Pigment & Resin Technology

Formulation of nanoscale copolymer-SiO2 dispersion via miniemulsion polymerization for application in

white inkjet ink
Liping Zhang Anli Tian Chunxia Wang Fushun Bai Shaohai Fu
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Liping Zhang Anli Tian Chunxia Wang Fushun Bai Shaohai Fu , (2017),"Formulation of nanoscale copolymer-SiO2 dispersion
via miniemulsion polymerization for application in white inkjet ink ", Pigment & Resin Technology, Vol. 46 Iss 1 pp. 48 - 55
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 Formulation of nanoscale copolymer-SiO2
dispersion via miniemulsion polymerization
for application in white inkjet ink
Liping Zhang
Key Laboratory of Eco-Textile, Jiangnan University, Wuxi, China
Anli Tian
Key Laboratory of Science and Technology of Eco-Textile, Jiangnan University, Wuxi, China
Chunxia Wang
Jiangnan University, Wuxi, China
Fushun Bai
Suzhou Sunmun Technology Company, Suzhou, China, and
Shaohai Fu
Textile and Clothing College, Jiangnan University, Wuxi, China
Downloaded by Fudan University At 10:02 19 February 2017 (PT)

Abstract
Purpose – The purpose of this study is to prepare nanoscale copolymer-silicon dioxide (SiO2) dispersion for formulating textile printing white ink.
Design/methodology/approach – Nanoscale copolymer-SiO2 dispersion was prepared via miniemulsion polymerization. The miniemulsion
formulation was optimized for preparing stable SiO2/O/W miniemulsion and nanoscale copolymer-SiO2 dispersion. The nanoscale copolymer-SiO2 was
investigated by transmission electron microscope (TEM), X-ray diffraction (XRD), differential thermal gravity (DTG) and thermogravimetric analysis
(TGA). The performance of white inks from this colorant was further investigated.
Findings – Nanoscale copolymer-SiO2 had a core-shell structure with about 45 nm encapsulated copolymer layer when it was synthesized under
optimal miniemulsion formulation 60 per cent mass ratio of styrene (St) to KH570-SiO2, 5.0 per cent hexadecane to St and 2.0 per cent concentration
of DNS-86. The nanoscale copolymer-SiO2 white ink had high thermal and centrifugal stability with high purity and color fastness.
Research limitations/implications – The miniemulsion polymerization conditions required a careful control before favorable results could be
achieved.
Practical implications – The nanoscale copolymer-SiO2 dispersion and white ink prepared by this method showed excellent stability. This research
could accelerate the textiles inkjet printing application.
Originality/value – The reactive stabilizer DNS-86 is innovatively introduced into the miniemulsion polymerization to improve the stability of the
nanoscale copolymer-SiO2 dispersion. The white ink was formulated from nanoscale copolymer-SiO2 to improve the fastness of the printed fabrics.
Keywords Colorant, Inks, Composite materials, Miniemulsion polymerisation
Paper type Research paper

Introduction attention, not only as colorant in fabrics printing but also as a

Inkjet printing technology of textiles has developed sharply
over the past decade because of its suitability for
customization, small batch production and multicolor printing
besides its eco-friendliness, minimal residue of colorant and
auxiliary, low consumption of water and energy (Fu et al.,
2012; Leelajariyakul et al., 2008; Yoon and Choi, 2008).
Concerning the development of inkjet printing technology,
white pigment ink has attracted more and more people’s
The current issue and full text archive of this journal is available on
Emerald Insight at: www.emeraldinsight.com/0369-9420.htm
Pigment & Resin Technology
46/1 (2017) 48 –55
© Emerald Publishing Limited [ISSN 0369-9420]
[DOI 10.1108/PRT-08-2015-0074]
base colorant for most colorful textiles inkjet printing.
Inexpensive white oxide such as silicon dioxide (SiO2) is
commonly used for white inkjet inks, but this oxide compounds
easily aggregate and form sediments during usage and storage
because of their high specific gravity and high –OH content on
This work was supported by the National Natural Science Foundation of
China (Grant No. 21346009), the Universities and Enterprises
Prospective Joint Research Project of Jiangsu Province (BY2012050), the
Fundamental Research Funds for the Central Universities (JUSRP11505)
and a Project Funded by the Priority Academic Program Development of
Jiangsu Higher Education Institutions. The authors also thank the
Jiangnan University for supporting in the course of research.
Received 7 August 2015
Revised 29 October 2015
17 January 2016
21 March 2016
19 April 2016
Accepted 21 May 2016

48
 Nanoscale copolymer-SiO2 dispersion
Liping Zhang et al.
their surface (Capel-Sanchez et al., 2004). This defect has limited
the use of silicon dioxide been used in textile inkjet printing.
To overcome this problem, various techniques such as
in-situ polymerization (Gil and Casagrande, 2007;
Hashemi-Nasab and Mirabedini, 2013; Sondi et al., 2000),
emulsion polymerization (Han et al., 2011; Reculusa et al.,
2004) and polymer-encapsulated SiO2 (Chalaye et al., 2001;
Huang et al., 1995) have been developed over years, but the
poor stability of SiO2 dispersion still remained which is a
disadvantage of high-quality white inkjet ink (Giesche and
Matijević, 1994; Huang et al., 1995). Preparation of
polymer-encapsulated SiO2 (polymer-SiO2) via miniemulsion
polymerization has been regarded as the most promising
method to improve the stability of SiO2 dispersion (Tissot
et al., 2001; Xiong et al., 2002). In this method, the particle
size and rheological behavior of the dispersion can be easily
controlled by changing structure and amount of monomers,
stabilizers and co-stabilizers (Miller et al., 1995; van Zyl et al.,
2004). At the same time, the polymer-encapsulated around
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SiO2 can reduce the particle-specific gravity, shield the
hydrogen bond interaction among the particles and produce
strong electrostatic repulsive forces by introducing in
functional polymer which also takes part in the film-forming
during the UV drying of the printed fabric. The stability of the
dispersion, color fastness and handle of the printed fabrics are
thus improved with this novel colorant (Asua, 2002; Joumaa
et al., 2006; Qi et al., 2006; van Zyl et al., 2004). Nonetheless,
problems such as large particles size and poor storage stability
over elevated temperatures coupled with complicated
formulation process have not been addressed.
Figure 1 Preparation process of nanoscale copolymer-SiO2 by miniemulsion polymerization method
49
Pigment & Resin Technology
Volume 46 · Number 1 · 2017 · 48 –55
In this article, a stable nanoscale copolymer-SiO2 dispersion was
prepared via miniemulsion polymerization with reactive
dispersant and further applied to formulate the white pigment ink
for textile inkjet printing. The properties of nanoscale
copolymer-SiO2 dispersion and the white ink were investigated
in details.
Experimental
Materials
The fabric (plain knitted 100 per cent cotton, scoured and
bleached, 32 tex and 120 g/m2) was supplied by Tianran Co.
Ltd., Wuxi, China. ␥-methacryloxypropyltrimethoxysilane
(KH570) was purchased from Jiangsu Chenguang Co. Ltd.,
China. SiO2 (particle size 50 nm) was provided from Suzhou
Shiming Co. Ltd., China. Sodium bicarbonate (NaHCO3),
styrene (St), methylmethacrylate (MMA), n-butyl acrylate
(BA), cetyl alcohol (CA), hexadecane (HD), Tween-80 and
ammonium persulfate (APS) were all purchased from
Sinopharm Chemical Reagent Co. Ltd., China. Dispersant,
DNS-86 (T.P. Figure 1) was purchased from Hanke
Chemical Reagent Co. Ltd., China. The distilled water was
used in the whole experiments.
Preparation of nanoscale copolymer-silicon dioxide
dispersion
The process for preparation of nanoscale copolymer-SiO2 is
summarized in Figure 1. KH570-modified SiO2
(KH570-SiO2) with a diameter of 62 nm was prepared from
SiO2 and KH570 according to our previous research (Tian
et al., 2015); 10 g KH570-SiO2, a desired amount of
 Nanoscale copolymer-SiO2 dispersion Pigment & Resin Technology
Liping Zhang et al. Volume 46 · Number 1 · 2017 · 48 –55

monomer and co-stabilizer, was added into a beaker and
stirred for 30 min. The mixture was dispersed by Ultrasonic
JY98-3D homogenizer (NingBo Scientz Biotechnology Co.
Ltd, China) to obtain the organic phase. The aqueous phase
was prepared with 80 mL distilled water containing 0.05 g of
NaHCO3 and desired amount of dispersant. The organic
phase was added into the aqueous phase slowly under stirring
and then ultrasonicated to obtain the SiO2/O/W dispersion.
The SiO2/O/W dispersion was transferred to a reactor and
purged with nitrogen gas for 30 min. APS (1.5 per cent mass
ratio to monomer) was injected into the reactor, and the
temperature was raised to 75°C for 2 h. Finally, the mixture
was filtered with paper (pore size 500 nm) to obtain nanoscale
copolymer-SiO2 dispersion. The nanoscale copolymer-SiO2
dispersion was centrifuged at 12,000 r/min to obtain
nanoscale copolymer-SiO2 precipitates. The sediment was
washed three times with methanol and then dried at room
temperature; 10 g nanoscale copolymer-SiO2 was dispersed in
40 g distilled water. The pH value of the mixture was adjusted
to 8, and then treated with ultrasonic machine for 30 min to
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Characterization of nanoscale copolymer-SiO2
The particle size (D) and zeta potential were determined by
dynamic light scattering method using Malvern Zetasizer
Nano ZS90 instrument.
X-ray diffraction (XRD) were carried out on a RBD upgraded
PHI-5000C ESCA system (Perkin Elmer) with Mg K radiation
(h ⫽ 1253.6 eV) or Al K radiation (h ⫽ 1486.6 eV).
Thermogravimetric analysis (TGA) was performed using
Perkin-Elmer TGA-7 under nitrogen. Particle morphology
was observed under a HITACHI H-7000 transmission
electron microscope (TEM).
Stability of nanoscale copolymer-silicon dioxide dispersion
Stability to temperature (ST) was estimated in terms of relative
changes in average particle size of the dispersion before (d0)
Figure 2 (a) Effect of mass ratio of St to KH570-SiO2 on particle
size of SiO2/O/W (DM) and nanoscale copolymer-SiO2 (DC), (b) effect
of HD content on the DM and DC and (c) effect of DNS-86

give nanoscale copolymer-SiO2 dispersion. concentrations on DM and DC

For the preparation of KH570-SiO2 dispersion, 10 g
KH570-SiO2 and 0.2 g DNS-86 was dispersed in 39.8 g of
distilled water. The procedure was similar to the preparation
of nanoscale copolymer-SiO2 dispersion.

Formulation of white inkjet inks

White inkjet inks were prepared with the nanoscale
copolymer-SiO2 dispersion and KH570-SiO2 dispersion,
respectively. The formulation on weight ratio is given as
follows: 30 per cent nanoscale copolymer-SiO2 dispersion or
KH570-SiO2 dispersion, 30 per cent glycerol, 1.2 per cent
Tween-80 and 38.8 per cent distilled water. The above
components were mixed under stirring until a homogeneous
dispersion was obtained. The white inkjet ink was obtained
after filtering through a 500-nm pore sieve.

Inkjet printing
The cotton fabrics were printed using Mimaki JV4-180 digital
ink-jet printer (Mimaki Engineering Co. Ltd., Japan) with a
built-in software and a piezoelectric drop-on-demand print head.

Table I Effect of monomer and co-stabilizer structures on particle size

of SiO2/O/W miniemulsion and nanoscale copolymer-SiO2 dispersiona
Monomer Dispersant Co-stabilizer DM (nm)b DC (nm)c ⌬d (nm)d
MMA DNS-86 HD 221.5 239.1 17.6
BA DNS-86 HD 183.6 203.8 20.2
St DNS-86 HD 173.4 176.4 3.0
St DNS-86 – 1043.7 – –
St DNS-86 LA 201.7 212.5 10.8
St DNS-86 CA 187.8 192.6 4.8
St Tween-80 HD 345.7 – –
St SDS HD 235.8 218.4 17.4
Notes: a Mass ratio of KH570-SiO2 10%, mass ratio of monomer and
KH570-SiO2 60%, mass ratio of co-stabilizer and monomer 5.0%,
mass ratio of APS to monomer 1.5%, concentration of DNS-86 1.5%,
ultrasonication time 10 min, polymerization temperature 70°C for 4
h; b average particle size of SiO2/O/W miniemulsion; c average particle
size of nanoscale copolymer-SiO2 dispersion; d difference of DM and DC

50
 Nanoscale copolymer-SiO2 dispersion Pigment & Resin Technology
Liping Zhang et al. Volume 46 · Number 1 · 2017 · 48 –55

Figure 3 (a) TEM images of nanoscale copolymer-SiO2; water spreading on the surface of (b) nanoscale copolymer-SiO2 and (c) KH570-SiO2
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and after storage for 24 h at a desired temperature (dT), as The whiteness of printed fabrics was measured using a
given in equation (1): colour-eye-7000A (X-rite, USA) with UV calibrated, specular
component included, illuminant D65 and 10-degree
冉
Sr ⫽ 1 ⫺
ⱍd0 ⫺ drⱍ
d0 冊 ⫻ 100% (1)
supplemental standard observer settings. The rubbing
fastness, washing fastness and light fastness of the printed
fabrics were evaluated according to AATCC standard
Centrifugal stability (SC) was determined by absorbance at methods 8-2001, 61-2003 and 16-2003, respectively.
510 nm of original samples before (A) and after (A1)
centrifuging for 30 min at desired centrifugal speeds, as given
Figure 5 (a) TGA and (b) DTG curves of KH570-SiO2 and nanoscale
in equation (2):
copolymer-SiO2
A1
Sc ⫽ ⫻ 100% (2)
A

Water spreading behavior was observed on a DSA-100 Model

Drop Shape Analyzer.

Characterization of white inkjet ink

Apparent viscosity of the dispersion (ink) was measured using
Brookfield DV-III at 25°C with shear rate 30 s⫺1. The surface
tension was measured using a ring method in Drop Shape
Analysis System DSA100.

Figure 4 XRD of nanoscale copolymer-SiO2

51
 Nanoscale copolymer-SiO2 dispersion Pigment & Resin Technology
Liping Zhang et al. Volume 46 · Number 1 · 2017 · 48 –55

Figure 6 (a) Temperature and (b) centrifugal stability SiO2 and
nanoscale copolymer-SiO2 dispersions
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when St was used as the monomer. Meanwhile, the difference
value (⌬d) of the particle size of SiO2/O/W miniemulsion
(DM) and nanoscale copolymer-SiO2 dispersion (DC)is only
3.0 nm, which was smaller than the other SiO2/O/W
miniemulsion prepared from MMA or BA. This is due to the
strong ␲–␲ interaction force between St and KH570-SiO2
surface result in stable SiO2/O/W miniemulsion. Co-stabilizer
is an important component in O/W miniemulsion to reduce
the O/W miniemulsion surface energy and control Ostwald
ripening effect (Ariyaprakai and Dungan, 2010; van Zyl et al.,
2004). It can be observed that SiO2/O/W miniemulsion
without co-stabilizer has a large DM value, whereas the particle
size of SiO2/O/W miniemulsion decreased sharply when LA,
CA or HD was used as co-stabilizer. In addition, the
difference (⌬d) in DM and DC can be neglected when HD was
used as co-stabilizer, which suggests that SiO2/O/W
miniemulsion is in its most stable state. This could be
attributed to the long alkane’s chains of HD, which effectively
reduced the Ostwald ripening effect (Ariyaprakai and
Dungan, 2010; Mouran et al., 1996; Wang et al., 1997).

Compared to Tween 80 and SDS, DNS-86 has strong

adsorption force with the oil droplet because of its long
hydrophobic chain which prefers to attach to the benzene ring.
Besides, DNS-86 participated in the polymerization process
through its double bond (Xiong et al., 2002) resulted in a
smaller difference value (⌬d).
Figure 2(a) shows that the particle size of both SiO2/O/W
miniemulsion and nanoscale copolymer-SiO2 reached
minimum when mass ratio of St to KH570-SiO2 was 60 per
Results and discussion cent. Moreover, the difference value (⌬d) of DM and DC can
Preparation of nanoscale copolymer-silicon dioxide be neglected under this mass ratio, suggesting that SiO2/O/
W miniemulsion was virtually stable and all monomers were
dispersion
polymerized with KH570-SiO2. Continuous increase in the
A stable SiO2/O/W miniemulsion is the precursor to achieve
amount of St in SiO2/O/W miniemulsion resulted in large
stable nanoscale copolymer-SiO2 dispersion; hence, the
particle size for both SiO2/O/W miniemulsion and
miniemulsion conditions should be careful controlled and
copolymer-SiO2. Conversely, inadequate St led to unstable
deserve to be studied.
SiO2/O/W miniemulsion because some amounts of SiO2
As shown in Table I, both SiO2/O/W miniemulsion and
particles were probably not been coated because of the lack
nanoscale copolymer-SiO2 dispersion had small particle size of copolymers. Figure 2(b) shows that 5 per cent mass ratio
of HD to St was enough to control the SiO2/O/W
Table II Basic properties of white pigment ink miniemulsion Ostwald ripening rate. Figure 2(c) shows the
effect of DNS-86 concentration on particle size of SiO2/O/
Stability
W miniemulsion and nanoscale copolymer-SiO2 dispersion.
␩ ␥ D (%)
Both DM and DC values declined as the DNS-86
White ink prepared from (mPa.S) (mN/m) (nm) STa SCb
concentration increased. When DNS-86 concentration was
Nanoscale copolymer- in the range of 2.0 to 2.5 per cent, relative stability was
SiO2 dispersion 4.04 32.8 176.4 96.3 90.8 observed and the difference between DM and DC (⌬d)
KH570-SiO2 dispersion 3.26 29.5 210.6 64.2 88 reached minimum.
Notes: a Storage at 60°C for 24 h; bcentrifuged at 3,000 r/min for 30 Based on the above results, it concluded that the nanoscale
min copolymer-SiO2 could be optimally prepared by using 60 per

Table III Color fastness of printed fabrics by white pigment ink

Rubbing fastness (grade) Washing fastness (grade)
Printed fabric with white ink prepared from Substrate Dry Wetting Tinting Changing Light fastness (grade)
Copolymer-SiO2 dispersion Cotton 4 3-4 5 3-4 5
Polyester 3-4 3-4 4-5 3 5
KH570-SiO2 dispersion Cotton 3 2-3 4 2 5-6
Polyester 2-3 2 5 2 5-6

52
 Nanoscale copolymer-SiO2 dispersion
Liping Zhang et al.
cent mass ratio of St to KH570-SiO2, 5 per cent mass ratio of
HD to St and 2.0 per cent by weight of DNS-86. In the
following experiments, all the nanoscale copolymer-SiO2
mentioned was prepared under optimal condition.
Figure 3(a) shows the morphology of nanoscale
copolymer-SiO2. Regular nanocomposites with average
diameter of 152 nm were observed. The diameter was 90 nm
larger than that of KH570-SiO2, suggesting the average
thickness of encapsulated copolymers layer was approximately
45 nm. Figures 3(b) and (c) show the wettability of nanoscale
copolymer-SiO2 and KH570-SiO2 against distilled water. It
can be seen that contact angle of nanoscale copolymer-SiO2
against distilled water was far smaller than that of
KH570-SiO2, which indicated that the DNS-86 remained in
copolymer-SiO2 surface through copolymerizing with St.
Figure 4 shows the XRD pattern of nanoscale
copolymer-SiO2. The 2␪ at 23.9° coincide with amorphous
SiO2, implying that the nanoscale copolymer-SiO2did not
undergo any significant crystal modification. The
thermophysical property of nanoscale copolymer-SiO2 was
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determined by TGA and differential thermal gravity (DTG)
analysis. As shown in Figure 5a, a weak peak at the range of
375 to 450°C was observed in the curve of KH570-SiO2,
which can be attributed to the desorption of KH570 on the
SiO2 particles. Signification weight decomposition (about 26
per cent) in nanoscale copolymer-SiO2 curve was also
recorded in the range of 375 to 450°C, which can be ascribed
to the pyrolysis of copolymers (Wu et al., 2004). According to
the corresponding DTG analysis, only one decomposed peak
at 410°C was observed, implying that the St monomers were
polymerized with KH570-SiO2 instead of the simple mixture.
Zeta potential of nanoscale copolymer-SiO2 dispersion and
KH570-SiO2 dispersion was ⫺49.6 mV and ⫺26.8 mV,
respectively. The high absolute zeta potential value of
Figure 7 Hiding performance of the colorful fabrics printed with white pigment ink
53
Pigment & Resin Technology
Volume 46 · Number 1 · 2017 · 48 –55
nanoscale copolymer-SiO2 dispersion could be ascribed to the
negative charges of sulphate groups introduced by DNS-86,
which is beneficial to improve the stability and wettability of
nanoscale copolymer-SiO2 dispersion due to its electrostatic
repulsion and hydrophilic character.
As shown in Figure 6(a), the stability of both KH570-SiO2
and nanoscale copolymer-SiO2 dispersions declined gradually
as the storage temperature increased. The stability of
nanoscale copolymer-SiO2 dispersion was 99 per cent
preserved for 24 h at 20°C and reduced to 96 per cent when
the storage temperature increased to 70°C, whereas the
stability of KH570-SiO2 dispersion was only 20 per cent when
stored temperature was 70°C for 24 h. Similarly, in Figure
6(b), the nanoscale copolymer-SiO2 dispersion shows higher
centrifugal stability than KH570-SiO2 dispersion. This
illustrates that nanoscale copolymer-SiO2 dispersion has
excellent stability to high temperature and centrifugal force.
This can be attributed to copolymer which is difficult to peel
off from SiO2 surface even at severe conditions. Moreover, the
specific gravity of nanoscale copolymer-SiO2 was reduced
because encapsulated low-density copolymers layer, which
also contributed to improving its stability.
Properties of white pigment ink
The physical properties of white pigment ink are summarized
in Table II. White ink prepared from nanoscale
copolymer-SiO2 dispersion had smaller particle size and
higher stability than KH570-SiO2 dispersion, indicating that
the nanoscale copolymer-SiO2 dispersion is more suitable for
preparation of white inkjet printing inks.
Table III shows the fastness of printed cotton fabrics and
polyester fabrics with white inks. It can be seen that the
printed fabrics with white pigment ink which prepared from
nanoscale copolymer-SiO2 dispersion had higher rubbing and
 Nanoscale copolymer-SiO2 dispersion
Liping Zhang et al.
washing fastness than that from KH570-SiO2 dispersion,
which can be ascribed to the presence of the copolymers took
part in the film-forming process. In addition, it should be
noted that the light fastness of printed fabrics with white
pigment ink prepared from nanoscale copolymer-SiO2
dispersion is lower than that of KH570-SiO2 dispersion. The
reason may be caused by the copolymer that encapsulated
onto pigment surface.
The hiding power of the white pigment ink prepared from
different dispersion was shown in Figure 7. It can be seen that
the hiding power of the white pigment ink prepared from
nanoscale copolymer-SiO2 dispersion was higher than
KH570-SiO2 dispersion. It can be seen that the particle size of
the former was smaller than latter.
Conclusions
Nanoscale copolymer-SiO2 was synthesized by miniemulsion
polymerization method. The optimal condition for
formulating stable SiO2/O/W miniemulsion and nanoscale
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copolymer-SiO2 dispersion was 60 per cent mass ratio of St to
KH570-SiO2, 5.0 per cent HD to St and 2.0 per cent
concentration of DNS-86. Nanoscale copolymer-SiO2
prepared by this stoichiometry had a core-shell structure with
a 45-nm encapsulated copolymer layer. The white pigment
ink prepared from the nanoscale copolymer-SiO2 dispersion
had small particle size with high thermal and centrifugal
stability. The fabric printed by this white pigment ink showed
high whiteness and color fastness.
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Corresponding author
Shaohai Fu can be contacted at: shaohaifu@hotmail.com

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