Dental Materials Journal 2011; 30(4): 493500

Design of a new, multi-purpose, light-curing adhesive comprising a silane

coupling agent, acidic adhesive monomers and dithiooctanoate monomers
for bonding to varied metal and dental ceramic materials
Kunio IKEMURA1, Hisaki TANAKA1, Toshihide FUJII1, Mikito DEGUCHI1, Noriyuki NEGORO1, Takeshi ENDO2
and Yoshinori KADOMA3
Department of Research and Development, Shofu Inc., 11 Kamitakamatsu-cho, Fukuine, Higashiyama-ku, Kyoto 605-0983, Japan
Molecular Engineering Institute, Kinki University, 11-6 Kayanomori, Iizuka, Fukuoka 820-8555, Japan
3
Department of Applied Functional Molecules, Division of Biofunctional Molecules, Institute of Biomaterials and Bioengineering, Tokyo Medical and
Dental University, 2-3-10 Kanda-Surugadai, Chiyoda-ku, Tokyo 101-0062, Japan
Corresponding author, Kunio IKEMURA; E-mail: k-ikemura@shofu.co.jp
1
2

A newly designed, light-curing adhesive was investigated for its bonding effectiveness to porcelain, alumina, zirconia, Au, Au alloy,
Ag alloy, Au-Ag-Pd alloy, and Ni-Cr alloy. Four experimental adhesives were prepared using varying contents of the following: a
silane coupling agent [3-methacryloyloxypropyltriethoxysilane (3-MPTES)], acidic adhesive monomers [6-methacryloyloxyhexyl
phosphonoacetate (6-MHPA), 6-methacryloyloxyhexyl 3-phosphonopropionate (6-MHPP) and 4-methacryloyloxyethoxycarbonylphthalic
acid (4-MET)], and dithiooctanoate monomers [6-methacryloyloxyhexyl 6,8-dithiooctanoate (6-MHDT) and 10-methacryloyloxydecyl
6,8-dithiooctanoate (10-MDDT)]. After all adherend surfaces were sandblasted and applied with an experimental adhesive, shear
bond strengths (SBSs) of a light-curing resin composite (Beautifil II, Shofu Inc., Kyoto, Japan) to the adherend materials after 2,000
times of thermal cycling were measured. For the experimental adhesive which contained 3-MPTES (30.0 wt%), 6-MHPA (1.0 wt%),
6-MHPP (1.0 wt%), 4-MET (1.0 wt%), 6-MHDT (0.5 wt%) and 10-MDDT (0.5 wt%), it consistently yielded the highest SBS for all
adherend surfaces in the range of 20.8 (4.8)30.3 (7.9) MPa, with no significant differences among all the adherend materials (p>0.05).
Therefore, the newly designed, multi-purpose, light-curing adhesive was able to deliver high SBS to all the adherend materials
tested.
Keywords: M
 ulti-purpose light-curing adhesive, Silane coupling agent, Dithiooctanoate monomer, Dental ceramic, Precious metal
alloy

INTRODUCTION
The field of adhesive dentistry has made a significant
progress over the past decade. A large part of this success
is attributed to the major advances in a bonding
technology1). Notably, the major advances are ascribed
to an advanced adhesion-promoting monomer (adhesive
monomer). It was developed to enhance the bond strength
for a multitude of adherend materials that coexist in the
oral environment, ranging from dental hard tissues (e.g.,
enamel and dentin) to dental precious metal alloys (e.g.,
gold and gold alloys), dental non-precious metals, and
dental ceramics [e.g., silica-based ceramics (dental
porcelain), zirconium oxide (zirconia)-based ceramics,
and aluminum oxide (alumina)-based ceramics]2). The
current trend in the development of dental adhesive
systems seeks to simplify bonding steps for convenience,
with a constant quest to optimize both speed and
efficiency. Therefore, there emerges a clinical demand
for the development of single-bottle, multi-purpose
primers or adhesives which are able to provide strong
and durable adhesion indiscriminately to a variety of
adherend materials.
The typical structure of an adhesive monomer
consists of three parts: a polymerizable functional group,
a connecting group, and an adhesion-promoting group3).
Acidic adhesive monomers and sulfur-containing
Received Jan 20, 2011: Accepted Mar 31, 2011
doi:10.4012/dmj.2011-012 JOI JST.JSTAGE/dmj/2011-012

monomers are classified as two different categories of

adhesive monomers: the former contains acidic groups
such as carboxylic acid, phosphoric acid or phosphonic
acid, while the latter contains a sulfur atom in their
structures. For acidic adhesive monomers, they play a
key role in the action of recently developed self-etching
primers and adhesives in that they can interact
chemically as ligand monomers not only with
hydroxyapatite in dental hard tissues4), but also with
metal oxides on the surfaces of non-precious metals5) and
with alumina-based and zirconia-based ceramics6). For
sulfur-containing monomers, they are able to chemically
interact with metal atoms on the surfaces of precious
metals7-9).
Chemical adsorption of organic sulfur
compounds on precious metal surfaces, followed by a
spontaneous assembly of organic thiol-like molecules,
eventually results in the formation of monolayer films on
precious metal surfaces10,11). Silane coupling agents
possess alkyloxysilane group as an adhesion-promoting
group in their structures. For this reason, silane coupling
agents are considered as a category of adhesive monomers
for silica-based ceramics because of strong adhesion
achieved via a silane coupling reaction.
Multi-purpose primers, which contained silane
coupling agents, acidic adhesive monomers, and sulfurcontaining monomers for bonding to porcelain, zirconia,
dental precious and non-precious metal alloys, were

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Dent Mater J 2011; 30(4): 493500

developed recently12-14).
However, multi-purpose,
light-curing adhesives or bonding resins which contain
the same ingredients listed above are rarely reported
let alone single-bottle adhesives. In our previous studies,
acidic adhesive monomers bearing carboxylic acid or its
anhydride group15,16) and phosphonic acid group5,17) were
developed. Besides, eight kinds of acryloyloxyalkyl
and
methacryloyloxyalkyl
6,8-dithiooctanoates
(dithiooctanoate monomers) as novel sulfur-containing
monomers were also developed18).
The focus of our new research strategy is a singlebottle, multi-purpose, light-curing adhesive which bonds
light-curing resin composites to dental metal alloys for
fixed prosthodontics repair. To up the ante, this new,
multi-purpose adhesive should also display excellent
handling properties and which enables reductions in
both operation time and technical errors.
In the present study, we designed a multi-purpose,
light-curing adhesive which contained a silane coupling
agent, acidic adhesive monomers, and dithiooctanoate
monomers. The aim of the present study was to
investigate the effect of this newly designed, multipurpose adhesive on the bonding of a light-curing resin
composite to varied metal and dental ceramic materials:
porcelain, alumina, zirconia, pure gold, Au alloy, Ag
alloy, Au-Ag-Pd alloy, and Ni-Cr alloy.
The null
hypothesis was that this ternary combination of
functional monomers (silane coupling agent, acidic
adhesive monomers, and dithiooctanoate monomers)
would not result in high bond strength between the resin
composite and the all adherend materials tested after
2,000 thermal cycles.

MATERIALS AND METHODS

Preparation of reagents
Figure 1 depicts the chemical structures of the
dithiooctanoate monomers and phosphonic acid
monomers employed in this study.
For the
dithiooctanoate
monomers
namely
6methacryloyloxyhexyl 6,8-dithiooctanoate (6-MHDT)
and
10-methacryloyloxydecyl
6,8-dithiooctanoate
(10-MDDT), they were synthesized via an esterification
reaction
between
6,8-dithiooctanoic
acid
and
6-hydroxyhexyl
methacrylate
(6-HHMA)
or
10-hydroxydecyl methacrylate (10-HDMA) respectively

Fig. 1

according to the method described in our previous

study18). For the phosphonic acid monomers namely,
6-methacryloyloxyhexyl phosphonoacetate (6-MHPA)17)
and 6-methacryloyloxyhexyl 3-phosphonopropionate
(6-MHPP)5), they were synthesized via an esterification
reaction between 6-HHMA and phosphonoacetic acid or
3-phosphonopropionic acid respectively according to the
method described in our previous studies5,17). As for
4-methacryloyloxyethoxycarbonylphthalic acid (4-MET)
in the form of white needle crystals, it was synthesized
according to the method described in our previous
study16).
2,2-Bis[4-(2-hydroxy-3-methacryloyloxypropoxy)
phenyl]propane
(=bisphenol
A
diglycidyl
methacrylate)
(Bis-GMA)
was
synthesized
by
adding bisphenol A to glycidyl methacrylate in 1:2
molar ratio as previously reported19).
1,6-Bis
(2-methacryloyloxyethoxycarbonylamino)-2,4,4trimethylhexane
(UDMA)
was
synthesized
by
adding
2,4,4-trimethylhexane-1,6-diisocyanate
to
2-hydroxyethyl methacrylate in 1:2 molar ratio as
previously described15). Triethylene glycol dimethacrylate
(TEGDMA; Mitsubishi Rayon Co. Ltd., Tokyo, Japan),
D,L-camphorquinone (CQ; Tokyo Chemical Industry Co.,
Ltd., Tokyo, Japan), ethyl p-dimethylaminobenzoate
(EDAB; Wako Pure Chemical Industries, Ltd., Osaka,
Japan),
3-methacryloyloxypropyltriethoxysilane
(3-MPTES; Shin-Etsu Chemical Co., Ltd., Tokyo, Japan),
and hydrophobic fumed silica fillers (Aerosil R 972,
Nippon Aerosil Co., Ltd., Tokyo, Japan) were purchased
and used without further purification.
Preparation of experimental light-curing adhesives
Table 1 presents the compositions of four experimental,
single-bottle, light-curing adhesives (code names:
Si-AA-SS-1, Si-AA-SS-2, AA, and SS) to be investigated
in this study. According to the percent compositions
listed in Table 1, silane coupling agent, acidic adhesive
monomers, dithiooctanoate monomers, polymerizable
monomers, photoinitiator system, filler, and solvent
were added and uniformly mixed to produce the
respective experimental adhesives. All prepared, singlebottle adhesives (5.0 g) were placed in black plastic
containers. The code name of Si-AA-SS indicated a
combination of a silane coupling agent (Si), acidic
adhesive monomers (AA), and cyclic disulfides (SS) as

Schematic illustration of the chemical structures of dithiooctanoate monomers

(6-MHDT18) and 10-MDDT18)) and phosphonic acid monomers (6-MHPA17) and
6-MHPP5)) employed in this study.

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Dent Mater J 2011; 30(4): 493500

Table 1

Compositions (wt%) of experimental multi-purpose light-curing adhesives

Ingredient (wt%)

Code names of experimental adhesives

Abbreviation

Si-AA-SS-1

Si-AA-SS-2

AA

SS

Silane coupling agent

3-MPTES

30.0

30.0

Acidic adhesive monomer

6-MHPA
6-MHPP
4-MET

2.0

1.0
1.0
1.0

2.0

Dithiooctanoate monomer

10-MDDT
6-MHDT

0.5

0.5
0.5

0.5

Polymerizable monomer

Bis-GMA
UDMA
TEGDMA

30.0

15.0

15.0
10.0
10.0

15.0
10.0
10.0

15.0
10.0
10.0

Photoinitiator system

CQ
EDAB

0.2
0.3

0.2
0.3

0.2
0.3

0.2
0.3

Filler

R-972

3.0

3.0

3.0

3.0

Solvent

Ethanol
Acetone

19.0

27.5

59.5

61.0

The code name of Si-AA-SS indicates a combination of a silane coupling agent (Si), acidic adhesive monomers (AA),
and dithiooctanoate monomers (SS).
Table 2

Eight kinds of ceramic and metal adherend materials used in this study

Adherend

Code

Composition (mass%)

Manufacturer

Vintage Halo

Porcelain

SiO2, etc.

Shofu Inc.

Aluminum oxide

Alumina

Al2O3

Japan Fine Ceramics Co., Ltd.

Zirconium oxide

Zirconia

ZrO2 containing 3 mol% Y2O3

Japan Fine Ceramics Co., Ltd.

Pure gold

Au

Au (99.99)

Ishifuku Metal Industry Co., Ltd.

Super Gold Type 4

Au alloy

Au (70), Cu (13), Ag (10),

Pt (1), Pd (4), others (2)

Shofu Inc.

Sunsilver

Ag alloy

Ag (79), Zn (7), In (7),

Cu (5), others (2)

Sankin Kogyo Co., Ltd.

Castwell M. C.

Au-Ag-Pd alloy

Ag (45), Pd (20), Cu (18),

Au (12), others (5)

GC Dental Products Corp.

Dent Nickel

Ni-Cr alloy

Ni (63.5), Cr (15), Nb (5), Mn (5),

others (11.5)

Shofu Inc.

dithiooctanoate monomers.
Preparation of adherends
Eight kinds of adherend materials were examined in this
study. Their composition and manufacturer details are
given in Table 2. Three ceramic adherends used were
namely porcelain (Vintage Halo, Shofu Inc., Kyoto,
Japan), aluminum oxide (alumina) plate (Al2O3; Japan
Fine Ceramics Co., Ltd., Sendai, Japan), and zirconium
oxide (zirconia) plate (ZrO2 containing 3 mol% Y2O3;
Japan Fine Ceramics Co., Ltd., Sendai, Japan). Five
metal adherends used were pure gold (Au; Ishifuku
Metal Industry Co., Ltd., Tokyo, Japan), three types of

precious metal alloys [Au alloy (Super Gold Type 4,

Shofu Inc., Kyoto, Japan), Au-Ag-Pd alloy (Castwell
M.C., GC Dental Products Corp., Tokyo, Japan), and Ag
alloy (Sunsilver, Sankin Kogyo Co. Ltd., Tokyo, Japan)],
and one non-precious Ni-Cr alloy (Dent Nickel, Shofu
Inc., Kyoto, Japan). All dental alloys were cast using a
casting machine (Argon Caster, Shofu Inc., Kyoto,
Japan).
Shear bond strength measurement
Disk-shaped rods (6.00.1 mm in diameter, 4.00.1 mm
in height) of both ceramic and metal adherends were
embedded in an epoxy resin. Using porcelain for firing

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Dent Mater J 2011; 30(4): 493500

dental materials, the disk-shaped rods were made using

a vacuum electric furnace for firing porcelain (Twin Mat,
Shofu Inc., Kyoto, Japan). To prepare the bond surfaces
of adherends, the exposed flat ends of the rods were
polished under running water using #240 and #600
silicon carbide papers to obtain smooth and flat bonding
surfaces. The polished flat surfaces were subjected to air
abrasion treatment (50-m alumina beads; Shofu
Hi-alumina, Shofu Inc., Kyoto, Japan) under a pressure
of 0.25 MPa, ultrasonic-cleaned, and then air-dried.
After drying, a double-sided adhesive tape with a
4.0-mm-diameter hole was fixed on each adherend
surface to define the bonding area. An experimental
light-curing adhesive was applied on the bonding area
with a microbrush, air-blown, and then light-cured with
a visible light apparatus (Grip Light II, Shofu Inc.,
Kyoto, Japan) for 20 seconds. A cylindrical Teflon mold
(4.0 mm inner diameter, 2.0 mm height) was fixed on the
bonding area, and a light-curing resin composite
(Beautifil II, Shofu Inc., Kyoto, Japan) was packed into
the mold and light-cured for 30 seconds. After the mold
was removed, the resin-ceramic or resin-metal bonded
specimen was stored in 37C distilled water for 24 hours.
After water storage, the specimens (n=6 in each group)
were subjected to 2,000 times of thermal cycling whereby
they were alternately immersed in 4 and 60C water for
one minute each.
Shear bond strength (SBS)
measurements were made using a universal testing
machine (Model 5543, Instron Corp., Norwood, MA,
USA) at a crosshead speed of 1.0 mm/min.
Failure mode analysis
After SBS testing, the fracture surfaces of debonded
specimens were examined using a stereomicroscope
(Leica DM IL, Leica Microsystems Japan, Tokyo, Japan)
at 15 magnification. The failure modes were classified
as follows: interfacial failure, cohesive failure of adhesive
resin, or mixed failure. Interfacial failure, conventionally
known as adhesive failure, was defined as the fracture
Table 3

which occurred at the bonded interface between adhesive

and adherend. Cohesive failure was defined as cohesive
fracture of the adhesive resin on the debonded adherend
surface. Additionally, cohesive failure also included the
cohesive failure of adherend, such as fractured porcelain.
Mixed failure was defined as the failure mode in which
both interfacial and cohesive failures coexisted on the
debonded adherend surface.
After examining all the debonded specimens, the
failure modes of specimens in each group were identified
as I/M/C (=Interfacial failure/Mixed failure/Cohesive
failure) and numbered accordingly.
Statistical analysis
Statistical analysis was performed for the SBS data of all
the four experimental, multi-purpose, light-curing
adhesives. One-way analysis of variance (ANOVA) was
performed to determine the existence of significant
differences in SBS among the different types of
experimental adhesives for each adherend. Statistical
significance was set in advance at 0.05 probability level.
Multiple comparisons were performed using StudentNewman-Keuls test at =0.05.

RESULTS
Table 3 presents the effects of four experimental
light-curing adhesives (coded Si-AA-SS-1, Si-AA-SS-2,
AA, and SS) on the SBS of a light-curing resin composite
(Beautifil II, Shofu Inc., Kyoto, Japan) to the ceramic
(porcelain, alumina, and zirconia) and metal (Au, Au
alloy, Ag alloy, Au-Ag-Pd alloy, and Ni-Cr alloy)
adherends after 2,000 thermal cycles.
With Si-AA-SS-1 (which contained 30.0 wt%
3-MPTES, 2.0 wt% 6-MHPA, and 0.5 wt% 10-MDDT),
there were no statistically significant differences in SBS
(p>0.05) among all the adherend materials. However,
higher SBS values were seen for the metal adherends
than for the ceramics. For the three ceramic adherends,

Shear bond strengths of experimental multi-purpose, light-curing adhesives after 2,000 thermal cycles

Adherend

Shear bond strength [mean (standard deviation, SD), MPa]

Si-AA-SS-1

Si-AA-SS-2

Porcelain

17.7 (4.2)

26.4 (5.6)

5.3 (1.1)

fell off

Alumina

16.8 (4.7)

23.3 (4.9)

16.3 (3.0)

fell off

Zirconia

17.5 (5.0)

20.8 (4.8)

13.5 (3.4)

fell off

Au

19.5 (5.2)a

30.3 (7.9)a

fell off

6.7 (1.5)a

Au alloy

23.2 (5.3)a

28.4 (7.7)a

fell off

6.3 (1.2)a

Ag alloy

27.3 (6.5)a

27.8 (6.6)a

5.5 (0.8)a

5.7 (1.8)a

Au-Ag-Pd alloy

24.3 (5.6)a

28.2 (6.9)a

4.3 (1.3)a

5.8 (2.0)a

Ni-Cr alloy

26.9 (6.8)a

29.7 (7.1)a

14.0 (3.8)b

fell off

a
a
a

a
a
a

AA

SS
a
b
b

Note: n=6. One thermal cycle: 4C water for 1 min and 60C water for 1 min. Groups from the same column (adhesive)
that are identified with the same superscript letter are not significantly different (p>0.05). Fell off: Composite specimen
fell off from adherend during thermal cycling.

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Table 4

Failure modes of fractured specimens after SBS testing

Failure mode of fractured surfaces after debonding

Adherend

Si-AA-SS-1

Si-AA-SS-2

AA

I/M/C

I/M/C

I/M/C

I/M/C

Porcelain

2/4/0

0/3/3

6/0/0

6/0/0#

Alumina

2/3/1

0/3/3

3/2/1

6/0/0#

Zirconia

2/4/0

0/4/2

4/2/0

6/0/0#

Au

2/3/1

0/1/5

6/0/0#

6/0/0

Au alloy

1/4/1

0/1/5

6/0/0

6/0/0

Ag alloy

0/4/2

0/1/5

6/0/0

6/0/0

Au-Ag-Pd alloy

0/4/2

0/0/6

6/0/0

6/0/0

Ni-Cr alloy

0/3/3

0/0/6

5/1/0

6/0/0#

SS

Note: n=6. Failure mode: Number of specimens of Interfacial failure/Mixed failure/Cohesive failure in adhesive resin.
#
: Composite specimens fell off from adherends during thermal cycling.

mean SBS ranged between 16.8 (4.7) MPa and 17.7 (4.2)
MPa. For the five metal adherends, the range was 19.5
(5.2)27.3 (6.5) MPa. With Si-AA-SS-2 (which contained
30.0 wt% 3-MPTES, 1.0 wt% 6-MHPA, 1.0 wt% 6-MHPP,
1.0 wt% 4-MET, 0.5 wt% 6-MHDT, and 0.5 wt%
10-MDDT), there were no statistically significant
differences in SBS (p>0.05) among all the adherend
materials. For the three ceramic adherends, mean SBS
ranged between 20.8 (4.8) MPa and 26.4 (5.6) MPa. For
the five metal adherends, the range was 27.8 (6.6)30.3
(7.9) MPa.
With AA (which contained only 2.0 wt% of acidic
adhesive monomer 6-MHPA), there were no statistically
significant differences in SBS (p>0.05) among alumina,
zirconia, and Ni-Cr alloy. In contrast, the mean SBS
values of AA to porcelain, Au, Au alloy, Ag alloy, and
Au-Ag-Pd alloy were significantly lower than those to
alumina, zirconia, and Ni-Cr alloy (p<0.05). In particular,
composite specimens fell off (debonded) from both Au
and Au alloy adherends during thermal cycling. With SS
(which contained only 0.5 wt% of dithiooctanoate
monomer 10-MDDT), the composite specimens fell off/
debonded from all the three ceramic and Ni-Cr alloy
adherends during thermal cycling. For Au, Au alloy, Ag
alloy, and Au-Ag-Pd alloy, there were no statistically
significant differences in SBS which ranged between 5.7
(1.8) MPa and 6.7 (1.5) MPa.
Table 4 presents the failure mode distribution of
fractured specimens after SBS testing. With Si-AA-SS-2,
it was predominantly mixed failures and cohesive
failures in adhesive, but no interfacial failures between
adhesive and adherend.
With AA and SS, the
predominant failure mode was contrastingly that of
interfacial failure. There were a few incidents of mixed
failure but no cohesive failures, except between AA and
alumina. With Si-AA-SS-1 and Si-AA-SS-2 which
contained silane coupling agent, acidic adhesive
monomers, and dithiooctanoate monomers, they yielded

high SBS to all the adherend materials tested even after

2,000 thermal cycles. Predominant failure modes with
these two adhesives were namely mixed failure and
cohesive failure in adhesive. With AA, very low SBS
values were exhibited for porcelain, Au, Au alloy, Ag
alloy, and Au-Ag-Pd alloy. With SS, similarly low SBS
values were exhibited for all the adherend materials.

DISCUSSION
In the present study, we tried to design a new, singlebottle, multi-purpose, light-curing adhesive which
contained a silane coupling agent (3-MPTES), acidic
adhesive monomers (6-MHPA, 6-MHPP and 4MET)5,15-17), and dithiooctanoate monomers (6-MHDT
and 10-MDDT)18). With silane coupling agents, the
mechanism of their silane coupling reaction is that the
trialkyloxysilyl group [-Si-(OR)3] of silane coupling
agents, such as 3-MPTES, is hydrolyzed in acid solutions
to form reactive silanols [-Si-(OH)3]. Partial condensation
reaction follows and oligomers are formed, which are
adsorbed on silica-based ceramic surfaces by hydrogen
bonding. Dehydration condensation, which is applied
using heat treatment, then causes covalent chemical
bonds to be formed between silanes and silica-based
ceramics20).
With acidic adhesive monomers, the hypothetical
bonding mechanism to ceramics and non-precious
metal alloys can be understood as follows.
10-Methacryloyloxydecyl dihydrogen phosphate (MDP)
and 6-MHPA, both phosphorus-containing monomers,
chemically bond to metal oxides of ceramics and
non-precious metal alloys5,21). It was thought that the
phosphoric acid group [-O-P(=O)(OH)2] of MDP and
phosphonic acid group [-P(=O)(OH)2] of 6-MHPA promote
good interaction with metal oxides on the surfaces of
both aluminum oxide-based (Al2O3) and zirconium
oxide-based (ZrO2) ceramics as well as non-precious

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metal alloys. Moreover, phosphonic acid monomers

(6-MHPA and 6-MHPP) are water-soluble monomers,
whereas MDP is a water-insoluble monomer. This
means that phosphonic acid monomers can be partially
or completely ionized with a small amount of water on
the metal oxide surfaces of ceramics and non-precious
metal alloys. The ionized phosphonic acid monomer
selectively and immediately penetrates the metal oxide
structures and chemically interacts with the metal
cations in the metal oxide structures to form metal salts.
Hydrogen bonds are also formed between undissociated
phosphonic acid groups and metal oxides.
With
subsequent application of light irradiation, the
phosphonic acid monomers of light-curing adhesive
penetrate the metal oxide structures and photopolymerize
in situ at the resin-adherend interface, such as the resinalumina, resin-zirconia, and resin-Ni-Cr alloy bonding
interfaces.
Sulfur-containing monomers are able to chemically
interact with precious metal atoms7-9). It has been
reported that the cyclic -S-S- group of dithiooctanoate
monomers provided strong adhesion to Au, Au alloy, Ag
alloy, and Au-Ag-Pd alloy18). In the present study, the
experimental adhesive Si-AA-SS-2 which contained
3-MPTES, 6-MHDT, 10-MDDT, 6-MHPA, 6-MHPP, and
4-MET exhibited high SBSs to both precious and
non-precious metals alike: 30.3 (7.9) MPa for Au, 28.4
(7.7) MPa for Au alloy, 27.8 (6.6) MPa for Ag alloy, 28.2
(6.9) MPa for Au-Ag-Pd alloy, and 29.7 (7.1) MPa for
Ni-Cr alloy (Table 3).
Apart from precious and non-precious metals,
Si-AA-SS-2 also exhibited strong adhesion to porcelain,
alumina, and zirconia with no incidents of interfacial
failure (Table 4). Contrary to the effective bonding
performance of Si-AA-SS-2, AA and SS which did not
contain silane coupling agent but only either 6-MHPA or
10-MDDT showed insufficient bond strengths not only
to porcelain, but to the other adherend materials too
(Table 3). Their weak bond strengths were evidenced by
a high number of interfacial failures between adhesive
and adherends (Table 4). The outstanding bonding
performance of Si-AA-SS-2 to ceramic adherends was
attributed to the ternary combination of a silane coupling
agent, acidic adhesive monomers, and dithiooctanoate
monomers in its formulation.
It was reported that a combined application of a
hydrophobic phosphate ester monomer (MDP) with a
silane coupling agent on the silica-coated yttrium-oxidepartially-stabilized zirconia (YPSZ) ceramic yielded
stable shear bond strength, thus rendering this system
as a promising method for ceramic restorations in clinical
settings22). Apart from MDP monomer, it was reported in
another study that a commercial metal primer (AZ
Primer; Shofu Inc., Kyoto, Japan) which contained the
phosphonic acid monomer, 6-MHPA, delivered strong
bonding to alumina- and zirconia-based all-ceramic
prostheses23). In the present study, the bond strength
between Si-AA-SS-2 and zirconia was 20.8 (4.8) MPa. It
should be pointed out that bond strength values are
affected by the zirconia systems in use. In a recent

study24), the highest SBS values reported for four types of

commercially utilized zirconia systems and veneering
ceramics using an acrylic resin were in the range of 20.2
(5.1)40.5 (8.4) MPa.
The bonding ability as a multi-purpose, light-curing
adhesive should be validated by comparing with bonding
data previously reported for the combined effect of
sulfur-containing monomers and acidic adhesive
monomers on adhesion to precious and non-precious
metals8,25,26). In a study by Suzuki et al.7), the effect of
adding MDP (0.2 wt%) to a primer which contained
6-(4-vinylbenzyl-n-propyl)amino-1,3,5-triazine-2,4dithione (VBATDT) (0.5 wt%) on the tensile bond
strength (TBS) of MMA-PMMA/TBBO resin to metals,
after 2,000 thermal cycles, was investigated. It was
reported that the TBSs to Au, Ag, and chromium (Cr)
were 25.2 (3.6) MPa, 39.7 (2.6) MPa, and 34.2 (9.7) MPa
respectively7). In a study by Okuya et al.27), the effects of
three commercial metal primers (including Metal Link
Primer) on bonding of an MMA-PMMA/TBBO resin to
four pure metals and two dental alloys after 2,000
thermal cycles were investigated. Metal Link Primer
(M.L. Primer; Shofu Inc., Kyoto, Japan), which was
commercially launched in 2003, contained both 10-MDDT
and 6-MHPA to promote strong adhesion of adhesive
resins to both precious and non-precious metals and
their alloys. It was reported that the highest SBS values
achieved for pure Au and high-gold-content alloy were
33.5 MPa and 33.3 MPa with M.L. Primer27). Despite the
differences in bond testing methodology, Si-AA-SS-2
exhibited comparable bonding ability in this study for Au
(30.3 MPa) when pitted against the published bonding
data (namely, 33.5 MPa27) and 25.2 MPa7)).
When sulfur-containing monomers are combined
with acidic adhesive monomers, an intriguing issue is
the adsorption behaviors of these monomers on the
adherends and the impact thereof on bonding efficacy.
In a study by Suzuki et al.8), surface-enhanced Raman
scattering (SERS) spectroscopy and infrared reflection
absorption (IRA) spectroscopy were used to investigate
the adsorption behaviors of VBATDT and MDP on Au,
Ag, Cu, and Cr surfaces. Results showed that VBATDT
was chemisorbed mainly on Au, Ag, and Cu surfaces
with respect to thickness, whereas MDP was adsorbed
only on Cr. In a study by Koizumi et al.25), it was found
that the combined application of phosphonic acid
monomers (6-MHPA and 6-MHPP) and dithiooctanoate
monomers (6-MHDT and 10-MDDT) did not interfere
with the bonding of phosphonic acid monomers to base
metals nor dithiooctanoate monomers to precious metals.
Applying the findings of previous studies8,25) to the
present study, it could be suggested that 6-MHDTprecious metal and 10-MDDT-precious metal interactions
were independent from 6-MHPA-base Ni-Cr alloy and
6-MHPP-base Ni-Cr alloy interactions. Moreover, the
adhesion-promoting groups of sulfur-containing groups
and acid groups indubitably contributed to improving
the bond strengths to precious and non-precious metals
respectively. As for the cooperation of an exceedingly
large amount of silane coupling agent (30 wt% of

Dent Mater J 2011; 30(4): 493500

3-MPTES) together with both acidic adhesive monomers
and dithiooctanoate monomers on improving bonding to
all the adherend materials tested, 3-MPTES is a surfaceactive agent, and therefore, it was probable that the
exceedingly large amount of 3-MPTES in Si-AA-SS-1
and Si-AA-SS-2 promoted active mobility of both
phosphonic acid monomers and dithiooctanoate
monomers in the hydrophobic light-curing adhesives. As
a result, both phosphonic acid monomers and
dithiooctanoate monomers were able to chemically
interact with all the ceramic and metal adherends
unlike the adhesives AA and SS, which contained an
inactive solvent (acetone) for adhesion.
To design a new, single-bottle, multi-purpose,
light-curing adhesive, the effects of a ternary combination
of a silane coupling agent (3-MPTES), acidic adhesive
monomers (6-MHPA, 6-MHPP, and 4-MET), and
dithiooctanoate monomers (6-MHDT and 10-MDDT) on
adhesion to varied dental ceramic and metal materials
were investigated. Results of this study showed that the
experimental adhesive Si-AA-SS-2 was able to deliver
high SBSs to all the adherend materials tested. Based
on these results, the null hypothesis was rejected, which
stated that the ternary combination of the abovementioned functional monomers would not result in high
bond strength between resin composite and the all
adherend materials tested after 2,000 thermal cycles. In
this series of studies on multi-purpose adhesives, our
next target is to design a multi-purpose, self-etching
adhesive which contains dithiooctanoate monomers and
acidic adhesive monomers. The bonding performances of
this novel, multi-purpose, self-etching adhesive to dental
hard tissues, dental ceramics, and dental precious alloys
shall also be investigated and assessed.

CONCLUSIONS
Based on the findings in the present study, the following
conclusions were drawn:
1. With the experimental adhesive Si-AA-SS-2,
which contained 3-MPTES (30.0 wt%), 6-MHPA
(1.0 wt%), 6-MHPP (1.0 wt%), 4-MET (1.0 wt%),
6-MHDT (0.5 wt%), and 10-MDDT (0.5 wt%), high
shear bond strengths ranging between 20.8 (4.8)
and 30.3 (7.9) MPa were exhibited for dental
porcelain, alumina, zirconia, Au, Au alloy, Ag
alloy, Au-Ag-Pd alloy, and Ni-Cr alloy adherends.
2. The high shear bond strengths of Si-AA-SS-2 to all
the adherend materials tested after 2,000 thermal
cycles was attributed to the ternary combination
of a silane coupling agent (3-MPTES), acidic
adhesive monomers (6-MHPA, 6-MHPP, and
4-MET), and dithiooctanoate monomers (6-MHDT
and 10-MDDT) in its formulation.

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