Note: Descriptions are shown in the official language in which they were submitted.
CA 02842222 2014-04-07
A SURFACE TREATMENT INCLUDING A HEAT LABILE COMPONENT/CARRIER
COMBINATION
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No.
13/724,500
filed on December 21,2012 which is a continuation in part of Ser. No.
13/550,165 filed on July
16, 2012, which claims the benefit of 'U.S. Provisional Patent 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 this
Application also
claims the benefit of U.S. Provisional Application No. 61/580,429, filed
December 27, 2011,
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U.S. Provisional Application No. 61/580,431, filed December 27, 2011, U.S.
Provisional >Lt")
, vcr
0
Application No. 61/580,440, filed December 27, 2011, U,S, Provisional
Application No, Cri e¨
V- N-
O
ED a
61/580,767, filed December 28, 2011, U.S. Provisional Application No,
61/580,842, filed ( V.
CD
December 28, 2011, U.S. Provisional Application No, 61/580,858, filed December
28, 2011, and 0
U.S. Provisional Application No. 61/581,225, filed December 29, 2011, all of
which are hereby 0
incorporated by reference in their entirety,
BACKGROUND
_______________________________________________________________________________
0
The terms paints, coatings, stains, varnishes, sealants, films, inks, and the
like describe
0
several types of formulations applied to surfaces to protect and/or provide
aesthetic qualities to 0' SEMI.
the surfaces, Inks can additionally provide images and/or information. The
present disclosure
relates to formulations in the form of paints, coatings, stains, varnishes,
sealants, films, inks, and
the like (collectively, "surface treatments") which include a heat labile
component added to
impart a particular property to a surface to which a surface treatment is
applied. The heat labile
components include components which decompose and/or volatilize at
temperatures greater than
ambient temperatures. hi the surface treatments disclosed, a heat labile
component/carrier
combination is utilized to prevent decomposition and/or volatilization of the
heat labile
component at elevated temperatures incurred during application or subsequent
thereto. The use
of a heat labile component/carrier combination is particularly useful in a
surface treatment which
experiences elevated exposure temperatures either during a processing, curing
or drying stage or
which experiences elevated service temperatures after application because of
the treated
surface's environment. Examples of elevated exposure temperatures include, but
are not limited
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CA 02842222 2014-04-07
to drying temperatures, application temperatures, curing temperatures, and/or
temperatures
incurred during the surface treatment's service (collectively, "elevated
exposure temperatures").
The inclusion of a heat labile component/carrier combination into a surface
treatment can
provide important properties to a treated surface. For example, if the heat
labile component is a
biocide, such treated surfaces treated with a surface treatment containing a
biocide/carrier
combination 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
targeted organisms
(including bacteria, fungi, algae, viruses, and the like) which contact the
surface. Surfaces can
include porous and nonporous surfaces. Examples include, but are not limited
to metal; wood;
polymer, fabric, including woven and nonwoven fabrics; ceramic, glass,
composite, masonry,
stone; and other surfaces. Such surfaces find particular uses where a need
exists to create
surfaces on furniture, equipment, and 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
gradient across the applied surface leading to resistant strains, a surface
treated with a surface
treatment/biocide/carrier combination having a uniform distribution of the
surface treatment
including a biocide therein, lacks a concentration gradient and at proper
levels minimizes the
formation of resistant strains. In addition, performance of this treated
surface is not dependent
on whether a surface disinfectant was or was not applied according to
established procedures,
The ability to provide and maintain such substantially sterile coated surfaces
and minimize the
formation of resistant strains of microorganisms is particularly important in
a host of applications
involving surfaces we routinely touch and which contact the various fluids we
come in contact
with on a daily basis, The ability to maintain substantially sterile surfaces
is particularly
important in today's hospital, school, and home environments and in related
fields. The use of a
heat labile component/carrier combination allows a heat labile component to be
incorporated into
a surface treatment which is exposed to elevated temperatures at the
application stage or
subsequent to application.
Stability of the heat labile component can be important during the surface
treatment
processes and the use of the surface treated article/object. Many surface
treatments used to coat
or treat surfaces, artiele.s, synthetic fabrics, and the like, are subjected
to elevated temperatures to
either cure the surface treatment, to modify the surface in some way, or to
reduce the drying
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CA 02842222 2014-04-07
time. Depending on the surface treatment and the surface treated, such
processing temperatures
typically range from about 65 C to about 500 C. For a surface
treatment/biocide combination
to be successfully applied utilizing standard methods, the biocide must have
sufficient thermal
stability to survive the elevated temperatures during the processing step.
Currently only a
limited number of biocides have been successfully incorporated into surface
treatments which
must be applied and maintained at substantially ambient temperatures.
Subjecting these
compositions to elevated temperatures has typically inactivated the biocide
included in the
surface treatment.
In addition, some surfaces experience elevated temperatures above the
biocide's
3.0 decomposition temperature (or the decomposition temperature of other
heat labile compounds)
for periods of time after application of the surface treatment. For example, a
dark painted
surface exposed to sunlight for extended periods of time can reach
temperatures above the
biocide's decomposition temperature (80 C). Stove tops and interiors of
microwave ovens
similarly periodically reach elevated temperatures during their normal usage.
What is needed is
a range of surface treatment/heat labile component/carrier 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 selected to fulfill a specific
need, without regard to
whether or not the heat labile component alone has sufficient thermal
stability to survive the
necessay.processing involved with application/curing/or drying or service,
Further, methods are
needed for producing surface treatments derived from such surface
treatment/heat labile
component/carrier compositions, wherein the heat labile compound's necessary
properties are
maintained following one or several exposures of the article/object to
elevated temperatures.
The current disclosure addresses these needs,
3
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SUMMARY
In its broadest form, the present disclosure provides for a surface treatment
having an
exposure temperature and including a heat labile component adsorbed on a
carrier. The heat
labile component has a decomposition temperature, and the surface treatment's
exposure
temperature is greater than or equal to the heat labile component's
decomposition temperature.
The surface treatment is capable of experiencing its exposure temperature
without decomposition
of the heat labile component. The exposure temperature can be a processing
temperature the
surface treatment experiences during the treatments application or a service
temperature, a
temperature the treatment experiences following its application. In some
applications a surface
is typically treated with a surface treatment /heat labile component/carrier
combination, and
subjected to an elevated temperature. The elevated temperatures can occur in
an effort to cure,
drY, or otherwise modify the surface's properties or appearance or as a result
of the
environmental conditions the surface is exposed to. In these applications
exposure of a heat
labile component to the elevated temperatures without being adsorbed on a
carder would cause
the heat labile component to decompose or volatilize, Failure of an un-
adsorbed heat labile
component to survive can result in inactivation, decomposition, reaction,
volatilization and the
like, depending on the component's heat labile nature,
Examples of surface treatments include, but are not limited to, paints,
coatings, stains,
varnishes, sealants, films, inks, and the like, further including a one or
more components that
render treated surface toxic to and relatively free from a range of disease
and infection causing
microorganisms. For surface treatments that are subjected to elevated
temperatures and which
require heat labile components, the heat labile component can be adsorbed onto
a carrier particle
and the heat labile component/carrier combination utilized in the surface
treatment, Adsorption
onto the carrier particle substantially increases the thermal stability of the
heat labile component
and allows the heat labile component to survive repeated exposures to elevated
temperatures
above decomposition and/or volatilization temperatures. The surface treatment
compositions can
be a solid, a liquid, or a combination thereof, Useful heat labile components
include, but are not
limited to, a wide range of biocides, repellents, UV stabilizers, fragrances,
and the like, which
suffer decomposition, volatilization, or a combination thereof, upon normal
exposure to an
elevated temperature. The compositions disclosed herein are typically exposed
to elevated
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CA 02842222 2014-04-07
temperatures as part of an application process (processing temperatures) or
subsequent to the
surface treatment's application through the surfaces environment (service
temperatures).
A suitable carrier is typically a porous material which is stable and remains
solid at the
processing temperature (including an elevated temperature) upon which a
sufficient amount of a
heat labile component can be adsorbed, Certain carriers can have a relatively
low thermal
conductivity to minimize the transfer of heat into the particle. Carriers can
be porous inorganic
or organic in nature. Based on current work, examples of inorganic carriers
include porous silica
particles whereas examples of organic carriers include porous organic
polymers. Because some
heat labile components are not compatible when directly mixed, the loading of
a single heat
labile component onto a single carrier frequently provides improved results,
and the use of a
multiple of heat labile components/carriers avoids this potential problem. The
carrier particles
can be any size that doesn't interfere with application of the surface
treatment and subsequent
use of the treated surface, or the surfaces aesthetic qualities. Carrier
particles as small as 1
micron have been utilized to provide effective results. A more detailed
discussion of carriers
is will follow in the next section,
A further aspect of the present disclosure also provides a method for
preparing a treated
surface with a surface treatment/heat labile component/carrier combination.
One aspect of the
method involves the steps of: (a) applying a composition including a surface
treatment and a heat
labile component adsorbed on a carrier to a surface to form a treated surface,
wherein the surface
treatment has a processing or exposure temperature and the heat labile
component has a
decomposition temperature; (b) subjecting the treated surface to a processing
temperature for a
time sufficient to cure, dry, or otherwise modify the surface treatment; and
(c) cooling the treated
surface to form a protected surface including the surface treatment containing
the heat labile
component adsorbed on the carrier, where: (i) the processing or exposure
temperature is greater
than the heat labile component's decomposition temperature; (ii) the heat
labile component
adsorbed on. the carrier is distributed across the treated surface, and (iii)
the heat labile
component possesses properties, and the treated surface exhibits the
properties derived from the
heat labile component, The composition including a surface treatment and a
heat labile
component adsorbed on a carrier can be a solid, a liquid, or a combination
thereof, A still farther
aspect of this disclosure involves surfaces treated with a surface treatment
including a heat labile
component/carrier combination that has passed through an elevated temperature
either during
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CA 02842222 2014-04-07
application of the surface treatment or subsequent to application. The heat
labile components
involved possess a property that is exhibited by the treated surface
containing the heat labile
component/carrier combination following exposure to an elevated temperature.
A heat labile component includes a component that decomposes, reacts, or
volatilizes
when exposed to an elevated temperature changing Or destroying its properties
or removing the
component from the treated surface. Suitable heat labile components can
include materials
having a wide range of properties. Examples of heat labile components include,
but are not
limited to bacteriocides, fungicides, algaecides, viruscides, insecticides,
antibiotics, enzymes,
repellents (animal and insect), herbicides, pheromones, molluscicides,
acaricides, raiticides,
rodenficides, fragrances, and the like, Incorporation of these components in a
surface treatment
allows the properties associated with the component to be exhibited on or in
the vicinity of the
treated surface, even if during the processing of the surface or during its
service, the treated
surface is exposed to an elevated temperature sufficient to have caused
decomposition or
removal of the heat labile component without the carrier's presence.
A still further aspect of this present disclosure involves a method for
preparing a surface
treatment that includes the steps of providing a surface treatment; providing
a heat labile
component adsorbed on a carrier; and combining the heat labile component
adsorbed on a carrier
and the coating formulation. The surface treatment can be a coating
formulation selected from
the group consisting of paint, a coating, a stain, a varnish, a sealant, a
film, and an ink. The heat
labile component can be selected from the group consisting of a bactericides,
fungicides,
insecticides, rodenticides, volatile fragrances (including animal and insect
repellents), and
combinations thereof, In one example, the use of a volatile component/carrier
combination in a
printing ink of the type used in offset presses where heat is used to rapidly
dry the ink is
particularly useful, enabling certain pages or portions thereof to exhibit a
particular fragrance or
other property.
A still further aspect of the current disclosure involves a surface having a
surface
treatment including a heat labile component adsorbed on a carrier, where (a)
the surface
treatment has an exposure temperature; (b) the heat labile component has a
decomposition
temperature, and (c) the surface treatment's exposure temperature is > to the
heat labile
component's decomposition temperature; and the surface treatment is capable of
experiencing
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CA 02842222 2014-04-07
the exposure temperature without decomposition of the heat labile component.
The surface
treatment's exposure treatment can include a processing temperature or a
service temperature.
The heat labile component can be adsorbed on the carrier by contacting the
carrier with a .
liquid form of the heat labile component. If heat labile component is a liquid
at a temperature
below its decomposition temperature it can be used directly in its liquid
form. If the heat labile
component is a solid at the temperature necessary for placing on the carrier,
it can be dispersed
or dissolved in a solvent, prior to loading onto the carrier. Any remaining
solvent or dispersant
can be removed or evaporated to provide solid and flow-able carrier particles
containing the heat
labile component. If the solvent is compatible with the surface treatment
formulation in the
3.0 amount present, the solvent-wet loaded carrier particle can be used
directly without drying. For
a carrier to be loaded with a dispersion of the heat labile component, the
component's particle
size should be smaller than the carrier's pores being entered.
Surfaces suited for application of the surface treatments described herein and
which
require and/or experience an elevated temperature, include any surface which
can be heated to
facilitate curing, drying, or modification of the treated surface, As far as
the surface is
concerned, it must be capable of accepting the surface treatment, and any
subsequent period of
exposure to an elevated temperature. Examples of surfaces contemplated
include, but are not
limited to contiguous surfaces, mesh surfaces, porous surfaces, nonporous
surfaces, woven
surfaces, and the like. Examples of materials suitable for use as surfaces
include, but are not
N limited to, metal, polymeric materials, natural materials such as
cellulose, cotton and other
natural fibers. The combination of a surface and a surface treatment
containing a heat labile
component/carrier combination generally results in a useful property being
imparted to the
treated surface by the surface treatment, The presence of the heat labile
component/carrier
combination within the Surface treatment does not generally alter the surface
treatment's
appearance upon application, but the treated surface typically demonstrates
new properties based
on the heat labile components presence, Surfaces containing a heat labile
component/carrier
combination can remain sterile, kill microorganisms and the like upon contact,
and prevent the
spread of microorganisms though serial contact by other organisms. Surfaces
containing a
repellent, such as an animal and/or insect repellent, can maintain a region
about the surface free
of animals, insects and the like. A surface containing an insecticide can kill
insects sensitive to
the insecticide utilized that contact the treated surface, A surface
containing a combination
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CA 02842222 2014-04-07
pheromone/insecticide can attract pheromone sensitive insects and upon
contacting the surface
kill insects sensitive to the insecticide utilized,
Surfaces utilizing surface treatments containing heat labile biocides are
particularly
useful for controlling microorganisms which are spread by direct serial
contact or a combination
of serial contact and exposure to aerosols from sneezing and coughing and
direct contact.
Surface treatments including one or more enzymes can effect chemical
transformations upon
contact, thus decomposing pesticides, nerve gases, and the like. Finally,
surface treatments can
be designed to exhibit a single property or a plurality of properties.
Surfaces which will benefit
from the protection described herein include porous and nonporous surfaces.
Some examples of
surfaces which can be protected include, but are not limited to metal; wood;
polymer; fabric,
including woven and nonwoven fabrics; leather, ceramic, glass, drywall &
ceiling tile material,
composite, masonry, stone; and other surfaces.
A still further aspect of the present disclosure involves a surface including
a surface
treatment capable of killing and preventing the proliferation of a range of
microorganisms that
cause disease and/or infection. Such surface treatments include One or more
heat labile biocides
adsorbed onto one or more carrier particle enabling the one or more biocides
to maintain their
activity against a broad range of microorganisms even after experiencing
periods at an elevated
temperature. Other heat labile component/carrier combinations can similarly be
included in the
surface treatments.
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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.
As used in the specification and the claims, the singular forms "a," "an" and
"the" include
plural referents unless the context clearly dictates otherwise, Ranges may be
expressed in ways
including from "about" one particular value, and/or to "about" another
particular value. When
such a range is expressed, another implementation may include from the one
particular value
and/or to the other particular value. Similarly, when values are expressed as
approximations, for
example by use of the antecedent "about," it will be understood that the
particular value forms
another implementation. It will be further understood that the endpoints of
each of the ranges are
significant both in relation to the other endpoint, and independently of the
other endpoint.
"Optional" or "optionally" means that the subsequently described event or
circumstance
may or may not occur, and that the description includes instances where said
event or
circumstance occurs and instances where it does not. Similarly, "typical" or
"typically" means
that the subsequently described event or circumstance often though may not
occur, and that the
description includes instances where said event or circumstance occurs and
instances where it
does not.
Broadly considered, the method disclosed herein, generally involves subjecting
a.
formulation containing heat labile component/carrier combination to a
processing step carried
out at processing temperatures above the component's decomposition,
volatilization, and/or
inactivation temperature without the component's decomposition, evaporation,
and/or
inactivation. Examples of suitable formulation include, but are not limited to
paints, coatings,
Stains, varnishes, sealants, films, inks, and the like, individually and
collectively referred to
herein as "surface treatments" which experience exposure to an elevated
temperature related to
the treatment's application or derived from the treated surface's environment.
Decomposition,
evaporation, or inactivation is avoided by first adsorbing the heat labile
component onto a carrier
prior to exposure to an elevated temperature, by minimizing the magnitude of
elevated
CA 02842222 2014-04-07
temperature or by limiting the exposure time. An elevated temperature is a
temperature at or
above a heat labile component's decomposition or volatilization temperature.
Suitable carriers
are stable to the processing conditions, have the ability to load sufficient
heat labile component,
and can have a generally low thermal conductivity. The method generally
provides for
combinations including one or more heat labile components that could not
otherwise be
processed without transformation including decomposition. Because some
combinations of heat
labile components become intractable upon mixing, interfering with the loading
process, loading
a single component into a single carrier offers a way to avoid such
incompatibilities. This has
provided superior results, particularly where multiple heat labile components
are incompatible.
1.0 The use of multiple components in multiple carriers has proven
advantageous in creating
combinations of components in a surface treatment, even when none of the
components were
heat labile, but otherwise formed intractable combinations when mixed without
first being
loaded into a carrier.
Heat labile components can additionally involve materials that are volatile at
a surface
treatment's processing temperature and unless incorporated into a carrier
would vaporize,
providing a surface without the volatile component. Incorporation of the
volatile component into
a carrier prior to incorporation of the volatile component/carrier combination
into the surface
treatment has prevented substantial volatilization during processing of
surface treatments
containing volatile components. Volatile fragrances loaded into a carrier can
be successfully
incorporated into a range of surface treatments to provide treated surfaces
capable of slowly
emitting the fragrance over a long period of time. Additionally, volatile
materials such as animal
and insect repellants can be successfally loaded into surface treatments
rendering them capable
of repelling animals or insects for long periods of time.
Coil coating provides one example in which elevated temperatures are used to
cure a
coating or evaporate a solvent. Coil coating is a linear process for applying
a protective or
decorative organic coating to flat metal sheets or strips. Although methods
have been developed
for applying water-based, solvent-based, and powder coatings, water and
solvent-based coatings
are more commonly applied. Typically, a metal strip is passed through a
coating application
station where rollers coat one or both sides of the strip. The strip passes
through an oven where
the coatings are dried and cured. Upon leaving the oven the strip is cooled,
often with water, and
dried. For some applications, a primer is applied before a final topcoat is
applied. The coil
CA 02842222 2014-04-07
coating process is an efficient method for coating large amounts of metal
surface quickly, but
exposes the uncured coating to temperatures as high as 300-500 C. Such
elevated temperatures
can cause rapid decomposition or volatilization of heat labile components. The
use of heat labile
component/carrier combinations allows for incorporation of the heat labile
component into the
coating without decomposition or volatilization,
In addition, certain paints, stains, varnishes, sealants, films, inks
containing viruscides,
with or without additional biocides can be prepared and applied without the
use of the carrier
technology, for surface treatments not requiring an elevated temperature
and/or for surface
treatments not experiencing elevated temperatures during the surface
treatment's service. One
example of such a surface coating is a standard latex paint used for an.
interior application.
Depending on the nature of the viruscide, cationic or nonionic latexes are
sometimes selected.
In the discussion which follows, specific compositions and methods will be
described
with regard to one or more heat labile components. It is understood that other
heat labile
components discussed herein and not mentioned herein can be utilized similarly
to provide a
variety of surface treatments and treated surfaces which contain the other
heat labile components
distributed across the surface. Surface treatments can be applied by brushing,
spraying,
spreading, powder coating, rolling, dipping, and the like. A variety of
printing methods,
including ink jet printing and offset printing can also be utilized.
A first aspect of the present disclosure involves a method for the
incorporation of'a heat
labile component, such as a biocide, into a heat curable surface treatment
such as, for example, a
polyurethane or epoxy paint followed by a curing step wherein the uncured
treated surface is
exposed to an elevated temperature to effect curing of the surface treatment,
without
substantially decomposing the biocide, Prior to incorporation, the biocide is
adsorbed onto a
carrier. As noted above, suitable carriers are porous materials capable of
remaining solid at any
necessary processing temperatures and adsorbing a sufficient amount of a
biocide. The curing
step 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, but for a time
sufficient to allow the surface treatment to cure. The processing temperature
is typically
determined by the surface treatments properties and the nature of the
processing step. Once a
processing temperature has been determined, combinations of
polymer/carrier/biocide can be
11
CA 02842222 2014-04-07
provided and. maintained at that temperature for varying amounts of time to
determine a
maximum processing time.
Surface treatments can involve paints, coatings, stains, vanishes, dyes,
sealants, films,
inks, and the like. The terms utilized here are not meant to be restrictive,
but are only used to
illustrate the nature of the present disclosure. The terms frequently have
overlapping meanings.
For example, paint or stain can additionally be formulated to function as a
sealant, A varnish can
include a colorant, and provide both a colorant, and a film. With that
understanding, examples of
each of these surface treatments will be considered.
Paints and coatings:
Paints are typically applied to a surface to alter a surface's appearance,
whereas a coating
is typically a covering applied to a surface to alter the surface's properties
such as for example,
the surface's appearance, water permeability, corrosion resistance, wear or
scratch resistance,
and the like. Today's paints typically also serve to both alter a surfaces
appearance and as a
coating and are generally water-based (latex), oil-based, or powder coatings.
Latex and oil-based
paints are generally applied at ambient temperatures (in the order of 7 C to
35 C, but after film
formation can remain stable to temperatures as high as about 80 C or higher,
temperatures
sometimes achieved in periods of direct sunlight. Latex paints can be anionic,
cationic, or non-
ionic. Some oil-based paints and powder coatings undergo a heat curing process
that results in a
surface having a finished surface coating. Paints which undergo a curing step
at elevated
temperatures typically fall into two classes: thermoset and thermopla,stics.
Thermoplastics are
generally applied as a powder, and heated above the polymer's glass transition
temperature to
form a melt, which upon solidification forms a coating. Powdered thermoset
coatings, typically
melt in a similar manner, but also further polymerize to form a tough coating
upon cooling. The
heat labile component/carrier combination can be included in latex and/or oil
base paints in the
same manner as other solids such as pigments and the like are added.
Alternatively, the heat
labile component/carrier combination may be added to paint prior to
application by the end user
or by a of different heat labile componendcanier combinations can be added to
provide
combinations that would not be possible without employing a carrier system,
because of the
interaction of many heat labile components. The ability to load a paint with
several otherwise
incompatible components provides a benefit even to paint components that are
not heat labile.
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CA 02842222 2014-04-07
A powder coating is a coating that is applied as a free-flowing, dry powder.
Unlike most
other paints and coatings, a powder coating does not require a solvent to keep
the binder and
filler parts in a liquid suspension form. The powder is typically applied
electrostatically and is
then cured under heat to allow it to flow and form a "skin". There are two
main categories of
powder coatings: thermosets and thermoplastics. The thermosets incorporate a
cross-linking
agent into the formulation, When the powder is baked, the cross-linking agent
reacts with other
chemical groups in the powder to polymerize, improving the performance
properties. The
thermoplastic coating does not typically undergo any additional reactions
during the baking
process, but only melts and flows over the surface to form the final coating,
Powder coating are
primarily used for coating metals, such as aluminium extrusions used for
appliance cabinets, and
automobile and bicycle parts, Some powder coating technologies can be used to
coat other
materials, such as MDF (medium-density fibreboard). The most common polymers
used in
powder coatings are polyester, polyurethane, polyester-epoxy (known as
hybrid), straight epoxy
(fusion bonded epoxy) and acrylics. Powder coatings material can be
manufactured by mixing
polymer granules with hardener, pigments and other powder ingredients in an
extruder, heating
the mixture and extruding the melted mixture to provide a flat, cooled ribbon
that is broken into
small chips. The chips are milled and sieved to provide a fine powder. A heat
labile
component/carrier combination can be added either prior to extrusion or
following extrusion
before milling or after milling and sieving, if the carrier particles are
properly sized. The powder
coating process typically involves at least three steps: I) preparation or pre-
treatment of the
surface, (2) application of the powder, and (3) curing.
Liquid formulations of paints and coatings can also be applied and then cured
at an
elevated temperature. Curing involves driving off remaining solvent and in
certain instances,
additional polymerization/cross-linking. For latex and oil-base coatings, a
heat labile
component/carrier combination can be added at any stage of the formulation,
even just prior to
application, with proper mixing. Particle size of the carrier particles should
be in the same range
of any other solid components, such as for example pigments and the like.
Paints and coatings
containing selected heat labile component/carrier combinations can, after
exposure to an elevated
temperature, exhibit properties derived from a heat labile component that
includes bacteriocides,
fungicides, algaecides, viruscides, insecticides, antibiotics, enzymes,
repellents (animal and
insect), herbicides, pheromones, molluscicides, acaricides, miticides,
rodenticides, fragrances,
13
. AA
CA 02842222 2014-04-07
and combinations thereof. Exposure to an elevated temperature can occur during
application or
during service of the surface treatment.
Further paints and coatings suitable for inclusion of biocides, including
biocide/carrier
combinations include, but are not limited to polyurethane dispersions (PUD's),
silicone, silane,
and siloxane dispersions, silicone modified polyurethanes, and combinations
thereof, and
silicone resins. These paints and coatings can be formulated as clear coats or
with pigments,
and be applied by brush, roller, spray, and other known application methods.
The clear coats can
be applied over existing surfaces in good repair. Other surface treatments may
require some
surface preparation, repair, and/or priming before application.
Stains & Varnisihes:
Stains are typically penetrating formulations utilized to alter the color of a
surface,
whereas varnishes both impart a color and provide a coating. Both stains and
varnishes can be
formulated to cure at elevated temperatures forming further cross-linking and
altering the
durability of the surface. More commonly stains and varnishes are cured at
ambient
temperatures, but frequently during the surface's service, are exposed to
elevated temperatures.
Incorporation of a heat labile component in a carrier helps avoid
decomposition and/or
volatilization of any heat labile component incorporated in the stain or
varnish. Like paints and
coatings, the heat labile component/carrier combination can be added to the
formulation at the
same stage that other solids arc added, such as pigments and the like. Stains
and varnishes
containing selected heat labile component/carrier combinations can, after
exposure to an elevated
temperature, exhibit properties derived from a heat labile component that
includes bacteriocides,
fungicides, algaecides, viruscides, insecticides, antibiotics, enzymes,
repellents (animal and
insect), herbicides, pheromones, molluseieides, acaricides, mitieides,
rodenticides, fragrances,
and combinations thereof, The clear coats described above under paints and
coatings, may be
considered as varnishes in some applications.
Sealants:
Sealants can be colored or clear and are typically utilized to make a surface
impervious to
a liquid such as, for example, water. Sealants are frequently applied to
masonry, wood, and
other porous surfaces. The incorporation of a heat labile component/carrier
combination into a
14
CA 02842222 2014-04-07
sealant can be carried out in the same manner as described above for a paint
or coating. Masonry
surfaces provide more challenges regarding techniques that can be used to heat
the surface and
surface treatment. Infrared lamps and convection heaters, and combinations
thereof have
typically been used. Like paints and coatings, sealants can be latex, oil-
based, and, depending on
the surface, powder. The same techniques used to formulate paints and coatings
can typically be
utilized to formulate sealants. Sealants containing selected heat labile
component/carrier
combinations can, after exposure to an elevated temperature, exhibit
properties derived from a
heat labile component that includes bacteriocides, fungicides, algaecides,
viruscides,
insecticides, antibiotics, enzymes, repellents (animal and insect),
herbicides, pheromones,
molluscicides, acaricides, miticides, rodenticides, fragrances, and
combinations thereof,
Films;
Films can be prepared with a variety methods including the application of a
solution or
shiny, the curing of a powder coating, extrusion and the like. The resulting
film is a thin
membrane, skin, covering, or coating. Methods for applying a solution or
slurry to form a film
are similar to those used to apply paint or a coating. Solutions utilized for
form films can be
prepared by dissolving a polymer in an appropriate solvent that can evaporate
upon application
to leave a polymer film. Latexes can be similarly prepared and transformed
into a film. Finally,
polymer films can also be prepared from powders, in the same manner as powder
coatings. Spin
coating has developed as a method for applying a variety of films on to a
silica wafer and the
like. For some applications, a single film layer can be applied, For other
applications, multiple
layers of the same or a different film material can be applied. Films can be
prepared from a wide
range of materials including organic and inorganic polymers, ceramics, and the
like.
Films, including a heat labile component which will experience an elevated
temperature
during formation or during later service, can benefrt from the utilization of
a heat labile
component/carrier combination to protect the heat labile component at the
elevated temperatures.
In addition, the use of components loaded onto different carriers can enable
films to be prepared
from otherwise incompatible components, thus providing novel properties.
In :
CA 02842222 2014-04-07
Inks are typically applied to surfaces to impart an image and/or information.
Although
many inks cure at ambient temperature and conditions, other kinds of ink, such
as those used in
high speed printing presses such as lithograph or offset presses and other
applications are heat
cured to set the ink. In printing, it's often necessary to set the ink to
avoid smearing as the
printed web is cut and folded to form signatures. A variety of approaches have
been utilized to
cure/dry printing inks. The printed paper web in a lithograph or offset press
typically passes
between gas burners at a fast rate to rapidly dry the ink at relatively high
temperatures (but below
the paper's ignition temperature) within a few seconds. Ink jet technology has
advanced and
provides, yet another method for applying ink to a surface. Some inks designed
for nonporous
surfaces are also formulated to be stable to high temperatures, curing in the
range of about 150 to
about 300 C and remaining stable to temperatures ranging from about 300 to
about 800 C. The
ability to modify such an ink with a heat labile component requires the heat
labile component to
be formulated in a manner to withstand the heating and curing conditions.
Formulating such an
ink with a heat labile component/carrier combination provides this necessary
increased thermal
stability,
One type of heat cured ink utilized for garments includes Plastisol inks, a
family of inks
composed primarily of two ingredients, PVC resin (a white powder) and
plasticizer (a thick,
clear liquid). The Plastisol inks must be heated cured in the range of 143-166
C to properly
bond to a fabric, Tas containing selected heat labile component/carrier
combinations can, after
exposure to an elevated temperature, exhibit properties derived from a heat
labile component that
includes bacteriocides, fungicides, algaecides, viruscides, insecticides,
antibiotics, enzymes,
repellents (animal and insect), herbicides, pheromones, molluscicides,
acaricides, miticides,
rodenticides, fragrances, and combinations thereof.
Heat Labile 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, or which are incompatible with one or more other
components of the
formulation. A majority are biocides which have limited heat stability that
prevent their
incorporation into polymers by standard methods.
16
CA 02842222 2014-04-07
Biocides generally suitable for processing according to the current disclosure
include, but
are not limited to: Acetylcamitine, Acetylcholine, Aclidinium bromide,
Acriflavinium chloride,
Agelasine, Aliquat 336, Ambenonium chloride, Ambutonium bromide, Aminosteroid,
Anilitrium
chloride, Atracurium besilate, Benzalkonium chloride, Benzethoniurn chloride,
Benzilone,
Benzododecinium bromide, Benzoxonium chloride, Benzyltrimethylamnaonium
fluoride,
Benzyltrimethylammonium hydroxide, Bephenium hydrorynaphthoate, Berberine,
Betake,
Bethanechol, Bevonium, Bibenzonium bromide, Bretylium, Bretylium for the
treatment of
ventricular fibrillation, Burgess reagent, Butylscopolamine, Butyrylcholine,
Candocuronium
iodide, Cra-bachol, Carbethopendecinium bromide, Carnitine, Cefluprenam,
Cetrimonium,
o 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, Decarnethonium, 3-Dehydrocamitine,
Demecarium
bromide, Denatonium, Dequalinium, Didecyldimethylatnxnonium chloride,
Ditnethyldioctadecylammonami chloride, Diraethylphenylpiperazinium,
Dimethyltubocurarinium chloride, Di0C6, Diphernanil metilsulfate, Diphtbamide,
Diquat,
Distigmine, Domiphen bromide, Doxaenritun chloride, Echothiophate,
Edelfosirie,
Edrophonium, Emepronium bromide, Ethidium bromide, EufLavine, Fenpiverinium,
Fentonium,
Gallarnine triethiodide, Gantacurium chloride, Glycine betaine aldehyde,
Glycopyrrolate, Guar
hydroxypropyltrimoniurn chloride, Hemicholinium-3, Hexafluronium bromide,
Hexamethonium,
Hexocyclium, Homatropint, Hydroxyetlaylpromethazine, Ipratropium bromide,
Isometamidium
chloride, Isopropamide, Jatrorrhizine, Laudexium metilsulfate, Lucigenin,
Mepenzolate,
Methacholine, Methantheline, Methiodide, Methscopolamine, Methylatropine,
Methylscopolamine, Metocurine, Ivliltefosine, mpp+, Muscarine, Neuritic,
Obidoxime,
Otilonium bromide, Oxapium iodide, Oxyphenonium bromide, Palmatine,
Pancuronium
bromide, Pararosaniline, Pentarnine, Penthienate, Pentolinium, Perifosine,
Phellodendrine,
Phosphocholine, Pinaveriurn, Pipecuronium bromide, Pipenzolate, Poldine,
Polyquaterniura,
Pralidoxime, Prifiniurn bromide, Propantheline bromide, Prospidiinn chloride,
Pyridostigmine,
Pyrvinium, Quatemitun-15, Quinapyraraine, Rapacuroniuna, Rhodamine B,
Rocuronium
bromide, Safranin, Sanguinarine, Stearalkonium chloride, Succinylmonocholine,
Suxamethonium chloride, Tetra-n-butylammonium bromide, Tetra-n-butylaramonium
fluoride,
17
CA 02842222 2014-04-07
Tetrabutylammonium hydroxide, Tetrabutytammonium tribromide,
Tetraethylammonium,
Tetraethylammonium bromide, Tetramethylammonium chloride, Tetramethylammonium
hydroxide, Tetramethylammonitun pentafluoroxenate, Tetraoctylarnmonium
bromide,
Tetrapropylammoniura perruthenate, Thiazinatnium metilsulfate, Thioflavin,
Thonzonium
bromide, Tibezonium iodide, Tiemonium iodide, Timepidium bromide, Trazium,
Tridihexethyl,
Triethylcholine, Trigonelline, Trimethyl ammonium compounds, Trimethylglycine,
Trolarnine
salicylate, Trospium chloride, Tubocurarine chloride, Vecuronium bromide,
One group of heat labile biocides includes, but is not limited to, quaternary
amines and
antibiotics. Some specific preferred heat labile biocides include, but are not
limited to, N,N-
1.0 didecyl-N-methyl-N-(3-trunethoxysilylpropyl)ammonitun chloride, cetyl
pyridinium chloride,
N,N-bis(3-aminopropyl)dodecylamine, N-octyl-N-decyl-N-dimethyl-ammonium
chloride, N-di-
octadecyl-N-ditnethyl-ammonium chloride, and N-didecyl-N-dimethyl-ammonium
chloride.
Some specific antibiotics include, but are not limited to arnoxicillin,
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 benzisotbiazolinone 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, herbicides
rodenticides, animal and
insect repellents, and the like. Fragrances and other volatile heat labile
components can similarly
be incorporated into the various polymers at elevated temperatures.
The Carriers:
Suitable carriers are typically porous materials capable of adsorbing the heat
labile
biocide, remaining in a solid form during processing, and maintaining the
biocide in the adsorbed
state during processing. Although carriers studied thus far have had a
substantial porosity and a
high surface area (mostly internal), any level of surface area can be
utilized. The amount of
surface area primarily affects the amount of carrier needed to provide a
specific desired effect,
An additional property suitable for a carrier is a relatively low thermal
conductivity. Finally,
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CA 02842222 2014-04-07
carriers can be selected to alter the color and/or appearance of a treated
surface, if desired, or
provide a surface unaltered by the carrier's presence.
Inornanie Carriers: As a class, platy minerals generally perform well as
carrier
materials, Minerals suitable for use as carriers 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. At this time, substantial testing has been carried out
with silica (silicon
dioxide) as the carrier. Mixtures of carriers can also be utilized.
manic Carriers: A further class of carriers that has proven suitable includes
polymeric carriers. Preferred polymeric carriers remain solid at elevated
temperatures and are
capable of loading sufficient quantities of heat labile component. One example
of polymeric
carriers includes cross-linked macroreticular and gel resins, and combinations
thereof such as the
so-called plum pudding polymers, An example of a plum pudding resin includes a
crosslinked
macroreticular polymeric carrier containing particles of other resins within
their structure.
Suitable resins for imbedding within a macroreticular resin include other
macroreticular resins or
gel resins. Additionally, other porous or non-porous non-polymeric materials
such as minerals
can similarly be incorporated within the macroreticular resin,
Organic polymeric carriers can include polymers lacking a functional group,
such as a
polystyrene resin, or the organic polymeric carrier can have a functional
group such as a sulfortic
acid included. Generally, any added functional group should not substantially
reduce the organic
polymeric carrier's thermal stability. A suitable organic polymeric carrier
should also be able to
. load a sufficient amount of a heat labile component, and survive any
processing conditions, and
deliver an effective amount of the heat labile component to the upper regions
of the surface
treatment upon incorporation into any surface treatment system. Suitable
organic polymeric
carriers can be derived from a single monomer or a combination of monomers.
General methods for making macroreticular and gel polymers or resins 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 etrlenically
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
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CA 02842222 2014-04-07
(meth)acrylate, isobomyl (meth)acrylate, isodecyl (meth)acrylate, oleyl
(meth)acrylate, palmityl
(meth)acrylate, stearyl (meth)acrylate, hydroxyethyl (meth)acrylate, and
hydroxypropyl
(meth)acrylate; acrylarnide 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
example, N,N'-ditnethylarnino (meth)acrylate; and actylonitrile or
methacrylonitrile; and the
3.0 monomethacrylates of dialkylete glycols and polyalkylene glycols.
Descriptions for making
porous and niactoreticular polymers can be found in US, patent No. 7,422,879
(Gebhard et al.)
and U.S. patent No. 7,098,252 (Jiang etal.).
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,
iYelection of Components:
The choice of a specific surface treatment is generally made to provide a
treated surface
exhibiting one or more new and desired properties and a cost consistent with
its application.
Carriers are typically selected based-on their porosity, surface area, thermal
conductivity, and the
impact on the surface's appearance. Carriers having a low thermal conductivity
can be utilized,
but are not required, Porosity and surface area determine how much heat labile
component can
be loaded onto the carrier and generally reduces the amount of carrier
required. The thermal
conductivity is believed to contribute to how much above a heat labile
component's
decomposition temperature the polymer can be processed and how long the
processing step can
take. For example, a carrier having a high thermal conductivity may be
advantageous in
processing a polymer/heat labile component combination where the surface
treatment's
processing temperature is only slightly above the biocide's decomposition
temperature and/or the
CA 02842222 2014-04-07
processing time is relatively short. For processing temperatures well above
the heat labile
component's decomposition temperature or for processing for longer times, a
carrier having a
lower thermal conductivity may be advantageous. The selection of heat labile
component
primarily depends on the use of the polymer/heat labile component combination.
For example, if
the heat labile component is a biocide, the biocide loading can be tailored to
target specific
microorganisms or specific combinations of microorganisms, depending on the
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
repellents, and the like can be incorporated into a single polymer, depending
on. it end use and
the properties the treated surface is intended to exhibit.
The utilization of carriers in formulating surface coatings can prove useful
even when
one or more of the components loaded onto one or more carriers is not a heat
labile component.
For example, the addition of multiple components into a surface treatment can
result in
incompatibilities between the various components and between the components
and the surface
treatment formulation. By adding the various components to the surface
treatment formulation
in the form of individual component/carrier combinations, the
incompatibilities that would
otherwise result are generally avoided.
The Process:
The carrier/heat labile component combination has been produced by contacting
a carrier
with a liquid form of the heat labile component (typically a solution or a
suspension), allowing
adsorption onto the carrier to occur and evaporating any solvent to provide
the carrier/heat labile
component combination in the form of a flow-able powder, Heat labile
component/carrier
particles containing as much as 60% (by weight) heat labile component have
been prepared.
A processing temperature can be established for a surface treatment/heat
labile
component combination and a maximum processing time at the processing
temperature can be
established, before the processing is carried out. It's generally advantageous
to utilize
conventional application and processing equipment in a manner to minimize the
processing time
for the surface treatment/heat labile component combination. Generally, powder
coatings and
liquid formulations containing a heat labile component/carrier combination can
be applied and
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CA 02842222 2014-04-07
cured in any suitable manner. The elevated temperatures necessary for a curing
step can be
provided by infrared heaters, resistance heaters, ovens, solar heaters,
sunlight, radiant heaters,
gas burners, microwave, and the like. Surface treatments not requiring a heat
curing step as part
of the application can be applied and cured by standard methods and later have
the ability to
withstand elevated temperatures in the course of their service, Carrier/heat
labile component
loading into a surface treatment can run as high as about 40 wt. %
carrier/heat labile component.
For finished surface treatments where the heat labile component is a biocide,
biocide levels
within the surface ranging from about 0.25 wt.% to 10 wt.% have proven
effective against
microorganism's tested. However, both higher and lower loadings are
contemplated and will be
effective. The desired loading of a heat labile component/carrier will vary
substantially
depending on the type of heat labile component utilized and the property
intended to be exhibited
by the treated surface.
Applications Utilizing Biocidal Polymers to illustrate Utility:
Applications involving the surface treattnent/biocide combination taught
herein include, but are
not limited to a wide range of surfaces and equipment utilized in the medical
and consumer fields
including hospital, emergency treatment, first aid, and the like. The surface
treatments of this
present disclosure can be applied to a variety of surfaces found on/in
structures, articles,
containers, devices, woven/nonwoven articles, remediation materials, and the
like as well as their
components. Any product that is or could be constructed and coated with a
surface treatment
including a biocide/carrier combination, that otherwise requires processing at
an elevated
temperature, and which would benefit from the ability to limit the growth of
microorganisms can
be improved, by utilizing the polymer/biocide combinations taught herein. Some
specific
examples of structures that benefit from the application of surface treatments
include, but are not
limited to buildings, airliners, buses, trains, cruise ships, buses, and the
like. Some specific
surfaces include, but are not limited to things we touch such as: walls,
counter tops, furniture
components (e.g. a bed rail, a toilet seat, a shower stall, a sink, etc.), and
equipment (e.g. a bed
pan, a door handle, appliances, shopping cart handles, a writing instrument, a
computer
keyboard, a telephone, dental equipment, etc.) and surgical equipment In
addition, air filters
having components surface treated with a coating containing a biocide/carrier
combination can
minimize the microorganism content of the air circulating within a hospital,
an office building, a
22
CA 02842222 2014-04-07
hotel, a home, or other structure with central air handling equipment.
Finally, treated surfaces
can provide additional protection against 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.
Surface
treatments containing insecticides can be utilized to treat articles such as
siding, molding such as
baseboards, flooring, and the like to allow the killing of susceptible insects
that contact the
surface treatment/insecticide material.
Finally, the present disclosure provides for surface treatment formulations
utilizing the
carrier technology which can contain heat labile components that can be
selected from the group
io consisting of bactericides, fungicides, insecticides, rodenticides,
volatile fragrances (including
animal and insect repellents), and the like. Such surface treatment materials
are particularly
suitable for treating a variety of building materials, and for manufacturing
garbage cans,
recycling bins and other equipment designed to handle garbage, food wastes,
and the like.
Articles treated with this surface treatment formulation 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 repellents in surface
treatment materials
utilized for garbage handling equipment/articles handling and exposed to food
products can also
keep pets and wild animals away. This is particularly desirable for garbage
cans/equipment
awaiting pickup in unattended locations. Surface treatments can be selected to
provide the
appropriate level of protection and. safety to for each application, and to
avoid the leaching
substantial amounts of heat labile component into the environment.
Prenaration of the Carrier Package:
250 grams of Si02, 200 grams, 200 grams of an solution of N Bis(3-
antinopropyl)
dodecylamine chloride (as a 60% N,N Bis(3-aminopropyl) dodecylarnine chloride)
and 40 grams
of fumed silica (Si02) were combined and mixed in a high speed mixer (about I
20Orpm) for
about 2 minutes at ambient temperature to provide a flow-able powder.
Sufficient amounts of
additional dilute solutions of the N-Bis(3-arninopropyl)dodecylamine chloride
were added to
convert the flow-able powder into a wet paste. The following components were
added to the wet
paste; 20 grams T102, 20 grams of Ion pure (silver iodide coated onto 5-10
micron glass beads),
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CA 02842222 2014-04-07
30 grams of DUSOBULYLPHENOXYETHOXY 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 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-aminopropypdodecylamine 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-DIMETHYLHYDANTO1N,
(6) 3-I0D0-2-PROPYNYL BUTYL CARBAMATE,
(7) D1DECYL DIMETHYL AMMONIUM CHLORIDE,
(8) N-ALKYL (C14.50%, C12-40%, C16-10%) DIMETHYL BENZYL AMMONIUM
CHLORIDE,
(9) 1,3-DI-(HYDROXYMETHYL)-5,5-DIMETHYLHYDANTO1N,
(10) 3-(HYDROXYMETHYL)-5,5-DIMETHYLHYDANTOIN, 5,5-
DIMETHYLHYDANTOIN,
(11) 5-CHLOR0-2-METHYL-4-1SOTHIAZOLIN-3-0NE,
(12) 2-METHYL-4-ISOTHIAZOLIN-3-ONE,
(13) N-ALKYL (C14-60%,C16.30%, C12-50%, C18-5%) DIMETHYL BENZYL
AMMONIUM CHLORIDE,
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CA 02842222 2014-04-07
(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,
(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-DIMETHYLHYDANTOM,
(22) 1,3-DIBROM0-5,5-DIMETHYLITYDANTOIN,
(23) BORIC ACID
(24) N-TRICHLOROMETHYLTH10-4-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-IODO-2-PROPYNL BUTYL CARBAM.ATE,
(29) (TETRACHOROISOPHTHALONITRILE)
The carrier package was milled to about 1 micron and dried to provide a free-
flowing powder.
Prenaratkm of masterbatch biocide/resin combinations:
The carboxyl functional polyester resin was extruded at a temperature
sufficient to form a
melt with the addition of 10% by weight of the biocide carrier package. The
extruded material
was cooled to form a solid, the solid was broken into chunks, ground and
ultimately milled. An
epoxy resin biocide combination was similarly prepared to form a biocide/epoxy
combination.
Masterbatch materials containing 15-20 wt.% can also be prepared to increase
the biocidal
activity,
Preparation of the Coating Package:
General Procedure - The coating materials including the carrier package were
combined
and mixed through a high intensity mixer for about 3 minutes. The resulting
premix material
CA 02842222 2014-04-07
was extruded at about 80-85 C and the resulting extruded material chilled to
form a solid sheet.
The solid sheet of material was broken into chips and ground to form a powder
suitable for
application as a powder coating.
l'ia.paration and Aoolication of Latex and Oil Base Coatinas:
The carrier package described above can be included in a latex or oil base
coating with
agitation to ensure complete mixing. The resulting latex or oil base coatings
can be dried at
elevated temperatures and utilized at elevated service temperatures without
decomposition of the
heat labile component adsorbed on the carrier.
Preparation of Clear Polyester Coatina:
950 g of Polyester Primid (a Carboxyl functional polyester resin); 38 g of a
Primid
(hydroxyalkylaraide crosslinker); 10 g of rheoflow (a flow agent); and 100 g
of biocide/resin
masterbatch (10% biocide in Polyester Primid) were combined and processed
according to the
procedure described for the preparation of a coating package to provide a
clear powder coat
material. Primid is a registered trademark of EMS Chernie Ag Cotporation, Via
Innovativa 1
Domat/Ems SWITZERLAND. Increased amounts of the masterbatch material can be
utilized to
increase the biocidal activity,
Preparation of_Epoxy Powder Coating!
275 g of epoxy resin (Epotec YD901), 275 g of a carboxyl functional polyester
resin
50/50 hybrid (benzene-1,3-dicarboxylic acid; dimethylbenzene-1,4-
dicarboxylate,2,2-
dimethylpropane-1,3-diol;ethane-1,2.diol), 34.5 g of ptef modified pe
wax/BENZOINzhydroxy-
1 z-di(pheul)ethanone, 188 g if titanium, 22 g of titanium extender, 8 g of
pigment (red) yellow,
and black), 100 g of barium sulfate, 100 g calcium carbonate, and 100 g of
biocide epoxy resin
combination (10 biocide in epoxy resin) were combined and processed according
to the
procedure described for the preparation of a coating package to provide a
clear powder coat
material. Increased amounts of the masterbatch material can be utilized to
increase the biocidal .
activity.
26
CA 02842222 2014-04-07
AIDEgliC36011 of Powder Coat Materials:
Coatings based on the polyester clear coat and the epoxy powder coatings were
applied to
a surface for testing, Sheets of cold rolled steel (3 inches by 5 inches) were
powder coated with
an electrostatic spray gun according to standard procedures and the coated
sheets cured at about
Testing of Coated Samples:
(a) Testing Protocol:
CALCULATION OF TiThRS
Viral and cytotoxicity titers will be expressed as -logic of the 50 percent
titration endpoint for
infectivity (TCID50) or cytotoxicity (TCD50), respectively, as calculated by
the method of
= )]
- Log of 1st dilution inoculated x Logan o utton
Qeometric Mean = Antilog of: Logial,+ Lo EINg
4*
(X equals TCI)50/vo Wine inoculated for each test or control replicate)
carried out.
Calculation of Log Reduction
27
CA 02842222 2014-04-07
Virus Control TCID50¨ Test Substance TC1D5c, = Log Reduction
Calculation of Percent Reduction
Calculation of Percent Reduction
TCB:).5,0 test
% Reduction = 1 - [ _______________________________ x 100
TCiD5c, virus control
o.)) Testing: Feline Calicivirus 1 (ATCC VR-782)
The F-9 strain of Feline Calicivirus obtained from the American Type Culture
Collection,
Manassas, VA (ATCC VR-782) was utilized in testing. Stock virus was prepared
by collecting
supernatant fluid from 70-100% infected culture cells. The cells were
disrupted, centrifuged and
the supernatant fluid removed, aliquoted, and the titer stock virus stored at
5 -70 C. Cultures of
Crandel Reese feline kidney (CRFK) cells obtained from the American Type
Culture Collection,
Manassas, VA (ATCC CCL-94) were utilized as indicator cells. The test media
utilized was
Minimum Essential Medium (MEM) supplemented with 5% (v/v) heat-inactivated
fetal bovine
serum (FBS). Tests were carried out on pre-coated and pre-cut sections of
material
(approximately 50 rum x 90 mm or 2 inches by 3 1/2 inches) and controls of a
similar size.
Samples and control were dipped in ethanol and allowed to dry before testing.
Just prior to
testing, the stock virus was titered by a 10 fold serial dilution and assayed
for infectivity in order
to determine the starting titer of the virus.
Test samples and control samples contained in sterile petri dishes were
inoculated with a
100 aliquots of the test virus. The inoculated test samples were covered
with a film prepared
from a sterile stomacher bag, and the film pressed down sufficiently to spread
the virus over the
film and maintained at room temperature (20 C) for 5 minutes. Following the
exposure time, a
1.00 mL aliquot of test medium was pipefted individually onto each test and
control sample.
The surfaces of each of the samples or control materials were individually
scraped with a sterile
plastic cell scraper, the test mediums individually collected, and the
separate collected materials
mixed with a vortex type mixer before undergoing 10 fold dilutions, A control
measurement was
28
CA 02842222 2014-04-07
carried out with a test sample by substituting 100 pi of test medium for the
virus, After 1 hour
in a controlled chamber at room temperature and at 50% relative humidity, the
sample was
processed in the same manner as the virus seeded samples.
The different samples were finally utilized in an infectivity assay involving
the CRFK
cell line, CRFK. cells in multi-well culture dishes were inoculated with 100
JAL of the dilutions
prepared from the test and control samples. Uninfected indicator cell cultures
(cell controls) are
inoculated with test medium alone. Cultures were incubated at 31-35 C in a
humidified
atmosphere of 5-70/D CO2. The cultures were microscopically scored
periodically for seven days
for the absence or presence of cytotopathic effect. The polyester powder coat
samples tested
demonstrated a 90,0% reduction in viral toxicity following a 5 minute exposure
time (a log
reduction of 1.00 login), whereas the epoxy powder coating samples
demonstrated a 68.4%
reduction following a 5 minute exposure (a log reduction of 0.5 login). The
table below
summarizes these results.
Table 1
5 Minute Exposure Time
Reduction Polye,ster Coating Epoxy Coating
% Reduction 90.0% 68,4%
Logio Reduction 1.00 Logi 0.50 Logi()
Applicants' disclosure has been illustrated with examples of thermoset powder
coatings.
Other surface treatments include, but are not limited to, paints, coatings,
stains, varnishes,
sealants, films, inks, and the like (collectively, "surface treatments").
These surface treatments
can be prepared utilizing the procedures provided herein to incorporate heat
labile components
and/or incompatible components therein that retain their physical properties
in the resulting
surface treatment. This procedure also allows for the formation of new
combinations of
otherwise incompatible components. Heat labile components can include, but are
not limited to,
a wide range of biocides, repellents, UV stabilizers, fragrances, and the
like, Specific examples
of heat labile biocides include, but are not limited to bacteriocides,
fungicides, algaecides,
viruscides, insecticides, antibiotics, enzymes, repellents (animal and
insect), herbicides,
pheromones, molluscicides, acaricides, raiticides, rodenticides, fragrances,
and the like. Other
29
CA 02842222 2014-04-07
heat labile components with or without biocidal properties can also be
incorporated into the
coatings utilizing the procedures taught herein.
While applicant's disclosure has been provided with reference to specific
embodiments
above, it will be understood that modifications and alterations in the
embodiments disclosed may
be made by those practiced in the art without departing from the spirit and
scope of the
invention. All such modifications rad alterations are intended to be covered,
