Hybrid Layer as a Dentin-Bonding Mechanism

Nohito Nakahayashi, Ph.D.*

Mitsuo Nakamura, Ph.D.'
Nohoroir Yasudu. Ph.D. '

A number of mechanisms (both mechanical and chemical)have been proposed

as the cause of dentin adhesion. Extensive research in Japan during the past 10
years has shown that strong, long-livedbonds between resin and living dentin will
form when a monomer such as 4-META, which contains both hydrophilic and
hydrophobic chemical groups, penetrates the tissue and polymerizes in situ. This
resin-impregnation creates a transitional 'hybrid" layer. that is neither resin nor
tooth, but a hybrid of the two. The thin layer of resin-reinforced dentin locks the two
dissimilar substances together on a molecular level, sealing the surface against
leakage and imparting a high degree of acid resistance.

0 nce Dr. Buonocore pointed the way, it became

apparent that strong, durable bonds to etched
enamel were relatively easy to create.' However, similar
success bonding to dentin has remained elusive. The
problem. of course,is the fundamental difference in the
nature of the two tissues.
Enamel is largely inert, composed primarily of
hydroxyapatitewith very low water content.
Dentin, on the other hand, is lMng tissue. Its
chemicalstructure involvesboth inorganic and organic
materials, and it features a highly complex physical
structure that varies with the depth of the tissue.
Depending on the particular tooth, the age of the
patient, and the depth of the preparation, the substrate
surface can consist of widely varying proportions of
intertubular dentin, peritubular dentin, and sclerotic
dentin. The dentin may be very de=...or highly po-
rous. Near the dentin-enamel junction (DEJ) only l
percent of the surface area consistsoftubules. N e a r the
pulp, tubules can comprise as much as 22 percent of
the surface area.aFurthermore,those tubules commu-
nicatewithaveryvul~erablepulpthatreactsadvemely
to mechanical,t.hen.1~4biological, or chemical insult.
Andtomakematterswwse.thedentlnissaturatedwith
agygenandwater,Thoughwatercontentvstriesaccord-
ing to the type and depth of dentin, approximately 13
percent of overall dentinal volume is fluid.3
Is it possible to chemically bond to dentin? Twenty
years ago the research community believed it was, and
the first two generations of dentin 'adhesives" claimed
to create chemical bonds to the dentin. Unfortunately,
these agents performed much better in the laboratory
than in the mouth. With the exception of covalent
bonds, chemical bonds are vulnerableto degradationin
the oral environment, which results in leakage, discol-
oration, and secondary caries.
Based on research conducted over the past decade
at the Institute of Medical and Dental Engineering. the
authors have seen little to indicate that durable graft
polymerization (i.e., chemical adhesion)to ground den-
tin can be achieved. First of all, it is extremely ditllcult
to achieve effective chemical reaction when one of the
materials is a solid. because the frequencyof molecular
collisions is very low. (Most chemical reactions are
designed to take place in SoMion.) Furthermore. there
are a number of limiting criteria that any chemical
reaction involving dentin would have to meet:
1. It would have to occur at body temperature.
2. It must not involve monomem or catalysts that
might injure the pulp.
3.The reaction must be completed within 10 min-
Utes.

HYBRID
h 1963 Masuhara et al reported that when M-n-
butyl bosane EBB)was used as an initiator, methyl
methanylate (&lMf% ch a w grafted to the collagen
in wet ivory and produced an egcellent bond.' The

133
 .idhwoii w,i\ srronc .ind rxtrrrriely durable. As 01 THL3 to enamel. A number of new organic molecules
,J.iniIan' l!W 1 . \miples ol this system have k*enaging were studicd.7'Though virtually all of them significantly
in water for 15 yrars at 37 C and the h i d is still improved the bond (Table 1). by far the most stable
I I inct lon,d bonds whcre achieved when small amounts of 4-
Linfortunately. the system did not adhere togroiind met hacryloxyet hyl trimellitate anhydride (4-META)were
dentin. added to the monomer.H
In 1969 this MMA-THB system was introduced as Microscopic examination of enamel that had been
a n orthodontic- adiiesivc called "Direct E3onding-Sys- bonded with this new copolymer yielded a surprising
tern' for enumel bonding.' " It was one of the first dental finding.According to the generally-accepted, tag-theory
adhesives commercially introduced alter Huonocore of enamel bonding, pretreatment using phosphoric acid
proposed thc concept of 'wid-etching enamel. creates mechanical undercuts by selectively attacking
While exploring ways to improve the MMA-TBB the interprismatic material. The resin adhesive then
system at the Institute for Medical and Dental Engineer- locks into these undercuts to create mechanical reten-
ing. we discovered that the addition of monomers that tion. In other words. even the best monomers could not
contained both hydrophobic groups (like the phenyl penetrate beyond the depth of the etch. A n yet, that is
group) and hydrophilic groups (like the carboxyl group) precisely what examination of the 4-META-resin-to-
dramatically enhanced the bonding stability of MMA- tooth interface suggested was happening. The resin
appeared to penetrate beyond the etch and encapsulate
the prisms (Figs. 1 and 2). Chemical analysis of the
interface showed that the tags themselves were pure
resin, but at the end of the tags there was a thin zone,
where the resin had impregnated the interprismatic
Additwe Etchant' Bond MPo Strengih Reference material and formed a new material that was part tooth
-- - .~- - . - .
and part resin. We called this zone a resin-reinforced
None 10-3 133 2 49 10 tissue the "hybrid layer." Because no such layer was
5% HPPM' 10-3 104 2 38 18
3%HNPM' 10-3 105 t 40 19
found when we examined the MMA-TE3B-to-enamel
EDTA 3 - 2 209 ?: 28 20 interface, we hypothesized that this hybrid was the
5% 4-META' 10 - 3 173 .t 49 19 reason for the dramatic difference in bond stability.
1-1 163 i: 02 10 The hybrid layer is highly acid resistant. It remains
EDTA 3 2- 157 .t 24 21 intact even after both enamel and dentin have been
596Phenylc1 10-3 105 5 1.8 22 dissolved in HCl. This suggested the intriguing possi-
-10 - 3 fOr 3Qs: EDTA fW bos. bility of simultaneously bonding to the tooth and ren-
tSeeFie1. dering it caries-resistantwithout the use of fluoride.

A B
Flgam I. SEM ofencapsulated dprisms. A. ?he 4-META-basedadhcslvc penetrates beyond the etch and diffuses into the
tnkrpdemtk Ussue. 7he hybrid It forrns when It combtnes Wlth this tlssue Is hlghly acid mistant.The honeycomblike pattern Is
t h c v matahl that mnatncd aReh theenamel rods- dimolvedin HCl. B.When 4-METAwasomitted hmn the formula. the
xxstn -not penetrate the intqi-bmatictissucto forma hybrid.” R curcdrestn. E: enamel.

134
 f iybrid L;\yrr as a I)entin-Bonding Mechanism

DENTIN HYBRID LAYER

It was discovered that the 4-META/MMA-TBB sys-
I
Elchlnp
tem formed tenacious bonds not only to enamel. but
also to cast metals, amalgam, acrylic. and composite.
However, initial results applying the new 4-METAJ
MMA-TBB system to dentin were disappointing.’
Fusayama et a1 proposed that phosphoric acid was a n
appropriated pretreatment for dentinaswell as
But when phosphoric acid was used to prepare the
dentin. the 4-META-based resins produced very low
bond strengths. SEM examination found no evidence of
the expected hybrid layer formation. It appeared that
the acid was not only decalcifying the dentin, but was

m
also denaturing the collagen, decreasing its diffusivity
and preventing monomer contalning 4-META and 4-
Resln Resin MET from penetrating the tissue to form a hybrid.
Building on the suggestion of Dr. Raphael Bowen. a
technique was developed involvinga short pretreatment
using an aqueous solution of 10 percent citric acid and

u
Generally accepted concept
C Hybrd

Hybrld concept
proms a. Traclimnd envnel bonding theory postulates that
resin tags mecbnkaIiy lock into undercuts in the etched
e n d . The hybrid conceptproposesthat bondingstability will
incnase stgnlacantty if the rrsfn tags arc supplemented by a
thin u 3 of~resin-ninfomdtissue & y M d layer).
3 percent ferric chloride. l o In contrast to the phosphoric
acid, a short 10-second treatment with the 10-3 solu-
tion permitted the operator to dissolve a thin layer of
calcium without damaging the collagen. The strength of
the 4-META/MMA-TBB system to bovine dentin pre-
pared with the 10-3solution increased by a factor of 200
percent to 18 MPa.
Interestingly, when the ferric chloride was elimi-
nated from the etching formula, and the dentin was
prepared wlth a 10 percent solution of citric acid, the
bond strength plummetted to just 6 MPa, which was no
better than when the surface was prepared with phos-
phoric acid. The resin tag length in both the 6 MPa and
the 18 Mpa samples was identical. The only observed
dtfference was that the 18 MFb samples showed forma-
tion of a win impregnated zone -a hybrid layer. The
6 MPa sample showed no hybrid layer (Fig. 3).The ferric

A B

135
<JCN'R!SAl.OF ESTtiFTlC DEWISTHY VOLUME 3.NUMBER 4 July/Augusl 1 9 9 1
tons in the 10-3solutlon arc essential to the preserva-
tion of the cwllagcn bundles 50 they can become infil-
trated and entangled by the p l y (MMA-co-4-MET)
resin.
The long resin tags formed when a bonding agent
flows into the tubules may be very impressive in SEM
photographs: however. these experiments suggest that
they contribute only minimally to the overall dentin
bond strength.
If treatment period is increased from 10 seconds to
30 seconds, the 10-3solution can also be used to etch
enamel. 'I'
Water-Triggered Polymerization
As mentioned earlier. dentinal tissue is rich in
oxygen and water. Oxygen and water prevent emcient
polymerization of most bonding agents, so they nor-
mally impede the bonding mechanism.
The catalyst in the 4-META/MMA-TBB system is
unique in that oxygen and water actually enhance its
effectiveness. In fact, TBB requires the presence of
water and oxygen to lnltiate polymerization. When a
drop of CBB-Metabond (a 4-META/MMA-TBB based
cement) i s gently floated in a bowl of water, it begins
polymerizing first wherever it touches the water.
The benefits of a dentin bonding agent that starts
curing wherever it contacts water and oxygen are
obvious.First of all, it assures effective polymerization
in deep preparations where the dentin is highly
tubularized and impossible to dry (and even if the
dentist manages somehow to dry it. what can he do
about the oxygen in the tissue?).
Effective polymerkation in fluid-filled deep dentin
reduces the chance of fhe monomer that might act as
a pulpal initant. (Some studies of traditional bonding
agents suggest that as much as 50 percent of the
monomer remains unpolymerfied.l')
Initiation T6B - H,O - 0,
Resin
Tooth
136
The unique water-compatibilityof the TBB catalyst
may also be a major reason why the 4-META/MMA-TBB
system is the only one 90 far shown to form strong
dentln bonds in the face of tubular fluid under pulpal
pressure. I Z - I 4
Finally. because water and oxygen act in concert
with TE3B as an initiator, the 4-META resin polymerizes
first within the dentinal tissue itself. All resins shrink as
they cure. Furthermore. they shrink toward the point
where polymerization begins. This suggests that the 4-
META/MMA-Tf3B system shrinks toward the dentin
during polymerization and thus presemes the high
degree of tissue-infiltration that was established before
polymerization began.
In contrast, a more traditional self-cure adhesive
based on the BPO-amine system begins curing at the
center of its mass. and therefore tends to pull away from
the tissue as it shrinks. Worse yet. light-cure adhesives
begin polymerizing at the point farthest from the tooth
surface, so they create the maximum chance for micro-
scopicpolymerizationgaps at the tissue interface (Fig.4).
CONCLUSION
Based on our work at the Institute for Medical and
Dental Engineering Wokyo Medical and Dental Univer-
sity), we believe that the traditional conceptions of
dentin bonding should be modified to include the hy-
brid layer mechanism in which certain monomers can
infiltrate the dentin and combine with the collagen and
hydroxyapatiteto form a new material that is part tooth
and part resin.
When true hybridization occurs, bond strength
(particularly to deep, wet, highly tubularized dentin)
increases dramatically. The hybrid layer forms an acid-
resistant envelope that seals the dentin, preventing
hypersensitivity and secondary caries.
BPO-mine Irradiation
 Hybrid Layer as a Denth-Bonding Mechanlsm

Three characteristics are netessary for the forrna-

tion of the hybrid layer:
1. The dentinal peptides (including collagen) must
not be denatured when the dentin is decalcified.
Furthermore. if the acid is too aggressive, it may
expose collagen below the hybrid layer leaving a
zone of weak dentin that is susceptible to long-
term degradation.l5.l8
2.The bonding resin must include monomers with
both hydrophilic and hydrophobic groups that
can penetrate the dentin and combine with it.
3.The catalyst must allow polymerization in the
presence of oxygen and water.

To date the system that best meets these criteria is

the 4-META/MMA-TBB system with a dentin pretreat- 5- c. Dentin is prepared ustng a solution of 10% citric
ment of 10 percent acid and 3 percent ferric &ionide add with 3% ferric chloride (10-3)and the enamel is prepared
using phosphoric acid.
(F'ig. 5). T w o commercial products are built on this
system: C&B-Metabond and Amalgambond (Fig. 6):
Parkell Products-Marketed in Japan by Morita under
the name 'Superbond C&B" and 'Superbond D Liner."

6. D.the application d t h e Ch+ETA/h4MA-TBBadhe-

s i n ls Shawn.

Fialpc 5. Use of 4-META-based adhesive to rrpair cewkal

aosions.A. Pretreatment.

137

Figure& &cause4-METAwillmcdlatebondsbetwwnawlde
range of materials (metals. plastics. porcelain, etc.) a number of
adheslve products have been built on this molecule. However, of
these only the 4-META/MMA-TBBsystem, whlch forms the
bask of C&B-Metabondcement and t h e h l g a m b o n d bonding
agent has been shown to form a substantial dentln/resin hybrid
layer.
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