the presence of a 5%
fetal bovine
serum organic soil load at 35-37 C with
>90% relative humidity.
Under the conditions of this investigation, MACTTm 3.0, biopolymer,
demonstrated a
>99.99% (>4.82 Logio) reduction of Pseudomonas aeruginosa (ATCC 15442)
following a 5
minute exposure time as compared to the untreated control material (FDA/Poly
Pro) when tested
in the presence of a 5% fetal bovine serum organic soil load at 35-37 C with
>90% relative
humidity.
Under the conditions of this investigation, MACTTm 3.0, biopolymer
demonstrated a
>99.99% (>4.63 Logio) reduction of Pseudomonas aeruginosa (ATCC 15442)
following a 1
hour exposure time as compared to the untreated control material (FDA/Poly
Pro) when tested in
the presence of a 5% fetal bovine serum organic soil load at 35-37 C with >90%
relative
humidity.
E) Acinetobacter baumannii (ATCC 19606)
MACTTm 3.0, biopolymer, demonstrated a >99.99% (>4.34 Logio) reduction of
Acinetobacter baumannii (ATCC 19606) following a 5 minute exposure time as
compared to the
untreated control material (FDA/Poly Pro) when tested in the presence of a 5%
fetal bovine
serum organic soil load at 35-37 C with >90% relative humidity.
MACTTm 3.0, biopolymer, demonstrated a >99.99% (>4.60 Logio) reduction of
Acinetobacter baumannii (ATCC 19606) following a 1 hour exposure time as
compared to the
untreated control material (FDA/Poly Pro) when tested in the presence of a 5%
fetal bovine
serum organic soil load at 35-37 C with >90% relative humidity.
Under the conditions of this investigation, MACTTm 3.0, biopolymer
demonstrated a
>99.99% (>4.34 Logio) reduction of Acinetobacter baumannii following a 5
minute exposure
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time as compared to the untreated control material (FDA/Poly Pro) when tested
in the presence
of a 5% fetal bovine serum organic soil load at 35-37 C with >90% relative
humidity.
Under the conditions of this investigation, MACTTm 3.0, biopolymer
demonstrated a
>99.99% (>4.60 Logio) reduction of Acinetobacter baumannii following a 1 hour
exposure time
as compared to the untreated control material (FDA/Poly Pro) when tested in
the presence of a
5% fetal bovine serum organic soil load at 35-37 C with >90% relative
humidity.
F) Clostridium difficile - spore form (ATCC 43598)
MACTTm 3.0, biopolymer, demonstrated a <79.7% (<0.69 Logio) reduction of
Clostridium difficile - spore form (ATCC 43598) following a 2 hour exposure
time as compared
to the untreated control material (FDA/Poly Pro) when tested in the presence
of a 5% fetal
bovine serum organic soil load at 35-37 C with >90% relative humidity.
Under the conditions of this investigation, MACTTm 3.0, biopolymer
demonstrated a
<79.7% (<0.69 Logio) reduction of Clostridium difficile - spore form following
a 2 hour
exposure time as compared to the untreated control material (FDA/Poly Pro)
when tested in the
presence of a 5% fetal bovine serum organic soil load at 35-37 C with >90%
relative humidity.
G) Methicillin Resistant Staphylococcus aureus - MRSA (ATCC 33592)
MACTTm 3.0, demonstrated a >99.99% (>4.44 Logio) reduction of Methicillin
Resistant
Staphylococcus aureus - MRSA (ATCC 33592) following a 55 second exposure time
as
compared to the untreated control material (FDA/Poly Pro) when tested in the
presence of a 5%
fetal bovine serum organic soil load at 35-37 C with >85% relative humidity.
MACTTm 3.0, demonstrated a >99.99% (>4.57 Logio) reduction of Methicillin
Resistant
Staphylococcus aureus - MRSA (ATCC 33592) following a 2 minute exposure time
as compared
to the untreated control material (FDA/Poly Pro) when tested in the presence
of a 5% fetal
bovine serum organic soil load at 35-37 C with >88% relative humidity.
MACTTm 3.0, demonstrated a >99.99% (>4.54 Logio) reduction of Methicillin
Resistant
Staphylococcus aureus - MRSA (ATCC 33592) following a 1 hour exposure time as
compared to
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the untreated control material (FDA/Poly Pro) when tested in the presence of a
5% fetal bovine
serum organic soil load at 35-37 C with >90% relative humidity.
Anti-Fun2a1 Test Results
H) Aspergillus niger (ATCC 6275)
The following protocol for data analysis described above for the bacterial
studies was
utilized in evaluating the effectiveness of MACTTm 3.0, samples against this
fungal strain.
MACTTm 3.0, demonstrated no reduction of Aspergillus niger (ATCC 6275)
following a
5 minute exposure time as compared to the untreated control material (FDA/Poly
Pro) when
tested in the presence of a 5% fetal bovine serum organic soil load at 35-37 C
with >90%
relative humidity.
MACTTm 3.0, demonstrated a 64.5% (0.45 Logio) reduction of Aspergillus niger
(ATCC
6275) following a 1 hour exposure time as compared to the untreated control
material (FDA/Poly
Pro) when tested in the presence of a 5% fetal bovine serum organic soil load
at 35-37 C with
>90% relative humidity.
The present invention contemplates modifications as would occur to those
skilled in the
art. It is also contemplated that a variety of materials incapable of
surviving intimate contact
with a molten phase at elevated temperatures can survive such processing by
first being
incorporated into an appropriate carrier material as disclosed herein, and
that such variation of
the present disclosure might occur to those skilled in the art without
departing from the spirit of
the present invention. All publications cited in this specification are herein
incorporated by
reference as if each individual publication was specifically and individually
indicated to be
incorporated by reference and set forth in its entirety herein.
While the disclosure has been illustrated and described in detail in the
figures and
foregoing description, the same is to be considered as illustrative and not
restrictive in character,
it being understood that only selected embodiments have been shown and
described and that all
changes, modifications and equivalents that come within the spirit of the
disclosures described
heretofore and/or defined by the following claims are desired to be protected.
In addition, all
41
CA 02842245 2014-01-15
WO 2013/012797 PCT/US2012/046906
publications cited herein are indicative of the level of skill in the art and
are hereby incorporated
by reference in their entirety as if each had been individually incorporated
by reference and fully
set forth.
42
