Applied Surface Science 255 (2009) 6221–6225

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Applied Surface Science

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

TiO2-based superhydrophobic–superhydrophilic patterns: Fabrication via an

ink-jet technique and application in offset printing
Shunsuke Nishimoto a,*, Atsushi Kubo b, Kenji Nohara c, Xintong Zhang a, Noriaki Taneichi b,
Toshiki Okui b, Zhaoyue Liu a, Kazuya Nakata a, Hideki Sakai c, Taketoshi Murakami a, Masahiko Abe c,
Takashi Komine b, Akira Fujishima a
a
Kanagawa Academy of Science and Technology, KSP Building West 614, 3-2-1 Sakado, Takatsu-ku, Kawasaki, Kanagawa 213-0012, Japan
b
Tokyo Ohka Kogyo Co., Ltd., 1590, Tabata, Samukawa-machi, Koza-gun, Kanagawa, 253-0114, Japan
c
Faculty of Science and Technology, Tokyo University of Science, 2641, Yamazaki, Noda, 278-8510, Japan

A R T I C L E I N F O A B S T R A C T

Article history: A superhydrophobic–superhydrophilic pattern was prepared on an anodized Al plate by a new

Received 8 September 2008 fabrication process. The process consists of five key steps: (1) TiO2 coating of the plate, (2) surface
Received in revised form 20 January 2009 modification with self-assembled monolayers (SAMs), (3) formation of aqueous UV light-resistant ink
Accepted 28 January 2009
Available online 6 February 2009
patterns by an ink-jet technique, (4) photocatalytic decomposition of SAMs and surface conversion to the
superhydrophilic state and (5) removal of the aqueous ink patterns by water washing. It is particularly
noteworthy that the wettability pattern can be quickly formed on the plate, without the use of a
PACS:
photomask. The fabricated superhydrophobic–superhydrophilic pattern is shown to be applicable to
82.65.+r
offset printing.
Keywords: ß 2009 Elsevier B.V. All rights reserved.
TiO2 photocatalyst
Superhydrophobic–superhydrophilic
Self-assembled monolayers
Ink-jet technique
Offset printing

1. Introduction examples of superhydrophobic–superhydrophilic patterns have

The wettability of a solid surface with a liquid, which is
governed by its chemical properties and microstructure, is an
important property of the surface. In recent years, superhydro-
philic surfaces (usually arbitrarily defined as exhibiting a water
contact angle (CA) < 58) and superhydrophobic surfaces (usually
arbitrarily defined as having a water CA > 1508) have received
intensive attention due to their industrial significance [1–17].
The titanium dioxide (TiO2) surface has been well known to
exhibit superhydrophilic wettability, as a result of ultraviolet (UV)
irradiation [1]. Furthermore, TiO2 films with fairly rough surfaces
can be readily converted to a superhydrophobic state via
modification with self-assembled monolayers (SAMs) of hydro-
phobic compounds, such as octadodecylphosphonic acid (ODP) or
octadecyltrimethoxysilane (ODS) [7–9,13,14]. Accordingly, a few
* Corresponding author. Present address: Department of Material and Energy
Science, Graduate School of Environmental Science, Okayama University, 3-1-1
Tsushima-Naka, Okayama 700-8530, Japan. Tel.: +81 86 251 8905;
fax: +81 86 251 8905.
E-mail address: s-nishi@cc.okayama-u.ac.jp (S. Nishimoto).
been reported by patterning TiO2 surfaces with hydrophobic SAMs,
which are then decomposed by area-selective UV irradiation [15–
17]. A large wettability contrast on the patterned surface is suitable
for the accurate manipulation of water-soluble or water-dispersed
materials. Therefore, such superhydrophobic–superhydrophilic
patterns on TiO2 surfaces are of interest for various applications,
for example, in the area-selective deposition or transfer of
functional materials, and in offset printing. However, the UV
irradiation steps specified in the previously reported fabrication
processes are time-consuming [15–17]. Because the area-selective
UV irradiation times, for UV light intensities of 1–100 mW cm 2,
necessary to decompose the organic molecule layers on the
surface, are a minimum of several minutes, area-selective UV
irradiation is necessary for a prolonged period of time for
application in which a UV laser is used, due to the need to scan
the surface with the relatively small laser spot. Though the use of
photomasks can shorten the UV irradiation process, photomasks
have to be prepared before the patterning. This is also unsuitable
for practical applications.
Consequently, we developed a new rapid fabrication process to
produce TiO2-based superhydrophobic–superhydrophilic patterns.

0169-4332/$ – see front matter ß 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2009.01.084
6222 S. Nishimoto et al. / Applied Surface Science 255 (2009) 6221–6225
Fig. 1. Schematic diagram of the patterning and reusing processes.
Our approach consists of five key steps, as shown in Fig. 1. First, the
TiO2 photocatalyst is coated on a fairly rough substrate, e.g.,
anodized Al. Second, the sample surface is modified with an ODP
SAM. Third, aqueous UV light-resistant ink is patterned by an ink-jet
method. Fourth, the SAM on the TiO2 surface is decomposed by
full-area UV irradiation. Fifth, the patterned aqueous ink is removed
by water washing. Because the ODP-modified surface has been
covered selectively with the aqueous UV light-resistant ink, the ODP
areas covered with the ink are not decomposed under UV irradiation.
On the other hand, the ODP areas not covered with ink are
decomposed under UV irradiation, and those areas are converted to a
superhydrophilic state. As a result, the wettability pattern is
expected to be rapidly formed on the substrate without the use of
a photomask.
Moreover, the present report demonstrates the use of a
fabricated superhydrophobic–superhydrophilic pattern on an
offset printing plate. According to a previous report, it was
suggested that TiO2-based wettability patterns can be applied in
offset printing, which is a familiar process in the printing industry
[18]. The principle of offset printing is as follows: a wettability-
patterned surface is typically formed by (1) photosensitive
polymer coating on an anodized Al plate, (2) light illumination
through a photomask and (3) development treatment, and the
surface based on a photosensitive polymer pattern is used on the
conventional printing plate. In the printing process, the plate is
first moistened with water, which selectively fills in the hydro-
philic areas. Then, an oil-based printing ink is spread over the
whole surface. Because the moistening water exists on the
hydrophilic areas, no oil-based ink adheres in these areas. As a
result, an ink pattern is formed on the plate. Finally, the patterned
ink is transferred to a rubber pad (‘‘blanket’’), which then transfers
it to the paper. While the conventional printing plate cannot be
reused, due to the strong bonding between the photosensitive
polymer and the plate, the TiO2-based printing plate is reported to
be reusable. That is, after the printing process, the remaining
patterned hydrophobic organic molecules (ODP SAMs in our case)
on the plate can be photocatalytically decomposed by UV
irradiation, and the plate surface converted back to the initial
state. In addition, little organic waste solution is discharged in the
fabrication process of the TiO2-based printing plate, because the
patterning is possible in a dry process without the use of
photoresist. On the other hand, the organic waste solution is
discharged in the conventional process (development treatment).
Consequently, the TiO2-based printing plate is an environmentally
friendly material.
2. Experimental
The TiO2 coating was carried out as follows: commercial
anodized aluminum plates (e.g., Kodak, presensitized offset plate
Posi/standard type GP), whose photosensitive polymer was
previously removed by development treatment, were used as
substrates. A TiO2 anatase sol (TAYCA, TKD-701), which was
diluted with 2-propanol at a concentration of 2.0 wt%, was used for
dip-coating the substrate, which was withdrawn at a rate of
0.5 mm s 1. Then, the substrate was heated at 100 8C for 1 h and
then irradiated with a UV light (black-light lamp, UV intensity:
1 mW cm 2) overnight to clean the surface. The TiO2-coated
surface was modified with a monolayer of ODP by a previously
reported method [14,16], involving immersion in a 0.5-mM 2-
propanol solution of ODP for 48 h. After that, the substrate was
removed from the solution and rinsed thoroughly with 2-propanol
followed by heat treatment at 100 8C for 1 h. The patterning was
carried out by use of a home-built ink-jet printer, with the use of an
aqueous UV light-resistant ink, which was prepared by mixing a
commercial dye (Tokyo Chemical Industry Co., Ltd., Direct Blue 86,
3 wt%) and pigment (BASF Japan Ltd., UVINUL3050, 2 wt%) into a
mixed solvent of triethanolamine, diethylene glycol and deionized
water (1:3:25, w/w/w). After drying at 80 8C for 20 min, the
resulting sample was irradiated with a UV light (Philips-TUV75W,
UV intensity: 7 mW cm 2). Finally, the aqueous ink pattern on the
sample was removed by water washing.
The printing test of the resulting sample was performed with a
commonly used proof press (Dainippon Screen, KF123-GL). After
the printing test, the surface of the printing plate was cleaned with
a commercial plate-cleaner (Tokyo Printing Ink, TC-2) to remove
the remaining printing ink, and the surface was irradiated with a
UV light (Philips-TUV75W, UV intensity: 7 mW cm 2) for approxi-
mately 5 h to recover the initial state of the sample, i.e., that
existing before the ODP modification (Fig. 1, step 2). Then, the
surface was patterned again, and a secondary printing test was
performed.
The surfaces of the samples were examined with an optical
microscope (Keyence, VH-5100), a scanning electron microscope
(Hitachi, S-4800) and a scanning probe microscope (Digital
Instruments, Nanoscope IV). The water CA of the samples was
measured with a contact angle meter (Kyowa, CA-X) at room
temperature and analyzed with commercial software.
3. Results and discussion
Fig. 2 shows SEM images of the sample surface before and after
the TiO2-coating. After the TiO2-coating, the surface of the plate
was uniformly covered with TiO2 particles. Furthermore, the
overall surface roughness parameters (rms, measured by AFM) of
the samples before and after the TiO2-coating were 266 nm and
360 nm, respectively. Consequently, the TiO2 photocatalyst was
coated on the anodized Al plate without affecting its surface
roughness.
Fig. 3 shows the changes in water CA for the ODP-modified plate
and the photographs of water droplets on the plate before and after
UV irradiation (inset). The ODP-modified plate showed a water CA
of about 1548. The superhydrophobic state is considered to be
generated by the combination of a moderately porous TiO2 surface,
which traps air beneath a water droplet [10–12], and a dense
hydrophobic SAM on the metal oxide surface [7–17]. After UV
irradiation, the surface rapidly lost its hydrophobicity, and the TiO2
surface was transformed to a superhydrophilic state, with a water
 S. Nishimoto et al. / Applied Surface Science 255 (2009) 6221–6225 6223

Fig. 2. SEM images of anodized Al plates (a) before and (b) after TiO2-coating.

CA of nearly 08 due to the photocatalytic decomposition of the ODP
SAM. Furthermore, this superhydrophilic state (water CA < 58) of
the surface was maintained for at least 2 weeks in the dark with the
ambient atmosphere at room temperature.
It is well known that the compatibility between the surface and
the ink-jet ink is very important for the resolution of the patterning
[19]. If the surface energy of the ink-jet ink is as high as that of
water, the ODP-modified superhydrophobic surface can repel the
droplets of ink. On the other hand, the ink-jet ink can spread over
the surface, if its surface energy is too low for the super-
hydrophobic surface. Therefore, an aqueous UV light-resistant ink
with a fairly low surface energy (CA on the ODP-modified plate,
658) was employed in the ink-jet patterning to form fine patterns
on the superhydrophobic surface. As a result, fine ink patterns
were successfully obtained on the ODP-modified plate, as shown in
Fig. 4. Furthermore, the water CA of areas covered with the
aqueous UV light-resistant ink was more than 150 8 after UV
irradiation for 30 min followed by water washing. This indicates
that the aqueous UV light-resistant ink functioned as a photomask.
In addition, the superhydrophobicity of finely patterned areas was
also maintained under UV irradiation, even though the UV
irradiation time was prolonged. While the patterning with the
use of a photomask needs to be carried out carefully due to the
attack of photocatalytically active species diffusing from the bare
TiO2 surface through the gap between the photomask and the TiO2
surface [20], the present process did not require this careful
manipulation. That is, it was suggested that the ink directly
adhering on the ODP SAM-modified surface protected the latter
against the diffusing active species. As a result, the super-
hydrophobic–superhydrophilic pattern was successfully obtained
by the new rapid process via the ink-jet technique.
Subsequently, we performed a proof printing test to evaluate
the prepared superhydrophobic–superhydrophilic pattern and
investigated the reusability of the printing plate with the
procedure shown in Fig. 1. During the printing test, it was found
that the superhydrophobic area repelled the moistening water,
which was entrapped in the superhydrophilic areas. As a result, the
ink pattern was successfully formed on the plate. Furthermore, if
the oil-based ink accidentally adhered on the superhydrophilic
surface, it could be easily removed from the surface by additional
moistening, in a manner similar to that for TiO2-based self-
cleaning surfaces [2,4,5]. Fig. 5 shows photographs of images

2
Fig. 3. Changes in water CA of the ODP-modified TiO2-coated sample surfaces under UV irradiation (UV intensity: 7 mW cm ). Inset: shapes of water droplets on the sample
surfaces.
6224 S. Nishimoto et al. / Applied Surface Science 255 (2009) 6221–6225

Fig. 4. Photograph of the aqueous UV light-resistant ink pattern formed on the ODP-modified TiO2-coated sample surface by the ink-jet technique. Inset: an optical
micrograph of the ink line.

printed on paper on the proof press with the use of the prepared
printing plate. As shown in Fig. 5 (left), clear color printing with a
resolution of 133 LPI (line per inch) was possible with the TiO2-
based superhydrophobic–superhydrophilic pattern. Therefore, the
superhydrophobic–superhydrophilic pattern prepared via the ink-
jet technique was demonstrated to be applicable in offset printing.
After the printing test, the remaining ink on the surface was
removed by the use of the plate-cleaner, and the surface was
irradiated with a UV lamp for approximately 5 h. As a result, the
whole sample surface exhibited superhydrophilicity. After the
repetition of the ODP modification, the surface was patterned
again with an image different from that of the first printing test,

Fig. 5. Photographs of posters (309 mm  570 mm) printed by the superhydrophobic–superhydrophilic pattern formed on the pristine plate (left) and reused plate (right).
 S. Nishimoto et al. / Applied Surface Science 255 (2009) 6221–6225
and a second printing test was carried out with the proof press
to confirm the reusability of the printing plate. As shown in
Fig. 5 (right), a clear image was able to be printed again. It is
noteworthy that the locations of the images were different,
comparing the pristine plate and the reused plate. However,
there was no memory effect, i.e., the images on the pristine plate
did not appear on either the reused plate or the printed paper.
Therefore, it was confirmed that the TiO2-based printing plate
was reusable. In addition, a printing test was carried out with a
web press. As a result, it was found that more than 5000 pages
were able to be printed by the prepared printing plate with a
maximum printing speed of 40,000 copy h 1. This indicates that
the TiO2-based printing plate possesses durability sufficient for
practical application.
4. Conclusions
The surface of the TiO2-coated anodized Al plate was converted
to a superhydrophobic state by means of ODP SAM modification.
The superhydrophobic–superhydrophilic pattern was formed by
a new process, which consists of the formation of aqueous UV
light-resistant ink patterns by the ink-jet technique, UV irradia-
tion and water washing. The present process can shorten the area-
selective UV irradiation time, without the use of a photomask.
Superhydrophobic–superhydrophilic patterns were prepared on
an offset printing plate. Clear color printing with a resolution of
133 LPI (line per inch) was possible, and the printing plate showed
sufficient durability for web press printing. Furthermore, the
TiO2-based printing plate was reusable. Consequently, the
patterning technique reported here is promising for practical
applications.
6225
Acknowledgements
Z.L. acknowledges the Japan Society for the Promotion of
Science (JSPS) for a Postdoctoral Fellowship. We are grateful to
Prof. D.A. Tryk for a careful reading of the manuscript.
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