Dentin Bonding Durability of Two-step Self-etch Adhesives

with Improved of Degree of Conversion of Adhesive Resins

Kento Satoa / Keiichi Hosakab / Masahiro Takahashic / Masaomi Ikedad /Fucong Tiane /
Wataru Komadaf / Masatoshi Nakajimag / Richard Foxtonh / Yoshihiro Nishitanii /David H. Pashleyj /
Junji Tagamik

Purpose: To evaluate (1) the initial and long-term microtensile bond strengths of two-step self-etch adhesives with
different degrees of conversion (DC); (2) the elastic modulus of the respective adhesive resins; (3) the water sorp-
tion of the respective adhesive resins.
Materials and Methods: Two two-step self-etch adhesives, Clearfil SE Bond (CSE) and Clearfil SE Bond 2 (CSE2)
were used in this study. The DC was determined using ATR/FT-IR with a time-based spectrum analysis. Midcoronal
flat dentin surfaces of 24 human molars were prepared with 600-grit SiC paper for microtensile bond strength
(μTBS) testing. CSE and CSE2 were applied to the dentin surfaces according to the manufacturer’s instructions,
followed by composite buildups. The μTBS was measured after water storage for 24 h, 6 months, and 1 year. The
elastic modulus (before and after 1 month of water immersion) was determined by the three-point flexural bending
test and water sorption values by the water sorption test.
Results: CSE2 showed significantly higher DC than CSE. The μTBS of CSE2 was significantly higher than that of CSE
in all water storage periods. One-year water storage decreased the μTBS of CSE; however, it did not decrease that
of CSE2. Regarding the polymerized adhesive resins, the elastic modulus of CSE2 was significantly higher than that
of CSE before and after water immersion (p < 0.001), and the water sorption of CSE was higher than that of CSE2.
Conclusions: The higher DC of adhesive resins of two-step self-etch adhesives resists water aging and improves
the initial bond strengths and durability of the resin-dentin bond.
Keywords: two-step self-etch adhesive, degree of conversion, microtensile bond strength, water sorption, elastic
modulus.

J Adhes Dent 2017; 19: 31–37. Submitted for publication: 01.07.16; accepted for publication: 05.11.16
doi: 10.3290/j.jad.a37726

a g Junior Associate Professor, Cariology and Operative Dentistry, Department of

Graduate Student, Cariology and Operative Dentistry, Department of Oral
Health Sciences, Graduate School of Medical and Dental Sciences, Tokyo Oral Health Sciences, Graduate School of Medical and Dental Sciences, Tokyo
Medical and Dental University, Tokyo, Japan. Experimental design, performed Medical and Dental University, Tokyo, Japan. Experimental design, co-wrote
the experiments, wrote the manuscript. and proofread the manuscript, contributed substantially to discussion.
b h Clinical Senior Lecturer, Department of Restorative Dentistry, King’s College
Assistant Professor, Cariology and Operative Dentistry, Department of Oral
Health Sciences, Graduate School of Medical and Dental Sciences, Tokyo London Dental Institute, King’s College London, London Bridge, London, UK.
Medical and Dental University, Tokyo, Japan. Experimental design, performed Proofread the manuscript, contributed substantially to discussion.
the experiments, wrote the manuscript. i Professor and Chair, Department of Restorative Dentistry and Endodontology,
c Clinical Fellow, Cariology and Operative Dentistry, Department of Oral Health Medical and Dental Sciences School, Kagoshima University, Kagoshima,
Sciences, Graduate School of Medical and Dental Sciences, Tokyo Medical Japan. Proofread the manuscript, contributed substantially to discussion.
and Dental University, Tokyo, Japan. Consulted on and performed statistical j Regents’ Professor, Department of Oral Biology, College of Dental Medicine,
evaluation, contributed substantially to discussion. Georgia Regents University, Augusta, Georgia, USA. Co-wrote and proofread
d Junior Associate Professor, Department of Oral Prosthetic Engineering, Gradu- the manuscript, contributed substantially to discussion.
ate School, Tokyo Medical and Dental University, Tokyo, Japan. Consulted on k Professor, Cariology and Operative Dentistry, Department of Oral Health
and performed statistical evaluation. Sciences, Graduate School of Medical and Dental Sciences, Tokyo Medical
e Assistant Professor, Department of Cariology and Endodontology, Peking Uni- and Dental University, Tokyo, Japan. Idea, hypothesis, study design, wrote the
versity School and Hospital of Stomatology, Beijing, China. Contributed sub- manuscript.
stantially to discussion.
f Junior Associate Professor, Fixed Prosthodontics Unit, Department of Restora- Correspondence: Assistant Professor Keiichi Hosaka, Cariology and Operative
tive Sciences, Division of Oral Health Sciences, Graduate School, Tokyo Dentistry, Department of Oral Health Sciences, Graduate School of Medical and
Medical and Dental University, Tokyo, Japan. Performed the experiments, con- Dental Sciences, Tokyo Medical and Dental University, 1-5-45, Yushima, Bunkyo-
tributed substantially to discussion. ku, Tokyo 113-8549, Japan. Tel: +81-3-5803-5483; e-mail: [email protected]

Vol 19, No 1, 2017 31

Sato et al

C urrently, the self-etch adhesives (SEAs) are widely used

in clinical practice.1,24 SEAs are based on the use of
acidic functional monomers that can simultaneously demin-
have examined the effects of direct/indirect light inten-
sity,28 light-curing distance,39 light-curing time,39 and types
of light-curing units.7,39 On the other hand, optimizing the
eralize and prime dentin. Self-etch adhesives eliminate the ingredients of adhesives is another approach, because the
rinsing phase, which not only lessens clinical application DC of adhesive resins depends on photo-initiators,38 sol-
time, but also significantly reduces the technique sensitivity vents,2 filler loading, functional monomers,19 and methac-
and risk of making errors during application.4 SEAs can be rylate monomers, such as bis-GMA and TEG-DMA.29
classified into two-step adhesives (2-SEAs) and one-step Regarding the effect of DC on the resin-dentin bond du-
adhesives (1-SEAs). Previous in vitro studies have reported rability, a moderate correlation was reported between DC
that 2-SEAs show higher bond strengths to tooth tissues and μTBS reduction of five 1-SEAs and one etch-and-rinse
than do 1-SEAs.12,27 Two-step SEAs, which involve the ap- adhesive after 5000 thermal cycles.6 On the other hand,
plication of an additional layer of solvent-free hydrophobic increasing the DC by prolonging the light-curing time in-
resin, create stronger adhesive layers than do 1-SEAs, creased the nanoleakage, but did not increase the durabil-
which contain hydrophilic monomers, water, and volatile sol- ity of resin-dentin bonds of 1-SEAs.11 To the extent of the
vents.20 authors’ knowledge, the influence of the DC of adhesive
However, even relatively hydrophobic adhesive resins of resins in 2-SEAs on the durability of bonding when the
2-SEAs absorb water. This decreases their mechanical prop- same self-etch primer is used has never been investi-
erties,14,15 because water can penetrate into nanometer- gated. Therefore, the objective of this study was to evalu-
sized spaces between polymer chains or cluster around ate the effect of DC on initial and long-term bonding effi-
polar functional groups that are capable of hydrogen bond- cacy of 2-SEAs to human dentin, elastic modulus, and
ing, due to its small molecular size and high molar concen- water sorption. The null hypothesis tested was that the DC
tration.30 Extrinsic and intrinsic water diffusion into the ad- of 2-SEAs has no effect on the initial and long-term μTBS
hesive layer and the resin-dentin interface hastens to dentin.
hydrolytic degradation of resin components within the hybrid
layer and/or adhesive layer and leads to plasticization of
the adhesive,13,34 loss of interfacial adhesive-dentin bond MATERIALS AND METHODS
strengths,31 and hydrolytic degradation in the resin-dentin
interface.20 In particular, the relatively thick adhesive layer Two 2-SEAs, Clearfil SE Bond (CSE; Kuraray Noritake; Tokyo
of 2-SEAs is potentially susceptible to extrinsic water ab- Japan) and Clearfil SE Bond 2 (CSE2; Kuraray Noritake)
sorption in the restorations.32 The adhesive layer overlying were used in this study. Their compositions are shown in
the hybrid layer may help preserve the integrity of the hy- Table 1. CSE and CSE2 both contain camphorquinone (CQ)
bridized dentin by sealing it from water,1,14 and by acting as as a photo-initiator. However, CSE2 contains an additional
a stress-absorbing layer. Therefore, if the adhesive layer photo-initiator for enhancing the catalyst system and im-
that couples composite to hybridized dentin becomes less proving the DC of an adhesive resin. The other ingredients
stiff over time by water absorption, it may adversely affect of these adhesives are same.
stress distribution across the bonded interface, possibly
resulting in either plastic deformation or debonding under Measurement of Degree of Conversion (DC)
repeated loading,18,23 which results in inferior durability of The polymerization process of the adhesive resins for CSE
the resin-dentin bond. As the mechanical behavior of or CSE2 was monitored by using a Fourier-transform infra-
2-SEAs exposed to water for extended periods of time is red spectrometer equipped with an ATR attachment (Nicolet
affected,8 improved mechanical properties of the adhesive 6700 FT-IR, Thermo Fisher Scientific; Waltham, MA, USA) at
layer are necessary to ensure longevity of the resin-dentin a resolution of 8 cm-1. The ATR diamond crystal permitted
bond.13,14 scanning between 650 and approximately 4000 cm-1. One
Since it is generally accepted that better mechanical drop of the adhesive resins of CSE or CSE2 was placed on
properties have been attributed to higher percentages of the diamond crystal of the ATR attachment. That is, the
monomer-to-polymer conversion in resin-based materials,2,9 primer was not tested. Photo-activation was performed
the degree of conversion (DC) of monomer into polymer using an LED light-curing unit (Pencure 2000, Morita; Tokyo,
(percentage of C=C bonds becoming C-C bonds as part of Japan) for 10 s. The distance between the light-guide tip
the polymer chain) plays an important role in the strength and the top of the diamond crystal was 10 mm (Fig 1).
and stability of dentin bonding.5 Additionally, incomplete Time-based spectral acquisition software (Spectrum Time
polymerization of adhesive resins results in enhanced water Base, Perkin-Elmer; Waltham, MA, USA) was used for con-
permeability of the adhesive layer and can accelerate hydro- tinuous and automatic collection of spectra during polymer-
lysis, leading to bond deterioration.11 Therefore, it is antici- ization at a rate of one spectrum every 0.2 s. Real-time in-
pated that a higher DC of the adhesive resin may lead to a frared spectra were continuously recorded for 40 s after
more desirable load transfer across the bonded interface light activation began. Three separate measurements for
over time and superior resin-dentin bond durabil- each adhesive were conducted. The light output of the light-
ity.9,17,19,28,33 To improve the polymerization efficacy and curing unit was 600 mW/cm2 as determined with a radiom-
increase the DC of the adhesive resins, previous studies eter (Demetron LED Radiometer, SDS/Kerr; Orange, CA,

32 The Journal of Adhesive Dentistry

 Sato et al

Table 1 Chemical composition and application mode of the materials tested

Material Ingredients Procedure

Adhesives Clearfil SE Bond Primer 10-MDP, HEMA, hydrophilic aliphatic dimethacrylates, Apply primer and leave it for
(CSE, Kuraray dl-camphorquinone, water, accelerators, dyes 20 s, then evaporate the water
Noritake; Tokyo with a mild air stream.
Japan)
Clearfil SE Bond 2 Adhesive CSE: 10-MDP, HEMA, bis-GMA, hydrophobic aliphatic Apply adhesive and use a light
(CSE2, Kuraray resin methacrylates, colloidal silica, dl-camphorquinone, air stream to make the adhesive
Noritake) initiators, accelerators film as uniform as possible.
CSE2: 10-MDP, HEMA, bis-GMA, colloidal silica, Light cure adhesive resin for
hydrophobic aliphatic dimethacrylates, dl- 10 s.
camphorquinone, new initiators, accelerators

Composite Clearfil AP-X Bis-GMA, TEG-DMA, camphorquinone,photo-initiators, pigments, Light cure for 40 s.
(Kuraray Noritake) silanated barium glass, silanated silica

10-MDP: 10-methacryloyloxydecyl dihydrogen phosphate; HEMA: 2-hydroxyethyl methacrylate; bis-GMA: bis-phenol A glycidylmethacrylate; TEG-DMA: triethylene
glycol dimethacrylate.

USA). The DC was assessed according to the changes in

absorbance ratio between the peak at 1637 cm-1 (methac- Light tip
rylate C=C stretching) and that at 1608 cm-1 (phenyl C=C
stretching) before and after light curing. The intensities of Adhesive resins
these two bands were integrated based on band height (CSE, CSE2)
methodology, and the change of the band ratio profile with
10 mm Diamond crystal
1637 cm-1/1608 cm-1 was monitored. The degree of con-
version (DC) was calculated by the following equation:

DC (%) = [1– (absorbancecured 1637 cm-1 / absorbancecured

1608 cm-1) / (absorbanceuncured 1637 cm-1 / absorbanceuncured
1608 cm-1)] x 100

Microensile Bond Strength (μTBS) Test

Infrared beam
Twenty-four freshly extracted caries-free human molars were
used in this study, according to the protocol approved by
Fig 1 Schematic of the polymerized specimens of the adhesive
the Human Research Ethics Committee, Tokyo Medical and resins to measure the DC using ATR-FTIR.
Dental University, Japan (No. 725). The occlusal enamel
was removed 90 degrees to the long axis of the tooth by
means of a model trimmer under running water to obtain
midcoronal dentin. The dentin surfaces were prepared with All of the beams from each group (3 or 4) were individually
600-grit SiC paper under running water for 60 s to create a bonded to a tensile testing jig using cyanoacrylate glue
standardized smear layer. The prepared teeth were then (Zapit, Dental Ventures of America; San Ramon, CA, USA)
randomly divided into two groups. The primers of two mounted in a tabletop testing machine (EZ Test, Shimadzu;
2-SEAs (CSE, CSE2) were applied to the dentin surfaces of Kyoto, Japan) and subjected to the μTBS test at a cross-
each group for 20 s, then the water was evaporated with a head speed of 1.0 mm/min after water storage at 37°C for
gentle air stream. After that, the bonding agent of CSE and 24 h, 6 months, or 1 year. The μTBS was determined by
CSE2 was also applied using a light air stream to make the calculation of the mean of three or four beams from the
adhesive film as uniform as possible, and then irradiated same tooth (n = 12). After the μTBS test, all of the frac-
with a light-curing unit (Pencure 2000, Morita) for 10 s at a tured specimens were observed using scanning electron
light output > 600 mW/cm2. After light curing the adhesive microscopy (SEM; JSM-5310, JEOL; Tokyo, Japan) to char-
resin, a composite, Clearfil AP-X (Shade-A2, Kuraray Nori- acterize their failure modes. The failure modes were classi-
take), was built up incrementally to a height of 5.0 mm to fied as: (1) C-D, cohesive failure in dentin; (2) C-A, cohesive
ensure sufficient bulk for the μTBS test. Each increment failure in adhesive resin; (3) C-R, cohesive failure in com-
was light cured for 20 s. After storage in 37°C tap water for posite; or (4) I-F, interfacial failure. The area ratios of each
24 h, 10 beams (surface area: 0.7 x 0.7 mm) were fabri- failure mode on the dentin sides were expressed as per-
cated from the central part of each bonded tooth using a centages of the overall fractured surface on the SEM micro-
low-speed diamond saw (Isomet, Buehler; Lake Bluff, IL, graphs by digitizing and subjecting them to quantitative
USA) under water spray coolant. The 10 beams of all image analysis using SemAfore software (Insinöörito-
bonded teeth were then randomly divided into three groups. imisto, J. Rimppi; Ojakkala, Finland).

Vol 19, No 1, 2017 33

Sato et al

Water Sorption Test where F is the force (N), L is the span length (10 mm), b is the
Just the adhesive resins of CSE and CSE2 (no primers) width of the plate (5.0 mm ± 0.1 mm), D is the vertical deflec-
were poured into round silicone molds (8.0 mm in diameter tion (mm) of the plates, and h is the thickness (2.0 mm). The
and 1.5 mm thick) and covered by a thin, transparent Mylar modulus of elasticity was expressed in MPa. The strain (ε)
strip. The adhesive resin in these molds was irradiated for produced by three-point bending was calculated as:
180 s with an LED light-curing unit (Pencure 2000, Morita)
at a light output > 600 mW/cm2 to fabricated polymerized ε = 6hd/L
resin disks (n = 8). The thickness and diameter of the spec- where h is the thickness of the plate (mm), d is the dis-
imens were measured using a digital caliper (Mitsutoyo; placement of the plate (mm), L is the span length of the
Kanagawa, Japan), rounded to the nearest 0.01 mm. These plate between the supports (5.0 mm).
measurements were used to calculate the volume (V) of Differences in the moduli of elasticity of the specimens
each specimen. Water sorption was determined according with and without immersion of specimens in water were
to the ISO specification 4049 (2000), except for the speci- calculated as percent decrease of the modulus of elasticity
men dimensions.34 Immediately after polymerization and (%ΔE), as follows:
dry storage for 24 h in a container filled with anhydrous sil-
ica gel, the disks were repeatedly weighed at intervals of ZE= - {(Ewet-Edry)/Edry} x 100
24 h until a constant mass (M1) was obtained. where Ewet was the modulus of elasticity of wet-group spec-
After measuring the initial dry mass (M1), the disks were imens and Edry was the modulus of elasticity of dry-group
individually immersed in tap water at 37°C for 24 h. After specimens.
water storage for 24 h, the disks were gently wiped with
absorbent paper, weighed, and put back in tap water. This Statistical Analysis
regime was repeated and continued until a constant wet The maximum DC and water sorption data were analyzed
mass (M2) was obtained. Water sorption (WS) was calcu- using Student’s t-test (α = 0.05). Normal distributions of
lated using the following formula: elastic modulus and μTBS were indicated by the Shapiro-
Wilk test (p > 0.05). Elastic modulus was analyzed using
WS = (M2 − M1)/V two-way ANOVA (α = 0.05), and the μTBS values were sta-
where M1 is the initial dry constant mass (μg) before water tistically analyzed using two-way ANOVA and the t-test with
immersion, M2 is the constant wet mass (μg) after water Bonferroni correction for multiple comparisons to test the
immersion, and V is the volume of the specimen in mm3. effect of the adhesives and the periods of water storage
Water sorption values were expressed in g/mm3. (24 h, 6 months, 1 year) (α = 0.05).

Three-point Flexural Test

The adhesive resins of CSE and CSE2 without mixing with RESULTS
primers were poured into silicone molds (5 x 18 x 2 mm)
and covered by a transparent thin Mylar strip. The adhesive Figure 2 shows the change of DC of the two test adhesive
resin in these molds was irradiated for 180 s with an LED resins over 40 s after the light activation began. Student’s
light-curing unit (Pencure 2000, Morita) with a light out- t-test revealed that the maximum DC of the adhesive resin
put > 600 mW/cm2 to fabricate sixteen polymerized resin of CSE2 was significantly higher than that of CSE
beams. Immediately after polymerization and dry storage in (p < 0.001) (Table 2). Table 2 shows the mean μTBS of the
a container filled with anhydrous silica gel for 24 h, the six- two 2-SEAs to dentin as a function of the water-storage pe-
teen specimens from each adhesive resin were divided into riod. There were no pre-test failures during specimen prep-
two groups. Half of specimens (dry group) were subjected to aration. Two-way ANOVA revealed that μTBS was influenced
a three-point flexural test for measuring modulus of elastic- by the adhesives (p < 0.001) and water storage periods
ity (E) (n = 8). The rest of the specimens (wet group) were (p < 0.001). In addition, there was a significant interaction
subjected to a three-point flexural test after storage in tap between the adhesives and water storage periods
water for 1 month, as 1 month is necessary in the water (p < 0.001). CSE2 showed significantly higher μTBS than
sorption test for the weight of specimens to reach a pla- CSE after each water storage period of 24 h, 6 months, and
teau. The three-point bending test was performed by cen- 1 year (p < 0.001). In CSE specimens, the μTBS after water
trally loading the beams using a universal testing machine storage for 1 year was significantly lower than the μTBS
(Autograph AGS-H, Shimadzu) at a displacement rate of after water storage for 24 h (p < 0.001). However, there
1 mm/min, sufficient to induce a 3% strain. The compres- were no significant differences between the μTBS after stor-
sive force necessary to induce a 3% strain in the beam was age for 24 h, 6 months, and 1 year (p = 0.25, 0.94, and
measured. Load displacement values were converted to 1.00, respectively) in CSE2 specimens. The failure mode
stress and strain. The modulus of elasticity values was cal- percentages are summarized in Fig 3. C-A failures were only
culated as the slope of the linear portion of the stress- seen in CSE specimens and increased over time, while C-A
strain curve from the following formula: failures were never seen in CSE2 specimens at any time
period. CSE2 specimens show similar failure mode distribu-
E = FL3/4Dbh3 tion among all the time periods. The water sorption values

34 The Journal of Adhesive Dentistry

 Sato et al

Failure mode
80
10 s light irradiation CSE 24h
70
Degree of conversion (%)

60 CSE 6m
50
CSE 1y C-D
40
C-A
30 C-R
CSE2 24h
I-F
20 CSE2 CSE

10 CSE2 6m

0
0 5 10 15 20 25 30 35 40 CSE2 1y

Time (s) 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%

Fig 2 The DC (%) vs time (s). Horizontal bar shows light-curing du- Fig 3 Percentage of failure modes of two 2-SEAs. C-D: cohesive
ration in s. CSE: Clearfil SE Bond; CSE2: Clearfil SE Bond 2. failure in dentin, C-A: cohesive failure in adhesive; C-R: cohesive fail-
ure in composite; I-F: interfacial failure. m: months; y: year.

Table 2 The degree of conversion (DC) and microtensile bond strengths (μTBS) of two 2-SEAs tested in this study

Materials DC (%), n = 3 μTBS (MPa), n = 12

24 h 6 months 1 year
CSE 56.0 ± 0.1A 71.5 ± 7.2Aa 66.6 ± 2.6Aab 53.1 ± 4.2Ab

CSE2 66.8 ± 0.2B 80.6 ± 5.1Ba 78.7 ± 5.5Ba 76.2 ± 4.7Ba

Values are mean ± SD. Different superscript letters indicate statistically significant differences in rows (lowercase) and columns (capital) (p < 0.05). CSE:
Clearfil SE Bond; CSE2: Clearfil SE Bond 2.  

Table 3 Water sorption, modulus of elasticity, and reduction rate of elastic modulus of two 2-SEAs tested in this
study

Materials Water sorption Modulus of elasticity (MPa), n = 8 Reduction of modulus

(μg/mm3) (n=8) of elasticity (%)
Dry Wet
CSE 72.8 ± 1.7A 1345 ± 93Aa 1058 ± 98Ab 21.4

CSE2 65.0 ± 3.1B 1568 ± 191Ba 1330 ± 212Bb 15.2

Values are mean ± SD. Different superscript letters in each column (capital) or row (lowercase) indicate statistically significant differences among storage periods
(p < 0.05). Reduction of modulus of elasticity (%): [{modulus of elasticity (wet group)-modulus of elasticity (dry group)}/modulus of elasticity (dry group)] x 100.
CSE: Clearfil SE Bond; CSE2: Clearfil SE Bond 2.

and moduli of elasticity (dry vs wet) of the polymerized ad- The percent reduction in modulus of elasticity was 21.4%
hesive resin of the two 2-SEAs are shown in Table 3. Stu- (CSE) and 15.2% (CSE2).
dent’s t-test revealed that water sorption of CSE2 was sig-
nificantly lower than that of CSE (p < 0.05). Two-way ANOVA
showed that modulus of elasticity was influenced by adhe- DISCUSSION
sive (p < 0.001) and storage condition (p < 0.001). In addi-
tion, there was no significant interaction between the adhe- In this study, the DC of CSE2 was significantly higher than
sives and storage conditions (p = 0.67). CSE2 showed a CSE. Regarding bond strengths, there was a significant in-
significantly higher modulus of elasticity than CSE at each teraction (materials x water storage time) (p < 0.001), and
storage condition (p < 0.001). The elastic modulus of both there were no significant differences between 24 h,
adhesive resins was reduced by water storage (p < 0.001). 6 months, and 1 year (p = 0.25, 0.94, and 1.00, respect-

Vol 19, No 1, 2017 35

Sato et al

ively) in CSE2 specimens, while in CSE specimens, the monomers both within the adhesive layer and in the under-
μTBS after water storage for 1 year was significantly lower lying demineralized dentin would play an important role of
than the μTBS after water storage for 24 h (p < 0.001). the resin-dentin bond, since previous studies have also re-
Therefore, the null hypothesis that DC of 2-SEAs has no ported that the DC of adhesive resins and the hybrid layer
effect on the initial and long-term μTBS of 2-SEAs to dentin are correlated with the resin-dentin μTBS.11 It is speculated
is rejected. In the literature, some studies found a correla- that a higher DC in adhesive resins may improve the quali-
tion between DC and the bond strengths of both self-etch ties of not only the adhesive layer but also hybrid layer.
adhesives and etch-and-rinse adhesives,11 but another The water sorption of CSE2 (72.8 ± 1.7 μg/mm3) was
study failed to find any correlation.25 This indicates that found to be significantly lower than that of CSE
the different compositions of various adhesives have a (85.8 ± 9.9 μg/mm3) (p = 0.03, Table 3). Moreover, the re-
major impact on these results, because bond strength is sults of the three-point bending test showed that the elastic
multifactorial. modulus of CSE2 was significantly higher than that of CSE
From the results of the DC measurements, it was found before and after water storage (p < 0.001). These findings are
that that the DC of CSE2 was significantly higher than that in accordance with previous studies showing that higher DCs
of CSE (p < 0.001). In this study, an LED light-curing unit of adhesive resins are correlated to lower water sorption21
was used because of the increasing use of LED lights by and better mechanical properties.9,10 We speculate that
clinicians. The DC of CSE significantly decreased when ir- CSE2 creates more cross linking of the polymerized adhesive
radiation was carried out using three different LED curing resins, resulting in less water sorption and higher elastic
lights instead of a quartz-tungsten-halogen curing light modulus compared to CSE. The reason why the water-stor-
(QTH), because of its narrower spectrum of wavelengths age–induced percentage reduction in elastic modulus for
which include the absorption range of the photo-initiators CSE2 (15.2%) was lower than that of CSE (21.4%) may also
used in the adhesive (QTH: 74.1%; LEDs: ca 64.7%- be because of the greater hydrophobicity of CSE2, since the
65.5%).7 The DC of CSE (56.0%) evaluated in this study is percentage reduction in the mechanical properties of adhe-
lower, but this would be due to the different light irradiation sives are related to their water sorption values.13 Interest-
duration. Both adhesive resins of CSE and CSE2 contain ingly, the elastic modulus of CSE2 even after water storage
CQ, which is the most widely and successfully used photo- was higher than that of CSE before water storage, which
initiator in dental restorative resins.16 Moreover, a newly means that the polymerized adhesive resin of CSE2 with a
developed photo-initiator has been added to CSE2. The sig- higher DC leads to higher mechanical properties than in CSE,
nificantly higher bond strengths at any water storage period with its lower DC regardless of moisture conditions, and can
and the DC of CSE2 compared to CSE may be due to the contribute to the mechanical stability of the resin-dentin bond.
additional photo-initiator of the adhesive resin of CSE2. On Failure mode observations using SEM provided important
the other hand, the residual component of the primer on information regarding which layer of the bonded assembly is
the dentin surface applied prior to the application of adhe- the major site of crack initiation and propagation. Cohesive
sive resin may affect the DC of the adhesive resins, and failures within the adhesive layer were only seen in the CSE
further research is needed.26 specimens, while it was not seen in the CSE2 specimens.
The adhesives containing 10-methacryloyloxydecyl dihy- This finding may also result from the additional photo-initia-
drogen phosphate (10-MDP) may chemically bind to the hy- tor in CSE2.
droxyapatite of dental hard tissues, providing higher me-
chanical strength37 and bonding stability40 due to the
presence of nanolayering of 10-MDP-calcium salts in the CONCLUSION
resin-dentin interface. However, some researchers reported
that the presence of nanolayering is unlikely to contribute The higher DC of adhesive resins of 2-SEA resists water
to the overall resin-dentin durability.35 In fact, some in vitro aging and improves the initial bond strengths and durability
studies have shown that the μTBS of CSE, which contains of resin-dentin bonding. This may indicate the potential that
10-MDP, to dentin decreases after long-term water stor- manufacturers can reach with 2-SEAs, if they use neat adhe-
age.3 The μTBS of CSE2 after both 24 h and 1 year was sives as a sealer for 2-SEAs and improve their hydrophilic/
significantly higher than that of CSE. Furthermore, there hydrophobic photo-initiator/accelerators. As a previous study
was a significant interaction (materials x water storage found that the bond strength data after 5-year in vitro aging
time) (p < 0.001), which revealed that the resin-dentin bond are more clinically relevant and may predict the long-term
created by CSE2 had superior durability compared to CSE. clinical performance,36 the 5-year durability of resin-dentin
We speculate that – compared to CSE9,17 – a well-polymer- bonds of CSE2 should be explored in future studies.
ized, stiffer adhesive layer and hybrid layer created by CSE2
should lead to better load transfer across the bonded inter-
face over time, and resist higher tensile stresses under ACKNOWLEDGMENTS
load, due to its higher mechanical properties. For different This work was supported by Grant-in-Aid for Scientific Research (C)
commercially available 2-SEAs, a significant correlation was #26462873 and Grant-in-Aid for Scientific Research (C) #15K11108
found between the mechanical properties of adhesive res- from the Ministry of Education, Culture, Sports, Science and Technol-
ins and their resulting μTBS.33 Polymerization of the resin ogy of Japan.

36 The Journal of Adhesive Dentistry

 Sato et al

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