Progress in Organic Coatings 73 (2012) 149–154

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Preparation and properties of polymer-encapsulated phthalocyanine blue

pigment via emulsion polymerization
Shaohai Fu a,∗ , Changsen Du b , Mingjun Zhang a , Anli Tian a , Xia Zhang a
a
Key Laboratory for Eco-Textile of Ministry of Education, Jiangnan University, 1800 Lihu Road, Wuxi 214122, Jiangsu, PR China
b
Kunshan Sunmin Science and Technology Development Co. Ltd., Kunshan 215337, Jiangsu, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Polymer-encapsulated phthalocyanine blue pigment dispersion was prepared with a polymerizable dis-
Received 25 November 2010 persant by emulsion polymerization method, and the effect of preparation conditions on the particle
Received in revised form 6 October 2011 size of dispersion was investigated. Dynamic light scattering measurement demonstrated that allyloxy
Accepted 11 October 2011
nonyl-phenoxypropanolpolyoxyethyleneetherammonium sulfonate (ANPS) was suitable for phthalocya-
Available online 27 October 2011
nine blue pigment modification. The polymer-encapsulated phthalocyanine blue pigment dispersion with
the small particles was obtained when the mass ratio of ANPS to phthalocyanine blue pigment, styrene
Keywords:
(St) to phthalocyanine blue pigment, and ammonium persulfate (APS) to St was about 0.2, 0.2, and 0.01,
Encapsulation
Phthalocyanine blue pigment
respectively. Transmission electron microscopy (TEM), Fourier transforms infrared spectra (FTIR) and
Polymerizable dispersant thermogravimetric analyses (TGA) provided supporting evidences for the encapsulation of phthalocya-
Emulsion polymerization nine blue pigment with the formed copolymer. The polymer-encapsulated phthalocyanine blue pigment
dispersion showed excellent stabilities to freeze–thaw treatment and centrifugal force.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction
Inkjet printing was one of the fastest growing textile print-
ing technologies for its eco-friendliness, low water and energy
consumption, and minimal dye residue in comparison with the
traditional printing. Pigmented inks are applicable for all sorts of
fabrics, and are the main colorants used for textile inkjet printing
[1,2]. Pigmented inks with high stability and excellent rub fast-
ness and color strength can usually be prepared by modifying the
pigments using a variety of techniques.
Milling pigments with aid of dispersants, especially polymeric
dispersants, is a common method for pigment modification. In
aqueous media, the polymeric dispersants can be adsorbed onto
pigment surface via anchor groups that help build voluminous
shells or intensify the charges around the pigment surface, thereby
avoiding pigment flocculation and coagulation [3,4]. At present,
many kinds of structured polymeric dispersant have been syn-
thesized for this purpose [5–7]. Encapsulating pigments with
polymeric materials is another effective process for pigment modi-
fication, such as emulsion or mini-emulsion polymerization [8–10],
phase separation [11,12], in situ polymerization [13,14], layer-
by-layer assembly [15], and sol-gel [16,17]. Among all of these
technologies, emulsion and mini-emulsion polymerization had
received the great attention due to its high performance in pigment
encapsulation [18,19].
Nowadays, some pigments that are encapsulated by polymer-
izable dispersant were also developed, for example, a fluorescent
pigment was encapsulated with methyl methacrylate and a
polymerizable anionic surfactant [20]. Mono-disperse fluorescent
polymer particles were prepared with styrene and a polymeriz-
able surfactant [21]. Although there were so many methods for the
pigment modification, how to prepare the encapsulated pigment
dispersion with nanoscale particles, narrow particle size distribu-
tion and high stability is still an interesting problem.
In this study, a novel method for pigment encapsulation was
devised. The phthalocyanine blue pigment dispersion was pre-
pared with aid of polymerizable dispersant first and then some
co-monomers and initiators were dropped, finally, the polymer-
ization was taken place via raising the temperature for preparation
of the polymer-encapsulated pigment dispersion. The preparation
conditions and properties of polymer-encapsulated phthalocya-
nine blue pigment were investigated.
2. Experimental
2.1. Materials

Press-cake of phthalocyanine blue pigment (Chart 1)

with water content of 43% was purchased from Xinguang
∗ Corresponding author. Tel.: +86 051085912105. Co., Ltd., China, and used after drying. Allyloxy nonyl-
E-mail address: shaohaifu@hotmail.com (S. Fu). phenoxypropanolpolyoxyethyleneetherammonium sulfonate

0300-9440/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2011.10.006
150 S. Fu et al. / Progress in Organic Coatings 73 (2012) 149–154
Chart 1. Chemical structure of phthalocyanine blue pigment.
(ANPS), sodium 3-allyloxy-2-hydroxypropanesulfonate (AHPS)
and sodium 2-hydroxy-3-(methacryloyloxy) propane-1-sulfonate
(HMPS) (Chart 2) were supplied by Adeka Co., Ltd., Japan. Ammo-
nium persulfate (APS) and azobisisobutyronitrile (AIBN) were
of AR grade, purchased from Shanghai Chemical Reagent Co.,
Ltd., China. Styrene (St), methyl methacrylate (MMA) and butyl
acrylate (BA) had inhibitors removed by passing them through
an inhibitor-removal column (purchased from Aldrich). Distilled
water was used in all the experiments.
2.2. Preparation of polymer-encapsulated phthalocyanine blue
pigment dispersion
30 g phthalocyanine blue pigment was added to a water solution
containing a desired amount of polymerizable dispersant (0.1–0.4
in terms of mass ratio to pigment) under stirring at 500 r/min. The
pH value was adjusted to 9 by dropwise addition of 0.1 mol/L NaOH
solution. The mixture was transferred to a bead mill (Minizeta 03E,
Netzsu, Germany) with ZrO2 bead (0.8 mm, mass ratio of ZrO2 to
pigment 5:1). Milling was performed for a desired time (0.5–3 h) to
give phthalocyanine blue pigment dispersions.
A quantity of APS (0.00125–0.02 in terms of mass ratio to
co-monomer) was dissolved in 60 mL deionized water. 12 g APS
solution and corresponding amount of co-monomer were added
to the phthalocyanine blue pigment dispersion. After the disper-
sion was emulsified on a high-speed stirrer machine for 20 min
at 25 ◦ C, it was transferred to a 4-neck flask equipped with stir-
rer, thermometer and condenser. The temperature was raised to
78 ◦ C and maintained for 30 min. The remaining APS solution was
injected into the flask in 30 min at 78 ◦ C and then maintained for
4 h. After the dispersion was cooled to room temperature, it was
centrifuged at 13,000 r/min for 1 h. The sedimentation was washed
with acetone and subsequently with distilled water to remove the
unreacted co-monomer, the polymerizable dispersant and copoly-
mers that were not adsorbed onto phthalocyanine blue pigment
Chart 2. Chemical structure of a: ANPS, b: AHPS, c: HMPS.
surface, and finally washed with ethanol. The product was dried at
80–90 ◦ C.
5 g product was added to 95 g distilled water. The mixture
was treated with ultrasonic waves for 5 min to give a polymer-
encapsulated phthalocyanine blue pigment dispersion.
2.3. Measurement
The particle size and its distribution (PDI) were measured by
dynamic light scattering (DLS) using a Malvern Zetasizer Nano-
ZS90 (Malvern Instruments, England). The measurements were
performed at 25 ◦ C with a fixed angle of 90◦ . The cumulative anal-
ysis was used for analyzing the DLS data of all the samples. Each
sample was measured for three times, and the particle size was
reported as an average diameter.
Fourier transforms infrared spectra (FTIR) of the original
phthalocyanine blue pigment and the polymer-encapsulated
phthalocyanine blue pigment (in KBr pellet) were recorded on a
Nicolet Nexus 560 FTIR spectrometer.
The morphology of pigment dispersions was observed by trans-
mission electron microscope (TEM) using a Phillips CM12 TEM. A
dispersion sample was diluted with distilled water until the sus-
pension was no longer opaque. One drop of the diluted suspension
was placed on a copper grid to support the sample. After removing
the excess liquid on the sample, the grid was left to dry.
The mass content of copolymer in the polymer-encapsulated
phthalocyanine blue pigment was measured by thermo gravimetric
analyses (TGA) using a Perkin-Elmer instruments Diamond TG/DTA
Analyzer with a heating rate of 5 ◦ C/min under air atmosphere.
The absorbance of dispersions was measured using an UV/vis
spectrophotometer (UV-2000, UNICO Instruments Co., Ltd., China)
by diluting to 2000 times. The wavelength of maximum absorbance
was determined to be 620 nm at which the absorbance was
recorded as A0 . The dispersion was centrifuged at 3000 r/min for
30 min. The absorbance of the supernatant dispersion (diluted
to 2000 times) at 620 nm was measured to be At . The relative
absorbance (R) was calculated according to Eq. (1):
At
R (%) = × 100 (1)
A0
The dispersion sample was sealed and stored at −10 ◦ C for
12 h and measured for its particle size d0 . The sample was then
stored at 60 ◦ C for another 12 h and measured for its particle
size dT . The freeze–thaw stability (S) was evaluated using Eq. (2).
Five freeze–thaw cycles were performed on the same dispersion
sample.
 
d0 − dT 
S (%) = × 100 (2)
d0
3. Results and discussion
3.1. Preparation of phthalocyanine blue pigment dispersion
Table 1 shows the particle sizes of phthalocyanine blue pigment
dispersions prepared using different polymerizable dispersants. As
can be seen, the use of ANPS resulted in a much smaller particle
size than the uses of AHPS and HMPS. This is because ANPS has
a longer hydrophobic chain than AHPS and HMPS that provides
stronger attractive forces toward phthalocyanine blue pigment. It
seems that the amount of ANPS affected the particle size to some
extent. A 0.2 mass ratio of ANPS to pigment is adequate to achieve
pigment dispersion with a small particle size. However, when the
mass ratio was lower than 0.2, the produced new surface of pigment
in dispersing process could not be completely occupied by ANPS so
that the dispersed pigment would combine with each other due
 S. Fu et al. / Progress in Organic Coatings 73 (2012) 149–154 151

Table 1
Effect of dispersing conditions on particle size of phthalocyanine blue pigment
dispersion.

Dispersant Mass ratio of Dispersing Particle

dispersant to pigment time (h) size (nm)

ANPS 0.2 2 124.6

AHPS 0.2 2 578.3
HMPS 0.2 2 491.0
ANPS 0.1 2 168.2
ANPS 0.3 2 121.7
ANPS 0.4 2 120.3
ANPS 0.2 0.5 143.5
ANPS 0.2 1 138.6
ANPS 0.2 3 125.8

to weak repulsive forces between the particles, leading to a poor

dispersing efficiency and a large particle size. Fig. 1. Effect of initiator on particle size distribution of polymer-encapsulated pig-
ment dispersion, mass ratio of styrene to pigment 0.2, and mass ratio of initiator to
Milling time is an important factor affecting the particle size
styrene 0.012.
of the polymer-encapsulated pigment dispersion. Table 1 shows
that the particle size of the ANPS-based dispersion was reduced
by extending milling time and reached a roughly constant value
for 2-h milling. In the dispersing process, particles may change
in two basic modes: dispersion under shear force and aggregation
via van der waals force. During the dispersing process, the disper-
sion rate was higher than the aggregation rate so that the particle
size decreased with an increase of milling time. The particle size
was reduced to a constant level when dispersion and aggregation
reached equilibrium.
From the results shown in Table 1, it can be concluded that an
optimal process for preparation of the phthalocyanine blue pig-
ment dispersion was accomplished by using a 0.2 mass ratio of Fig. 2. Effect of amount of styrene on particle size of polymer-encapsulated phthalo-
ANPS to phthalocyanine blue for a 2-h milling time. In the fol- cyanine blue pigment dispersion, mass ratio of APS to styrene 0.01.

lowing discussion, all the dispersions were prepared under these

conditions.
3.2. Preparation of polymer-encapsulated phthalocyanine blue
pigment dispersion
Three different co-monomers were used for preparing the
polymer-encapsulated phthalocyanine blue pigment dispersion.
Table 2 shows the performance of these co-monomers in terms
of the particle size and particle size distribution (PDI). Compared
with MMA and BA, St produced the smallest particle size and nar-
rowest size distribution of the dispersion. This is because of the
similarity of the benzene ring of St and the aromatic structure of
pigment molecule that could enhance the attractive forces between
St and pigment to form a complete encapsulation layer. In addition,
BA produced the largest particle size and broadest size distribution
because the BA-based copolymer had the lowest glass transition
temperature, and as such tended to tangle with each other. Fig. 1
shows the effect of the amount of St on the particle size of the
polymer-encapsulated phthalocyanine blue pigment dispersion. As
can be seen, the particle size increases with an increase of St, which
is probably because a thicker encapsulation layer around a pig-
ment particle as the amounts of styrene increases. Therefore, a 0.2
mass ratio of St to pigment is suitable for preparing the polymer-
encapsulated phthalocyanine blue pigment dispersion.
APS and AIBN were used as initiators for copolymerization that
was an important stage for pigment encapsulation. Fig. 2 illustrates
the particle size distribution of the polymer-encapsulated phthalo-
cyanine blue pigment dispersions that were prepared by using APS
and AIBN. As can be seen, APS produces a much smaller particle size
and narrower size distribution than AIBN. One important reason is
that, unlike the APS, AIBN is hydrophobic in nature and tends to be
adsorbed onto the phthalocyanine blue pigment surface when it is
added to the dispersion, and as result, the pigment inhibited the
copolymerization, thus no copolymers produced and encapsulated
the phthalocyanine blue pigment [22]. Moreover, St could be seized
some ANPS that adsorbed onto the phthalocyanine blue pigment,
thus leading to a large particle size. Fig. 3 shows the effect of the

Table 2
Particle size and PDI of polymer-encapsulated phthalocyanine blue pigment disper-
sion based on various co-monomers.a

Co-monomer Particle size (nm)b PDIb

Styrene 132.0 0.159

Methyl methacrylate 143.0 0.196
Butyl acrylate 188.5 0.231
a
The mass ratio of co-monomer to pigment was about 0.2, the mass ratio of APS
to co-monomer was about 0.01. Fig. 3. Effect of amount of APS on particle size of polymer-encapsulated phthalo-
b
Measured by DLS method. cyanine blue pigment dispersion, mass ratio of styrene to pigment 0.2.
152 S. Fu et al. / Progress in Organic Coatings 73 (2012) 149–154

Fig. 4. Emulsion polymerization process for encapsulation of phthalocyanine blue pigment.

amount of APS on the particle size of the polymer-encapsulated

phthalocyanine blue pigment dispersion. The smallest particle size
was reached by using a 0.01 mass ratio of APS to St. However, the
particle size tends to increase when the mass ratio of APS to St is
less or greater than 0.01. It is believed that a mass ratio less than
0.01 are not adequate for copolymerization so that the amount of
produced copolymer is limited for pigment encapsulation. There-
fore, the prepared pigment dispersion has a poor stability leading
to a large particle size. On the other hand, a mass ratio of APS to St
greater than 0.01 ensures a high monomer conversion by which a
large amount of copolymers is produced for pigment encapsulation
but may cause a thicker encapsulation layer to increase the particle
size.
It is hereby proposed that APS, St and ANPS are the
most suitable for preparing polymer-encapsulated phthalocya-
Fig. 5. FTIR spectra of (a) phthalocyanine blue pigment and (b) polymer-
nine blue pigment dispersion with an APS:St:ANPS:pigment
encapsulated phthalocyanine blue pigment, mass ratio of styrene to pigment 0.2,
mass ratio of 0.002:0.2:0.2:1. As illustrated in Fig. 4, the and mass ratio of APS to styrene 0.01.
emulsion–polymerization process for encapsulation of phthalo-
cyanine blue pigment includes four steps. In the first step,
phthalocyanine blue pigment is dispersed with aid of ANPS. In the The amount of copolymer adsorbed onto and encapsulated the
second step, the co-monomer and initiator are added to the dis- pigment particles were determined by TGA. Fig. 7 shows a graph
persion for emulsion by which the co-monomer and initiator are of weight loss vs. temperature over the range of 50–550 ◦ C. It can
adsorbed onto the pigment surface. In the third step, polymeriza- be seen that, as temperature was raised to 128 ◦ C, both the orig-
tion takes place in water to produce some active oligomers that inal phthalocyanine blue pigment and the polymer-encapsulated
subsequently diffuses and is adsorbed onto the pigment surface. phthalocyanine blue pigment had small weight losses that were
Finally, the active oligomers initiate the polymerization of St and probably ascribed to the evaporation of physically adsorbed water.
ANPS that adsorbed onto pigment surface and formed a copolymer It seems that the polymer-encapsulated phthalocyanine blue
layer. pigment had higher water content than that of the original phthalo-
cyanine blue pigment since the copolymer contained sulfonate
3.3. Characterization of polymer-encapsulated phthalocyanine groups (–SO3 − ). A subsequent weight loss of 14.21% in the polymer-
blue pigment encapsulated phthalocyanine blue pigment in the temperature
range of 250–450 ◦ C was ascribed to the decomposition of the
The encapsulation of phthalocyanine blue pigment with the copolymer layer that encapsulated the pigment particles.
formed copolymer was proved by the FTIR as shown in Fig. 5. The
absorbance bands at 2930 cm−1 and 2850 cm−1 were assigned to 3.4. Stability of polymer-encapsulated phthalocyanine blue
–CH2 stretching vibration, 720 cm−1 assigned to (–CH2 )6 stretching pigment dispersion
vibration, and 1200–1250 cm−1 assigned to S O stretching vibra-
tion. These characteristic frequencies belong to the copolymer of St The stabilities of the polymer-encapsulated phthalocyanine
and ANPS. blue pigment dispersion were tested in terms of centrifugal and
Fig. 6 provides a evidence that the polymer-encapsulated freeze–thaw treatments, the results are shown in Figs. 8 and 9.
phthalocyanine blue pigment has a clear core–shell structure, and It can be seen that the polymer-encapsulated phthalocyanine
the particle size of the polymer-encapsulated phthalocyanine blue blue pigment dispersion exhibited better stabilities to centrifu-
pigment (Fig. 6b) is much larger than that of phthalocyanine blue gal and freeze–thaw treatments than the phthalocyanine blue
pigment dispersion (Fig. 6a). pigment dispersion. This is because that, in the phthalocyanine
 S. Fu et al. / Progress in Organic Coatings 73 (2012) 149–154
Fig. 6. TEM photos of (a) phthalocyanine blue pigment dispersion (b) polymer-
encapsulated phthalocyanine blue pigment dispersion, mass ratio of styrene to
pigment 0.2 and mass ratio of APS to styrene 0.01.
blue pigment dispersion, ANPS was adsorbed onto phthalocya-
nine blue pigment via van der waals forces that were extremely
susceptible to the temperature and centrifugal forces. However,
in polymer-encapsulated phthalocyanine blue pigment dispersion,
Fig. 7. TGA curves of (a) original phthalocyanine blue pigment and (b) polymer-
encapsulated phthalocyanine blue pigment, mass ratio of styrene to pigment 0.2
and mass ratio of APS to styrene 0.01.
153
Fig. 8. Effect of centrifugal speed on relative adsorbance of the dispersion.
Fig. 9. Effect of freeze–thaw treatment cycles on change rate of particle size of the
dispersion.
the attractive forces between the copolymer and pigment were
strong enough to resist the encapsulation layer being peeled off
regardless of temperature and centrifugal forces.
4. Conclusions
The core–shell composite particles were formed with the
pigment in the center and the polymer in the shells via
emulsion–polymerization process using a polymerizable disper-
sant. St and APS were selected as the co-monomer and initiator
in the encapsulation process. The copolymers contained in
the polymer-encapsulated phthalocyanine blue pigment reached
to 14.21% when the mass ratio of APS:St:ANPS:pigment was
0.002:0.2:0.2:1. A four-step encapsulation process was proposed
to preparing the polymer-encapsulated phthalocyanine blue pig-
ment dispersion. The polymer-encapsulated phthalocyanine blue
pigment dispersion had an enhanced stability compared with the
conventional phthalocyanine blue pigment dispersion.
Acknowledgements
This work is supported by the Fundamental Research Funds for
the Central Universities (JUSRP21103) and Ph.D. Science Founda-
tion for Industry of Jiangsu Province (BK2009582), we thank the
Jiangnan University for supporting in the course of research.
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