Journal of Dispersion Science and Technology, 27:975–981, 2006

Copyright # Taylor & Francis Group, LLC

ISSN: 0193-2691 print/1532-2351 online
DOI: 10.1080/01932690600766967

Dispersion of Phthalocyanine Green G in Nonaqueous Medium

Using Hyperdispersants and Application in E-Ink
Jing Wang, Ya-qing Feng, Jian-yu Xie, Gang Li, and Xiang-gao Li
School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

Phthalocyanine green G modified with hyperdispersants was dispersed in tetrachloroethylene.

Dispersibility and zeta potential of modified phthalocyanine green G in tetrachloroethylene
were studied. The phthalocyanine green G particles modified with hyperdispersants were
characterized by FTIR and SEM. E-Ink containing dispersion liquid of phthalocyanine and
tetrachloroethylene was prepared by coacervation, in situ polymerization, and interfacial
polymerization. E-Ink prepared by coacervation and in situ polymerization had a reversible
electric response.

Keywords Phthalocyanine green G, hyperdispersants, E-Ink, coacervation, in situ polymerization,

interfacial polymerization

INTRODUCTION electrostatic repulsion between particles. In nonpolar media,

Electronic ink display, made of microcapsules including
charged particles and dyed fluid medium, has recently been
of great interest due to its advantages over ink-on-paper of
high reflectance, good contrast ratio, wide-viewing angle,
image bistability, and low power consumption.[1 – 3] After
April 2004, when the first white-and-black E-Ink displays
were introduced commercially by the E-Ink Corporation,
Sony Corporation, and Philips Corporation successfully,[4]
electronic ink display research has been focused on the pre-
paration of color electronic ink. But because there are still
many problems, such as contrast ratio, resolution, and video
speed, up to now research on color electronic ink displays is
in its beginning stages. To achieve high resolution and true
bistability in color display, the processes and materials
involved in electronic inks must be finely tuned. One of the
key processes affecting image quality is color electrophoretic
particles uniformly dispersing inside the organic medium of
microcapsules.
In order to overcome the flocculation and coagulation of
electrophoretic particles inside microcapsules, it is necessary
to build a voluminous shell around the particles or intensify
negative and/or positive charge on the surface (Figure 1).[5]
Conventionally, in polar media, such as water or alcohols,
ionic species adsorbed on the pigment surface give rise to
Received 23 November 2005; Accepted 6 December 2005.
Address correspondence to Xiang-gao Li, School of Chemical
Engineering and Technology, Tianjin University, Tianjin 300072,
China. E-mail: lnsychemistry@yahoo.com.cn
975
such as aliphatic and aromatic hydrocarbons and halogenated
derivatives, a thick adsorbed layer on the particles provides
stability through steric hindrance and other entropic
factors.[6] Since electronic ink utilizes nonpolar organic
solvent, the stability of the electrophoretic particles is
strongly dependent on the steric repulsion. Up to now, the
stability of the electrophoretic particles of E-Ink in nonpolar
solvent medium is mainly obtained by adding surfactants that
have C12–C18 carbon chains,[7,8] but these kinds of modified
electrophoretic particles easily reflocculate and recoagulate
inside microcapsules. In order to obtain more stable dispersion
liquids including electrophoretic particles, it is necessary that a
more effective stabilizing layer is absorbed onto the electro-
phoretic particle surface. Hyperdispersants are a kind
polymer with an affinic “anchoring functional group” and
soluble polymeric chains. Polymeric chains attached to the
electrophoretic particle surface by adsorption form a brush-
like layer that prevents flocculation and coagulation by
osmotic and entropic effects.[9]
Up to now, research on dispersion with hyperdispersants has
focused on the aqueous system,[11,12] there are few reports on
and dispersion with hyperdispersants in the nonpolar organic
system. We used hyperdispersants to disperse phthalocyanine
green G in the nonaqueous medium tetrachloroethylene and
applied it on E-Ink as the core material. We prepared different
kinds of E-Ink by coacervation, in situ polymerization, and
interfacial polymerization. Among them, E-Ink prepared by
coacervation and in situ polymerization had a reversible
electric response.
976 J. WANG ET AL.

where TD is the dispersibility; T0, light transmittance of reference

liquid, T0 ¼ 100; and TS, light transmittance of dispersed liquid, %.
Particle size was measured on a Horiba CAPA-700 disk
centrifuge photosedimentometer at 208C. A centrifugation
rate of 5000 rpm was selected.
z-Potentials were measured by a JS94J Micro-electrophoretic
FIG. 1. Mechanisms of particle stabilization. apparatus, based on the mechanism of the electrophoretic
method. This apparatus is simplified to measure the electrophor-
etic mobility. The potentials were measured three times and the
EXPERIMENTAL SECTION average of the three measurement is reported in this article.
z-Potentials were determined by Equation (2).
Materials
Materials used were phthalocyanine green G (CuPc(Cl)15, 1:5hm
z¼ ½2$
Tianjin University), assistant-hyperdispersant CH-11B 1
(derivative of phthalocyanine green), hyperdispersant CH-5 where z is the zeta potential; m, the electrophoretic mobility; h,
(A-B model polymer) (Shanghai Sanzheng Polymeric the liquid viscosity; and 1, liquid relative dielectric constant.
Materials Ltd. Co.), tetrachloroethylene, acacia, gelatin, Fourier-transform infrared (FTIR) spectra of the samples in
acetic acid, glutaraldehyde, sodium carboxy methylcellulose, the range 400 –4000 cm21 were made with a fully computeri-
sodium hydroxide, resorcinol, urea, formalin, hydrochloric zed BID-RAD FIS3000 spectrometer. The samples were
acid, triethylene tetraamine, OP-10, and 2,4-tolylene diisocya- ground with dried KBr powder and compressed into a disk.
nate (Tianjin Beifang Agent Co.). The micrographs of the samples were made with a Philips
XL-30 ESEM scanning electron microscope. Samples were
Preparation
coated with gold and then analyzed at 20 Kev.
Dispersion of CuPc(Cl)15 in the Medium
CuPc(Cl)15, assistant-hyperdispersant CH-11B and hyper- Test of Application in E-Ink
dispersant CH-5 were dispersed in tetrachloroethylene for 2 h
with F1 mm glass beads on a QM-ISP04, and a dispersion Preparation of GA-E-Ink by Coacervation
liquid was obtained. The composition of the samples First 1.00 g acacia and 1.00 g gelatin were dissolved in
prepared for this work is shown in Table 1. 50 mL of water with stirring at 508C for 30 minutes, then
gelatin solution was carefully added over about 20 s in order
Measurements and Characterization to avoid lumps. With agitation at 500 rpm, the dispersion
Dispersibility measurements were conducted on a Helios g fluids, prepared as described above, were introduced into the
UV-vis spectrophotometer at a wavelength of 650 nm. The dis- aqueous phase. The resulting fluid/water emulsion was emulsi-
persion liquids were treated by centrifugation at 1000 rpm. The fied for 20 min. The pH was then reduced to 4.4 over 5 min with
samples were prepared by diluting 0.50 mL of the upper liquids a 10% acetic acid solution, and the contents of the reactor were
in 5.00 mL tetrachloroethylene. Each light transmittance was slowly cooled to 108C. Then 3.00 mL of a 37% formalin
measured three times and the average of the three values is solution was added, the solution was further stirred for 60 min,
reported in this article. 0.40 g of sodium carboxymethylcellulose (NaCMC) was
The dispersibility was determined by Equation (1). added, and the pH was then raised to 8–9 by the addition of a
10 wt.% solution of sodium hydroxide (NaOH). The thermostat
T0 " TS bath was then set to 508C and stirred for another 60 min. Finally,
TD ¼ ½1$
T0 the precipitated microcapsules were washed with water many
times, and GA-E-Ink was obtained.
TABLE 1
Preparation of dispersion liquids Preparation of UF-E-Ink by in Situ Polymerization
First 0.2 g gelatin was dissolved in 200 mL water with
Sample no. Phthalocyanine/g CH-11B/g CH-5/g stirring at 508C for 30 min, then the reaction mixture was
cooled to room temperature, and 0.5 g resorcinol and 5.0 g
Sample 1 0.25 0.00 0.00
urea were added to the solution. The pH was reduced to 1.5 –
Sample 2 0.25 0.01 0.01
2.0 with 10% hydrochloric acid solution. With agitation at
Sample 3 0.25 0.01 0.03
500 rpm, the dispersion fluids, prepared as described above,
Sample 4 0.25 0.01 0.05
were introduced into the aqueous phase, and the resulting
Sample 5 0.25 0.01 0.07
fluid/water emulsion was emulsified for 20 min. Then the
Sample 6 0.25 0.01 0.10
contents of the reactor were heated to 608C, 4.6 g 37%
 DISPERSION OF PHTHALOCYANINE GREEN G IN NONAQUEOUS MEDIUM 977

formalin solution was added and reacted for 2 h. Finally, the

precipitated microcapsules were washed with water many
times, and UF-E-Ink was obtained.

Preparation of TT-E-Ink by Interfacial Polymerization

First, 0.32 g 2,4-tolyene diisocyanate and 0.02 g OP-10
were added to the dispersion fluids, prepared as described
above. With agitation at 500 rpm, the above oil phase was
introduced into the aqueous phase. Then 1.46 g triethylene tet-
raamine was added and emulsified. After reacting for 3 min,
the precipitated microcapsules were washed with water many
times, and TT-E-Ink was obtained.

Measurement of E-Ink Performance

Transmission microscope images of the microcapsules in
the presence of either electric field or no electric field were FIG. 3. Dispersibility of CuPc(Cl)15 with different concentrations of CH-5
recorded on a 53-XC transmission microscope. in tetrachloroethylene.

RESULTS AND DISCUSSION
Dispersibility Study
CuPc(Cl)15 is a nonpolar molecular, and hyperdispersant
CH-5 is a polymer with an affinic “anchoring functional
group” and soluble polymeric chains. Because CuPc(Cl)15
couldn’t provide polar anchoring positions for hyperdispersant
CH-5, assistant-dispersant CH-11B was used as bridge in order
to facilitate adsorption between CuPc(Cl)15 and hyperdisper-
sant CH-5. Due to assistant-dispersant CH-11B being a
derivate of phthalocyanine, it has physical and chemical pro-
perties similar to CuPc(Cl)15; it was adsorbed easily on the
CuPc(Cl)15 surface to provide polar anchoring positions for
hyperdispersant CH-5, as shown in Figure 2.
Figures 3 and 4 show the influence of the concentration of
CH-5 on the dispersibility in tetrachlorethylene.
Compared to CuPc(Cl)15 without hyperdispersant, the
increase in hyperdispersant CH-5 concentration continuously
improved dispersibility in the tetrachlorethylene. The
probable reason for this was that the particle size of
CuPc(Cl)15 gradually became small with increasing concen-
tration of hyperdispersant CH-5, as shown in Table 2. On
the other hand, as the concentration of CH-5 increased, the
adsorbed layer gradually became thick, reducing the density
of CuPc(Cl)15 to match the density of tetrachlorethylene (the
density of CuPc(Cl)15 is 2.00 g/cm3, hyperdispersant CH-5,
1.10 g/m3, tetrachlorethylene, 1.62 g/cm3). This improved
CuPc(Cl)15 dispersibility in the tetrachloroethylene.
z-Potential Study
Figure 5 shows the z-potentials of CuPc(Cl)15 particles dis-
persed in tetrachlorethylene as a function of CH-5 concentration.
Initially, the CuPc(Cl)15 particles were only slightly nega-
tively charged. A small increase in the CH-5 concentration
resulted in decreasing negative charge. As the concentration
of CH-5 increased, the negative charge of CuPc(Cl)15
increased. The reason for this was probably correlated with
the adsorption state on the CuPc(Cl)15 surface and the structure
of hyperdispersant CH-5 and assistant-dispersant CH-11B.
Assistant-dispersant CH-11B is a phthalocyanine derivate

FIG. 2. Hyperdispersant CH-5 mode of action of absorbing on CuPe(Cl)15

surface. FIG. 4. Dispersibility of CuPc(Cl)15 at different times in tetrachloroethylene.
978 J. WANG ET AL.

TABLE 2
Particle size of CuPc(Cl)15 with different amounts of CH-5 in tetrachloroethylene
Distribution of particle size Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6

1.50 , mm 4.6 12.7 0.0 0.0 0.0 0.0

1.50 –1.40 mm 2.2 7.0 1.5 10.5 2.5 0.6
1.40 –1.30 mm 4.4 1.9 0.1 0.0 0.0 0.0
1.30 –1.20 mm 4.0 7.8 1.8 3.8 2.4 3.7
1.20 –1.10 mm 4.3 0.0 3.9 3.7 1.6 2.8
1.10 –1.00 mm 8.3 3.1 4.4 1.9 2.6 3.3
1.00 –0.90 mm 12.7 5.0 7.4 3.9 4.2 4.5
0.90 –0.80 mm 14.6 6.3 8.5 4.7 2.5 4.8
0.80 –0.70 mm 9.3 7.8 17.0 5.9 4.5 2.6
0.70 –0.60 mm 4.2 10.9 7.7 7.2 4.9 5.7
0.60 –0.50 mm 10.6 12.0 12.4 6.7 5.1 5.6
0.50 –0.40 mm 7.1 11.9 10.8 10.7 6.7 5.4
0.40 –0.30 mm 8.8 8.6 11.3 14.0 9.2 8.6
0.30 –0.00 mm 4.9 5.0 13.2 27.0 53.8 52.4
D/mm 0.83 0.72 0.63 0.42 0.28 0.29

with negative groups, and hyperdispersant CH-5 is an A-B
model polymer. A has soluble polymeric chains, B has affinic
“anchoring functional groups” including –COOH, -OH, and
different amine groups. When the adsorption happened, CH-
11B was first adsorbed on the CuPc(Cl)15 surface to provide
positive anchoring positions for hyperdispersant CH-5. Then,
the amine groups of hyperdispersant CH-5 combined with the
negative groups by electrostatic force, and – COOH and –OH
of hyperdispersant CH-5 remained. Because tetrachloroethy-
lene had a big p bond, it could attract hydrogen ion of –
COOH and –OH to form – COO2 and – O2. This made
CuPc(Cl)15 have more negative charge. At low concentration
of hyperdispersant CH-5, hyperdispersant CH-5 was adsorbed
on the CuPc(Cl)15 surface by the laying of polymer chains
on the CuPc(Cl)15 surface. The CuPc(Cl)15 surface and
remaing – COOH, -OH were covered. The adsorption state
decreased CuPc(Cl)15 surface z-potential. As the concentration
of hyperdispersant CH-5 increased, polymer chains of hyperdis-
persant CH-5 stretched into the solvent, and the remaining
– COOH and – OH were exposed. Hence, the CuPc(Cl)15
z-potential increased, as shown in Figure 6.
Characterization
Fourier-Transform Infrared Spectra
Figure 7(a) corresponds to unmodified CuPc(Cl)15, (b) to
hyperdispersant CH-5, and (c) to modified CuPc(Cl)15. In the
spectrum of modified CuPc(Cl)15, the new peaks observed at
2924.016 and 2853.651 cm21 belong to C-H vibrations of
CH3- and -CH2-, and the peak at 1725.532 cm21 is attributed
to the vibration of the C55O. This could indicate that CH-5
absorbed on the CuPc(Cl)15 surface.

Scanning Electron Microscopy

The micrographs of CuPc(Cl)15 particles modified without
hyperdispersants and with hyperdispersants are shown in
Figure 8.
Figure 8 shows that the CuPc(Cl)15 particles modified without
hyperdispersants had stronger flocculation than those modified
with hyperdispersants. A possible explanation for this is that
the adsorption of hyperdispersants on the CuPc(Cl)15 surface
inhibited the aggregation of CuPc(Cl)15 particles.

Application in E-Ink
FIG. 5. z-Potentials of CuPc(Cl)15 with different concentrations of CH-5 On the basis of these results, the above dispersion liquids
in tetrachlroethylene. were used as material core of microcapsules in E-Ink
 DISPERSION OF PHTHALOCYANINE GREEN G IN NONAQUEOUS MEDIUM 979

FIG. 6. Intensified mechanism of z-potentials on the CuPc(Cl)15 surface.

prepared by coaceration, in situ polymerization, and interfacial Figure 9 shows the results of E-Ink produced using coacerva-
polymerizations. tion, in situ polymerization, and interfacial polymerization. It can
be seen that the E-Ink microcapsules have an apparent smooth
Micrographs of E-Ink surface. But these kinds of microcapsules are clearly different:
The micro graphs of E-Ink containing CuPc(Cl)15 in water fewer particles existed in the TT-microcapsules, whereas the
are shown in Figure 9. particles inside the GA-microcapsules and UF-microcapsules
appeared to be uniformly dispersed. It is suggested that
interfacial polymerization was not suitable for manufacturing
E-Ink when the above dispersion liquids are the material of

FIG. 7. FT-IR spectra: (a) CuPc(Cl)15, (b) hyperdispersant CH-5, (c) FIG. 8. SEM micrograph of CuPc(Cl)15 particles: (a) CuPc(Cl)15, (b)
modified-CuPc(Cl)15. modified-CuPc(Cl)15.
980 J. WANG ET AL.

FIG. 10. Device for checking the electric response of E-Ink.

between two Cu-electrodes, the direct current electric field

was applied by two Cu-electrodes.
Results showed that after the electric field was applied,
the TT-microcapsules were broken completely, whereas the
GA-microcapsules and UF-microcapsules were not broken.

FIG. 9. Micrographs of E-Ink: (a) GA-E-Ink, (b) UF-E-Ink, (c) TT-E-Ink.

core microcapsules. The reason is that the particles modified by

hyperdispersant CH-5 surface had some active groups, influen-
cing the dispersing of particles in the TT-microcapsules.

Electric Response of E-Ink

In order to investigate the movement of modified-
CuPc(Cl)15 particles in the microcapsules, we made a device
for checking the electric response of E-Ink as shown in FIG. 11. Electric response of GA-E-Ink: (a) E ¼ 0, (b) E ¼ 50 V/mm,
Figure 10. After a single layer microcapsules were placed (c) E ¼ 50 V/mm.
 DISPERSION OF PHTHALOCYANINE GREEN G IN NONAQUEOUS MEDIUM
FIG. 12. Electric response of UF-E-Ink: (a) E ¼ 0, (b) E ¼ 50 V/mm,
(c) E ¼ 50 V/mm.
Hence, we studied the electric response of GA-E-Ink and UF-
E-Ink.
Figures 11 and 12 shows the electric response of E-Ink
before and after applying the DC electric field.
When E-Ink was not applied the DC electric field, the par-
ticles were distributed in the center of the microcapsules
(Figures 11(a) and 12(a)). When E-Ink was applied the DC
electric field (E ¼ 50 V/mm), the particles moved quickly to
the side of the microcapsules (Figures 11(b) and 12(b)).
When the direction of the field was reversed, the particles
were pulled back to the opposite side of the microcapsules
(Figures 11(c) and 12(c)). From the observations, it is
981
suggested that the modified particles had reversible electric
response in the microcapsules.
CONCLUSIONS
A stability dispersion liquid containing tetrachloroethylene
and CuPc(Cl)15 modified with hyperdispersant CH-5 and
assistant-dispersant CH-11B was prepared. The z-potential
and dispersibility of modified-CuPc(Cl)15 particles in the tetra-
chloroethylene satisfied the demand of preparing E-Ink. Using
this dispersion liquid as the core material, E-Ink was prepared
by coacervation, in situ polymerization, and interfacial
polymerization. Among them, GA-E-Ink and UF-E-Ink had a
reversible electric response.
ACKNOWLEDGMENTS
This work was supported by the National High Technology
Research and Development Program of China (863 Program)
(No. 2004AA302010) and the Natural Science Foundation of
Tianjin City (No. 043186411).
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