Biomaterials 22 (2001) 3273–3283

Soft contact lens polymers: an evolution

Paul C. Nicolson*, Ju. rgen Vogt
Lens Business Unit Research and Development, CIBA Vision Corporation, 11460 Johns Creek Parkway, Duluth, Georgia, GA 30097-1556, USA

Abstract

A review of patents and literature reveals an evolution in materials technologies. The evolution has been driven by an increased
understanding of the physiological needs of the cornea, beginning with the first hydrogel lenses developed by Wichterle, followed by
a variety of high water hydrogels. Oxygen transmission requirements have been addressed through the use of siloxane and
fluorosiloxane containing hydrogels. An important development has been the appreciation of the importance of polymer phase
morphology on lens movement on the eye. In parallel with these activities have come the advancements in materials suitable to high
volume, low cost production necessary for today’s daily disposable lenses. r 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Contact lens; Polymer; Hydrogels; Siloxane hydrogels; Phases; Macromer

1. Introduction Permeability to oxygen is a key performance char-

acteristic for contact lenses. The expression Dk has
There has been a fairly continuous evolution in the become universally accepted, as the term referring
field of contact lens materials since 1930s. The technol- to the intrinsic property of a material to transport
ogy of vision correction using a lens in intimate contact oxygen through its bulk; it is thickness independent.
with the cornea was first reduced to practice in the form The term Dk=t (or Dk=l) refers to the oxygen transport
of a glass lens in the 1800s. In 1936, polymethylmetha- properties of a contact lens of thickness t (or l), in mm
crylate (PMMA), a resin having greater clarity than and is called oxygen transmissibility. Dk=l is generally
glass, was introduced. Through lathing of this new resin, viewed as a representation of the ability of a specific
the first commercial contact lenses were developed and lens to deliver oxygen to the cornea. The Dk is expressed
introduced. Wichterle forever changed the contact lens in terms of barrer. Dk=t is expressed in terms of
industry with his contributions of soft hydrogels barrer/mm.
including the process of lathing hydrogel materials as
zerogels and also, the direct spin casting of soft
hydrogels as a more viable, high volume production
process. 2. The ocular environment; the challenge for a
Soon after the commercial introduction as polymacon biomaterial
in 1970, Wichterle’s poly-hydroxyethylmethacrylate
(PHEMA) hydrogel was rapidly followed by a wide The ocular environment places high demands on the
range of new hydrogel polymers [1] driven by the performance of contact lenses as biomaterials. Ophthal-
obvious pursuit for a competitive position in this new mic compatibility of a contact lens on the eye requires
emerging soft contact lens market. The pursuit of new the lens maintain a stable, continuous tear film for
materials was also motivated by the understanding the clear vision, is resistant to deposition of tear film
cornea uses oxygen to maintain its clarity, structure and components, sustains normal hydration, is permeable
function and obtains its oxygen from the air as to oxygen to maintain normal corneal metabolism, is
illustrated in Fig. 1. permeable to ions to maintain movement and to be non-
irritating and comfortable. Therefore, the lens must
have excellent surface characteristics being neither
*Corresponding author. Tel.: +1-678-415-3930; fax: +1-678-415-
3747. hydrophobic nor lipophilic and must possess the
E-mail address: [email protected] appropriate bulk polymer composition and morphology
(P.C. Nicolson). to be successful.

0142-9612/01/$ - see front matter r 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 6 1 2 ( 0 1 ) 0 0 1 6 5 - X
3274 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283

Fig. 1. Diagram of the eye and the sources of oxygen for the cornea.

3. The quest for oxygen permeability that six nights of corneal compromise caused by wearing
conventional hydrogels can still cause problems in some
Innovations in contact lens materials designed to wearers [13–15].
better meet the oxygen needs of the eye appeared in 1978 A basic physical property of organosilicon containing
through the efforts of Gaylord [2–4], scientists at Dow polymers is their high permeability to oxygen. The
Corning [5,6] and others in the rigid gas permeable reported Dk of pure dimethylsiloxane is 600 barrer,
(RGP) contact lens field. Those innovations included the which is significantly higher than the 8–20 barrer of the
use of organosilicon containing compounds such as average hydrogel. This high permeability to oxygen
silicone acrylates composed of the tris-(trimethylsilox- comes about by virtue of the bulkiness of the siloxane
ysilyl-) (abbreviated TRIS) moiety, polydialkyl- and/or group (–Si(CH3)2–O–) and chain mobility that char-
diaryl-siloxane, as well as silicone resins. Since the focus acterizes such materials and which is responsible for the
of this paper will be soft contact lens materials, nothing high diffusivity of oxygen through siloxane-containing
further will be said concerning the rigid materials. materials. The first commercial, soft silicone lens,
First, why all the interest in high oxygen permeability elastofilcon A, was developed in 1980 by Dow Corning
(Dk)? The work done by DeCarle [7] in England, fitting [16]. This lens was a silicone elastomer containing no
contact lenses for overnight (extended wear) created a water and, as such, the lens manifested typical rubbery
demand for the convenience such a modality offered. behavior. These properties required the lenses be
Wearers were demanding ‘‘natural vision’’, waking up fabricated in small diameters, much like RGP lenses to
and seeing the alarm clock, etc., without the hassle of avoid binding or adhering to the cornea and therefore
daily lens removal and requisite cleaning and disinfec- were never able to deliver the comfort characteristics of
tion. However it was not long before the negative hydrogels. Further, the inherent lipophilicity of the
physiological effects of the corneal oxygen deprivation material required the lenses be surface treated. Elasto-
created by extended wear of the lenses available at that filcon Lenses are available today, only in aphakic
time began to be realized, first in Europe [8] in the late powers for children and adults [17].
1970s and then in the States in the mid 80s [9–11]. As a The achievement of higher oxygen permeability with
result, in the US in 1989, the Food and Drug high water hydrogels was pursued through the develop-
Administration rescinded all 30 night extended wear ment of high water (>50%) hydrogels that contained
approvals they had originally granted starting in 1981, strongly hydrophilic monomers such as N-vinylpyroli-
leaving the only approved extended wear modality to be dinone (NVP) and methacrylic acid (MAA). However,
six nights wear [12]. However, researchers have shown these endeavors soon reached their limit. Pure water has
 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283 3275

Fig. 2. Structural representation of a siloxane macromer.

a Dk of about 80 barrer. The revelation that a minimum

oxygen transmissibility (Dk=t) of 87 barrer/mm was
required for a lens to be worn safely overnight [18] Fig. 3. Structural representation of an acrylic monomer containing a
meant that thin, thus more oxygen transparent designs bulky siloxanylalkyl substituent.
were necessary in the high water hydrogels, if they were
to approach the required performance level. Poor
mechanical properties, difficult handling, difficult man- The macromer technologies differed largely in the
ufacture, uptake of tear proteins and care system linking groups, X and X0 employed. Condensation
components and the findings of corneal desiccation with chemistries, namely urethane, ester, carbonate, thiour-
those material/design combinations eliminated them ethane, urea and amide group formation were the
from serious consideration for extended wear. principle modes by which the final structures were
Therefore, there has existed, until very recently, the assembled. Urethanes were particularly popular in that
unmet need for soft contact lenses that can be worn for no by-products were formed although they were
extended periods without causing corneal oxygen criticized in some early patents as being undesirable
deprivation and the problems associated with it. More for use in medical devices, particularly contact lenses
recent research into the oxygen needs of the cornea has [23]. No reasons were given however.
led to the proposal that oxygen transmission greater Following these three earliest siloxane hydrogel
than 125 barrer/mm is needed to completely avoid low patents, a great number of patents have issued in the
oxygen-related effects [19], placing the performance field of siloxane- and later fluorosiloxane- and fluoro-
hurdle for new materials even higher. hydrogels for contact lenses. The bulk of these patents,
emanated from commercial enterprises, i.e. Bausch and
Lomb, CIBA Vision, and a number of Japanese
4. Siloxane-containing hydrogels companies such as Menicon and Shin Etsu reflecting a
commercial interest in developing new, better perform-
The high oxygen permeability of polysiloxanes, offset ing siloxane and/or fluorosiloxane hydrogel polymers
by their characteristic hydrophobicity and rubbery for contact lenses.
character led investigators to the design of a novel PDMS was not the only oxygen permeability enhan-
family of materials called siloxane hydrogels. It was cing component pursued for contact lens polymers. Rice
hypothesized such materials would offer the softness, at 3M presents novel macromers derived from perfluoro-
wettability and on-eye comfort of a conventional polyethers (PFPE) [24,25]. PFPE moieties function by
hydrogel, while at the same time provide the higher increasing the oxygen solubility in polymers (the k in the
oxygen transmission required by the cornea. Dk expression) while siloxanes increase diffusion (the D
Independently, in July and November 1977, and component) of oxygen. The PFPE technology appeared,
February 1978, CIBA-Geigy (Mueller and Kleiner briefly on the contact lens market as fluorofocon A
[20]), Toyo Contact Lens Company in Japan (Tanaka contact lenses, a terpolymer of a PFPE dimethacrylate,
et al. [21]) and Bausch and Lomb (Deichert et al. [22]), methyl methacrylate and NVP [26]. Their mechanical
respectively, each applied for patents on new families of properties fell somewhere between soft and rigid
high Dk polymers for contact lens polymers called materials, thus they were termed flexible lenses. Lacking
polysiloxane hydrogels. All three claimed these hydro- siloxane, fluorofocon A lenses did not manifest lipophi-
philic polysiloxane containing materials as being novel licity and their high Dk made them attractive for
compositions offering high oxygen permeability thereby extended wear. However, because they were neither hard
overcoming the shortcomings of conventional hydrogels nor soft and they contained significant amounts of
for extended wear. Mueller and Deichert both employed fluorochemicals which are relatively expensive, their
macromers derived from bi- and/or poly-functional, unique fitting behavior and high cost contributed to
methacrylated polydimethylsiloxane (PDMS) polyols, their relatively short life on the market.
(main-chain siloxanes) (Fig. 2) in combination with Building on the concept of permachor [27], the
hydrophilic monomers (NVP, HEMA). Tanaka, on relationship of structure to oxygen permeability devel-
the other hand used mono-functional bulky polysilox- oped by the packaging industry, other non-siloxane
ane-containing acrylates (pendant siloxanes) (Fig. 3). structures were studied. Patents on polyethylene/poly-
When Z is O and X00 is propylene, the monomer is TRIS. propylene oxide containing soft polymers with and
3276 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283

without water have issued [28,29]. Although the Dk

values reported are not as high as comparable materials
Fig. 4. Structural representation of isocyanatoethylmethacrylate
derived from siloxanes, the materials did outperform
(IEM) monomer.
conventional hydrogels with regard to oxygen perme-
ability. There have not been any contact lens polymers
derived from polyether technology that have been
commercialized to our knowledge. To date, there have amphiphilic segmented A–B–A type block macromers
been no reports of polymers for contact lenses that have where A represents a hydrophilic segment such as
the oxygen permeability characteristics of siloxane and polyethylene oxide or polyoxazoline with molecular
fluorosiloxane. weights in excess of 400 and B is a hydrophobic PDMS
or PFPE segment with molecular weights of 1000–5000
or more. Since these macromers are inherently hydro-
5. Siloxane macromer architecture philic, homopolymers as well as co- and terpolymers
with other hydrophilic and hydrophobic monomers
Siloxane hydrogel materials development, based on a have, in general, good soft contact lens bulk material
review of issued patents and patent applications, has properties, namely phase morphology (see below), water
followed different paths. Materials development strate- content and mechanical properties.
gies have included bi-functional macromers in large part Keough et al. [35] make a point in their patent about
but the architecture of those macromers has been varied the troublesome incompatibility of PDMS containing
significantly. In the simplest form, siloxane macromers components and hydrophilic monomers leading to
were assembled by ‘‘capping’’ one mole of a PDMS diol opaque, phase separated products. To resolve this, they
with 2 mol of methacryloyl chloride. Alternatively the disclose the preparation of PDMS macromers with
PDMS diol could be reacted with exactly 2 mol of a polar or hydrophilic side-chains. Such macromers are
diisocyanate, followed by consumption of the resulting claimed to have enhanced compatibility with hydro-
diisocyanate with HEMA. Simple bi-functional PDMS philic monomers. The hydrophilic side chains incorpo-
derivatives as described by Deichert and Mueller have rate PEO or glycol moieties. An earlier investigator,
been followed by chain extended PDMS [30] in an effort LeBoeuf, discloses similar hydrophilic side-chain silox-
to increase Si content as well as to reduce modulus in anes indicating the polymers derived from them are
such materials. Chain extension refers to the concept of more wettable and that the siloxanes are compatible
linking two or more PDMS moieties together in a linear with hydrophilic monomers [36,37]. Interestingly
fashion. The starting PDMS units, generally available as Ku. nzler reported problems of significant instability
a-o diols or diamines, are reacted with a diisocyanate in when the side chains are PEO in contrast to when
a stoichiometry such that the PDMS units are joined to glycols are incorporated [38]. The instability of PEO was
form an oligo-urethane or oligo-urea chain. The also reported by Nicolson in A–B–A lens polymers
commercial availability of a new isocyanate methacry- where A is PEO, the materials manifested a poor shelf
late, isocyanatoethylmethacrylate or IEM, (Fig. 4) life whereas when A is polyoxazoline, no such problems
simplified the construction of methacrylate macromers were observed [39].
for biomaterials. Other strategies followed to obtain compatibility with
Methacrylate end-capped, segmented hard–soft–hard hydrophilic components included PDMS macromers
polyurethane macromers have also been disclosed, containing side chains with polar fluoro-substituents
offering improved mechanical strength according to (–CF2 H). A second benefit of reduced lipophilicity,
the inventors [31]. The soft segment of the materials imparted by the fluoro-substituent, is claimed [40].
contained PDMS as well as other long chain, flexible Monomer compatibility is one of the main require-
moieties while the hard segment was composed of short ments of contact lens manufacturing processes. It allows
chain diols linked through di-isocyanates such as lenses to be produced in neat, one-step formulations.
isophorone di-isocyanate (IPDI). However, homogeneous mixtures can also be readily
Construction of methacrylate functional PDMS achieved through the use of compatibilizing solvents.
macromers by first reacting a di-isocyanate with the Mechanical properties of the final cured polymer,
PDMS diol followed by a monomer such as HEMA environmental, cost and lens formation methodology
inevitably lead to some chain extension even when exact considerations may all come into play in defining the
stoichiometry was used. Use of IEM reduced the extent formulation.
of that phenomenon and made macromer structure Bambury and Seelye introduced a new family of
more controlled and predictable. polysiloxanes employing vinyl carbonate- and vinyl
The hydrophobic and lipophilic character of PDMS carbamate-functionalized compounds [41]. They de-
led many investigators to explore more hydrophilic scribed siloxane copolymer hydrogel films that contain
polysiloxanes. Patents [32–34] report the preparation of NVP. Such vinyl-functional macromers co-polymerize
 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283 3277

more readily with NVP than do acrylate-functional

macromers, improving NVP incorporation into the final
polymer. Unique cross-linking agents containing both
vinyl and acrylate functions have also been disclosed
and have been claimed to improve co-polymerization
of vinyl and acrylate-functional monomers and macro-
mers [42]. Fig. 5. Structural representation of a latent hydrophilic monomer
according to Lai.

6. Hydrophilic co-monomers

Experience with silicone elastomer lenses binding

onto the cornea when fabricated in normal soft lens
designs led the field to conclude that some water in the
matrix is necessary if the goals of on-eye movement,
comfort and wettability were to be achieved. Incorpora-
tion of hydrophilic co-monomers was one means of Fig. 6. Structural representation of the monomer in Fig. 5 after
doing that. As mentioned above, A–B–A block macro- hydrolysis and ring opening.
mers are sufficiently hydrophilic to induce bulk water
absorption without the addition of hydrophilic mono-
mers. However additional hydrophilic co-monomers fractive index and modulus. Monomers containing
allow for a more straightforward adjustment of water fluorine offer the opportunity of maintaining oxygen
content in the course of material development. permeability while reducing the lipohilicity imparted by
HEMA was the original hydrophilic lens monomer the siloxanes. The more common hydrophobic co-
and continues today to be the most commonly used monomers disclosed however, are simple aliphatic esters
hydrophilic monomer in the conventional soft contact of (meth-)acrylic acid, such as methyl methacrylate
lens field. However the majority of siloxane hydrogel (MMA).
patents disclose more frequent use of NVP and Of particular importance in siloxane hydrogels is the
dimethylacrylamide (DMA), the latter having preferred use of bulky polysiloxane containing monomers, the
copolymerization kinetics with acrylic systems while the most common being those with the tris-(trimethylsilox-
former is cited more frequently with vinyl functional co- ysilyl-) (TRIS) moiety (Fig. 3). According to Lai the
monomers. The neutral and strongly hydrophilic nature incorporation of such monomers, partially replacing the
of these monomers helps to explain their appeal. more expensive PDMS macromers, is a viable strategy
Experience with methacrylic acid (MAA) as a hydro- to maintain oxygen permeability with the added
phile in contact lenses, namely its attraction of proteins advantage of reducing the modulus of the final polymer
from the tears, seems to make it less attractive. through reduction of the crosslinking density [44].
A latent monomer approach that appeared in a Lai
patent [43] was the incorporation of a vinyl substituted
oxazolinone (Fig. 5) which, when incorporated, is 8. Siloxane hydrogel polymer morphology
miscible with hydrophobic monomers in the formula-
tion. Up until 1995, literature and patents were silent on
When the finished polymer is heated in water, the phases in contact lenses. If phases were mentioned, they
oxazolinone ring-opens to form a hydrophilic amino were mentioned in the context of something that was to
acid moiety (Fig. 6). be avoided [35]. Phase separation and the resultant
typical opacity associated with it lies counter to the
optical performance required by such products. The
7. Hydrophobic co-monomers major message was that monomers employed in contact
lenses should be as compatible as possible to avoid
One would wonder why the need for additional phase separation.
hydrophobic monomers in polymer systems already rich Polysiloxanes and most hydrophilic polymers are
in hydrophobic siloxane macromers? Hydrophobic typically immiscible and when given the opportunity,
monomers have been described as being ‘‘toughening they will phase separate. Phase separation occurs when
agents’’ which improve mechanical strength, often at the cohesive interactions between chemically identical or
expense of oxygen permeability. They also provide an similar molecules are stronger than the adhesive inter-
additional means of fine tuning the final physical actions between chemically different molecules. If
properties of polymers, impacting water content, re- mutual disliking groups are part of the same molecule,
3278 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283

Fig. 7. Differential scanning calorimetric analysis of a two-phase siloxane hydrogel.

as exist in siloxane hydrogel (amphiphillic) crosslinked and hydrogel phases (Fig. 7). The presence of micro-
networks, covalent bonds limit the maximal separation phases alone was clearly not sufficient however. The
length between the phases. Separation lengths of about extent and continuity of both phases is key to on eye
100 nm or less generally lead to microphase separated movement and the achievement of high oxygen perme-
systems. Such systems then are optically clear as the ability. A conceptual model illustrating co-continuous
phase size is significantly less than the wavelength of phases is the cellulose sponge with continuous sponge
light. material and air ‘‘phase’’. Contrast this model with the
In distinct contrast to prior conceptions about phase Styrofoam cup where the air ‘‘phase’’ is discontinuous.
separation, Nicolson et al. [45–49] in a series of
comprehensive patents, describe the requisite properties
for an ophthalmically compatible siloxane hydrogel 9. Ion permeability and the prediction of on eye
contact lens, namely the need for separate, and co- movement
continuous ion/water permeable (ionoperm) hydrogel
and oxygen permeable (oxyperm) phases. An ophthal- Domschke et al. in a 1997 ACS presentation [50],
mically compatible lens is defined as a lens which has described the research and the ion permeability test
high oxygen transmissibility, moves on the eye and does method developed to further elucidate the presence and
not accumulate significant lipid or protein deposits as nature of the continuity of the hydrogel phase. A
some of the necessary and desirable features. percolation model distinguishes lens materials that bind
The revealation that co-continuous phases are neces- on the cornea to those that will move (Fig. 8).
sary to achieve an extended wear contact lens came Research is currently underway to determine just how
about from the clinical evaluation of a large number of water and ion permeability effect the ability of a lens to
prototype siloxane hydrogel-based contact lenses. move on the eye. Tighe has proposed that the
Although generally, these test lens compositions had permeation of ions through the lens material allows
properties suitable for a soft extended-wear contact lens, for the maintenance of a hydrodynamic boundary layer
clinical assessment revealed almost all of them ceased between the lens and the cornea to avoid hydrophobic
movement immediately or shortly after placement on binding [51]. There does seem to be a level of
the eye. It became clear that only those compositions permeability above which a lens material will move on
manifesting a certain level of ion permeability (e.g. the eye. The fact that greater permeability does not seem
sodium chloride) would move on the eye. Differential to promote greater movement supports the hydrody-
scanning calorimetry (DSC) analysis of these composi- namic boundary level theory and implies that once the
tions clearly showed the presence of separate siloxane layer is formed, its thickness is not critical. An accepted
 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283 3279

Fig. 8. Percolation curve and diagramatic representation of the phase morphologies derived from different siloxane hydrogel contact lenses
manifesting either adherence or movement when placed on the eye.

Fig. 9. Representations of the various morphologies in which bi-phasic materials can exist (IPN=interpenetrating network).

theory in the contact lens field is that surface character- ordered systems are unlikely in the contact lens polymer
istics of a lens will dictate its movement on the eye. It field. One possible exception may be the polymer
has been our experience that surface treatment of a lens systems disclosed by Hirt that may form mesophases
is not enough to overcome the bulk polymers physical [34].
performance with regards to movement. If a particular A model analysis evaluation of phase separated
lens material did not move on the eye, application of systems using the parameters of phase volume fraction
various surfaces did not change the outcome. [52] (Fig. 10) and the connectivity factor x [53] (Fig. 11),
yields models allowing the prediction of oxygen perme-
ability theoretically achievable (Fig. 12). Based on the
10. On phases analogy [53] between the integrated Fourier law and
Ohm’s law such calculations offer two boundary
Phase morphology can take many forms (Fig. 9). solutions, one representing the serial, the other the
Siloxane hydrogels disclosed in patents are random, parallel arrangements of the conductors. Both solutions
statistical polymers can be best represented as isotropic are shown in Fig. 12 as solid lines. The broken line in
structures, either as a dispersed system (only one phase between represents the geometrical mean of those two
is continuous) or as an interpenetrating polymer net- solutions. As can be deduced from such calculations a
work (IPN) (two phases continuous throughout the maximum oxygen permeability of 225 barrer could be
material). Anisotropic structures typical of highly obtained at 50% volume fraction of the PDMS phase
3280 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283

assuming the ideal connectivity x: With the less ideal macromer architecture or by attention to polymeriza-
(but more realistic) x ¼ 0:5 and the same PDMS volume tion kinetics, especially in polymers with relatively low
fraction of 50%, the predicted Dk is still as high as water contents (o30%). Such systems are particularly
194 barrer. It becomes obvious from such model advantageous for extended wear contact lens polymers
calculations that a material with dispersed oxygen as the lower water content allows for higher oxygen
transport phase would fall in its Dk value, far below permeability to be achieved. Amphiphilic segmented
the requirement for extended wear contact lenses macromers or prepolymers [34] composed of hydro-
(Fig. 12, right diagram). Furthermore, one can easily philic and hydrophobic segments bonded together can
conclude from such simple model considerations that a provide spontaneous co-continuous products. In poly-
complete phase separation (least amount of interphase mer systems prepared from all-hydrophobic macromers
regions) is essential for obtaining high oxygen perme- copolymerized with hydrophilic monomers such as
abilities. Also, the continuity of the oxygen transport DMA, inhibition of polymerization by oxygen has been
phase should be high (x ¼ 0:5 to 1) for maintaining shown to have a dramatic influence on continuous
Dk>100 barrer at a 50% volume fraction of PDMS. A ionoperm phase formation. Using ion permeability as a
similar treatment might be used to predict the ion diagnostic for the presence of a continuous hydrophilic
permeability. From such simple model treatment, one phase, we have shown that continuity is achieved only
can predict the theoretical maximum oxygen perme- when oxygen has been effectively excluded from the
ability of a perfectly phase separated (no inter-phase polymerizing mixture [45]. However, DSC analysis
regions) siloxane hydrogel contact lens which will move shows no difference between two polymers cured in
on the eye. Achievement of such a polymer system is a the presence and absence of oxygen implying that two
goal for future polymer research. phases still exist. One explanation for the DSC results is
The preparation of siloxane or fluorosiloxane hydro- that phase co-continuity is disrupted when an ambient
gel polymers with co-continuous phases, in our experi- environment is present [39].
ence, can be achieved either by careful design of the

11. Current commercial siloxane hydrogel contact lenses

There are two commercial siloxane-containing hydro-

gel products available on the international lens market,
lotrafilcon A from CIBA Vision and balafilcon A from
Bausch and Lomb. Lotrafilcon A is a fluorosiloxane
hydrogel with a Dk of 140 barrer, and a water content of
24%. Balafilcon A is a siloxane hydrogel with a Dk of 99
barrer and a water content of 34%. Both materials
Fig. 10. Representation of a simplified model of a bi-phasic material manifest a slightly higher modulus (>1 MPa) than most
for finite element analysis. current conventional hydrogels which gives them

Fig. 11. Refined, simplified model of a bi-phasic material showing the added refinement of connectivity x (the reduction factor of the width of the
‘‘bridge’’ to the neighboring island of the same phase).
 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283 3281

Fig. 12. Prediction of oxygen permeabilities achieveable with bi-phasic siloxane hydrogels using different values of connectivity x: Note that the
calculated permeabilities for the dispersions (x ¼ 0) are much lower compared to those of the co-continuous phase morphologies (x ¼ 1 and x ¼ 0:5).

Fig. 13. Structural representation of the type of fluorosiloxane macromer used in lotrafilcon A.

Fig. 14. Structural representation of the siloxane macromer in balafilcon A, n=25.

excellent handling characteristics. Both are marketed Balafilcon A is prepared from tris-(trimethylsiloxy-)
outside the US for up to 30 nights of extended wear. silyl-propylvinyl carbamate (TRIS-VC), a vinyl carbo-
Balafilcon A is approved for 6 nights extended wear in nate functional PDMS macromer (Fig. 14), co-polymer-
the US. FDA approval is pending for lotrafilcon A. ized with NVP and the vinyl carbamate derived from
Lotrafilcon A is based on a fluorosiloxane macromer b-alanine [54].
derived from PDMS and PFPE segments (Fig. 13), co-
polymerized with TRIS and DMA monomers.
The fluorosiloxane macromer is believed to impart a 12. Ongoing research in siloxane hydrogels
reduced lipophilicity to this bulk material compared to a
composition containing no fluorine. The ‘‘bulk’’ materi- Patents continue to appear in the realm of siloxane
al terminology refers to the fact that both these products hydrogel contact lens materials. The bulk of the activity
are surface treated as part of their manufacture. seems to reside in the corporate arena represented by
Although siloxane hydrogels absorb water, it has been Bausch and Lomb, CIBA Vision and more recently,
found that they require surface modification to over- Johnson and Johnson.
come their tendency to attract lipids present in the tear It is certainly apparent the goal of higher oxygen
film, which can de-stabilize the tear film on the anterior transmissibility has been achieved with Dk/t values of
surface of the lens and disrupt vision. Surface treatment 175 and 110 barrer/mm reported for lotrafilcon A and
is a complex subject and not within the scope of this balafilcon A, respectively. One new target in bulk or
paper. core materials would seem to be reduced modulus. The
3282 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283

two materials just mentioned have reported moduli disinfecting in the evening) are the main wearing
somewhat higher than conventional hydrogels owing to alternatives offered by the major manufacturers. The
the presence of the bulky siloxanyl groups and by virtue reduction in discomfort and mechanical insult offered by
of the relatively significant amounts of bi-functional soft polymers and recently the elimination of corneal
macromer present. Recent patents [55–60] disclose novel stress due to the oxygen availability provided by
macromer architectures claimed to provide polymers of siloxane hydrogels all promise to improve the physio-
lower modulus, largely through the use of mono- logical performance of contact lenses. Contact lens
functional entities, some with unique pendant or wearer demand for the convenience of extended wear
terminal groups. Lower modulus materials are generally and practitioner and regulatory agency demands for
believed to provide lenses which are easier to fit and greater safety and fewer adverse events continue to be
more comfortable for the wearer. These benefits must be the motivating forces for better contact lens technology.
considered in light of a possible trade-off in ease of The commercial realities then drive further innovations
handling. in materials designed to be produced in an efficient, low-
cost manner.
This paper has dealt mainly with bulk polymer
13. Process-driven materials development technology for contact lenses. Equally interesting and
challenging work is being done regarding the surface
With the advent of disposable contact lenses has come performance of contact lenses. Surface technologies
the demand for materials which may be processed delivering increased bio-compatibility, bio-activity and
through high-throughput, highly automated, lower cost bio-mimicry are equally if not more important than the
manufacturing processes. Recent patents disclose mate- bulk polymer characteristics. That is likely the next
rials that allow for such processing. Obviously, high frontier.
volume, automated processes have been designed to Contact lenses offer an attractive, effective option for
produce conventional hydrogels, for example etafilcon non-invasive sight correction. Perhaps the success in
A, the first disposable contact lens offered on the US contact lens materials innovations can best be measured
market. However patents reveal material innovations by the degree to which lenses offer the ametropes of the
that are designed to accommodate more cost effective world, viable alternatives to spectacles or refractive
and environmentally attractive processes [61–65]. A surgery options.
recent innovation in contact lens polymer development
for daily disposable lenses is nelfilcon A, a PVA based
hydrogel produced by an entirely new process allowing Acknowledgements
for high throughput, low cost manufacturing [66,67].
The process known as the LightstreamTM process The authors wish to thank John McNally, O.D., John
employs re-usable molds and a photo-lithographic Lally, Ph.D. and Bill Long for their helpful comments
process to form the edge. The novel raw materials during the preparation of this manuscript. We also wish
employed also obviate the need for post-cure extraction to thank Christine Irrgang for the DSC work.
typical of most contact lens manufacturing processes.
A Lai patents covering thermoplastic siloxane hydro-
gel materials, which can be processed to contact lenses
without the use of UV curing has recently appeared [68]. References
Vanderlaan et al. [69] disclose siloxane hydrogels based
on macromers that require low levels of diluent in the [1] Lai Y, Wilson A, Zantos S. Contact lens. Kirk-Othmer
pre-polymer composition. Encyclopedia of Chemical Technology, vol. 7, 4th ed. New York:
Wiley, 1993. p. 191–218.
[2] Gaylord N. US Patent 3,808,178, 1974.
[3] Gaylord N. US Patent 3,808,179, 1974.
14. Conclusion [4] Gaylord N. US Patent 4,120,570, 1978.
[5] Birdsall A, Fitzgerald J, Jones D, Polmanteer K. US Patent
Contact lens materials are a small microcosm in the 4,198,131, 1980.
[6] Mitchell D, US Patent 4,487,905, 1984.
world of biomaterials. Their evolution has been and [7] DeCarle J. Developing hydrophilic lenses for continuous wearing.
continues to be an interesting series of developments, Aust J Optom 1972;55:343–6.
driven by our greater understanding of ocular physiol- [8] Reuben M, Brown N, Lobascher D, Chaston J, Morris J. Clinical
ogy and the demand for products designed for the wide manifestations secondary to soft lens wear. Br J Ohthalmol
1976;60:529–30.
variety of intended wear modalities. Daily disposable
[9] Poggio E, Schein O, Kenyon K, Glynn R, Seddon J. The risk of
wear, extended wear, flexible wear (daily and overnight microbial keratitis among cosmetic soft contact lens wearers: an
wear at the patients discretion) or conventional wear incidence study and a case-control study. Washington: The
(insertion each morning and removal with cleaning and Contact lens Institute, 1998.
 P.C. Nicolson, J. Vogt / Biomaterials 22 (2001) 3273–3283 3283

[10] Poggio E, Glynn R, Schein O, Seddon J, Shannon M, Scardino V, [35] Keogh P, Ku. nzler J, Niu G. US Patent 4,260,725, 1981.
Kenyon K. The incidence of ulcerative keratitis among users of [36] LeBoeuf A. US Patent 4,261,875, 1981.
daily-wear and extended-wear soft contact lenses. N Engl J Med [37] LeBoeuf A. US Patent 4,294,974, 1981.
1989;321:779–83. [38] Ku. nzler J, Ozark R. Hydrogels based on hydrophilic side-chain
[11] Schein O, Glynn R, Poggio E, Seddon J, Kenyon K. The relative siloxanes. J Appl Polym Sci 1995;55:611–9.
risk of ulcerative keratitis among users of daily-wear, extended- [39] CIBA Vision; unpublished results.
wear soft contact lenses. N Engl J Med 1989;321:773–8. [40] Ku. nzler J, Ozark R. US Patent 5,321,108, 1994.
[12] FDA Practitioner Letter. Ulcerative keratitis and contact lens [41] Bambury R, Seelye D. US Patent 5,070,215, 1991.
wear. May 30, 1989. [42] Lai Y. US Patent 5,310,779, 1994.
[13] Schein O, Buehler P, Stamler J, Verdier D, Katz J. The impact of [43] Lai Y, Friends G, Valint P. US Patent 5,352,714, 1994.
overnight wear on the risk of contact lens associated ulcerative [44] Lai Y. The role of bulky polysiloxanylalkyl methacrylates in
keratitis. Arch Ophthalmol 1994;112:186–90. oxygen-permeable hydrogel materials. J Appl Polym Sci
[14] Hamano H, Watanabe K, Hamano T, Mitsunaga S, Katani S, 1996;56:317–24.
Okada A. A study of complications induced by conventional and [45] Nicolson P, et al. US Patent 5,760,100, 1998.
disposable contact lenses. CLAO J 1994;20:103–8. [46] Nicolson P, et al. US Patent 5,776,999, 1998.
[15] Boswall G, Ehlers W, Luistro A, Worrall M, Donshik P. A [47] Nicolson P, et al. US Patent 5,789,461, 1998.
comparison of conventional and disposable extended wear [48] Nicolson P, et al. US Patent 5,848,811, 1998.
contact lenses. CLAO J 1993;19:158–65. [49] Nicolson P, et al. US Patent 5,965,631, 1999.
[16] USP Dictionary of USAN and International Drug Names. [50] Domschke A, Lohmann D, Winterton L. On-eye mobility of soft
Rockville, MD: US Pharmacopeia, 2000, p. 259. oxygen permeable contact lenses. Proceedings of the ACS Spring
[17] Tyler’s Quarterly Soft Contact Lens Parameter Guide, Profes- National Meeting, San Francisco: PMSE, 1997.
sional Edition, vol. 18. Little Rock: Tyler’s Quarterly Inc., 2000. [51] Tighe B. Silicone hydrogel materials–how do they work? In:
p. 29. Sweeney D, editor. Silicone hydrogels: the rebirth of continuous
[18] Holden B, Mertz G. Critical oxygen levels to avoid corneal edema wear contact lenses. Oxford: Butterworth Heinemann, 2000.
for daily and extended wear contact lenses. Invest Ophthalmol Vis p. 1–21.
Sci 1984;25:1161–7. [52] Takayanagi M, Harima H, Iwata Y. J Soc Mater Sci Japan
[19] Harvitt D, Bonanno J. Re-evaluation of the oxygen diffusion 1963;12:389.
model for predicting minimum contact lens Dk/t values needed to [53] Marcussen L. Thermal conductivity. In: Ashworth T, Smith D,
avoid corneal anoxia. Optom Vis Sci 1999;76:712–9. editors. New York: Plenum, 1985. p. 585.
[20] Mueller K, Kleiner E. US Patent 4,136,250, 1979. [54] USPS Dictionary of USAN and International Drug Names,
[21] Tanaka K, Takahashi K, Kanada M, Kanome S, Nkajima T. US op.cit., p. 75.
Patent 4,139,513, 1979. [55] Ku. nzler J, Ozark R. US Patent 5,710,302, 1998.
[22] Deichert W, Su K, van Buren M. US Patent 4,153,641, 1979. [56] Ku. nzler J, Ozark R. US Patent 5,714,557, 1998.
[23] Keogh P, Ku. nzler J, Niu G. US Patent 4,259,467, 1981. [57] Ku. nzler J, Ozark R. US Patent 5,908,906, 1999.
[24] Rice D, Ihlenfeld J. US Patent 4,440,918, 1984. [58] Vanderlaan D, Hargiss M, Williams S, Nunez I, Alton M.
[25] Rice D, Ihlenfeld J. US Patent 4,818,801, 1989. European Patent Application 0940693, 1999.
[26] Isaacson W, President of 3M Vision Care, Minneapolis, MN, [59] Ozark K, Ku. nzler J. US Patent 5,959,117, 1999.
Private communication. [60] Meijs G, Laycock B. US Patent 5,981,615, 1999.
[27] Salame M, Steingeiser S. Barrier polymers. Polym Plast Technol [61] Mueller B. US Patent 5,508,317, 1996.
Eng 1977;8:155–75. [62] Mueller B. US Patent 5,583,163, 1996.
[28] Molock F. US Patent 5,039,769, 1991. [63] Mueller B. US Patent 5,782,460, 1998.
[29] Su K, Robertson R. US patent 4,740,533, 1988. [64] Mueller B. US Patent 5,789,464, 1998.
[30] Mueller K, Heiber S, Plankl W, US Patent 4,486,577, 1984. [65] Mueller B. US Patent 5,849,810, 1998.
[31] Lai Y, Baccei L. US Patent 5,034,461, 1991. [66] Mueller B. US Patent 6,106,749, 2000.
[32] Robertson R, Su K, Goldenberg M, Mueller K. US Patent [67] Mueller B. US Patent 6,113,817, 2000.
5,070,169, 1991. [68] Lai Y, Quinn E. US Patent 5,969,076, 1999.
[33] Goldenberg M. US Patent 4,929,692, 1990. [69] Vanderlaan D, Hargiss M. European Patent Application 0940447,
[34] Hirt T. US Patent 6,039,913, 2000. 1999.