DENTIN BONDING AGENTS

INTRODUCTION

• Bonding and adhesion comprise a complex set of physical, chemical and

mechanical mechanisms that allow the attachment and binding of one substance
to another.

• A dental bonding system performs three essential functions:-

(1) provides resistance to separation of an adherend substrate (i.e., enamel, dentin,
metal, composite, ceramic) from a restorative or cementing material;

(2) distributes stress along bonded interfaces; and

(3) seals the interface via adhesive bonding between dentin and/or enamel and the
bonded material, thus increasing resistance to microleakage and decreasing the
risk for postoperative sensitivity, marginal staining, and secondary caries.
HISTORICAL BACKGROUND
 MECHANISMS OF ADHESION

• If true adhesion of restorative materials to tooth structure is to be

achieved, three conditions must be satisfied:

1. Sound tooth structure must be conserved.

2. Optimal retention must be achieved.
3. Microleakage must be prevented.
• The fundamental mechanism of adhesion to tooth structure can be
regarded simply as an exchange by which inorganic tooth material
(hydroxyapatite) is replaced by synthetic resins.
• This process involves two parts:
(1) removing hydroxapatite to create micropores and
(2) infiltration of resin monomers into the micropores and subsequent
polymerization.
As a result, resin tags are formed that micromechanically interlock or
interpenetrate with the hard tissue.
• There may also be chemical interactions with the tooth substrate if
monomers having acidic or chelating functional groups are present.
• In general, the following factors can play major or minor roles in achieving
adhesive bonds:
• 1. Surface energy and wetting
• 2. Interpenetration (formation of a hybrid zone)
• 3. Micromechanical interlocking
• 4. Chemical bonding
• Wettability of a liquid on a solid can be characterized by the contact
angle that forms between a liquid and solid, as measured within the
liquid.
• Categories of wettability include -
• “mostly nonwetting” (>90 degrees),
• “absolutely no wetting” (180 degrees),
• “mostly wetting” (<90 degrees), and
• absolute wetting (0 degrees)
• Wettability can be enhanced by increasing the surface energy of the
substrates (e.g., dentin, enamel, and synthetic materials)
• The acidetch technique (see below), by which contaminants are removed
and microporosities are created, is widely used to generate high-energy
tooth surfaces and promote wetting by adhesive monomers.
• Enamel and dentin are hydrated, hydrophilic, and permeable to water.
• Even if an enamel or dentin surface is initially dried before applying an
adhesive, inadvertent contamination and diffusion can easily result in
water becoming strongly bound to both the hard tissue and the adhesive.
• Thus, for an adhesive monomer to wet hard tooth tissue as well as form a
durable bond in the moist environment of the mouth, it must be both
hydrophilic for water compatibility and hydrolytically stable to ensure
longevity.
 SMEAR LAYER

• Whenever both enamel and dentin tissues are mechanically cut, especially
with a rotary instrument, a layer of adherent grinding debris and organic
film known as a smear layer.
• left on their surfaces and prevents strong bonding.
• Application of acid is used to remove the smear layer from both enamel
and dentin.
• Alternatively, in dentin the smear layer can be left partially in place and
modified such that adhesive resins penetrate through it and bond to the
intact dentin structures below.
 ACID-ETCH TECHNIQUE

• The first meaningful demonstration of intraoral adhesion was reported by

Michael Buonocore (1955).
• Buonocore etched enamel surfaces with various acids, placed an acrylic
restorative material on the micromechanically roughened surfaces, and
found a great increase in the resin–enamel bond strength (~20
megapascals [MPa]).
• One of the surface conditioning agents he used, phosphoric acid, is still
the most widely used etchant today for bonding to both enamel and
dentin.
• Depending on the concentration, phosphoric acid removes the smear
layer and about 10 microns of enamel to expose prisms of enamel rods to
create a honeycomb-like, high energy retentive surface .
• The higher surface energy ensures that resin monomers will readily wet
the surface, infiltrate into the micropores, and polymerize to form resin
tags.
• The pattern of etching enamel may vary from -
• selective dissolution of either the enamel rod centers (type I
• etching)
• or the peripheral area (type II etching) as indicated by the resin tags
• In either case, the resin tags are approximately 6 µm in diameter and 10
to 20 µm in length and lead to micromechanical interlocking.
• Nakabayashi et al. (1984) revealed that hydrophilic resins can infiltrate the
surface layer of acid-demineralized collagen fibers that is produced in
etched dentin and it can form a layer of resin-infiltrated dentin with high
cohesive strength.

• Such a hybrid layer structure forms very strong resin bonds through the
development of an interpenetrating network of polymer and dentinal
collagen, together with numerous micromechanical interlocks at the
resin–hybrid layer interface.
• Dentin etching is more technique sensitive than enamel etching because of
the complexity of the dentin structure.
• Unlike enamel, dentin is a living tissue, consisting of 50 vol% (volume
percentage) of calcium phosphate mineral (hydroxyapatite), 30 vol% of
organic material (mainly type I collagen), and 20 vol% fluid.
• Acid etching removes hydroxyapatite almost completely from several microns
of sound dentin, exposing a microporous network of collagen suspended in
water.
• Whereas etched enamel must be completely dry to form a strong bond with
hydrophobic adhesive resins, etched dentin must be moist to form a hybrid
layer.
• The amount of water left in etched dentin is critical. If insufficient water is
present, the collagen network will collapse and produce a relatively
impermeable layer that prevents resin infiltration and subsequent
hybridization.
• If too much water remains, resin infiltration cannot fully replace the water in
the collagen network and, consequently, sets the condition for later leakage
into those locations.
• Therefore, a priming step is required to maintain a hydrated collagen network
while removing excess water.
 ETCHING TIME

• The optimal application time for the etchant may vary somewhat,
depending on previous exposure of the tooth surface to fluoride and
other factors.
• For example, a permanent tooth with a high fluoride content may require
a somewhat longer etching time, as do primary teeth.
• In the latter, increased surface conditioning time is needed to enhance
the etching pattern on primary tooth enamel that is more aprismatic than
permanent tooth enamel.
• Currently, the etching time for most etching gels is approximately 15
seconds.
 RINSING AND DRYING STAGE

• Once the tooth is etched, the acid should be rinsed away thoroughly with
a stream of water for about 20 seconds, and the rinsed water must be
removed.
• When enamel alone is etched and is to be bonded with a hydrophobic
resin (e.g., bisphenol A glycidyl methacrylate [bis-GMA]–based resin;),
• it must be dried completely with warm air until it takes on a white,
frosted appearance.
• Dentin, in contrast, cannot withstand such aggressive drying, which
would cause bond failure because of the formation of impermeable,
collapsed collagen fibers. In the total-etch technique, a dentin bonding
agent and primer must be used that are compatible with both moist
dentin and moist enamel.
 Challenge in Dentin Bonding

• Bonding to dentin presents a much greater challenge.-

1. Enamel is a highly mineralized tissue composed of more than 90% (by volume)
hydroxyapatite, whereas dentin contains a substantial proportion of water and
organic material, primarily type I collagen .
2. Dentin also contains a dense network of tubules that connect the pulp with the
dentinoenamel junction (DEJ)
3. Intertubular dentin is penetrated by submicron channels, which allow the
passage of tubular liquid and ibrils between neighboring tubules, forming
intertubular anastomoses. Dentin is an intrinsically hydrated tissue, penetrated
by a maze of luid-illed tubules.
4. Adhesion can be afected by the remaining dentin thickness after tooth
preparation. Bond strengths are generally less in deep dentin than in supericial
dentin.
• Whenever tooth structure is prepared with a bur or other instrument,
residual organic and inorganic components form a “smear layer” of debris
on the surface.
• smear layer ills the orifices of dentin tubules, forming “smear plugs” and
decreases dentin permeability by nearly 90% in vitro.
• composition of the smear layer is basically hydroxyapatite and altered
denatured collagen.
• altered collagen can acquire a gelatinized consistency because of the
friction and heat created by the preparation procedure.
• Submicron porosity of the smear layer still allows for diffusion of dentinal
fluid.
• Removal of the smear layer and smear plugs with acidic solutions results
in an increase of the fluid low onto the exposed dentin surface.
 CLEANNESS OF THE BONDING SURFACES

• The etched surfaces must be kept clean (free of contaminants) and

sufficiently dry until the resin is placed to form a sound mechanical bond.
• Although etching raises the surface energy, contamination can readily
reduce the energy level of the etched surface.
• Reducing the surface energy, in turn, makes it more difficult to wet the
surface with a bonding resin that may have too high a surface tension to
wet the contaminated surface.
• Thus, even momentary contact with saliva or blood can prevent effective
resin tag formation and severely reduce the bond strength.
• Another potential contaminant is oil that is released from the air
compressor and transported along the air lines to the air–water syringe. If
contamination occurs, the contaminant should be removed, and the
surface should be etched again for 10 seconds.
 OTHER FACTORS

• With those resins, curing (>6 vol% shrinkage) and thermal dimensional
change(coefficients of thermal expansion in excess of 100 parts per
million per degree Celsius [ppm/°C]) generated interfacial stresses
sufficient to rupture the bond to etched enamel.
• When the composite is bonded to one surface only (e.g., for a direct
facial veneer), stresses within the composite are relieved by low from the
unbonded surface.
• Stress relief within a three-dimensional bonded restoration is limited
however by its coniguration factor (C-factor).
 DENTIN BONDING AGENTS

• Dental bonding agents are designed to provide a sufficiently strong

interface between restorative composites and tooth structure to
withstand mechanical forces and shrinkage stress.

• The success of adhesives is dependent on two types of bonding: -

• 1. Micromechanical interlocking, chemical bonding with enamel and

dentin, or both
• 2. Copolymerization with the resin matrix of composite materials
 COMPOSITION
• Etchants-
• Etchants are relatively strong acids (pH = 1–2) used to remove smear layers and to
dissolve the mineral phase to allow formation of micromechanical interlocking in
enamel and in dentin.
• phosphoric acid at a concentration between 30% and 50%, typically 37%, is the
preferred etching agent to produce consistent etching patterns while not
damaging the pulp.
• Concentrations greater than 50% result in the deposition of an adherent layer of
monocalcium phosphate monohydrate on the etched surface, which inhibits
further dissolution.
• Generally, the etchant is supplied as an aqueous gel to allow precise placement
over a specific area.
• These gels are often made by adding colloidal silica (the same fine particles used in
microfilled composites) or polymer beads to the acid.
• Brushes are used to place the acidic gel, or the acid may be supplied in a
disposable syringe from which it can be expressed onto enamel and dentin.
 Primers

• Dentin etching is highly technique sensitive because the demineralized

collagen network readily collapses when dried.
• Therefore, priming is necessary to maintain an expanded collagen
network while removing residual water to allow for the infiltration of the
hydrophobic adhesive monomer.
• Primers are solutions containing hydrophilic monomers dissolved in a
solvent such as acetone, ethanol, or water.
• Such monomers exhibit hydrophilic properties through phosphate,
carboxylic acid, alcohol, or ester functional groups.
• HEMA (2-hydroxylethyl methacrylate, is a widely used primer monomer
because of its high hydrophilicity and solvent-like nature.
• Representative of these are HEMA-phosphate, phenyl-P (2-
[methacryloyloxyethyl]phenyl hydrogen phosphate), 10-MDP (10-
methacryloyloxydecyl dihydrogen phosphate), 4-MET (4-
methacryloyloxyethyl trimellitic acid), 4-META (4-methacryloyloxyethyl
trimellitic anhydride), and MAC-10 (11-methacryloyloxy-1,1′-
undecanedicarboxylic acid).
 Solvents

• Solvents also play important roles in priming systems.

• The most commonly used solvents are water, ethanol, and acetone. In
addition to the enhancement of wetting of hydrophilic dentin, each
solvent has a specific contribution to improve bond adhesion.
• Water can ionize acidic monomers as well as re-expand the collapsed
collagen network.
• Ethanol and acetone have better miscibility with relatively hydrophobic
monomers, and their “water-chasing” ability facilitates water removal.
 Adhesives

• For dentin bonding, the primary purpose of adhesives is to fill the

interfibrillar space of the collagen network, creating a hybrid layer and
resin tags to provide micromechanical retention upon polymerization.
• In addition, adhesive layers also should prevent fluid leakage along the
restorative material’s margin, since they make up the major part of the
intermediate layer between dentin and/or enamel and restorative
composites.
• It is evident that adhesives need to be hydrophobic so that fluid will not
be allowed to permeate through the intermediate layer.
• At the same time, adhesives require a certain hydrophilicity to diffuse into
the hydrophilic, primer-wetted dentin.
• Generally, adhesive resins are composed mainly of hydrophobic
dimethacrylates such as bis-GMA, TEGDMA, and urethane
dimethacrylates (UDMA), and a small amount of a hydrophilic monomer
such as HEMA.
 Initiators

• Similar initiator systems are used in both adhesives and restorative

composites.
• Polymerization can be initiated either through a photoinitiator system
consisting of a photosensitizer (e.g., camphorquinone) and an initiator
(e.g., tertiary amine), through a self-cure system that includes a chemical
initiator (e.g., benzoyl peroxide [BPO]), or through a dualcure initiator
system.
 Filler Particles

• Nanometer-sized silica particles have been added to some adhesives to reinforce

the adhesive and thereby produce higher bond strengths.
• However, the strengthening effect of the fillers in adhesives is uncertain because it
is not clear whether these fillers can actually penetrate into the demineralized
collagen networks, since the interfibrillar space of the collagen networks is within
the range of 20 nanometers (nm) while the filler particles have a size of
approximately 40 nm.
• The other reason for the addition of fillers is to effectively modify adhesive
viscosity to a thicker, pastier consistency.
• When such an adhesive is applied to an etched dental surface, it yields a thicker
bonding layer that can promote increased bond strength by preventing oxygen
inhibition.
• Moreover, a thick adhesive layer can reduce shrinkage stress because it is more
compliant compared with restorative composites.
 Other Ingredients

• Glutaraldehyde (Probond, Dentsply, York, PA) is added as a desensitizer.

• The monomer 12-methacryloyloxydodecylpyridinium bromide, MDPB
(Clearfil Protect Bond, Kuraray America, New York, NY) and parabene
(Adper Prompt-L-Pop, 3M ESPE, St. Paul, MN) are used as antimicrobials.
• Fluoride (Prime & Bond NT, Dentsply, York, PA) is added to prevent
secondary caries. Benzalkonium chloride (e.g., Etch 37, Bisco, Schamburg,
IL) and chlorhexidine (e.g., Peak LC Bond Resin, Ultradent Products, South
Jordon, UT) are used to prevent collagen degradation.
• The latter products have recently been shown in laboratory studies to
prevent protease enzymes (matrix metalloprotease enzymes or proteins
[MMPs]) from being activated and subsequently denaturing the hybrid
layer collagen.
 CLASSIFICATION

• When discussing dentin-bonding agents, it has become customary to

describe the generations (first generation, second generation, etc.) of
bonding agents that have led sequentially from the earliest, relatively
ineffective materials to the current materials, which provide reliable
functional bonds.
• This classification was developed by van Meerbeek et al. (2003).
• it is based on two general approaches to etching, priming, and applying
the bonding resin to dentin and enamel surfaces, and further subdivided
into the number of steps in the process.
• Thus, the major categories of bonding systems are known as “etch-and-
rinse” and “self-etch” systems, with two subcategories, each according to
the number of clinical steps involved.
• First Generation-
• the development of the surface-active comonomer NPG-GMA
• was the basis for Cervident (S.S. White Burs, Inc., Lakewood,
• NJ), which is considered the irst-generation dentin bonding
• system.141,142 heoretically, this comonomer could chelate with
• calcium on the tooth surface to generate water-resistant chemical
• bonds of resin to dentinal calcium.143,144 he in vitro dentin bond
• strengths of this material were, however, in the range of only 2 to
• 3 MPa.145 Likewise, the in vivo results were discouraging as
• Cervident had poor clinical results when used to restore NCCLs
• without mechanical retention.
• Second Generation-
• second-generation dentin bonding systems typically
• had in vitro bond strengths of only 1 to 5 MPa, which was consider
• ably below the 10-MPa value estimated as the threshold value for
• acceptable in vivo retention.84,148 In addition to the problems caused by the
loosely attached smear layer, these resins were relatively
• devoid of hydrophilic groups and had large contact angles on
• intrinsically moist surfaces.149 hey did not wet dentin well, did
• not penetrate the entire depth of the smear layer, and therefore
• could not reach the supericial dentin to establish ionic bonding.84
• Whatever bonding did occur was due to interaction with calcium
• ions in the smear layer.150
• he in vitro performance of second-generation adhesives after
• 6 months was unacceptable.1
• Third Generation-
• The concept of phosphoric acid etching of dentin before application
• of a phosphate ester–type bonding agent was introduced by
• Fusayama et al. in 1979.155 Because of the hydrophobic nature of
• the bonding resin however, acid etching did not produce a signiicant
• improvement in dentin bond strengths despite the low of the
• resin into the open dentinal tubules.86,156 Pulpal inlammatory
• responses were thought to be triggered by the application of acid
• on dentin surfaces, providing another reason to avoid etching. Most other third-
generation materials were designed not to
• remove the entire smear layer, but to modify it and allow penetration
• of acidic monomers such as phenyl-P or PENTA (see Table 5.2).
• Despite promising laboratory results, some of the bonding mecha
• nisms never resulted in satisfactory clinical results
 Etch-and-Rinse Adhesives

• Three-step (fourth generation): At this time, the most established, most

reliable adhesion method in this category consists of three steps:
• (1) an acid etchant application,
• (2) application of the primer, and
• (3) application of the actual bonding agent or bonding resin.
• The primer contains hydrophilic functional monomers dissolved in an
organic solvent such as acetone, ethanol, or water.
• The third step is the application of a hydrophobic resin
• Two-step ( fifth generation):
• A simplified method in this category combines the primer and adhesive
resin into one application.
• This etch-and-rinse strategy is the most effective to achieve efficient and
stable bonding to enamel.

• Etching, usually with a 30% to 40% phosphoric gel that is rinsed away,
promotes the dissolution of enamel rods, creating porosities that are filled
by bonding agents through capillary action and then followed by
polymerization of resin.
 Self-Etch Adhesives

• Two-step (sixth generation): This approach does not involve a separate etching
step. In this case an acidic monomer which is not rinsed, is used to condition and
prime the tooth at the same time.
• There are two types of self-etch adhesives (van Meerbeek et al., 2001), mild and
strong varieties.
• Strong self-etch adhesives have low pH (<1) and have been documented with a
bonding mechanism that resembles the etch-and-rinse adhesives.
• Mild self-etch adhesives (pH = 2) only partially dissolve the dentin surface, so a
substantial amount of hydroxyapatite remains available within the hybrid layer.
• Specific carboxyl or phosphate groups of functional monomers can then chemically
interact with this residual hydroxyapatite.
• Because this layer has some mineral content, the bond to dentin is better than that
of etch-and-rinse adhesives.
• However, this interfacial zone can be more prone to hydrolytic degradation
because the structure is more hydrophilic.
• One-step (seventh generation): The simplified method in this category
combines conditioner, primer, and bonding resin into a single step.
• Most one-step or “all-in-one” systems are delivered by a bottle, vial, or
single-unit dose applicator, which are formulated as a single component.
• However, Adper Promp L-Pop (3M ESPE, St. Paul, MN) is a variation on
this theme, in which two liquid components are packaged in separate
“blister” compartments in a single dispenser.
• Bursting one blister causes the two components to blend and form a
single component, which is then applied immediately using a brush that
forms the handle of the blister pack.
• This version of one-step, twocomponent, self-etching primer–adhesive
• One-step, self-etch adhesives are an attractive approach for clinicians
because of the reduced and less complex number of clinical steps
required compared with multistep etch-and-rinse adhesives.
• There is no need for rinsing or drying of the tooth structure because of
the lack of an etch step.
• For bonding composite cores, three-step, etch-and-rinse (fourth-
generation) systems are usually recommended.
• For bonding anterior and posterior composites and cementation of
veneers with resin cements, two-step etch-and-rinse (fifth-generation)
systems provide the best performance.
• For bonding posterior composites, selfetch, two-step (sixth-generation)
systems are the better choice.
• Dual-cure one-step, self-etch (seventh-generation) systems are advised
for esthetic posts and ceramic restorations bonded with resin cement,
while light-cured one-step, self-etch (seventh-generation) systems are
recommended for bonding posterior composite restorations.
• Eighth Generation –
• In 2010, voco America introduced voco futura bond DC as 8th generation
bonding agent, which contains nano sized fillers .
• In the new agents, the addition of nano-fillers with an average particle
size of 12 nm increases the penetration of rsin monomers and the hybrid
layer thickness, which in turn improves the me- chanical properties of the
bonding systems .
• Nano-bonding agents are solutions of nano-fillers, which produce better
enamel and dentin bond strength, stress absorption, and longer shelf life .
• It has been observed that filled bonding agents produced higher in vitro
bond strength.