Dental Materials Journal 2015; 34(3): 327–335

The effect of polymerization conditions on the amounts of unreacted monomer

and bisphenol A in dental composite resins
Ha-Jeong KWON1*, Yoon-Jong OH1*, Jong-Hwa JANG2, Jung-Eun PARK1, Kyung-Suk HWANG3 and Yong-Duk PARK1

1
Department of Preventive and Social Dentistry, Kyung Hee University, Hoegi-dong, Dongdaemoon-gu, Seoul 130-701, Republic of Korea
2
Department of Dental Hygiene, Hanseo University, 360 Daegok-Ri, Haemi-Myun, Seosan-Si, Chungnam 356-706, Republic of Korea
3
Department of Dental Technology, Shinhan University, Howon-dong Uijeongbu, Gyeonggi-do, Republic of Korea
Corresponding author, Yong-Duk PARK; E-mail: iam2875@khu.ac.kr

The aim of this study was to analyze the unreacted monomers of four commonly used composite resins, which were released after
curing with different polymerization conditions. Four composite resins, consisting of two hybrid types and two flowable types from
two manufacturers, were photopolymerized using different curing times and curing distances. After polymerization, samples were
extracted for analysis at different time points up to 24 h. Released monomers were analyzed by reversed-phase liquid chromatography
at UV 210 nm. Longer curing times and shorter curing distances resulted in higher polymerization rates and decreased release of
TEGDMA and UDMA, but changes in curing time and distance had no significant effect on Bis-GMA. Release of BPA increased with
increase in curing time or decrease in curing distance, in contrast to the results of TEGDMA and UDMA. Polymerization conditions
need to be differently applied according to both monomer and resin types.

Keywords: Composite resin, Polymerization, Monomer, Bisphenol A formation, Curing conditions

controversial endocrine disruptor10,11). In this study, BPA

INTRODUCTION
In recent years, rapid rise in the number of patients
undergoing aesthetic dental procedures has led to
increased interest in the use of composite resins,
which can be manufactured to be of the same color as
natural teeth. The organic phase of composite resins
is constituted of dimethacrylate monomers. The
most common monomers include triethylene glycol
dimethacrylate (TEGDMA) urethane dimethacrylate
(UDMA), and bisphenol A glycerolate dimethacrylate
(Bis-GMA)1).
The use of composite resins involves the conversion
of monomers to polymers through photo- or chemical
polymerization, and unreacted monomers are released.
Previous reports have shown that polymerization rates
can vary from 50% to 70%2), and residual unreacted
monomers that are released into the oral cavity produce
systemic side effects and/or local adverse effects on
tissues and cells3). The mechanical properties of
restorative resins are influenced by unreacted
monomers4): insufficient polymerization of monomers
causes wear resistance to deteriorate and discoloration5).
Released unreacted monomers can cause dental pulp
irritation by accessing the pulp via dentinal tubules
due to an insufficient cavity lining3), leading to the
proliferation of micro-bacteria located at the interface
between the restorative material and dental tissues6).
Moreover, these monomers can access the vascular
system by penetrating the dentin, causing soft tissue
irritation and allergic reactions, as well as cytotoxic,
genotoxic, mutagenic, or estrogenic effects7-9).
Bisphenol A (BPA) is present as a trace impurity
in the starting materials for resins, and it is also a
was investigated in conjunction with dimethacrylate
monomers (TEGDMA, UDMA, Bis-GMA).
The amounts of monomers released from commercial
dental resins under different polymerization conditions
(e.g., light source, curing intensity) have been principally
investigated using HPLC-UV12-14) or HPLC-mass
spectrometry15,16).
The safe use of composite resins with aesthetically
pleasing results is dependent on several factors such
as light wavelength17), exposure time18), distance from
light guide exit19), light source13), and light intensity20).
These factors influence the degree of polymerization,
hardness of the composite solid, and the amount of
released cytotoxic monomers21). Nevertheless, most
composite resins are accompanied with manufacturer
information on polymerization time and intensity, but
not polymerization distance.
In this study, unreacted monomers which were
released after curing with different polymerization
conditions were measured for four composite resins
(from two manufacturers) that are commonly used in
South Korea. Amounts of unreacted monomers were
measured to evaluate the degree of conversion from
monomer to polymer according to monomer and resin
types. Curing time and distance were considered
independent variables for each type of composite resin.
MATERIALS AND METHODS
Reagents
Analytical solvents and chemicals were used for all
experiments in this study. HPLC-grade acetonitrile was
purchased from Fisher Scientific (Fairlawn, NJ, USA).

*Authors who contributed equally to this work.

Received Aug 11, 2014: Accepted Jan 6, 2015
doi:10.4012/dmj.2014-230 JOI JST.JSTAGE/dmj/2014-230
328 Dent Mater J 2015; 34(3): 327–335
Bisphenol A glycerolate dimethacrylate (Bis-GMA),
urethane dimethacrylate (UDMA), and 2-hydroxy-
4,6-dimethoxyacetophenone (internal standard) were
purchased from Sigma-Aldrich (St. Louis, USA).
Triethylene glycol dimethacrylate (TEGDMA) was
purchased from Wako (Osaka, Japan), and
4,4'-isopropylidenediphenol (BPA) was purchased from
Junsei (Tokyo, Japan).
A Millipore membrane filter (type HA, pore size:
0.45 µm, mixed cellulose esters) was used for solvent
filtration. All samples were filtered through disposable
syringe filters (hydrophobic polytetrafluoroethylene
(PTFE) membrane; pore size: 0.20 µm; Advantec MFS,
Inc., Tokyo, Japan) before injection. Standard solutions,
sample solutions, and the mobile phase were prepared
with 18 MΩ deionized water produced by a Millipore
Direct-Q 3 Water Purification System (Billerica, MA,
USA).
Preparation of composite resin specimens
Four composite resins consisting of two hybrid types
(Filtek Z250 and Gradia Direct) and two flowable
types (Filtek Z350 XT and UniFil Flow), which are
commonly used in dental clinics, were used in this
study. Shade A2 was chosen to minimize the effect of
color on photopolymerization. The resins were placed
into a silicon mold (diameter: 8 mm; thickness: 2 mm)
on a glass plate and then covered with glass to minimize
the effects of oxygen and produce a flat surface. The
composite resins were photopolymerized by a halogen
curing unit (Elipar TriLight, 3M ESPE) whose maximum
irradiation intensity was 700 mW/cm2.
To investigate the effects of curing time, the
composite resins were cured for 20, 40, and 60 s at a
fixed curing distance of 10 mm. To investigate the
effects of curing distance, the composite resins were
cured at 0-, 5-, 10-, and 20-mm distances between the
cover glass and halogen curing unit for a fixed curing
time of 20 s. Five specimens of each composite resin
were tested for each polymerization condition.
Extraction of unreacted monomers
Immediately after polymerization, cured composite
resin specimens were soaked in 1 mL of methanol and
stored at room temperature for 24 h. After 1 h and
then 12 h, the specimens were moved to 1 mL of fresh
methanol solvent. From 0 to 1 h, 1 to 12 h, and 12 to 24
h, monomers extracted from methanol-soaked samples
were analyzed by HPLC after the treatment described
as follows.
Unreacted monomers dissolved in methanol were
filtered by a disposable syringe filter (Hydrophobic
PTFE, pore size: 0.20 μm, Advantec MFS, Tokyo, Japan).
Methanol solvent was diluted to one tenth of its original
concentration using deionized water, and 2-hydroxy-
4,6-dimethoxyacetophenone was added to be used as an
internal standard. Concentration of internal standard
was 10 μg/mL for all extracted samples, and injected
volume was 10 μL.
The amount of monomer in raw resin before
polymerization was measured to calculate the
polymerization rate. Raw resin was dissolved in
methanol by vortexing for 1 min, and then filtered using
a disposable syringe filter. It was also diluted to one tenth
of its original concentration using deionized water, and
the internal standard was added as described above.
Measurement conditions for liquid chromatography
Unreacted monomer measurements were performed
using the UltiMate 3000 system (Dionex, Sunnyvale,
CA, USA), which was equipped with a pump, column
compartment, and diode array detector (DAD). Data
acquisition was performed using the Chromeleon software
(Dionex, Sunnyvale, CA, USA). Chromatographic
separation was performed using a Hypersil GOLD
C18 column (150 mm×2.1 mm internal diameter; 3 µm
particle size; Thermo, Waltham, MA, USA) protected
by a KrudKatcher Ultra in-line filter (Phenomenex,
Torrance, CA, USA).
The mobile phase consisted of water (solvent A) and
acetonitrile (solvent B). The gradient program of the
mobile phase was a linear gradient from A:B (93:7) to
(35:65) for 15 min, isocratic elution with A:B (35:65) for
15 min, and final equilibration at A:B (93:7) for 4 min.
Flow rate was 0.2 mL/min, and separation temperature
was 20°C. Components were identified by comparing
the elution time with those of reference compounds
and by their UV spectra. UV detection was performed
at 210 nm.
Analytical method validation
Stock solutions of reference standards (1 mg/mL)
were prepared in methanol. Calibration curves were
obtained by plotting the peak area ratios (analytes/
I.S.) using standard solutions diluted at nine standard
concentrations (0.01, 0.02, 0.05, 0.1, 2, 5, 10, 25 and
50 mg/L). Concentration of the internal standard
(6.2-hydroxy-4,6-dimethoxyacetophenone) for all
analytes was 10 mg/L. To assess the precision of the
analytical method, standard mixtures (1 mg/L) were
injected five times and the working sample extracted
from a resin specimen was repeatedly analyzed five
times in a day (intra-day precision) for five days (inter-
day precision).
RESULTS
Four types of monomers and the internal standard
were completely analyzed in 40 min using a water-
acetonitrile gradient elution system. 6.2-hydroxy-4,6-
dimethoxyacetophenone was added to be used as an
internal standard to account for loss or errors arising
from the whole experimental process or instrumental
instability. Calibration curves showed good linearity
over the concentration range up to 50 mg/L, and the
correlation coefficients of the four parabens were higher
than 0.99. Limits of detection (LOD) and quantification
(LOQ) were 0.01–0.03 and 0.03–0.09 mg/L respectively.
The RSD values of retention time were less than 1.3%,
and those of peak area ratios were less than 7% in
 Dent Mater J 2015; 34(3): 327–335 329

extracted resin solutions, indicating good repeatability
of the proposed analytical method (Table 1).
At three different time points up to 24 h after
polymerization, the amounts of released monomers
extracted from methanol were measured using the
HPLC method. Value of %released unreacted monomer
(%RM) was calculated using the following formula:
Released monomer from resin specimen
%RM= ×100
Initial monomer before polymerization
As for the initial monomer amount, it was calculated by
multiplying the monomer content in raw material by
the weight of each specimen. Table 2 shows the initial
content (w/w%) of each monomer in the raw material

Table 1 Analytical parameters of the proposed method for determination of monomers

Parameters BPA TEGDMA UDMA Bis-GMA

Linearity
Range (mg/L) 0.03–50 0.06–50 0.03–50 0.06–50
Slope±SD 0.097±0.006 0.044±0.002 0.028±0.001 0.042±0.003
Intercept±SD 0.047±0.0.022 0.022±0.036 0.010±0.046 0.087±0.053
R2 0.9999 0.9998 0.9997 0.9995

Repeatability (%RSD, n=5)

Retention time of STD 0.63 0.84 1.03 1.14
Peak Area ratio of STD 2.07 3.3 2.85 2.3
Intra-day of samples 6.7 3.1 5.4 3.8
Inter-day of samples 5.6 6.4 3.7 5

Sensitivity (mg/L)
LOD (S/N=3) 0.01 0.02 0.01 0.02
LOQ (S/N=10) 0.03 0.06 0.03 0.06

Table 2 The initial contents (w/w%) of monomers in raw composite resin (n=5)

TEGDMA UDMA Bis-GMA

Z350 6.20±0.83 2.33±0.19 8.12±0.46

Unifil 12.47±1.13 44.76±2.93 0.29±0.01

Z250 1.05±0.03 8.26±0.63 4.25±0.27

Gradia N.D. 17.47±2.11 N.D.

N.D., Not detected

Table 3 The average ± standard deviation of released unreacted monomer rates (%) from four resin composites according to
different curing time (n=5)

20 s 40 s 60 s
Component Resin
1h 12 h 24 h Total 1h 12 h 24 h Total 1h 12 h 24 h Total

Z350 2.5±1.2 1.1±0.2 0.4±0.1 4.0±1.5 1.3±0.2 0.4±0.0 0.2±0.0 1.8±0.2 1.1±0.1 0.4±0.1 0.1±0.0 1.6±0.1
TEGDMA Unifil 2.0±0.3 0.8±0.1 0.4±0.1 3.2±0.4 1.5±0.4 0.4±0.1 0.1±0.0 2.0±0.5 1.2±0.4 0.2±0.0 0.1±0.0 1.5±0.4
Z250 3.4±0.3 0.4±0.1 0.1±0.1 3.9±0.4 2.0±0.3 0.4±0.2 0.2±0.1 2.5±0.5 1.7±0.1 0.2±0.1 0.1±0.0 2.0±0.2

Z350 0.8±0.3 0.3±0.1 0.2±0.0 1.3±0.4 0.3±0.1 0.1±0.0 0.1±0.0 0.4±0.1 0.3±0.1 0.2±0.0 0.1±0.0 0.5±0.1
Bis-GMA Unifil 6.3±0.9 1.6±0.1 6.1±1.9 13.6±2.4 1.6±0.2 5.9±1.0 3.2±1.1 10.8±0.9 4.4±1.4 4.8±0.7 4.8±0.6 14.0±2.5
Z250 1.4±0.1 0.6±0.1 0.3±0.0 2.2±0.1 1.0±0.1 0.7±0.5 0.1±0.0 1.8±0.5 3.6±0.4 0.3±0.0 0.2±0.2 4.1±0.4

Unifil 1.4±0.1 1.3±0.1 1.2±0.2 3.9±0.3 1.3±0.2 0.8±0.1 0.5±0.1 2.7±0.5 1.1±0.3 0.6±0.0 0.5±0.1 2.2±0.4
UDMA Z250 3.5±0.2 0.8±0.1 0.3±0.0 4.7±0.2 2.1±0.2 0.9±0.8 0.1±0.0 3.1±0.9 1.9±0.2 0.4±0.0 0.2±0.1 2.4±0.2
Gradia 7.0±0.8 5.6±0.9 2.6±0.4 15.2±1.7 4.1±0.1 2.8±0.2 1.2±0.1 8.1±0.2 3.9±0.2 2.2±0.2 0.9±0.1 7.0±0.5
330 Dent Mater J 2015; 34(3): 327–335

before polymerization. Average specimen weights
of Gradia, UniFil, Z250, and Z350 were 0.17±0.00 g,
0.22±0.01 g, 0.22±0.00 g, and 0.20±0.00 g respectively.
At 1 h, 12 h, and 24 h after light curing, Table 3
shows the rates of release of unreacted TEGDMA, Bis-
GMA, and UDMA at these time points as a function of
different curing times, whereas Table 4 shows these
data as a function of different curing distances. The
corresponding bar graphs are shown in Fig. 1.
Gradia did not contain TEGDMA and Bis-GMA
in the raw material. Z350 contained UDMA in its
raw material, but UDMA was not detected after
polymerization. Therefore, the data of UDMA in Z350
and those of TEGDMA and Bis-GMA in Gradia were
omitted in Tables 3 and 4.
For TEGDMA, more than half of unreacted

Table 4 The average ± standard deviation of released unreacted monomer rates (%) from four resin composites according to
different curing distance (n=5)

0 mm 5 mm 10 mm 20 mm
Component Resin
1 12 24 Total 1 12 24 Total 1 12 24 Total 1 12 24 Total

Z350 1.9±0.4 0.7±0.3 0.2±0.0 2.8±0.7 2.5±0.3 1.1±0.3 0.4±0.1 4.0±0.3 2.5±0.4 1.0±0.3 0.3±0.1 3.9±0.7 4.8±0.9 2.1±0.6 0.9±0.2 7.8±1.5
TEGDMA Unifil 2.1±0.7 1.1±0.9 0.5±0.4 3.7±1.9 1.9±0.2 1.1±0.5 0.3±0.1 3.3±0.8 2.6±0.3 1.0±0.1 0.5±0.1 4.0±0.5 5.3±1.3 3.9±1.8 1.2±0.2 10.3±3.0
Z250 2.1±0.5 0.7±0.2 0.1±0.1 2.9±0.7 2.0±0.3 0.3±0.1 0.1±0.0 2.3±0.5 2.5±0.2 0.4±0.0 0.1±0.0 2.9±0.2 5.0±0.7 1.3±0.3 0.2±0 6.5±1.0

Z350 0.3±0.1 0.2±0.1 0.2±0.1 0.8±0.2 0.4±0.1 0.2±0.1 0.4±0.1 1.0±0.1 0.7±0.5 0.3±0.1 0.4±0.2 1.3±0.5 0.5±0.1 0.5±0.1 0.7±0.3 1.7±0.4
BIS-GMA Unifil 6.2±0.6 1.1±0.5 4.4±0.5 11.8±1.5 4.7±0.5 5.7±1.0 3.7±0.7 14.1±0.8 3.9±0.2 3.0±0.2 5.4±1.0 12.4±1.1 5.5±0.7 5.0±1.2 0.8±0.1 11.3±1.1
Z250 1.2±0.2 0.5±0.1 0.2±0.1 1.9±0.3 1.1±0.1 0.4±0.1 0.1±0 1.7±0.2 1.2±0.1 0.5±0 0.2±0.0 1.9±0.1 0.9±0.1 0.7±0 0.3±0 1.9±0.1

Unifil 1.4±0.1 1.3±0.3 1.0±0.4 3.8±0.7 1.3±0.1 1.6±0.5 0.9±0.2 3.8±0.7 1.6±0.1 1.2±0.0 1.1±0.1 3.9±0.2 2.2±0.3 2.4±0.9 2.4±0.2 7.1±1.3
UDMA Z250 2.1±0.4 0.6±0.1 0.2±0.1 2.9±0.6 1.9±0.3 0.5±0.1 0.1±0.0 2.6±0.4 2.3±0.2 0.6±0.1 0.2±0.0 3.1±0.2 3.6±0.4 1.4±0.1 0.3±0.0 5.3±0.4
Gradia 4.6±0.5 3.8±0.6 1.4±0.3 9.9±1.2 4.8±0.3 4.2±0.5 1.6±0.4 10.6±1.1 5.8±0.5 5.6±0.5 2.0±0.1 13.4±0.6 6.6±0.5 6.7±0.6 3.5±0.3 16.7±0.5

Fig. 1 Released monomers (%) from composite resin specimens after light curing according
to different curing times and curing distances.
(A) TEGDMA; (B) Bis-GMA; (C) UDMA.
p, q, r, s
: Same letters are not significantly different by one-way ANOVA at p=0.05,
followed by the Duncan test for post hoc comparison.
 Dent Mater J 2015; 34(3): 327–335 331

TEGDMA was released within 1 h and more than
90% within 12 h. In Z350, about 4.0% of TEGDMA
was released when cured for 20 s, less than half of
TEGDMA when cured for 40 s. Values of %released
TEGDMA cured for 40 and 60 s were 1.8% and 1.6%
respectively. In UniFil, value of %released TEGDMA
was 3.2% when cured for 20 s, approximately twice the
value of that cured for 60 s (1.5%). In Z250, value of
%released TEGDMA also decreased as curing time
increased from 20 to 60 s. The decrease in Z250 was
accompanied with significance differences between 20
and 40 s, and between 40 and 60 s (p<0.05). Value of
%released TEGDMA increased as the distance between
the upper surface of specimen and the curing light
increased. There were no significance differences for
curing distances less than 10 mm, but value of %released
TEGDMA dramatically increased when the curing
distance was 20 mm.
Bis-GMA was detected in three types of composite
resins (except Gradia). The average rate of release of
Bis-GMA was lowest when curing time was 40 s, but
the difference was not significant. In Z350, value of
%released Bis-GMA increased as the curing distance
increased such that value of %released Bis-GMA at 20-
mm curing distance was twice of that at 0-mm curing
distance. For UniFil and Z250, there were no significance
differences in %released Bis-GMA according to curing
distance.
UDMA was detected in three types of composite
resins (except Z350). Gradia showed higher values
of %released UDMA than UniFil and Z250. Value of
%released UDMA decreased as curing time increased
and as curing distance decreased, as in the case of
TEGDMA. Release rate was decreased to 53–69% with

Table 5 The average ± standard deviation of released BPA amount (μg/g) from four resin composites according to different
curing time (n=5).

Curing Z350 Unifill Z250 Gradia

condition 1 12 24 Total 1 12 24 Total 1 12 24 Total 1 12 24 Total

20 s N.D. 2.8±2.5 5.2±1.5 8.0±2.8
Curing
40 s N.D. 5.2±0.8 10.2±2.1 15.4±2.8
Time
60 s 1.5±3.3 19.4±7.5 10.6±4.3 31.4±10.8
0.8±1.3 1.0±0.3 3.2±4.2 5.0±5.7 N.D 0.4±0.1 6.0±0.3 6.4±0.4 1.4±1.8 7.4±3.7 8.8±7.0 17.6±9.4
N.D. 1.0±0.4 10.5±2.3 11.5±4.1 3.1±3.4 2.8±1.4 8.7±0.3 14.6±5.3 13.3±8.4 3.7±0.9 7.0±0.5 24.0±10.9
4.5±5.7 2.2±0.8 13.1±6.8 19.9±5.4 4.2±1.1 1.6±2.2 7.0±0.8 12.8±4.3 26.0±14.2 3.5±0.8 4.8±1.5 34.3±22.1

0 mm N.D. 9.1±4.3 3.0±3.1 12.1±5.2 0.8±0.2 17.5±1.9 0.7±0.2 19.0±9.2 11.7±0.8 15.9±6.9 4.1±2.6 31.7±18.2 8.6±3.3 8.4±1.6 10.8±3.8 27.8±14.2
Curing 5 mm N.D. 5.8±2.8 5.0±4.6 10.9±6.3 N.D. 4.7±0.6 N.D. 4.7±0.6 N.D. 1.9±2.5 2.0±2.2 3.9±4.1 4.7±1.4 3.8±0.7 5.8±2.4 14.3±4.7
Distance 10 mm N.D. 3.3±2.5 4.5±1.3 7.8±3.9 0.7±0.2 1.4±0.6 N.D. 2.2±0.7 N.D. 0.5±0.3 0.6±0.6 1.1±0.6 1.5±0.3 7.8±3.2 7.4±3.9 16.8±14.2
20 mm N.D. 2.2±0.2 2.6±0.8 4.8±1.1 N.D. N.D. N.D. N.D. N.D. 0.9±4.4 1.6±2.9 2.5±1.4 1.2±0.7 4.6±1.1 6.3±3.5 12.1±8.5

N.D., Not detected.

Fig. 2 Released amount (μg/g) of BPA from composite resin specimens after light curing
according to different curing times and curing distances.
p, q, r, s
: Same letters are not significantly different by one-way ANOVA at p=0.05,
followed by the Duncan test for post hoc comparison.
332 Dent Mater J 2015; 34(3): 327–335
change in curing time from 20 to 40 s, and to 76–87%
with change in curing time from 40 to 60 s. For UniFil
and Z250, there were no significance differences in the
release rate for curing distances less than 10 mm, but
the release rate dramatically increased when the curing
distance was 20 mm. For Gradia, values of %released
UDMA cured at 5 mm, 10 mm and 20 mm were 10.6%,
13.4%, and 16.7% respectively, and the differences were
significant (p<0.05).
BPA was detected in all types of composite resins
after polymerization, but it was not detected in the raw
material of Z350 (5.6 μg/g in UniFil, 4.8 μg/g in Gradia,
and 3.3 μg/g in Z250). BPA was not detected in many
of the extracted samples. Where BPA was not detected,
it was assigned a value of 0 μg and these values were
included in the calculation of the mean content of BPA
extracted from resin specimens. Generally, BPA was
released in greater quantities with increase in curing
time and decrease in curing distance, as shown in Table
5 and the bar graph in Fig. 2.
In Z350 and UniFil, the amount of released BPA up
to 24 h doubled with 20 s’ increase of curing time. In
Z250, the release amount of BPA was lowest when cured
for 20 s, and there was no significant difference between
the curing times of 40 and 60 s. In Gradia, release
amount of BPA increased as curing time increased.
Release amount of BPA tended to increase with
decrease in curing distance. In Z350, the average
amount of released BPA decreased with increase in
curing distance, but there were no significant differences
among the curing distances of 0, 5, and 10 mm. In
UniFil, the release amount of BPA was significantly
different at each curing distance. In Z250 and Gradia, the
release amount of BPA cured at 0 mm was dramatically
higher than the other curing distances, and those cured
at 5, 10 and 20 mm were not significantly different.
DISCUSSION
Polymerizable and tooth-colored restorative materials
have become widely popular in aesthetic dentistry.
Monomers employed in these polymerizable materials
(e.g., TEGDMA, UDMA, Bis-GMA) are blended with
fillers, typically silica of various particle sizes and
distributions, to create composite resins. Composite
resins have had good success in dental clinics when
polymerized by light-curing or chemical methods22).
However, the polymerization process is usually
incomplete and a slight amount of monomers can diffuse
into the oral cavity and the pulp. Therefore, research
efforts remain unabated to determine the amount
of unreacted monomers and improve the degree of
polymerization.
In the present study, methanol —instead of
artificial saliva— was used as the solvent for resin
specimens for accelerated testing. Monomers were
almost not detected in artificial saliva (Taliva®
solution, Hanlim Pharm, Seoul, South Korea) extracts
because they are hardly water-soluble. Results of this
experiment agreed with a previous report in that almost
every compound could be detected in the extracts from
methanol, whereas only a few were found in water
extracts15). To some extent, the amount of unreacted
monomers extracted in methanol served to reflect the
long-term exposure quantity of monomers released from
dental resins into the oral cavities of patients.
We investigated the release rates of unreacted
monomers for various kinds of resins under different
polymerization conditions. In this study, unreacted
monomers were generally calculated to be below 10%,
while polymerization rate (%) was reported to be about
50% to 70% in previous studies2). Higher polymerization
rates were shown in this study due to newer resin
materials and techniques, but unreacted monomers
were still detected in the composite resins.
According to Sigusch et al.21), exposure time and
light intensity were important parameters for
conversion from monomer to polymer. Pilo et al.23)
and Sakaguchi et al.24) compared the increments in
temperature from light curing according to curing time.
They reported that temperature rapidly increased up
to 20 s, and then showed plateau phenomenon after
that curing time. Thus, discussion about the effects on
temperature was excluded from this study for curing
times of 20–60 s.
Light intensity decreased as curing distance
increased. Previous study showed a logarithmic
correlation between intensity and distance25). It was
also reported that light intensity was strongly correlated
with composite resin hardness26). Thus, resin materials
need to be polymerized at as close in proximity to the
curing light as possible to supply enough light intensity,
but it is not easy to satisfy all clinical demands. In light
of the above-described factors, we sought to find the
optimal polymerization conditions to minimize monomer
elution.
Unsuitable curing conditions may adversely affect
the degree of polymerization of composite resins and
cause composite resin properties to deteriorate. This
would lead to an increase in the release of unreacted
monomers, which can cause cytotoxicity.
Many studies have documented the cytotoxic
effects of Bis-GMA and TEGDMA, which are the
major components of composite resins27). Indeed,
both monomers are reported to be highly cytotoxic in
primary and immortal cell cultures, such as fibroblasts
derived from the human pulp, periodontal ligament or
gingiva28).
Polydorou et al.16) investigated the degree of
polymerization by analyzing monomers with curing
times ranging from 0 to 80 s. Price et al.19) investigated
the Knoop hardness of composite resins after curing
at different distances. We measured the amounts of
unreacted monomers using two hybrid types and two
flowable types of resins to find the optimal curing time
and distance in a bid to minimize the release of harmful
substances.
We fixed the curing distance at 10 mm whilst
analyzing the effect of curing time on polymerization,
based on a previous report which suggested that 9
 Dent Mater J 2015; 34(3): 327–335
mm was an optimal curing distance considering the
distance from the posterior teeth to the gingiva19). When
analyzing the effect of curing distance on polymerization,
curing time was fixed at 20 s as per the suggestion of
the manufacturers. Thus, data of 20 s in Table 3 and
of 10 mm in Table 4 were actually obtained from same
polymerization condition. Specimens used for testing
the effects of curing time and curing distance were
made separately. Thus for each experiment, we cited
the data of each Table. Before making each composite
resin specimen, the type and amount of monomer of
each commercial composite resin were checked using
the described chromatographic method to calculate the
conversion ratio from monomer to polymer.
TEGDMA shows strong cytotoxicity and is an
immunosuppressive agent29); thus, it is important to
minimize its release to the oral cavity. TEGDMA was
found in Z350, UniFil, and Z250 based on the analysis of
the raw composite resin in methanol. The release rate of
unreacted TEGDMA decreased as curing time increased;
thus, a longer curing time could increase the degree of
polymerization. In the comparison of curing distances,
there were no significance differences in release rate
from 0 to 10 mm, except for Z350. However, for all the
three composite resins, release rate became significantly
increased when curing distance was 20 mm. Therefore,
our findings suggested that TEGDMA-based composite
resins should be photopolymerized for more than 40 s at
a distance less than 10 mm.
Bis-GMA and its metabolites were reported to
decrease ICAM-1 expression in TNFα-stimulated
cells, decrease the recruitment of leukocytes to sites of
inflammation30), stimulate growth in estrogen-sensitive
target tissue, and cause a significant increase in uterine
collagen content31). Bis-GMA, like TEGDMA, was a
component of Z350, UniFil, and Z250. There was no
correlation between the amount of unreacted Bis-GMA
and curing time. The value of %released Bis-GMA in
Z350 decreased with increasing curing time, whereas
the highest release of Bis-GMA in Z250 occurred at 60 s
of curing time. There were also no significant differences
in %released Bis-GMA according to curing distance,
except for Z350. In other words, the polymerization of
Bis-GMA was less affected by curing time and distance
than other monomers. It is hence important that factors
which could increase polymerization and minimize the
release of unreacted monomers be identified when using
Bis-GMA-based dental resins.
UDMA is also widely used in dental restorative
materials in its polymeric form. However, even a small
amount (1.0 mM) of UDMA can cause DNA damage
and apoptosis in lymphocytes32). We found that the
value of %released UDMA increased with increasing
curing distance. Release rates were not significantly
different up to 10 mm of curing distance, but increased
significantly at 20 mm. The value of %released UDMA
decreased with increasing curing time. In Z250 and
Gradia, only half the amount of UDMA was released
when cured for 60 s than when cured for 20 s. These
results agreed with a previous study by Brambilla
333
et al.33), who found that a reduction in curing time
significantly increased monomer release from the resin.
It was also stated that the presence of compounds
such as TEGDMA and UDMA, or their degradation
products, could encourage bacterial growth with a
biochemical mechanism yet to be clarified33). Therefore,
UDMA-based resins should be cured with a duration
longer than 20 s.
Monomer release rates from the four types of
composite resins varied despite identical polymerization
conditions. For example, %released UDMA from Gradia
was more than double those of Z250 and UniFil for
the same curing time and distance. This could be due
to differences in additives such as photoinitiators and
photosensitizers, as well as differences in their ratios.
The effects of photoinitiators and photosensitizers
on polymerization and their interaction with the
polymerization condition require further investigations.
BPA is not a component of dental materials.
However, a trace amount of BPA may be present
because it is synthesized from BPA derivatives (e.g., Bis-
GMA, Bis-EMA, Bis-DMA), which are commonly used in
dental materials34).
Unlike other monomers, the release of BPA
increased with increasing curing time. Moreover, BPA
was detected in the specimens of Z350 whose raw
material did not contain BPA. Therefore, it was
speculated that BPA was decomposed from other
monomers during polymerization in Z350. We reckoned
that BPA underwent a decomposition mechanism when
it was exposed to light for an extended period of time.
Release of BPA was highest at 0-mm curing distance. This
meant that BPA-based resins could be photo-decomposed
and release BPA under high light intensity.
Some BPA derivatives with ester bond (-O-CO-)
linking BPA molecules to resin, such as Bis-DMA, can
be broken by esterase present in saliva, subsequently
forming BPA35). However, BPA derivatives with ether
(-O-) linkage, such as Bis-GMA and Bis-EMA, do not
undergo this hydrolysis reaction to form BPA36). Kadoma
and Tanaka37) reported that BPA was produced from
Bis-DMA, but no BPA was formed from Bis-GMA by
chemical-induced hydrolysis. Apart from enzymatic
hydrolysis, photodecomposition of BPA derivatives
in dental materials needs to be investigated because
photolysis of ether linkage is already known in the field
of chemical engineering38).
The release of BPA increased as curing time
increased or as curing distance decreased. This was in
contrast to the results of TEGDMA and UDMA in that
short curing time and long curing distance tended to
cause higher monomer release. It was speculated that
photolysis of BPA occurred under high light intensity.
Released BPA might exist as impurities in composite
resins, or BPA might be produced from the decomposition
of BPA-based resins during polymerization. Strong
light intensity due to short irradiation distance might
promote the degradation of BPA-based resins to BPA.
Results of this study suggested that different curing
times and distances are recommended according to the
334 Dent Mater J 2015; 34(3): 327–335
main ingredients and component ratios of commercial
composite resins. Manufacturers of the composite
resins used in this study made no curing distance
recommendations, but suggested a curing time of 20 s.
An optimal curing distance might be difficult to prescribe
because of the different oral conditions of each patient,
but general guidelines would be clinically beneficial.
Although clinicians would prefer a faster curing time,
it is important to cure the resin for an appropriate
duration to promote biocompatibility and a safe oral
environment.
In this study, a halogen light unit was selected to
polymerize the composite resins based on the curing
time recommended by the manufacturers. A plasma
unit could greatly decrease the curing time with higher
light intensity than the halogen unit, but issues on
heat generation and polymerization shrinkage by fast
polymerization remain controversial39). Nomoto reported
that the most efficient wavelength was 470 nm, and
the most adequate wavelength was in the 450–490 nm
wavelength range40). Halogen lamps emit a wide range
of wavelengths covering a large part of the spectrum.
On the other hand, LEDs emit light of a narrow
spectral distribution with wavelengths ranging from
440 to 490 nm only. Due to the narrow emission
spectrum, LEDs have higher energy efficiency.
However, their application is limited to only composite
resins which use camphorquinone as a photoinitiator41).
LEDs also require a longer curing time than halogen
light units due to their low irradiance42,43). Of late,
advanced LEDs are considered an excellent light source
because of reduced risk of heat damage to the dental
pulp with extended wavelength range and rectification
of some shortcomings43). Therefore, further studies are
needed to compare released monomer amounts after
polymerization using LEDs to demonstrate the effect of
light source on monomer release.
CONCLUSION
In this study, four types of monomers from four kinds
of dental composite resins were analyzed by
chromatographic method. To measure the degree
of conversion from monomer to polymer by
photopolymerization, the amount of unreacted monomer
was determined by analyzing released monomers in
methanol solvent from resin specimens subject to
different curing times and distances.
Generally, the values of %released TEGDMA and
UDMA decreased as curing time increased and as curing
distance decreased. On the other hand, the values of
%released BPA and Bis-GMA did not demonstrate any
obvious relationship with curing time and distance.
Optimal polymerization conditions and polymerization
rates were different for each monomer and for each
composite resin. Therefore, optimal polymerization
times should be provided for each composite resin
product considering its main monomer materials to
promote improved biocompatibility and safety.
ACKNOWLEDGMENTS
This research was supported by the Basic Science
Research Program through the National Research
Foundation of Korea (NRF), funded by the Ministry of
Education, Science and Technology (2012R1A5A2051381)
and by the Ministry of Science, ICT and Future
Planning (2013R1A1A1A05007175).
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