Color Stability of Adhesive Resin Cements After Immersion in Coffee
Color Stability of Adhesive Resin Cements After Immersion in Coffee
Color Stability of Adhesive Resin Cements After Immersion in Coffee
DOI 10.1007/s00784-014-1272-8
ORIGINAL ARTICLE
Abstract significantly greater than the others. The water sorption and
Objectives Marginal discoloration of luting cement may af- solubility significantly correlated with the ΔEs.
fect the appearance of esthetic restorations. This study evalu- Conclusions The ΔEs of the adhesive resin cements examined
ated the color stability of current adhesive resin cements after after 1-week coffee immersion were significantly different
immersion in coffee. among the products. The product showing greater water sorp-
Materials and methods Four dual-cured resin cements tion and solubility displayed greater color change.
(Clearfil SA cement Automix Universal, Maxcem Elite Clinical relevance Adhesive resin cements should be careful-
Clear, Maxcem Elite Yellow, and RelyX Unicem2 Automix ly selected when the marginal appearance of the ceramic
A2) and two chemical-cured resin cements (Super-Bond C&B restoration is important.
Clear and Super-Bond C&B Esthetic) were examined. The
CIE L*a*b* of 2.0-mm-thick disc-shaped specimens was
Keywords Adhesive resin cements . Color stability . Water
measured using a spectrophotometer on a white background
sorption . Water solubility
(n=6). The color differences (ΔE) after 1-day and 1-week
immersion in 37 °C water or coffee were analyzed by two-
way ANOVA by selecting immersion solution and product as
main factors, followed by Tukey’s HSD test (α=0.05). Water Introduction
sorption and solubility were also evaluated.
Results The two-way ANOVA of the ΔEs suggested that the Ceramic restorations such as all-ceramic crowns, porcelain
two main factors and their interaction were significant. The laminate veneers, and ceramic inlays and onlays are popular
ΔEs after coffee immersion were significantly greater than due to their esthetic appearance. Adhesive resin cements are
those after water immersion, except for Super-Bond C&B the material of choice for the luting of ceramic restorations
Esthetic. The ΔEs after water immersion were not significant- because of their excellent esthetics and good mechanical
ly different among the products; those of Maxcem Elite Clear properties such as flexural strength, compressive strength,
and Maxcem Elite Yellow after coffee immersion were and shear and tensile bond strength [1–3]. The adhesive nature
of the resin cements promotes superior retention and fracture
resistance of the restorations [4–6]. The adhesive resin ce-
M. Shiozawa ments are categorized based on bonding procedure and/or use:
Removable Partial Prosthodontics, Department of Masticatory total etch, bond, plus resin; one-step etch-bond, plus resin;
Function Rehabilitation, Division of Oral Health Sciences, Graduate self-adhesive resin; and dual-affinity adhesive resin [2]. These
School, Tokyo Medical and Dental University, 1-5-45 Yushima,
cements are also categorized by polymerization type:
Bunkyo-ku, Tokyo 113-8549, Japan
chemical-cured, light-cured, and dual-cured [2, 4, 5].
H. Takahashi (*) : Y. Asakawa : N. Iwasaki Recently, dual-cured adhesive resin cements have often been
Oral Biomaterials Engineering, Course for Oral Health Engineering, selected for luting because of their ability to self-cure under
School of Oral Health Care Sciences, Faculty of Dentistry, Tokyo
Medical and Dental University, 1-5-45 Yushima, Bunkyo-ku,
restorations [7]. Dual-cured adhesive resin cements can be
Tokyo 113-8549, Japan hardened in deep areas or beneath restorations where the
e-mail: [email protected] curing light cannot penetrate, while they can also be
Clin Oral Invest
polymerized by the curing light at the restoration margins for listed in Table 2. They were prepared at 23±2 °C according
easy removal of excess cement [5]. to each manufacturer’s instructions. The dual-cured type was
Because adhesive resin cements at the restoration margins prepared using the light-curing mode. The chemical-cured
are exposed to the oral environment, discoloration of resin type was prepared using the bulk-mix technique.
cements is caused by not only intrinsic but also extrinsic
factors. Intrinsic factors are material-related factors such as Color stability measurement
the composition of the resin matrix [8] and filler [9], the
loading and particle size distribution of the filler, the type of Disc-shaped specimens (10 mm in diameter and 2.1 mm thick)
photoinitiator [10] and polymerization systems [11], and the were prepared in an acrylic mold (n=6). The dual-cured
conversion ratio of the carbon-carbon double bonds [12]; specimens were polymerized with a light-emitting diode
these intrinsic factors are accelerated by UV irradiation [13] (LED) light-curing unit (Elipar S10, 3 M ESPE, Seefeld,
or thermal change [12]. Extrinsic factors are stains caused by Germany) with light intensity of 1,200 mW/cm2 for 40 s on
food components, beverages, and smoking; these factors are each side. The chemical-cured-type specimens were polymer-
modulated by the conversion ratio and physicochemical char- ized in an incubator at 37±2 °C for 1 h. The specimens were
acteristics of the resin cements, such as water sorption rate ground sequentially using a series of SiC grinding sheets
[14] and surface roughness [15]. (#600, 1,000, and 1,500). The grinding and polishing proce-
Discoloration of the adhesive resin cements affects the dures were performed on one side of the specimens to make
esthetic appearance of ceramic restorations. Marginal discol- 2.0-mm-thick specimens. The final thickness was checked
oration of ceramic inlays and onlays increases with time due to with a digital micrometer (MDC-25 M, Mitsutoyo, Tokyo,
the color changes in adhesive resin cements [16]. Therefore, Japan) having an accuracy of ±0.01 mm. Before each mea-
these cements need to have sufficient color stability to maintain surement, the specimens were ultrasonically cleaned in dis-
good esthetics. Adhesive resin cements usually contain an tilled water for 10 min and dried with compressed air. Each
adhesive functional monomer consisting of hydrophilic and specimen was immersed in distilled water at 37±2 °C for 24 h
hydrophobic functional groups. Hydrophilic functional groups in a 100-mL brown glass vial. Before performing the colori-
are considered to possess higher water sorption [7, 17, 18], and metric measurements, the specimens were removed from the
thus, they undergo greater color change. However, the color vials and washed with distilled water, gently wiped with filter
stability of current adhesive resin cements after immersion in paper, and dried by shaking in air for 30 s.
discoloring media has not been clearly elucidated. The CIE L*a*b* values of the polished surfaces of each
Many investigations evaluated the color stability of resin- specimen were measured on a white glossy photo paper
based composite materials in a variety of beverages such as (KA420PG, Seiko Epson Corp., Nagano, Japan): L*=91.57,
coffee [8, 9, 13, 14, 19–25], black tea [8, 11, 13, 14, 19, a* = −1.02, and b* = 1.56 using a spectrophotometer
22–25], red wine [8, 9, 11, 13, 22–25], and cola [8, 19, 20, (Crystaleye, Olympus Corp., Tokyo, Japan) [26]. Prior to data
22–25]. These beverages are common in people’s daily diet acquisition, the spectrophotometer was calibrated using a
and are reported to have the potential to stain restorative calibration plate and positioned at a consistent distance of
materials. The results of these experiments showed that the 16 mm from the specimen surface using the special contact
color changes were generally greater in red wine, coffee, and cap for object measurement. The light source illumination of
tea compared to cola [19, 8, 23, 24]. Coffee is considered to be seven-band LED lights corresponding to average daylight
one of the beverages with a higher potential to stain [8]. (D65) was irradiated at a 45° angulation, and the diffusion
The objective of the present study was to evaluate the color refraction light was measured. The color difference (ΔE) was
stability of current adhesive resin cements after immersion in obtained by calculating the color difference between the spec-
coffee. The null hypothesis was that the immersion solution imen before and after immersion in one of the solutions using
and the type of adhesive resin cements had no influence on the the following equation:
color change of adhesive resin cements.
h i1=2
ΔE ¼ ðL1 −L2 Þ2 þ ða1 −a2 Þ2 þ ðb1 −b2 Þ2
Materials and methods
Materials and immersion solution where L* refers to the brightness, a* for redness to greenness,
and b* for yellowness to blueness. The subscripts 1 and 2 refer
The four dual-cured adhesive resin cements and two to the color coordinates before and after immersion, respec-
chemical-cured adhesive resin cements evaluated in the pres- tively. A high ΔE value indicates great color difference. Three
ent study are listed in Table 1; four cements were tooth- measurements were taken for each specimen, and the average
colored and two were transparent. Their compositions are value was recorded.
Clin Oral Invest
Product Code Shade Polymerization type Filler content (wt%)a Lot no. Manufacturer
Two types of immersion solution were prepared: distilled LED light-curing unit for 40 s on each side and then
water and coffee solution. The coffee solution was prepared stored in the incubator at 37±2 °C for 15 min. The
by dissolving 0.51 g of instant coffee powder (Nescafe Gold chemical-cured-type specimen was polymerized in the in-
Blend, Nestle Japan, Kobe, Japan) in 50 mL of distilled water cubator at 37±2 °C for 1 h. The specimens were removed
[9]. Six specimens of each resin cement were immersed in one from the mold and kept in a desiccator maintained at 37±
of the immersion solutions in a shaking incubator (37±2 °C, 2 °C. After 22 h, the specimens were removed and stored
1 Hz frequency). The immersion solution was changed every in another desiccator kept at 23±2 °C for 2 h and then
day. The color measurements were taken after 1-day and 1- weighed using a precision digital balance (AUW120D,
week immersion. Shimadzu, Kyoto, Japan; the minimum reading is
0.01 mg). This cycle was repeated until a constant mass
Water sorption and solubility was obtained, i.e., until the mass loss of each specimen
was not more than 0.1 mg in any 24-h period. The
The water sorption and solubility of each resin cement diameter and height of each specimen were measured to
were determined according to ISO 4049:2009. Disc-shaped calculate the volume. The specimens were immersed in
specimens (15 mm in diameter and 1 mm thick) were distilled water at 37 °C for 1 week, then removed, gently
prepared using a metal mold (n=5). The dual-cured-type dried with filter paper, and weighed again. The specimens
specimen was exposed to overlapping irradiation with the were returned to the desiccators using the above-
CSA Paste A 10-Methacryloyloxydecyl dihydrogen phosphate Silanated barium glass filler, silanated dl-Camphorquinone, benzoyl
(MDP), Bis-GMA, TEGDMA, hydrophobic colloidal silica peroxide, initiator
aromatic dimethacrylate
Paste B Bis-GMA, hydrophobic aromatic dimethacrylate, Silanated barium glass filler, silanated Accelerators, pigments, surface-
hydrophobic aliphatic dimethacrylate colloidal silica treated sodium fluoride
MEY Base paste Urethane dimethacrylate Fluoroalminosilicate glass Camphorquinone
MEC Catalyst paste Bis-GMA, glycerol dimethacrylate, glycerol Barium aluminoborosilicate glass
phosphate dimethacrylate
RXU Base paste Methacrylate monomers containing phosphoric Silanated fillers Initiator components, stabilizers,
acid groups, methacrylate monomers rheological additives
Catalyst paste Methacrylate monomers Alkaline (basic) fillers, silanated fillers Initiator components, stabilizers,
pigments, rheological additives
SBE Catalyst Tri-n-butylborane (TBB), acetone
SBC Monomer Methyl-methacrylate, 4-methacryloxyethyl
trimellitate anhyderide (4-META)
Polymer Polymethyl-methacrylate Pigments (esthetic)
mentioned procedure until a constant mass was obtained. carbon. Three randomly selected areas of the specimen surface
The water sorption and solubility were calculated using were observed using a scanning electron microscope (S-4500,
the following equations: Hitachi High-Technologies Corp., Tokyo, Japan).
Table 3 Color difference (ΔE) after immersion in distilled water and coffee solution for 1 day and 1 week
Standard deviations are in parentheses, and the same superscript letter denotes homogenous subsets (p>0.05)
63.6–68.2 wt% of inorganic filler; however, a trace of inor- followed by MEC and MEY. Pre-polymerized filler par-
ganic filler was found in the chemical-cured-type cements. ticles were found in CSA. No inorganic filler particles
These results corresponded with the filler content claimed by were observed in SBC and SBE, but partially dissolved
the manufacturer except for RXU, which was smaller than crushed poly(methyl methacrylate) (PMMA) particles
manufacturer claimed value. This discrepancy might be due to were seen.
using the standard ash method. Figures 2 and 3 showed the relationships among the
SEM images of representative areas of the specimens water sorption and solubility and the color differences
are displayed in Fig. 1. The size of inorganic filler after 1-week coffee and water immersion, respectively.
particles was largest in CSA, approximately 70 μm,
Table 4 Water sorption and solubility after water immersion for 1 week
(μg/mm3) Table 5 Filler content of adhesive resin cements (wt%)
Polymerization type Code Water sorption Water solubility Polymerization type Code Filler content
Dual-cured CSA 6.4 (0.1) 0.3 (0.0) Dual-cured CSA 64.6 (0.3)
MEC 16.0 (0.2) 2.5 (0.3) MEC 68.2 (0.1)
MEY 12.0 (0.1) 1.1 (0.1) MEY 67.9 (0.1)
RXU 7.9 (0.2) −0.8 (0.1) RXU 63.6 (0.1)
Chemical-cured SBC 7.1 (0.2) 0.2 (0.2) Chemical-cured SBC 0.1 (0.1)
SBE 7.2 (0.1) 0.1 (0.0) SBE 0.1 (0.2)
Clin Oral Invest
The ΔE after coffee immersion significantly correlated have been reported to vary, depending on the curing mode
with both the water sorption and solubility (p=0.006 [31]. The dual-cured type cements at the restoration margins
and 0.01), but those after water immersion did not are usually polymerized by the curing light for easy removal
(p=0.12 and 0.39). of excess cement. Therefore, the dual-cured-type cements in
the present study were prepared using the light-curing mode.
The color difference will be increase when the oxygen
inhibited layer is present on the specimen surface. However,
Discussion measured surface was polished and the oxygen inhibited layer
did not exist on the specimen surface in the present study. In
The dual-cured adhesive resin cements evaluated in the pres- clinical situation, the oxygen-inhibited layer might exist and
ent study were self-adhesive resin cements, which have been this layer would be more stained compared to the results of the
advertised as bonding to the tooth structure without any pre- present study.
treatment. Several in vitro studies reported promising results The adhesive resin cement is used to place a restoration on
with respect to dentin bond strength compared to resin- the tooth. Therefore, the white background was selected in the
modified glass ionomer cements and conventional resin ce- present study. The color difference after coffee immersion
ments [27–30]. greatly increased as the immersion period increased, but those
Luting cements at the restoration margins are usually ex- after water immersion only slightly increased. This tendency
posed to the oral environment. In the present study, marginal was similar to the results of previous studies of resin-based
discoloration of the dual-cured and chemical-cured resin ce- composite materials [8, 23, 24]. The two-way ANOVA
ments caused by intrinsic and extrinsic factors was simulated.
The physical properties of dual-cured adhesive resin cement
Fig. 2 Relationship between water sorption and color difference after 1- Fig. 3 Relationship between water solubility and color difference after 1-
week immersion. r2 with * was statistically significant (p<0.05) week immersion. r2 with * was statistically significant (p<0.05)
Clin Oral Invest
revealed that the two main factors, immersion solution and acceptability threshold varied among the reports. The ΔE
product, and their interaction were significant. The null hy- value of perceptibility for dental composite veneer restora-
pothesis that the immersion solution and the type of adhesive tions and tooth substance was 3.7 [33]. The ΔE values of color
resin cements had no influence on the color change of adhe- perceptibility and acceptability threshold for denture teeth
sive resin cements was rejected. The color differences after were 2.6 and 5.5, respectively [34]; those for dental ceramics
coffee immersion were different among the products. The were 1.8 and 3.5, respectively [35]; and those for denture teeth
coffee solution caused greater color changes to MEC and were 1.9 and 4.2, respectively [36]. In the present study, ΔE
MEY. values after 1-week water immersion, which were less than
The products that underwent greater color change resulted 2.3, were smaller than previously reported acceptability
in greater water sorption and solubility. In the present study, threshold, while those after 1-week coffee immersion of
six adhesive resin cements containing an adhesive functional MEC and MEY were greater than the previously reported
monomer with hydrophilic functional groups were selected. acceptability threshold of 5.5. Furthermore, other studies re-
The color difference after coffee immersion of adhesive resin ported individual thresholds for the L*, a*, and b* directions
cements was greater compared to that of composite resins [37] or L, C, and H directions [38]. There were no significant
containing no adhesive functional monomer [9, 13, 20]. differences between perceptibility and acceptability thresh-
According to the results in the present study, adhesive func- olds, which were 1.25 in the a* and L* directions and 2.8 in
tional monomer might responsible for greater color change. the b* direction [37]. In the present study, ΔL*, Δa*, and Δb*
The thickness of the specimen for the color measurement values of all products after 1-week water immersion were less
was 2.0 mm due to its handling and intention to reduce the than perceptibility and acceptability thresholds. After 1-week
background effect. However, the thickness of the specimen for coffee immersion, ΔL* values of all products were greater
the water sorption measurement was 1.0 mm according to ISO than 1.25; Δa* values of MEC and MEY were greater than
4049. If the thickness of the water sorption specimen was 1.25; and Δb* values of all products except for CSA and SBE
2.0 mm, surface area and amount of water sorption would were greater than 2.8. The color difference after coffee im-
increase, but the required time until saturation would be mersion might be recognized by the change of brightness, the
extended. However, the tendency of the water sorption among ΔL* value.
tested products would be the same regardless of the thickness One week of coffee immersion was considered to simulate
of the specimen. about 1 year of coffee drinking, with the assumption that one
Water sorption is mostly due to absorption in the resin cup of coffee is consumed for 30 min each day. Moreover, the
matrix [23]. The composition and content of the resin matrix coffee manufacturer reports that the average time for con-
and the bond strength of the resin-filler interface influence the sumption of one cup of a drink among coffee drinkers is
degree of water sorption. Greater water sorption causes the 15 min, and the average consumption of coffee is 3.2 cups
expansion and plasticizing of the resin, which creates micro- per day [25]. Based on this data, 1-week coffee immersion
cracks. As a result, food and beverage stains penetrate into the might simulate 7-month coffee drinking if coffee solution
micro-cracks or the interfacial gaps between the resin and constantly remained in the mouth during drinking. Because
filler, causing the discoloration [23]. Therefore, the product actual contact time of coffee with oral tissues during drinking
that showed higher water sorption produced greater color is shorter, 1-week coffee immersion probably simulated lon-
change after coffee immersion. The brown colorant of cof- ger than 7-month coffee drinking. After 1-week coffee immer-
fee, which is reported to be due to the water-soluble sion, adhesive resin cements evaluated in the present study
polymer compounds produced during the roasting proce- showed great color change, which was considered clinically
dure [32], might be absorbed and adsorbed into the resin unacceptable. Therefore, discoloration of adhesive resin ce-
matrix, resin-filler interface, and micro-cracks on the ce- ments with time would be a clinical problem. These resin
ment surface. The filler particle size and composition of cements should be used where the restoration margin
the resin matrix and filler were different among the prod- does not cause esthetic problems, e.g., beneath the gin-
ucts. There was no obvious relationship between the filler gival margin.
content and the color difference after coffee immersion. In the present in vitro study, the effect of 1-week coffee
SBC and SBE contained only PMMA filler, which was and water immersion on the color stability of adhesive
dissolved by the resin monomer MMA. The resin-filler resin cements was evaluated. However, tooth brushing or
interface was tightly sealed. This might be a reason why thermal cycling effects were not simulated. Therefore, the
SBC and SBE had smaller color changes compared to the limitation of the present study is that the clinical perfor-
other products. mance of the adhesive resin cements examined was not
Several investigations evaluated the perceptibility and ac- evaluated. Future studies are needed to evaluate the effects
ceptability threshold for color differences of dental materials of these factors on the long-term color stability of adhesive
in CIELAB color space [33–36]. The color perceptibility and resin cements.
Clin Oral Invest
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melanoidins. J Agric Food Chem 50:6527–6533 ity of color difference of denture teeth. J Dent 40(Suppl 1):
33. Johnston WM, Kao EC (1989) Assessment of appearance match by e10
visual observation and clinical colorimetry. J Dent Res 68:819–822 37. Lindsey DT, Wee AG (2007) Perceptibility and acceptability of
34. Douglas RD, Steinhauer TJ, Wee AG (2007) Intraoral determination CIELAB color differences in computer-simulated teeth. J Dent 35:
of the tolerance of dentists for perceptibility and acceptability of 593–599
shade mismatch. J Prosthet Dent 97:200–208 38. Perez Mdel M, Ghinea R, Herrera LJ, Ionescu AM, Pomares H,
35. Ghinea R, Pérez MM, Herrera LJ, Rivas MJ, Yebra A, Paravina RD Pulgar R, Paravina RD (2011) Dental ceramics: a CIEDE2000 ac-
(2010) Color difference thresholds in dental ceramics. J Dent Suppl ceptability thresholds for lightness, chroma and hue differences. J
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