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UV curable screen printing ink for glass and

ceramic surfaces

Initial situation
Figure 1
UV curing of the
printing layer on
Glass as a substrate for screen printing
glass becomes more and more important to-
day. At present, ceramic printing inks
for glass offer by far the best results in
terms of stability, scratch resistance and
durability. Because the temperatures
required to sinter ceramic printing inks
are between 650 °C and 800 °C, it is
neither easy nor cheap to work with
ceramic printing inks. Furthermore, they
tend to contain toxic heavy metals such
as lead or cadmium.

As an alternative to ceramic printing


inks, solvent based inks with an organic
matrix were established. Since the ear-
ly 70‘s, solvent-free UV curable printing
inks have become more important for
the screen printing process. One of the
reasons was that UV curable inks offer
substantial advantages compared to
conventional printing inks in complex
applications like printing on packag-
ing materials. With UV curable printing
inks it is possible to realize a six- to ten-
color print in a very short time because
UV curing is a very fast process. With
solvent inks, every color must be cured
separately for a certain length of time.
The application of UV curable printing
inks saves time, space and energy and
reduces the rejection by about 90 %.
Kurzdarstellung Druckfarbe für Glas- und Keramikoberflä-
chen wurde Neuland betreten. Es gelang, UV curable screen printing inks for
In einem durch den Freistaat Bayern im Rah- ein UV-härtbares Hybridpolymerbindemittel glass normally have an insufficient ad-
men des Förderprogramms „Neue Werk- zu entwickeln, das auch ohne thermische
stoffe in Bayern“ geförderten Verbundpro- Nachhärtung spülmaschinenbeständige Be- hesion to glass under the influence of
jekt wurde in Zusammenarbeit mit der Fa. schichtungen auf Glasoberflächen ergibt. humidity or water. The dishwashing re-
Pröll KG, Weißenburg, eine UV-härtbare sistance of prints made with conven-
Siebdruckfarbe auf Basis der hybriden Poly- Vor Beginn des Forschungsvorhabens exis- tional organic UV curable screen print-
merwerkstoffe speziell für Glas- und Kera- tierten bereits einige UV-Druckfarben, die ing inks only achieves 5 to 10 cycles.
mikoberflächen entwickelt. nach Herstellerangaben auch für Glas ge-
eignet waren. Die Spülmaschinenbeständig-
Das Fraunhofer ISC hatte bereits vor Beginn keit nach DIN EN 12875-1 lag jedoch unter
des Projekts umfangreiche Erfahrungen in 10 Zyklen. Durch den Einsatz des UV-härt-
der Entwicklung von Hybridpolymeren zur baren Hybridpolymerbindemittels konnte
Beschichtung von Glas- und Keramikober- die Spülmaschinenbeständigkeit auf min-
flächen mit thermisch härtbaren Systemen destens 50 Zyklen gesteigert werden.
sowie zur Beschichtung von Kunststoffen
mit thermisch und UV-härtbaren Systemen.
Bei der Entwicklung einer UV-härtbaren

36 Fraunhofer ISC Annual Report 2006


UV curable screen printing ink for glass and ceramic surfaces

The project

In cooperation with Proell KG, Weißen-


burg in Bavaria, a UV curable screen
printing ink for glass surfaces has been
developed. The UV curable binder of
this printing ink is derived from the hy-
brid polymers of Fraunhofer ISC and is
based on methacrylate silanes, alumini-
um alkoxides and urethane acrylates.

Customer’s specification

The printing ink should be suitable for


both screen and pad printing process-
es, UV curable at room temperature
(Figure 1) without additional thermal
post treatment and should be prefera-
bly a solvent-free, one-component sys-
tem with a minimum storage time of
six months. It should not contain any
toxic components and be suitable for
opaque, semitransparent and translu-
cent prints.

The binder should be adaptable to or-


ganic and inorganic pigments (TiO2,
carbon black) and pigments should not
be based on toxic heavy metals. UV
curing was to be carried out with two
mercury medium pressure lamps, pow-
er length 120 W/cm; curing speed
10 m/minute.

Figure 2
Vacuum distillation of
the volatile reaction
products in a short
path evaporator

Fraunhofer ISC Annual Report 2006


37
UV curable screen printing ink for glass and ceramic surfaces

Before the project began, Fraunhofer


ISC had already gained substantial ex-
perience in the development of hy-
brid polymers with high adhesion and
dishwasher resistance when applied
on glass substrates by thermal curing
at a minimum temperature of 160 °C.
For plastic surfaces, a UV curable hy-
brid polymer had been commercialized.
At project start, ten systems based on
sol-gel hybrid nanotechnology were
formulated, which, in principle, were
adequate for glass surfaces. After a
Figure 3 screening process, one system was se-
UV cured printings
lected as fulfilling the majority of the
before (left) and after
(right) 50 cycles in a specified requirements.
dishwasher resistance
test (EN 12875-1) Durability requirements for the cured While thermally curable systems are
print: mainly based on epoxy-silane and fur-
ther organic epoxide components,
• Adhesion to all glass and ceramics the selected hybrid polymer is an
substrates (Cross Cut Test according (meth)acrylic- based system.
to ISO 2409)
• Hard, scratch and abrasion resistant The elimination of reaction products
surface that are in a chemical equilibrium with
• Permanent adhesion even after in- water in the sol-gel process normal-
fluence of humidity and water for a ly leads to the gelation of the mixture.
certain time Therefore, the distillation of the volatile
• Resistant against silvering baths products of the hydrolysis reaction
• Dishwashing resistance: minimum (alcohol) from hybrid polymers pro-
40 cycles (EN 12875-1) duced by the sol-gel process was one
• Alkaline- and acid-proof decisive step in the product develop-
• Resistant against household cleaning ment. The evaporation of the volatile
agents and solvents components was necessary because
• UV stability: 3 to 5 years for outdoor otherwise no printing ink with suf-
applications ficiently high viscosity and adequate
processing time could have been ob-
tained.

By skillful selection of reactive dilu-


ents and prepolymers, the solids con-
tent of the developed hybrid polymer
binder could be increased so that after
the vacuum distillation (ablation of the
volatile reaction products, Figure 2) the
binder was suitable for printing inks.

38 Fraunhofer ISC Annual Report 2006


UV curable screen printing ink for glass and ceramic surfaces

Customer Benefit

Proell KG was able to formulate a


UV curable screen printing ink suit-
able for printing on glass on the basis
of hybrid polymer binders developed
at Fraunhofer ISC. Proell produced the
new screen printing ink either by dis-
persing pigments directly in the hybrid
polymer binder in a triple-roll mill and
doing the final formulation by adding Contact
further organic components or by tak- Karl J. Deichmann
Phone +49(0)9 31/41 00-624
ing pigmented prepolymer plastics and
deichmann@isc.fraunhofer.de
adding the hybrid polymer binder after-
wards. Dr. Johanna Kron
Phone +49(0)9 31/41 00-6 31
With the obtained printing ink Proell kron@ isc.fraunhofer.de
KG was able to manufacture screen
Cooperation
printings with high adhesion and abra-
Proell KG, Weißenburg, Bavaria,
sion resistance on glass. The high UV Germany
energy that was necessary for the cur-
ing of the hybrid polymer prints could Funding
be reduced from initially 5 to 6 kJ/cm2 Bavarian Ministry of Economic Affairs,
(range 200 to 400 Nm) to a practicable Infrastructure, Transport and Technology -
Bavarian state research program
value of 1 kJ/cm2. The final values con- “Neue Werkstoffe in Bayern”.
cerning adhesive strength and abrasion
resistance of these prints were, how-
ever, only achieved after one week of
storage at ambient temperature or by
thermal post curing.

Figures 3 shows prints produced at


Fraunhofer ISC before and after 50
dishwashing cycles.

Fraunhofer ISC Annual Report 2006


39