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Title:
Electrically conductive hydrogels
United States Patent: 7,816,412
Issued: October 19, 2010
Inventors: Yahiaoui; Ali
(Roswell, GA), Spencer; Anthony Stephen (Woodstock, GA), Bolian; Charles
(Buford, GA)
Assignee: ConMed
Corporation (Utica, NY)
Appl. No.: 11/709,996
Filed: February 23, 2007
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Training Courses -- Pharm/Biotech/etc.
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Abstract
Electrically conductive adhesive
hydrogels formed from a composition which generally includes a monomer, an
initiator, an organic solvent, and a cross-linking agent are suitable for
use as skin contact adhesives and, particularly, suitable for use as an
electrical interface for disposable medical devices. The present hydrogels
provide for reduced skin irritation and/or malodor properties, hydrate a
subject's skin, readily wet around a subject's skin surface hair, and
protect against burning of a subject upon or due to electrical stimulation
through the hydrogel.
Description of the
Invention
SUMMARY
The present invention provides for an electrically conductive hydrogel
formed from a composition including a monomer, at least one initiator, a
cross-linking agent, and an organic solvent. The pH of the hydrogel may be
maintained in the range of 3 to 8.5 in the absence of a dual buffer
system. An acidic salt or the acid form of a monomer may be used to
maintain the pH of the hydrogel in the range of 3 to 8.5. The hydrogel may
be formed from a composition that does not include a solubilizer for the
at least one initiator. Desirably, the organic solvent is dimethyl
sulfoxide and is between about 0.5% and about 5% by weight of the
composition. Additionally, the composition may include a buffer.
The monomer of the composition is desirably N,N-Dimethylaminoethyl
acrylate dimethyl sulfate quaternary, dimethyl amino ethyl methacrylate,
acrylamido methyl propane sulfonic acid or their salts. The monomer
desirably is about 10% to about 80% by weight of the composition and is
more desirably about 40% to about 75% by weight of the composition.
The cross-linking agent is about 0.01% to about 2% by weight of the
composition and the initiator comprises about 0.01% to about 2% by weight
of the composition. Desirably, the initiator is a chemical initiator, a
photo initiator, or both. When the initiator is a chemical initiator, it
may be thermally activated and may be disulfide based, peroxide based, or
persulfate based or may be a sodium metabisulfite. Additionally, the
initiator may be a hydrophobic initiator.
Additionally, the composition may desirably include skin health agent,
which reduces irritation to the skin, particularly irritation caused by
the use of dimethyl sulfoxide as an organic solvent. These skin health
agents include aloe vera, glycerin, vitamin E, vitamin B, provitamin B,
vitamin E acetate, or chitosan.
Another aspect of the invention addresses an electrode which includes an
electrically conductive adhesive hydrogel formed from a composition. The
composition includes a monomer, at least one initiator, a cross-linking
agent, and an organic solvent. The pH of the hydrogel may be maintained in
the range of 3 to 8.5 in the absence of a dual buffer system. Desirably,
the composition may further include a skin health agent which may include
an electrically conductive hypoallergenic layer which is in communication
with the electrically conductive hydrogel.
Yet another aspect of the invention addresses a composition for an
electrically conductive hydrogel. The hydrogel includes at least one
monomer, at least one initiator, a cross-linking agent, and an organic
solvent. The pH of the hydrogel may be maintained in the range of 3 to 8.5
in the absence of a dual buffer system.
DETAILED DESCRIPTION
The invention disclosed herein is directed to electrically conductive
hydrogels. The hydrogels include a monomer, initiator, cross-linking
agent, and an organic solvent. The hydrogels are electrically conductive
adhesive hydrogels which are good electrical conductors suitable for use
in disposable medical devices, for example. These hydrogels are desirably
non-irritating to the skin, are sufficiently wet to adhere to skin, and
are readily removable from skin when desired. The organic solvent of the
hydrogel acts as a solvent for the initiator and provides a significant
cost savings over the use of a solubilizer for the initiator.
It will be appreciated that while reference is generally made throughout
this disclosure to a hydrogel, in addition to referring to the end
product, the term hydrogel, also may refer to the polymerizing formulation
or hydrogel precursor which is converted to a hydrogel upon exposure to
certain conditions (e.g., ultraviolet or UV curing, heat, etc.) as
discussed elsewhere herein.
In the interests of brevity and conciseness, any ranges of values set
forth in this specification contemplate all values within the range and
are to be construed as support for claims reciting any sub-ranges having
endpoints which are whole number values within the specified range in
question. By way of a hypothetical illustrative example, a disclosure in
this specification of a range of from 1 to 5 shall be considered to
support claims to any of the following ranges: 1-5; 14; 1-3; 1-2; 2-5;
2-4; 2-3; 3-5; 34; and 4-5.
Compared to conventional conductive hydrogel formulations, the hydrogels
of the present invention exhibit enhanced polymerization as evidenced by
clear or substantially clear gel solutions, the absence of precipitates or
presence of only limited precipitates, generally high electrical
conductivity values, and are characterized by the absence of solubilizers
for the initiator. Thus, the amount of undesirable residual functional
monomer and/or other monomeric residues in the hydrogel which are
unpolymerized is reduced. The present hydrogels exhibit these enhanced
polymerization and electrically conductive properties without the need for
expensive solubilizers for the initiator.
An additional advantage of the hydrogels of the present invention is that
they may utilize an electrolyte or combination of electrolytes as
conductivity enhancers.
Clear gel solutions of the present inventions are demonstrated when there
is no residue or precipitates visible in the formulation with the naked or
unaided eye. Substantially clear gel solutions are demonstrated by either
an amount of residue or precipitate in the solution that does not cause
the solution to demonstrate unsatisfactory conductivity values. Generally
speaking, satisfactory electrical conductivity values are values ranging
from about 30 mS/cm to about 50 mS/cm.
With regard to the functional monomer, it is contemplated that the
hydrogels may be formed from any suitable monomer. In at least one aspect
of the present invention, the hydrogel may be formed by free radical
polymerization in the presence of water. Initiation of the formation of
the hydrogel may be begun by ultra-violet curing with an initiator and a
multifunctional cross-linking agent. While only one initiator is
necessary, the hydrogel precursors may contain one or more second
initiators. The initiators can be photo-initiators or chemical initiators
such as those activated by heat or by reduction/oxidation (redox)
reactions.
While any suitable monomer is contemplated by the present invention,
exemplary functional monomers include: N-vinyl pyrrolidone (NVP),
hydroxyethyl methacrylate (HEMA), methacrylic acid (MA) or its salt,
styrene sulfonic acid (SSA) or its salt, potassium sulfopropyl acrylate (KPSA),
dimethyl acrylamide (DMA), dimethyl amino ethyl methacrylate (DMAEMA) or
its quaternary salt derivative, acrylamido methyl propane sulfonic acid
(AMPS) or its salt, and the combination of any of the above. Additionally,
the acid and salt of an exemplary functional monomer may be included in
the hydrogel. Desirably, the hydrogels of the present invention are made
from various classes of monomers including acrylates, vinyls, amides,
esters, etc, of which can be electrically neutral, cationic or anionic.
Combination of functional monomers also is possible to achieve desired
physical, chemical mechanical and electrical properties. Compared to prior
hydrogels, the hydrogels of the present invention hydrate the skin's
surface more effectively and lower the skin's electrical resistance
resulting in lower generation of heat and lower incidence of burning upon
electrical stimulation. In addition, the present hydrogels more
effectively wet around skin hair and, consequently, more sufficiently
contact a subject's skin resulting in increased efficacy in procedures
such as defibrillation as well as reduced heating and burning of skin
surfaces and, generally require no preparation of the skin surface prior
to use. Further, the present hydrogels are self-preserving and are
resistant to degradation because of the compatibility of the monomer with
the other ingredients present in the hydrogel.
Generally speaking, the monomer is desirably between about 10 to about 80%
by weight of the composition, more desirably between about 40 to about 75%
by weight of the composition, and even more desirably between about 50 to
about 75% by weight of the composition.
Examples of specific desirable cationic acrylates are:
acryloyloxyethyltrimethyl ammonium chloride which is readily available
from CPS Chemical Co. (New Jersey) or Allied Colloid (U.K.);
acryloyloxyethyltrimethyl ammonium methyl sulfate which is also available
from CPS Chemical Co. or Allied Colloid; and, acrylamidopropyltrimethyl
ammonium chloride, which is available from Stockhausen (Germany). The
desired process for making hydrogels with these exemplary acrylates is
described in detail below.
A cationic acrylate hydrogel suitable for the present invention will
generally be somewhat clear in color, viscous, and tacky to the touch. The
hydrogel tends to be sufficiently adhesive to a subject's skin, yet
sufficiently cohesive to be easily removable from the subject's skin and
separable from itself. As noted above, the hydrogels suitable for the
present invention can be formed by in-situ free radical polymerization of
a water soluble monomer in the presence of water, desirably by
ultra-violet curing with at least one initiator, multi-functional
cross-linking agent(s), and a solvent. For example, an appropriate
acrylate monomer, water, electrolyte (e.g. sodium sulfate), initiator or
catalyst (e.g., 1-hydroxycyclohexylphenol ketone, etc.), multi-functional
cross-linker (e.g., methylene-bis-acrylamide, etc.), and solvent (e.g.,
dimethyl sulfoxide.) are combined, placed in a mold, and exposed to an
appropriate amount of ultra-violet radiation.
Examples of co-monomers which may be used with the present invention
include co-monomers soluble in water and, even more desirably, include
anionic co-monomers. The amount of co-monomer to be used may be in the
range of about 5 to about 50% by weight, desirably about 10 to about 30%
by weight, based on the amount of reactants used. Examples of suitable
co-monomers include: unsaturated organic carboxylic acids such as acrylic
acid, methacrylic acid, maleic acid, itaconic acid, and citraconic acid
and salts thereof, unsaturated organic sulfonic acids such as styrene
sulfonic acid, methallyl sulfonic acid, 2-sulfoethyl acrylate,
2-sulfoethyl methacrylate, 3-sulfopropyl acrylate, 3-sulfopropyl
methacrylate, acrylamido-methylpropane sulfonic acid and salts thereof,
N,N-dimethylacrylamide, vinyl acetate, other radically polymerizable ionic
monomers containing a carbon-carbon double bond, and non-N-vinyl lactam
co-monomers useful with N-vinyl lactam monomeric units such as
N-vinyl-2-pyrrolidone, N-vinyl-2-valerolactam, N-vinyl-2-caprolactam, and
mixtures thereof. Among the ionic monomers enumerated above, particularly
desirable selections are 3-sulfopropylacrylate or methacrylate, and salts
thereof. Examples of cations involved in the formation of such salts
include sodium, potassium, lithium, and ammonium ions. Ionic monomers may
be used singly or in a mixture of two or more monomers.
Any suitable organic solvent may be used. The desirability of a specific
organic solvent and/or the amount thereof may vary or depend in part on
the other components and quantities thereof selected to make up the
hydrogel precursor. The use of any organic solvent capable of dissolving
the initiator up to an amount equal to the initiator's solubility limit is
desired. Suitable organic solvents include, but are not limited to,
dimethyl sulfoxide and glycerine.
The organic solvent is adapted to dissolve the initiator (hydrophobic or
hydrophilic) and is water soluble. The organic solvent is adapted to
dissolve hydrophobic additives such as lipids, anti-oxidants, drugs, and
fragrances. Additionally, the organic solvent is adapted to dissolve skin
health agents such as aloe Vera, glycerin, vitamin E, vitamin B,
provitamin B, vitamin E acetate, or chitosan.
It is contemplated that a organic solvent may be present in a positive
amount up to about 20% by weight of the hydrogel precursor and, more
desirably, between about 0.5% to about 5% by weight of the hydrogel
precursor.
Present hydrogels may include an optional buffer system to help control
the pH, prevent discoloration, and/or prevent breakdown due to an extended
presence of water (i.e., hydrolysis). The use of a buffer system with the
present hydrogel is desired to provide the hydrogel with a commercially
suitable shelf-life (i.e., a shelf-life of over one year) without
discoloration. Suitable buffers include, but are not limited to,
conventional buffers such as sodium hydroxide, sodium potassium tartarate,
and/or sodium phosphate monobasic, all of which are commercially readily
available from Aldrich Chemical Co., Inc., Milwaukee, Wis.
In addition, the use of buffers also helps to prevent electro-chemical
burning of a subject by helping to prevent pH changes and/or shifts as a
current is driven through a pair of hydrogel electrodes. Typically, in
prior systems, as current is driven through a pair of hydrogel electrodes,
one electrode becomes more acidic (i.e., its pH decreases) while the other
electrode becomes more basic (i.e., its pH increases). This pH shifting
problem is particularly prevalent if current is driven through such
electrodes for a long period of time (e.g., over 1 hour), such as during a
procedure wherein a patient's heart is being paced. The desired use of a
buffer system as is suggested in the present invention helps safeguard
against such pH changes as current is driven therethrough and thereby
enables use of the electrodes made from the present hydrogel for longer
periods (e.g., over 24 hours) without electro-chemical burning.
Therefore, it is desired that buffer (or a suitable alternative as
described below) be included to stabilize the resulting polymer, to avoid
hydrolysis of the hydrogel, and to avoid pH shifts due to the passage of
direct current through the hydrogel. Buffers help both to reduce or
prevent corrosion of metal conductors and also are conductivity enhancers
themselves. Some buffers prevent undesirable yellowing of the hydrogel.
The present hydrogel may include sufficient buffer to maintain the pH of
the hydrogel in a range of about 3 to about 8.5, and more desirably about
5.5 to about 7, but the pH may be adjusted as desired. In most aspects of
the present invention, a buffer may be present in the hydrogel precursor
in an amount up to about 10% by weight, and more desirably from about 0 to
about 5% by weight of the hydrogel precursor.
As an alternative to the use of conventional buffers, an amount of the
acidic form of the monomer used may be used in the hydrogel precursor to
adjust the pH of the hydrogel. Desirably, an amount of the acidic form of
the monomer will be combined with the salt of the monomer so that an
additional conventional buffer may not be needed. In this regard, pH is
conventionally adjusted in hydrogels by utilizing a dual buffer system
including a non-monomeric acidic salt such as an aluminum potassium
sulfate and an additional buffer having a pH greater than 7 such as sodium
hydroxide. For example, conventionally, aluminum potassium sulfate, or
another non-monomeric acidic salt, is added to the hydrogel precursor in
an amount to stabilize the resulting polymer, however, the amount utilized
may result in an unacceptable drop in pH. Because of this drop in pH,
sodium hydroxide, or another buffer having a pH greater than 7, is added
to the hydrogel precursor to bring the pH up to a satisfactory level.
This dual buffer system creates many potential problems such as buffer
incompatibility with the monomer and formation of a substantial amount of
precipitates in the hydrogel which may lead to a potential decrease in
conductivity.
Additionally, an acidic salt may be used by itself, and not as part of a
dual buffer system, to maintain the pH in the desired range.
However, utilizing the salt of the monomer in conjunction with the acid
(as a pH adjuster) eliminates potential problems such as buffer
incompatibility with the monomer while still increasing shelf life and
stability of the monomer solution.
The present invention also contemplates the inclusion of other additives,
such as conductivity enhancers, pharmaceuticals, humectants, plasticizers,
skin health agents, and the like. These other additives may be included
either before or after a curing step. The appropriateness of such
additives is generally dependent upon the intended end use of the
particular hydrogel.
Any suitable additive or combination of additives such as those suggested
above is contemplated. The specific additive and/or the amount thereof
which is included may vary or depend in part on the other components and
quantities thereof selected to make up the hydrogel. Exemplary skin health
agents and/or skin care ingredients include but are not limited to
vitamins (e.g., B, D, E, E acetate, etc.), antioxidants, chitosan, aloe
Vera, hyaluronic acid (HA), heparin, chondroitin sulfate, dextran sulfate,
and collagen IV. Still other exemplary additives may include but are not
limited to anti-inflammation agents, anti-oxidants, aesthetic agents
(e.g., color dyes to alter appearance of the hydrogels), or fragrances.
Additionally, the skin health agent (i.e. chitosan glycolate, silk
hydrolyzate, or polyvinylpyrrolidone) may be an electrically conductive
layer which is in communication with the electrically conductive hydrogel.
In this regard, the skin health agent may optionally not be present in the
hydrogel but may act as a separate hypoallergenic layer in communication
with the hydrogel in order to reduce skin irritation of the patient.
Desirably, this separate hypoallergenic layer will not decrease the
conductivity of the hydrogel.
Additionally, the use of suitable conductivity enhancer is contemplated.
The specific enhancer and/or the amount thereof which is included in the
hydrogel may vary or depend in part on the other components, and
quantities thereof selected to make up the hydrogel. Exemplary
conductivity enhancers include but are not limited to salts such as
potassium chloride, sodium chloride, potassium sulfate, sodium sulfate and
the like. These salts are desired inasmuch as human bodies use them for
conduction. Additional examples of salts which may be appropriate are
lithium chloride, lithium perchlorate, ammonium chloride, calcium
chloride, and/or magnesium chloride. Other chloride salts, iodide salts,
bromide salts, and/or halide salts also may be suitable.
Other salts, such as salts of weak organic acids or polymeric electrolytes
may be desirable. These salts are compatible with human bodies and with
the chemistry of the hydrogels of the present invention and may be used as
conductivity enhancers where desired chloride salts might interfere (i.e.,
corrode) with aluminum and/or stainless steel metal components used to
interface the hydrogel with medical equipment. Examples of salts which may
be suitable include sodium citrate or magnesium acetate.
Although use of a conductivity enhancer is optional, the amount of
conductivity enhancer in a hydrogel of the present invention is desirably
in the range of none to an amount which will enhance the conductivity of
the hydrogel. For example, if a conductivity enhancer is utilized, the
conductivity enhancer may desirably be present in an amount between
greater than about 0 (e.g., 0.01%) to about 15% by weight of the hydrogel
precursor and, even more desirably, between greater than about 0 (e.g.,
0.01%) to less than about 5% by weight of the hydrogel precursor.
The addition of conductivity enhancers may be desired even though the
hydrogel of the present invention is a polyelectrolyte ionically
disassociated in water and, therefore, conductive. In use, a lower
specified quantity of polyelectrolyte (and thus a hydrogel having a
correspondingly lower viscosity) may be desired in situations such as when
the hydrogel must wet around chest hair. In such cases, the addition of a
conductivity enhancer may be useful.
However, while the addition of a conductivity enhancer to a hydrogel or
hydrogel precursor has generally been thought to provide for better
electrical conductivity when compared to hydrogels without the added
conductivity enhancer, it has been discovered that at least some aspects
of the present invention which do not include an added conductivity
enhancer demonstrate better "in use" conductivity as compared to those
hydrogels which included a conductivity enhancer. For example, in certain
instances, salts, despite being inherently electrically conductive because
of their ionicity, may negatively yield undesirable effects such as the
"salting out" effect which may result in phase separation and/or
contribute to the reduced conductivity of certain formulations. This is
especially true the longer the shelf life a hydrogel may be subjected to.
As indicated herein, an optional buffer and/or one or more of the optional
polyelectrolyte additives (e.g., HA, chondroitin sulfate, phospholipids,
etc.) may exhibit conductivity enhancing properties; however, the buffer
and/or polyelectrolyte additives are not contemplated to be included in
the determination of the amount of a conductivity enhancer in the hydrogel
as the buffer and/or polyelectrolyte additives may not form a continuous
path within the gel and between the gel and the skin.
As is mentioned above, initiators are used in the polymerization of the
hydrogel precursors described herein. Examples of initiators which may be
used include IRGACURE.RTM. 184 (1-hydroxycyclohexyl phenyl ketone),
IRGACURE.RTM.. 2959
(4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-methylpropyl)ketone)), and
DAROCURE.RTM. 1173.alpha.-hydroxy-.alpha.,.alpha.-dimethylacetophenone),
all commercially available from Ciba Specialty Chemicals. These
ultraviolet UV initiators are desired because they are non-yellowing.
Other initiators which may maintain the desired water-white and
water-clear appearance of the present hydrogels also are desired.
Additional examples of suitable initiators (which may be photo initiators
or thermal initiators) may include benzoyl peroxide,
azo-bis-isobutyro-nitrile, di-t-butyl peroxide, bromyl peroxide, cumyl
peroxide, lauroyl peroxide, isopropyl percarbonate, methylethyl ketone
peroxide, cyclohexane peroxide, tutylhydroperoxide, di-t-amyl peroxide,
dicumyl peroxide, t-butyl perbenzoate, benzoin alkyl ethers (such as
benzoin, benzoin isopropyl ether, and benzoin isobutyl ether),
benzophenones (such as benzophenone and methyl-o-benzoyl benzoate),
actophenones (such as acetophenone, trichloroacetophenone,
2,2-diethoxyacetophenone, p-t-butyltrichloro-acetophenone,
2,2-dimethoxy-2-phenyl-acetophenone, and p-dimethylaminoacetophenone),
thioxanthones (such as xanthone, thioxanthone, 2-chlorothioxanthone, and
2-isopropylthioxanthone), benzyl 2-ethyl anthraquinone, methylbenzoyl
formate, 2-hydroxy-2-methyl-1-phenylpropane-1-one,
2-hydroxy-4'-isopropyl-2-methyl propiophenone, .alpha.-hydroxy ketone,
tetramethyl thiuram monosulfide, allyl diazonium salt, and combinations of
camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate. Other suitable
initiators may be found in, for example, Berner, et al., "Photo
Initiators--An Overview", J. Radiation Curing (April 1979), pp. 2 9.
Although only one initiator is necessary, the hydrogel may contain one or
more second initiators. The one or more second initiators can be photo or
chemical initiators.
Where there is only one initiator, the amount of initiator is desirably
within the range of about 0.01 to about 5% by weight of the hydrogel
precursor, more desirably, within the range of about 0.05 to about 2% by
weight of the hydrogel precursor and, even more desirably, within the
range of about 0.1 to about 0.5% by weight of the hydrogel precursor.
Where one or more second initiators are present, the amount of one or more
second initiators is desirably within the range of about 0.01 to about 5%
by weight of the hydrogel precursor, and more desirably within the range
of about 0.05 to about 2% by weight of the hydrogel precursor and, even
more desirably, within the range of about 0.1 to about 0.5% by weight of
the hydrogel precursor. However, where multiple initiators are present, it
is generally desirable that the combined amount of the initiators be about
5% or less by weight of the hydrogel precursor, and more desirably within
the range of about 0.02 to about 5% by weight of the hydrogel precursor.
UV curing parameters to achieve desired polymer properties are well known
to those skilled in the art. A photo initiator for the present purposes
tends to operate by absorbing select wavelengths of UV to produce radical
initiating species to induce monomer polymerization. The wavelengths and
curing area set the style of UV bulb used in the curing process.
Inhibition of polymerization due to dissolved oxygen, monomer inhibitors,
or other radical scavenging moieties may be overcome by changing the
power, by pulsing, and/or by using initiator accelerators.
It will be appreciated that each photo initiator is responsive to a
specific or narrow wavelength range of UV light. At least one aspect of
the present invention takes advantage of this property and incorporates
two or more photo initiators in a hydrogel precursor. The addition of more
than one initiator in a hydrogel precursor allows for a broader range of
the energy or range of wavelengths emitted by a UV source to be utilized.
The utilization of multiple initiators can further reduce solubility limit
concerns and related compatibility concerns, as more efficient
polymerization may be able to be achieved with two initiators present in a
hydrogel precursor than with either of the initiators used alone at the
same overall initiator concentration.
The synergistic effect of initiators has not been previously identified or
exhibited in previous hydrogels which incorporated one photo initiator, if
any initiator at all. It is further believed that the inclusion of
initiators having different rates of initiation and/or the inclusion of
initiators which begin initiation of polymerization of the monomer at
different times relative to each other (such as that which may be
experienced by multiple initiators (e.g., a thermally activated chemical
initiator (TACI) and a photo initiator)) contributes to a higher yielding
polymerization. That is, for example, where two photo initiators are
included, one may have a lower UV wavelength trigger and may be more
energetic (providing for a faster rate of initiation and reaction) than
the other initiator which is triggered by a higher UV wavelength or range.
The faster initiator may also die or be consumed faster than the other. It
is contemplated that it may be advantageous to have polymerization occur
at different rates and/or at a mixed rate which may not be obtainable with
one initiator or with an initiator which is suitable for a particular
hydrogel precursor. An example of initiators which are not triggered or
activated simultaneously, may be found in the present invention where a
photo initiator and a TACI are in a hydrogel precursor, and the photo
initiator is triggered by a UV source and reacts with the monomers in the
precursor so as to generate heat to trigger the TACI.
While numerous combinations and variations of initiators are possible, it
is believed that the combination of multiple initiators provides more
favorable kinetics which affords a higher probability of more extensive
polymerization of the monomer and/or other monomeric residues.
It is a further discovery of the present invention that a TACI may be
included to take advantage of the benefits of multiple initiator
polymerization. As some heat is necessary to trigger a TACI, it is
contemplated that a TACI will generally be included only where heat will
be present in or produced in the hydrogel precursor in a sufficient amount
to trigger the TACI. As radical polymerization reactions induced by photo
initiators are known to be exothermic and thus to generate heat in
response to UV exposure, at least one aspect of the present invention is
directed to the inclusion of a TACI in a hydrogel precursor where a photo
initiator is also present so as to allow the TACI to take advantage of the
heat generated by the radical polymerization reaction induced by a photo
initiator. It is also contemplated that a TACI can be included where
multiple photo initiators are present. The presence of multiple photo
initiators provides for the potential benefits of multiple initiators
discussed above yet also provides for the triggering of a TACI where the
heat generated by one photo initiator may be insufficient to trigger or
fully trigger the TACI (depending on the photo initiators and the TACI
involved), whereby the TACI can further promote or complete the
polymerization of the functional monomer and other monomeric residues in a
hydrogel precursor. Multiple TACIs are also contemplated.
It is believed that literature reports and/or clinical experience lack any
report or descriptions of utilizing the combination of one or more photo
initiators and a TACI in order to obtain the more complete polymerization
of a hydrogel precursor, thereby leading to a more stable, less
malodorous, and/or less skin irritating hydrogel.
As is also noted above, cross-linking agents are desirably used to
cross-link the present hydrogels. Examples of multi-functional
cross-linking agents which may be used include, for example,
methylene-bis-acrylamide and diethylene glycol diacrylate which are both
commercially available from Polysciences, Inc., Warrington, Pa. Additional
examples of cross-linking agents which may be satisfactory for use in the
present invention include: poly(ethylene glycol) diacrylate, triethylene
glycol-bis-methacrylate, ethylene glycol-bis-methacrylate, ethylene
glycol-dimethacrylate, bisacrylamide, triethyleneglycol-bis-acrylate,
3,3'-ethylidene-bis(N-vinyl-2-pyrrolidone), trimethylolpropate
trimethacrylate, glycerol trimethacrylate, polyethylene glycol
dimethacrylate, and other multifunctional polyacrylate and
polymethacrylate crosslinkers.
The amount of cross-linking agent is desirably within the range of about
0.01 to about 2% by weight of the hydrogel precursor and, more desirably,
within the range of about 0.05 to about 0.5% by weight of the hydrogel
precursor.
Claim 1 of 32 Claims
1. A substantially precipitate free
electrically conductive hydrogel formed from a composition comprising: a
monomer; at least one initiator; a cross-linking agent; and an organic
solvent, wherein the composition does not comprise a dual buffer system,
the pH of the electrically conductive hydrogel is maintained in the range
of 3 to 8.5 in the absence of the dual buffer system and wherein the
composition does not comprise a solubilizer for the at least one
initiator.
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