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Adhesive Dental Materials-A Review: John W. Nicholson

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International Journal of Adhesion & Adhesives 18 (1998) 229 — 236

Adhesive dental materials—A review


John W. Nicholson
Dental Biomaterials Department, University of London, King+s Dental Institute, Caldecot Road, London, SE5 9RW, UK

Accepted 21 April 1997

Abstract
The use of adhesive substances in dentistry, particularly in the restoration of decayed teeth, is growing. Adhesive materials are also
used for securing brackets to the teeth in orthodontic treatment and for luting the form of artificial teeth known as jacket crowns in
place. In recent years, there has been considerable growth in the use of adhesive systems to repair teeth damaged by caries. In this
application, adhesive materials show two important advantages over traditional materials, such as silver amalgam, namely: (i) that
marginal leakage is prevented, thereby eliminating the development of secondary caries; and (ii) that adhesive materials are more
clinically conservative, since they allow the dentist to repair the tooth without removing excessive amounts of healthy tissue. Teeth
repaired in this way are stronger and more likely to last that those treated with silver amalgam fillings. Adhesive dental materials
include the glass—ionomer and zinc polycarboxylate cements, and also the dentine bonding agents used to bond composite resin
restorations to the dentine of the tooth. This article reviews these materials and their clinical applications and discusses likely future
developments in the light of the changes occurring in oral health and age distribution of the population. ( 1998 Elsevier Science Ltd.
All rights reserved.

Keywords: adhesive dentistry; bonding agents; glass—ionomer; zinc polycarboxylate; composite resin; dentine and enamel

1. Introduction dentine, leading to an undermining of the enamel surface


layer of the tooth [3].
Dentistry is concerned with the repair and treatment of Because caries is not immediately life threatening, we
the teeth in order to give proper function and, secondar- tend to assume that it is an unimportant condition.
ily, good aesthetics. The main dental treatments that However, this is not true. The infection it causes can lead
employ adhesives are orthodontics and restoration. In to other more serious conditions, including the poten-
orthodontics misplaced teeth are realigned to improve tially fatal one of endocarditis. Swelling can develop as
function by subjecting them to forces using special wires. the infection moves from the tooth and may move to the
Orthodontic devices come in two types, fixed and re- neck, leading to a condition known as Ludwig’s angina
moveable appliances. In fixed appliances, wires are at- [4]. In extreme cases, this swelling can block the wind-
tached to the teeth by way of brackets, and tightened to pipe, leading to death by asphyxiation [4].
apply the required force. Traditionally the brackets have Dental repair can thus be seen to be important. Repair
been clamped to the teeth mechanically, but increasing materials are the subject of considerable research at the
they are applied using a dental adhesive [1]. moment, with an emphasis on aesthetic materials (i.e.
Numerically much more common than orthodontic those that match as closely as possible the colour and
treatment is the repair of teeth damaged by caries. Dental translucency of the tooth) that are capable of being
caries is a preventable condition, but very widespread, bonded to the cleaned tooth surface. There are two major
possibly the most common disease of the civilised world clinical benefits of using adhesive materials. Firstly, ma-
[2]. It occurs as the result of metabolic activity by the terials that are properly bonded to the tooth do not allow
bacteria of the plaque, leading to the production of acids bacteria to gain access in the space between the filling
such as lactic acid from sugar in the diet, and involves and the tooth, a phenomenon known as microleakage.
a localised attack on the enamel and dentine of the tooth. When this occurs, the bacteria cannot be removed by
Caries begins on the surface of the tooth and gradually brushing, and their metabolic activity results in extensive
bores into the bulk. Its progress through the enamel is decay within the tooth, so-called secondary caries. There
relatively slow, but it moves more rapidly through den- may also be pain to the patient as the caries develops
tine. This causes the decay to balloon out on reaching the close to the pulp.

0143-7496/98/$—see front matter ( 1998 Elsevier Science Ltd. All rights reserved.
PII: S0143-7496(98)00027-4
230 JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236

The second clinical advantage of using adhesive mater- Table 1


ials is that less of the healthy tooth tissue needs to be Approximate composition of enamel and dentine
removed in cavity preparation prior to placement. The Enamel Dentine
reason that placement of a silver amalgam is preceeded
by such extensive drilling is that amlagam does not Mineral phase (hydroxyapatite) 97% 69%
Organic phase (mainly collagen) 1% 20%
adhere to the tooth [1]. Consequently, to repair a lesion Water 2% 11%
with amalgam, the clinician has to create a cavity that is
capable of retaining the hardened filling mechanically.
This means cutting a cavity that has a large volume but
a small access, a process which removes healthy tooth adhesive bond. Moreover, unless care is taken, applying
tissue, and also weakens the remaining structure. a bonding agent to dentine can cause adverse pulpal
reaction [7], and possibly enlargement of the tubules
[8, 9].
2. Adhesion in dentistry Most cavities involve the dentine [10]. When a cavity
is cut into this substance, the surface that results consists
Unlike adhesive bonding in other fields of technology, of disordered dentine, known as the smear layer. Gener-
adhesion in dentistry involves a living substrate that may ally clinicians recommend that this smear layer be
show considerable variation. The structure of a typical removed prior to bonding, so that bonding may be de-
incisor tooth is shown in Fig. 1, and from this it can be veloped on a clean surface [11, 12]. This is readily
seen that the enamel layer is relatively thin, whereas the accomplished, for example by washing with aqueous
dentine is much thicker. solutions of either citric acid or ethylenediaminetetra-
In practical terms, adhesion to enamel and dentine acetic acid, EDTA. However, in the late 1980s, Douglas
presents different problems. This is because they have argued that the smear layer is not simply debris, but
different compositions, as shown in Table 1, and also a deranged form of dentine that retains its attachment to
different anatomies. Enamel is smooth and continuous, the underlying structurally sound dentine [13]. As a re-
whereas dentine has numerous tubules running through sult, for a while clinical opinion changed towards the
it. These tubules connect with the pulp, the vital and soft view that the smear layer was an asset [14], and that this
inner section of the tooth [5]. Consequently, dentine is was the surface to which bonding should be made. How-
a dynamic substrate in which physiological activity ever, studies such as those by Davidson et al. [15] have
brings about continual changes [6]. The cut surface of shown that those bonding systems that left the smear
dentine consists of exposed ends of the tubules, and layer intact were more prone to premature failure than
physiological fluid flows up these, creating a moist envi- systems which removed it, and opinion is shifting back to
ronment that interferes with the development of an the view that the smear layer should be removed to
develop maximum bond strength and durability.
In order to bond composite resins to dentine special
bonding agents are required [16]. This is a difficult area
of clinical dentistry, partly due to the enormous variety of
substances available to the clinician [17]; in late 1996,
there were 84 different brands of dentine bonding agent
on the market (R. Erickson, 3M Dental, Private com-
munication, 1996), most of them based on unique formu-
lations. The most important of these are discussed later
in the article.
To bond a material to the harder enamel, a form of
mechanical retention is employed. This does not involve
drilling, but rather the use of acidic etchant, typically
a viscous gel of phosphoric acid at a concentration of
37%. This acid-etch technique was developed by
Buonocore [18] and involves the gel being applied to the
enamel for a very short time, typically 15 s, in which time
the acid causes a selective demineralisation leading to the
development of a roughened surface. The surface changes
greatly in appearance, becoming chalky, due to the devel-
opment of microporosity within the surface. This treat-
ment also increases the surface energy of the enamel,
Fig. 1. Structure of a typical incisor tooth. allowing hydrophobic monomers of the composite resin
JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236 231

to spread across the surface and penetrate the micro- ployed for attaching crowns to posts and for the adhesion
porosity [19], thus forming a strong attachment. of orthodontic brackets [1].

3. Zinc polycarboxylate cements 4. Glass–ionomer cements

The first truly adhesive dental restorative material was The development of the glass—ionomer cement arose
the zinc polycarboxylate cement, introduced by Smith in from previous fundamental studies on dental silicate ce-
the late 1960s [20]. This material is prepared from deac- ments, materials which were formed from special basic
tivated zinc oxide, admixed with a minor amount (10%) glasses and aqueous phosphoric acid [27]. It was assisted
of magnesium oxide. Deactivation of the zinc oxide is by work on the zinc polycarboxylate cement [20] in
achieved by heating, and leads to the development of pale which Smith showed that dental cements exhibiting the
yellow colouration, due to the loss of a small amount of property of adhesion could be prepared from poly(acrylic
the oxygen to generate the non-stoichiometric form of acid). Glass—ionomers have therefore been described as
the oxide ZnO where x is less than or equal to hybrids of dental silicates and zinc polycarboxylates.
(-~x)
70 ppm [21]. This basic powder is then reacted with However, although this view seems attractive, it is not
aqueous poly(acrylic acid) to form the cement. The re- actually correct [28]. A practical cement cannot be pre-
sulting cement is a reasonably brittle material, though it pared from these two components alone, because the
shows some moderate plasticity for some time after dental silicate glass is not sufficiently basic to react with
formation [22]. Typical properties are shown in Table 2. aqueous poly(acrylic acid). In fact, to make a glass—
The set cement comprises zinc poly(acrylate) as the ionomer cement required new glasses of altered basicity
matrix, with unreacted zinc oxide/magnesium oxide pow- and it was only later, when the discovery of the effect of
der embedded in it. The powdered base thus acts jointly the additive (#)-tartaric acid was made [29], that glass-
as a reactant and filler. es similar in composition to the old dental silicate glasses
Zinc polycarboxylate cements have been shown to could be used.
behave somewhat like thermoplastic composites The initial problem was to enhance the reactivity of the
with very weak crosslinks between the polyacrylate glass towards the polymer. Early cements set sluggishly,
chains [23]. One consequence of this is that there being unworkable relatively quickly but taking a con-
is a relatively large plastic zone at the fracture tip, siderable time to harden. They also remained sensitive to
which in turn makes the material senstitive to the thick- moisture loss and water ingress for extended periods of
ness at which it is used [24]. The plastic zone size for time after setting. The glass that first approximated to an
an experimental zinc polycarboxylate was found to acceptably reactive component, so-called G200, was high
vary with the molecular weight of the poly(acrylic acid) in fluoride, and itself highly opaque. It thus gave cements
from 40 lm at a molecular weight of 11 500 to 290.0 lm whose translucency was very low and hence which were
at a molecular weight of 383 000 [24]. A subse- unacceptable aesthetically.
quent study confirmed this effect of an optimum adhesive The early difficulties began to be solved following the
layer thickness for a commercial zinc polycarboxylate in discovery of the effect of (#)-tartaric acid. This material,
clinical use, showing it to have an optimum layer added in small amounts, improved the manipulation of
at 205 lm, which was assumed also to be the approxim- the cement paste by modifying the setting rate, extending
ate size of the plastic zone at the crack tip as the bond the working time and sharpening the set. The resulting
failed [25]. material thus has significantly enhanced handling prop-
Zinc polycarboxylate cements are used a variety of erties [30]. However, despite the fact that more than
clinical procedures, all of which rely on the inherently 20 years have passed since this discovery of its effect, the
good adhesion of the material to a number of substrates precise mode of action of (#)-tartaric acid remains un-
[26]. For example, they are used to line cavities prior to clear.
placement of the main restorative material, they are em- Clinically, the use of glass—ionomer cements was de-
veloped to exploit the adhesion of the cement to natural
tooth material. An early suggestion was the use in sealing
Table 2 deep fissures in the surface of molars, in which bacterial
Properties of zinc polycarboxylate cement
plaque otherwise accumulates [31]. This application also
Property Typical components/values exploited the fluoride-releasing capability of the material.
Other suggestions to emerge early in the development of
Liquid 40—45% polyacid these materials included their use as restoratives for so-
Powder:liquid ratio 2.5—3.0:1 called Class V erosion lesions (i.e. cavities along the gum
Setting time/min 2—4
line thought to be caused by heavy brushing), as liners or
Compressive strength/MPa 80—100
bases beneath composite resins and in minimal cavity
232 JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236

restorations [32—34]. This latter idea was extended to a clear, ion enriched layer due to interpenetration of the
develop the so-called tunnel preparation [35], in which vital tooth tissue with the porous cement surface. This
caries is removed from within the tooth while preserving layer is stronger than the bulk of the cement, and conse-
the maximum amount of surface enamel. This is followed quently resists failure in shear bonding experiments.
by injecting glass—ionomer cement, which sets and acts as Glass—ionomer cements are relatively brittle materials
the core which binds the enamel shell together. Most of and, as mentioned, they suffer the important disadvan-
these have become more or less routine procedures in tage of sensitivity to early moisture damage. In an at-
clinical dentistry. tempt to overcome these problems, resin-modified
Modern glass—ionomers undergo a sharp set to yield glass—ionomers have been devloped in the last ten years
a brittle material approximately four minutes from the or so.
start of mixing. This is the time at which the metal matrix Resin-modified glass—ionomers are a group of dental
band, used as a former for the surface of the restoration, restorative materials that consist substantially of
can be removed and the placement examined for defects. glass—ionomer components, i.e. water-soluble polymeric
The material is still, though, slightly susceptible to water acid, ion-leachable glass and water, but also include
uptake and/or loss, which inhibits the setting reaction organic, photopolymerizable monomers and their asso-
and results in an inferior material. To overcome this ciated initiation system [40]. The first of these materials
problem, a newly placed cement is usually painted with was described in a patent application, since abandoned,
a waterproof sealant as the matrix band is removed [36]. and comprised simply a mixture of ingredients, including
Manufacturers typically supply a special varnish sealant, 2-hydroxyethylmethacrylate, HEMA (I), to act as cosol-
but this does not necessarily provide a sufficiently imper- vent for the organic and aqueous components [41].
meable finish, at least as just a single coat. An alternative Shortly afterwards, the development of a cement-forming
procedure adopted by some clinicians is to employ a low system based on graft copolymers of poly(acrylic acid)
viscosity light-cured unfilled resin system. As the matrix was announced. In these materials, a minor proportion of
band is removed, a generous amount of such resin is the carboxylic acid functional groups were replaced with
allowed to flow over the cement restoration. When the crosslinkable branches that were terminated in vinyl
contour is completed, further resin can be added if neces- groups [42]. For these materials, too, HEMA was re-
sary, and the whole protective coating cured by irradia- quired in order to retain all of the components in a single
tion with light. The resinous layer can be removed after phase.
24 h, at which time the cement can be finished by polish-
ing under air/water spray. This technique gives optimum
translucency and physical properties.
Glass—ionomers continue to harden slowly after the
initial setting is complete, developing a compressive
strength of 180—220 MPa at 24 h [37]. Measuring adhes- (I) Hydroxyethylmethacrylate, HEMA
ive bond strength is somewhat problematical. Many The resin-modified glass—ionomers, whatever the de-
studies have been carried out, and treated the results as tail of their composition, have been shown to adhere to
though they are a measure of the interfacial adhesion enamel and dentine [43], though bond strengths seem
between the glass—ionomer and the substrate, usually less than for the self-hardening glass—ionomers [44]. This
dentine or enamel. However, glass—ionomers typically had led some manufacturers to specify that dentine bond-
fail cohesively within the cement itself, and most of the ing agents of the type used for composite resins should be
reported values of bond strength, which are low used with these materials. Resin-modified glass—
(3—6 MPa) are actually measures of the shear strength of ionomers have also been shown to release clinically use-
the cement. ful amounts of fluoride [45, 46]. On the other hand, they
Rather than rely on apparent shear bond strengths, have been found to swell in aqueous media [47], a pro-
other evidence has to be considered that indicates the cess which seems to be driven by the chemical potential
bond between the cement and enamel is very strong. of the solvent system, and is therefore greater in pure
Retention rates for glass—ionomers placed in Class V cav- water than in, for example, 0.9% sodium chloride solu-
ities, where inherent adhesion is essential, show them to tion, or than would be expected in saliva [48].
be excellent. For example, one commercial glass— Despite these disadvantages, overall the combination
ionomer cement, Ketac-Fil (ex. ESPE, Seefeld, Germany) of bonding to the tooth, fluoride release, and control of
showed a retention of at least 86% after 4 years [38,39]. setting has made resin-modified glass—ionomers attract-
These retention rates are superior to bonded composite ive to clinicians. At least one has predicted that these
resins, even though in vitro measurements showed them materials are likely to make obsolete the use of silver
to have much higher shear bond strengths, of the order of amalgam within the foreseeable future, at least in chil-
15 MPa. Glass—ionomers show good compatibility with dren’s dentistry [49], where long term durability is not
the tooth surface, and this can develop with time into required.
JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236 233

5. Composite resins worse by the high polymerisation shrinkage of the poly-


mer matrix [54].
Although glass—ionomer cements are used as aesthetic As previously mentioned, bonding to enamel is
restoratives in particular applications, they are less wide- achieved using the micromechanical attachment that fol-
ly used than the so-called composite resins [50]. This is lows from treating the surface with phosphoric acid gel.
generally the aesthetic material of choice for repairing Resulting bond strengths are high, for example, values of
teeth, and may be used to repair damage caused by caries 20—24 MPa for shear bonding can be obtained on etched
or by trauma. human enamel [55]. Bonding to dentine, by contrast,
There are a variety of materials within class of dental tends to give lower values, typically in the region
composite resin, but most are based on bis-GMA (II), as 8—15 MPa.
patented by Bowen in January 1959. This substance is Although micromechanical attachment is generally
the reaction product obtained from bisphenol A and associated with bonding to enamel, modern agents
glycidyl methacrylate, and cures by an addition process for bonding to dentine are assumed to act, partly at least,
involving the terminal methacrylate groups [51]. The by this mechanism. A small proportion of the bond-
bis-GMA liquid is highly viscous and practical formula- ing agent is able to flow into dentinal tubules, and
tions are produced by adding liquid diluents comprising to harden to form a tag which holds the layer in place
monomers of lower molar mass. These include diethylene [56]. However, this is not the most important mechanism
dimethacrylate (III) or its triethylene analogue. Being of adhesion. In applying a bonding agent to the dentine
methacrylate terminated, these molecules react in much surface, a resin—dentine hybrid zone is formed, and
the same way as bis-GMA at the cure stage. Alternative this considerably reinforces the bonding zone [57].
monomers, urethane dimethacrylate may also be used in This hybrid zone has been shown to be typically some
dental composite resins [52]. 2—5 lm wide, and to form through the infiltration

(II) Bis-GMA monomer of liquid bonding agent into tubules with widened open-
ings [58]. The formation of such a hybrid layer has
been shown to be more important than tag formation
in creating a clinically durable bond between the com-
posite resin and the tooth. Results have shown that
bonding agents which do not flow into the tubules, and
hence cannot form tags, can promote good adhesion
(III) Diethylene diemethacrylate diluent solely through the development of the hybrid zone
For clinical use, composite resins are usually supplied [59, 60].
as one-paste systems that are cured by exposure to visible A number of organic compounds have been con-
light, typically blue light at 470 nm. Initiation in such sidered for use as bonding agents. One interest-
formulations is effected by an a-diketone, such as cam- ing example was the organophosphorus compound used
phorquinone, with an amine reducing agent. Exposure of as the very first dentine bonding agent of all, de-
this initiator system to light yields the free radicals re- veloped by Hagger in the early 1950s. This was based
quired to effect polymerisation of the monomer molecules on glycerophosphoric acid dimethacrylate (IV) [61]
[53]. and sold under the name of Sevriton Cavity Seal.
Composite resins are aesthetically attractive mater- Like many molecules employed in dentine bonding
ials, having the translucency and colour to match a agents, glycerophosphoric acid dimethacrylate has
variety of shades of natural teeth. They also show a non-polar tail and a strongly polar head. It was
good durability in the oral environment, both in terms thought to bond to the calcium of the dentine via
of resistance to erosion and wear, and in terms of the phosphate groups [62], though this was never dem-
colour stability. However, their major disadvantage is onstrated conclusively. Whatever its method of action,
their lack of adhesion to dentine. Bond failure in these it did not prove very effective, since it was hydro-
systems stems from lack of wetting of the tooth surface lytically unstable and bond failures occured during cli-
due to their hydrophobic character and is made nical testing [63].
234 JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236

Another successful bonding system, known as Scotch-


bond (ex. 3M Dental), employed the halophosphorus
ester of bis-GMA in conjunction with triethylene glycol
dimethacrylate diluent and benzoyl peroxide as a resin
component, used in conjunction with an ethanolic solu-
tion of tertiary aromatic amine plus sodium benzenesul-
phonate. The phosphate esters appear capable of substi-
tution into the hydroxyapatite lattice, and are stabilised
against hydrolysis by the sulphonate part of the system.
Unlike the Gluma system, this adhesive was designed to
leave the smear layer intact and was used in two coats.
Polymerisation occured once the composite resin was
(IV) Glycerophosphoric acid dimethyacrylate placed over the top of the system, and gave quite accept-
Other dentine bonding agents have been developed in able bond strengths, i.e. of the order of 8 MPa [67,68].
the years since these early reports, and materials gener- The presence of ethanol as catalyst carrier was also
ally have much improved properties [64]. An organic helpful towards bonding since it displaced surface bound
derivative of phosphoric acid, 2-methacryloxyethyl water, thus assisting efficient dentine wetting.
phenyl phosphoric acid (V), has been used with some There is considerable research in this field at the mo-
success [65]. Like a number of other bonding agents, this ment, with a strong trend being to develop multifunc-
material, available under the name Clearfil, is essentially tional monomers, which are hydrophilic and can act
a methacrylate derivative with both a hydrophilic and partly by etching the dentine. Surface pretreatments are
a hydrophobic functional group. There is considerable often used in conjunction with these substances. These
doubt that it undergoes any chemical reaction at the are generally designed to increase the local concentration
dentine surface [66], though this was suggested origin- of multivalent ions capable of chelating with appropriate
ally. However, the bonding agent becomes incorporated substances, and include mixtures such as aqueous 10%
into the setting composite resin too rapidly to allow citric acid/3% ferric chloride [1].
much in the way of surface reaction, which is anyway
made unlikely by the presence of moisture on the surface.
On the other hand, there is evidence that this particular 6. Polyacid-modified composite resins
derivative assists the liquid composite resin to penetrate
the dentinal tubules, thereby enhancing the development Polyacid-modified composite resins are new dental
of resin tags to assist micromechanical attachment. restorative materials that show predominantly the char-
acteristics of conventional composite resins, but include
some of the features of glass—ionomer cements [53]. They
set by an addition polymerisation as a result of irradia-
tion with visible light at 470 nm wavelength, have good
aesthetics, and are bonded to dentine using specially
designed bonding agents. They are also capable of some
neutralisation, as a consequence of the small number of
carboxylic acid groups in the functional molecule. The
presence of ion-leachable glasses in the formulation pro-
(V) 2-Methyacryloxyethyl phenyl phosphoric acid motes this neutralisation, albeit some time after the initial
Bonding systems have been designed to interact either setting, and the formation of the resulting polysalt is
with the mineral phase or the collagen of the dentine. An claimed to assist the process of fluoride release.
early example was a simple mixture of HEMA and glu- The first two commercial materials of this type on the
teraldehyde, known to clinicians as Gluma. In this mix- market were named, respectively, Dyract [69] and Com-
ture, the gluteraldehyde would bind to the collagen, leav- poglass [70] and these are the ones whose properties
ing the HEMA to infiltrate the surface of the dentine to have been reported to date. The manufacturers have
form the hybrid zone, and also to copolymerise with the coined the term compomer for these materials, a useful
monomers of the composite resin when that was placed trivial name which indicates that the materials combine
on top of the bonding mixture. This type of bonding aspects of the technologies of composite resins and
system was found to function better when used following glass—ionomers. This combination is not straightforward
surface conditioning with citric acid or ethylene—diamine because, although the key component has carboxylic acid
tetra-acetic acid, presumably because the relatively de- functional groups, these groups are not present in suffi-
mineralised and clean surface was better able to admit the cient quantities to confer water-solubility on the molecu-
organic monomer for the formation of the hybrid zone. le. Consequently these materials do not actually set by
JW. Nicholson / International Journal of Adhesion & Adhesives 18 (1998) 229—236 235

a neutralisation, but only by polymerisation, and also evidence [74], is nonetheless influencing clinical practice.
they lack the ion-exchange bonding mechanism that All of these trends place adhesion in dentistry at the
gives true glass—ionomers their inherent adhesion to den- forefront of dental research. The development of new
tine and enamel [36]. The multifunctional monomer, materials is continuing rapidly, and most if not all of the
known as TCB resin (VI) is used in Dyract, and is newer restorative materials are being expected to show at
illustrated below: least some adhesion to enamel and dentine. Yet the
mouth is an inhospitable place for materials, subjecting
them to high humidities and large shearing and compres-
sive forces. Given these constraints, progress to date in
finding materials capable of developing reliable and dur-
able adhesive bonds under these conditions has been
remarkable.

(VI) TCB resin


The commercial polyacid-modified composite resins References
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