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Progress in Organic Coatings xxx (2014) xxx–xxx

Contents lists available at ScienceDirect

Progress in Organic Coatings

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

Review

“Green ink in all colors”—Printing ink from renewable resources

Tobias Robert ∗
Fraunhofer-Institute for Wood Research – Wilhelm-Klauditz-Institut WKI, Bienroder Weg 54E, 38108 Braunschweig, Germany

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

Article history: Over the last years many printing ink manufacturers moved toward more sustainable inks. Drivers for this
Received 23 April 2014 development are besides resource scarcity and a higher legislative burden, an increasing environmental
Accepted 14 August 2014 awareness throughout the population and as a result a growing demand for inks with a small ecological
Available online xxx
foot print. Thus, water-based and UV-curing systems have already started to replace solvent-based inks,
which results in a reduction of volatile organic compounds (VOC) released during the printing process. In
Keywords:
addition, materials derived from renewable resources, are more frequently used to replace petrochemical
Printing inks
ink ingredients, such as polymeric binders, solvents and different additives. These developments often
Renewable resources
Binder resins
go hand in hand with an economical benefit as these inks allow for reduced drying times and lower
UV-curing inks equipment cost to name but a few. Nonetheless, many inks are still mainly derived from petrochemi-
cal feedstock. This review gives an overview of the developments in the field of printing inks derived
from renewable materials, discusses advantages and drawbacks of the systems described and addresses
problems unsolved so far.
© 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
1.1. Printing inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. Inks based on renewable resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.1. New generation of renewable printing inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2.2. UV-curing printing inks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction The manufacturing of printing inks traditionally involves

renewable resources, such as colophony and vegetable oils,
In spite of the increasing importance of digital media over the nonetheless the majority of the ink formulations consist to a high
last decades, printing still plays an important role in our daily lives degree of components from petrochemical feedstock, which results
and more than one million tons of ink are produced in Europe annu- in a considerable environmental impact.
ally [1]. Even though the market for printed media is declining, Over the last years more and more inks (partially) composed
there is an increasing demand for inks in other areas of the prin- of renewable resources were introduced to the market (see Table 1
ting industry, such as packaging and digital print. Therefore, the for some examples). In addition, research efforts have been made to
printing ink market is growing by 3% per year which leads to an identify new renewable materials that can be used in the manufac-
increasing demand for traditional as well as new printing inks. In ture of printing ink in order to reduce dependency on petrochemical
addition, resource scarcity, increased legislative burden, and rising resources and lessen the environmental impact. Another way to
environmental awareness forces ink manufactures to develop more more sustainable inks is the use of water-based and UV-curing
sustainable inks. inks due to the reduction of solvents applied in the printing indus-
try, which leads to lower VOC emission. However, especially for
∗ Tel.: +49 5312155357. the UV-curing inks, formulations based on renewable materials are
E-mail address: tobias.robert@wki.fraunhofer.de scarce.

http://dx.doi.org/10.1016/j.porgcoat.2014.08.007
0300-9440/© 2014 Elsevier B.V. All rights reserved.

Please cite this article in press as: T. Robert, “Green ink in all colors”—Printing ink from renewable resources, Prog. Org. Coat. (2014),
http://dx.doi.org/10.1016/j.porgcoat.2014.08.007
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Table 1
A range of commercially available printing inks based on renewable materials [2].

Brand name Company Renewable Content H

K + E Arrowstar, Flint Group Soy-based, binder 100%
Arroweb, Starbase renewable
Reflecta, Resista, Huber Group 80% renewable,
HO H
Quickfast vegetable oil
Grüne Tinte® Prometho Almost entirely O
renewable 1
Sicura Eco Siegwerk 50% renewable
Eco-Sure Gans Ink 73% renewable
Fig. 1. Abietic acid (1), main component of tall oil rosin.
Eco-Set Series American Offset Vegetable based, >24%
printing ink renewable
SunLit Diamond Sun Chemical 100% vegetable oil flexible and driers help with the oxidative drying process. Adhesion
promoters or wetting agents enhance the binding to the printing
stock and biocides prevent microbiological degradation of the ink,
All in all, besides the traditional high degree of renewable to name but a few.
resources and the progress made over the last years, further
research efforts in this field are of great interest. This might not
2. Inks based on renewable resources
only replace existing petrochemical ink systems, but also lead to
the development of more sustainable inks with new properties for
Johannes Gutenberg is mostly known for his invention of the
specialized fields of application.
metal-based movable types, which allowed for a fast type setting
The main goal of this review is to give an overview primarily of
and therefore increased printing speed. But almost as important
academic research efforts in the field of sustainable inks and the
were his contributions related to printing inks. As the water-based
consequent impact on the printing industry. Especially inks based
inks, which were mostly used at the time were not compatible
on renewable resources and UV-curing inks will be in the focus of
with his metal-based types, he invented new oil-based printing
this work to reveal further potential for improvements and give a
inks by heating different vegetable oils, such as linseed or walnut
short outlook on possible new and more sustainable alternatives. To
oil. Within a century water-based printing inks were almost obso-
the best of our knowledge, no overview on printing inks compris-
lete and inks were exclusively made by heating vegetable oils. This
ing renewable components has been made recently. Therefore, this
process is called heat bodying, which leads to the conjugation of
review also aims to address open question and unsolved challenges
the double bonds present in the fatty acids and subsequent poly-
in this field.
merization through pericyclic reactions and other mechanisms [4].
Printing ink compositions then virtually have remained unchanged
1.1. Printing inks over the next 300 years, until the progress in the chemical industry
at the beginning of the 20th century led to new synthetic materials
In order to develop alternatives to established inks based on which resulted in the development of printing inks with improved
renewable resources, it is important to have a good understanding properties and new fields of application [5].
of the ink composition [3]. All printing inks are composed of four Today, roughly 100 years later, resource scarcity and the
types of ingredients: increased environmental awareness result in enhanced research
efforts in printing inks partially based on renewable materials,
1. Colorant which were used in the early days of letterpress.
2. Vehicle or binder Many printing ink binders are derived from tall oil rosin, also
3. Solvent known as colophony. It is obtained from pine trees all over the
4. Additives world either from the living tree (gum rosin) or weathered wood
(wood rosin). In addition, it is a by-product of the Kraft-process,
The colorant can either be a pigment or a dye. Pigments which is one of the main processes in the pulp and paper industry to
(inorganic and organic) are almost exclusively used in printing pro- extract cellulose from wood. The rosin is obtained after distillation
cesses. They are dispersed solids that are insoluble in the support of the tall oil and mainly consists of different resin acids, especially
material (solvent). Dyes are soluble in the support material and abietic acid (1, Fig. 1).
have several drawbacks compared to pigments, such as lower light These resin acids can be modified by reactions with different
fastness and lower resistance to water. compounds, natural or synthetic to obtain binders with a wide
The vehicles or binders have multiple functions in the ink. They range of properties. The most common rosin binders are phenol
disperse the pigments in the support material and bind it on the formaldehyde modified resins to form di- or trifunctionalized acid
printing stock. In addition, they are utilized to modify the rheolo- derivatives of type 2, as building block for polyesters, which are
gical and mechanical properties of the inks. Traditionally phenolic then used as binders for printing inks (Fig. 2). Despite being par-
resins derived from tall oil rosin (colophony) or alkyd resins are tially derived from wood, a renewable resource, the major part of
applied, but also other synthetic resins, e.g. polyacrylates can be the binders depends on fossil fuels. In addition, due to the increased
used. worldwide demand, the market for tall oil rosin has been volatile
Solvents dissolve the binders and adjust the viscosity of the ink over the last years with periods of very high prices, which obviously
for the different printing processes. Depending on the application puts an enormous pressure on printing ink manufactures. There-
they can have high or low vapor pressures and evaporate during fore, new alternatives are of high interest.
the printing process. Depending on the printing process and the
viscosity of the binder no additional solvent might be necessary, 2.1. New generation of renewable printing inks
leading to a solvent-free ink (100% system).
Additives are used to improve the ink properties. These com- The oil crises in the mid 1970 led to enhanced research efforts
pounds include surfactants to reduce the surface tension and throughout the chemical industry to reduce the dependency on
thereby the wetting problem. Plasticizers make the dried ink more crude oil. This was also true for the printing industry. The American

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O O
HO OH
H OH OH H of the initiators are essential to ensure fast drying.
n printing inks, one of their major drawbacks is the potential compe-
H H
R R
iPr iPr
2 ing oil can have a serious environmental and economic impact. In
Fig. 2. Rosin modified phenolic resin (2) as binder building block.
Newspaper Publishers Association developed an ink formulation
based on “gilsonite” (a form of natural asphalt) and tall oil fatty
acids [6]. They also developed soybean oil-based vehicles for litho-
graphic inks. However, despite having good printing properties,
most of these inks were not economically compatible with the
existing petrochemical-based inks and therefore only a few found
application in the printing industry.
Later, Erhan and co-workers developed vehicles derived from
soybean and other vegetable oil [7]. After alkali removal of the free
acids, the oils were subjected to heat bodying. These polymers were
then used as binders in a solvent-free ink formulation. Interest-
ingly, this method is very similar to the early ink-making process
outlined above. The resulting ink had similar or improved proper-
ties compared to the petroleum-based inks and the binders were
more transparent, which made a reduction of the pigment load-
ing possible. In addition, the viscosity of the formulation could be
adjusted by the reaction time of the heat bodying and batches of
binder with different viscosity could be blended, which allowed for
easy adjustment of the viscosity. The same group then further stud-
ied this class of binders by formulating a range of different black
and colored inks [8] and looked at the dependency of the viscosity
as a function of molecular weight [9]. In addition, biodegradabil-
ity tests showed that the soy oil-based inks are degraded more
than twice as fast compared to conventional inks [10]. Also VOC
emissions were examined, which proved to be another advantage
[11].
However, the disadvantage of these inks was the high temper-
ature and long reaction time needed for the heat bodying process,
which accounts for the biggest cost factor. Therefore, a reduction of
both reaction time and temperature would make these inks more
economically viable. In this context, it was shown that organic cat-
alysts, such as quinones [12] or anthraquinones [13] are effective,
but have to be applied in high concentrations to sufficiently accel-
erate the reaction. As alternative, Mello and co-workers recently
showed that it is possible to reduce the reaction time by up to 60%,
by using 0.1 mass% of a Ni(II)-catalyst [14].
Despite the costs for the polymerization process, the inks devel-
oped by Erhan and co-workers, were introduced to the market as
Soyink® and were able to compete with existing inks. This was
particularly true for the colored systems, where the higher trans-
parency of the binder vehicles led to a reduced pigment loading
and hence lower production costs.
All in all, these works set the stage for development and com-
mercialization of several soy-based inks over the last years. As a
result, soy inks are applied nowadays in many print applications.
Instead of using polymeric binders that need to be synthe-
sized by heat bodying, it was shown that it is possible to use
low-molecular soy oil-based rosin esters as resin precursors for
lithographic inks [15]. The unsaturated esters can be crosslinked
through a heat-induced radical polymerization in the presence of
different radical initiators, such as peroxides or metal salts, which
leads to instant drying of the ink. However, temperatures of up to
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3
180 ◦ C are needed during the printing process similar to the tem-
peratures for solvent-based inks. In addition, considerable amounts
Despite of the widespread application of edible vegetable oils in
tition with food production [16]. To circumvent this problem, Mello
and co-workers recently reported the transformation of used fry-
ing oil to binders for printing inks again by heat bodying [17]. This
is especially interesting as the disposal and treatment of used fry-
first experiments the group was able to show that the performance
of the resulting ink is compatible with existing systems, which
might lead to further developments in this area. Most certainly,
this renewable resource has a huge potential for further applica-
tions, not at least as currently only 2.5–3.5% of the 2.4 billion liters
of the used frying oil produced in Brazil annually is recycled.
Another approach to more sustainable inks is the replacement
of the petrochemical solvents in ink formulations with renewable
solvents. Two groups employed fatty acid methyl and butyl esters
(FAME and FABE) to replace petrochemical solvents in printing inks
[18]. They were able to show that these esters can be a renewable,
cost effective alternative, without a reduction in ink performance.
However, in both examples, rosin-modified phenolic resins derived
from petrochemical feedstock were used as binder vehicles.
In addition, these fatty acid esters have the tendency to migrate
through packaging material, due to the low molecular weight. More
structural complex esters with higher molecular weight derived
from fatty esters have been developed to avoid or minimalize the
migration, which is especially important for print applications in
food packaging [19].
As another non-food alternative, karanja oil was studied as a
binder component in printing inks [20]. However, as second binder
component a phenolic resin was used and the ink formulation in
this case still comprised of 26% mineral oil distillate. Furthermore,
due to its dark coloration, karanja oil is not suited for the formu-
lation of colored inks and its pungent smell makes the application
potential questionable.
Also the performance of more volatile solvents from renew-
able resources was examined by replacing petrochemical-derived
alcohols and esters with alcohols and esters from the side stream
of the bioethanol production from sugarcane [21]. However, the
volatile solvents applied do not help to reduce the VOC forma-
tion during the printing process and again a phenol-based resin
is used.
As a phenol resin-free alternative Ryu and co-workers devel-
oped a polyphthalate based rosin resin as a vehicle for printing ink
with improved properties compared to a standard phenolic resin
[22]. The resin is synthesized after isomerization of abietic acid (1)
to levopimaric acid (3), which undergoes a Diels-Alder reaction in
the presence of maleic anhydride (Scheme 1). The resulting anhy-
dride 4 is further modified by a reaction with diols to yield the
polyester resin.
As a different approach to renewable printing inks a variety
of polysaccharides has been studied, some as additives, others as
binders to replace tall oil-based binders. Commercially available
modified corn starch with high molecular weights was used in low
concentrations of 0.5–2% to improve the printing quality [23]. As a
more recent example starch was applied in higher amounts as an
additive with commercially available inks, which resulted in good
water resistance and improved color strength, gloss and heat resis-
tance to name a few [24]. As a low molecular starch derivative,
dextrins have also been employed as binders [25] and additives [26]
for printing inks. But again, starch and its derivatives directly com-
pete with food production. To avoid this, non-edible polysaccha-
rides might be a better alternative. For example, cellulose additives
were used as binders in several ink formulations. A binder based on
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O O
HO HO
maleic O
anhydride
1 180 °C 180 °C, 2h O
iPr
O
3 4

Scheme 1. Synthesis of phenol-free resin precursor 4.

HO O

O O
O OH O
O O O O OH
O Lignin
O
O O O O OH
O
O O n HO OH
O O OH OH
O
O O
O O
HO OH O
O O

Fig. 3. Schematic representation of cellulose acetate propionate (CAP).

OH O
O O

cellulose acetate propionate (5, Fig. 3) was developed having the Lignin O
O
advantage to release solvents quicker than other resins tested [27].
6
However, no water-based or 100% systems of this kind have
been reported, limiting its scope of application especially with a -OOC
VOC reduction in mind. As a renewable alternative for food pack- O O
aging a printing ink with methylcellulose as binder component has HO OH
been reported by Del Moro et al. [28]. Hydroxyalkyl cellulose was OH O
used as a binder for a water-based printing ink especially suited for O O H
photographic paper [29]. Chitosan has also been studied as additive HO O O HO O
in ink-jet inks to reduce blurring between the colors, by decreasing O O O n
O O O
the coagulation time of the colorants [30]. O OH OH
Especially interesting from an environmental and economic O
O
stand point is the use of waste products of side streams of exist- OH
ing processes. Hemicellulose and lignin (6 and 7, Fig. 4) are side HO
products of the pulp and paper industry and a substantial share of
the black liquor, which is often burned. Only a few material uses of 7
these two compounds are in place at the moment. In case of lignin,
Fig. 4. Simplified structures of lignin (6) and hemicellulose (7).
only 2% of this compound extracted worldwide is at the moment
exploited as a chemical commodity [31]. Therefore new applica-
tions, e.g. in the printing industry are highly desirable. Early works undergo crosslinking upon UV-irradiation in the presence of
on the use of lignin and lignin derivatives in printing inks have been photoinitiators, resulting in an instant “drying” of the ink. These
reported in the late eighties and early nineties of the last century inks, either 100% systems [36] or water-based [37] are more and
[32]. However, this did not result in a widespread application of this more applied in the printing industry and show a stable growth
class of inks in the printing industry. Nonetheless, a recent exam- over the last years. This can be explained with several advantages
ple in which a nitrated lignin is utilized as a binder component compared to solvent-based inks: the virtually instant drying
shows that the printing ink manufacturers are aware of the high allows for higher printing speeds and reduced energy demand,
potential of lignin as printing ink component [33]. Where hemi- as heat drying is no longer necessary. In addition, these inks
cellulose is concerned, Kela and co-workers recently reported its are especially suited for printing on non-absorbent surfaces, like
application as waterborne flexographic ink binder [34]. In the plastic packaging. Moreover, VOC emissions due to the evaporation
experiments described ink formulations consisted of either of solvents are substantially reduced which makes ventilation
unmodified hemicellulose or hemicellulose modified by etherifica- and solvent recovery systems obsolete and also reduces the fire
tion or esterification [35]. Preliminary tests in printing applications hazard and as a consequence the insurance premiums for the
showed good performance of the formulated inks. printing company [38]. Despite these advantages, UV-curing inks
also suffer from several drawbacks. After the printing process,
2.2. UV-curing printing inks residual reactive diluents and photoinitiators remain in the ink.
This might pose a contamination problem, not only in the field of
Another approach to printing inks with a lower environmental food packaging [39]. Moreover, ink formulations usually consist
impact is the use of UV-curing formulations. These systems consist of acrylated monomers and prepolymers as binder precursors.
of binder precursors (prepolymers and reactive diluents) that Acrylates proved to exhibit an allergenic potential which might

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O economic, health and environmental value not only for the printing
O O O O
R O
O R Epoxidized Soybean Oil
O to increasingly use renewable materials, not at least due to eco-
O
HO
O
O OH OH
O O
O O
R O
O O
O R
O O
O in this field, to the best of our knowledge, no inks with a substantial
Scheme 2. Synthesis of acrylated soybean oil (for clarity, only one of the fatty acid
esters is shown in detail).
lead to severe contact allergies, a known occupational skin disease
[40]. In addition, there are only a few examples where renewable
resources are used in the UV-printing inks.
Recently an overview on renewable feedstock in UV-curable
materials was given by Robin and co-workers with some poten-
tial applications in the printing industry [41]. But also some work
was dedicated directly toward more sustainable UV-curing prin-
ting inks. For example, epoxidized vegetable oil has been used
as a binder precursor. It can be directly crosslinked by a cationic
photopolymerization reaction in the presence of epoxidized reac-
tive diluents and a cationic photoinitiator [42]. Furthermore,
Rengasamy and colleagues developed soy oil-based UV-curable
acrylate oligomers derived from epoxidized soy oil (Scheme 2) [43].
Because of their good film forming properties these binder pre-
cursors are promising candidates for a broad range of applications,
including printing inks. In fact, a similar chemically drying prin-
ting ink composition has been described before, where the binder
precursors are composed of acrylated vegetable oils [44].
It was also shown, that carbohydrates can be used as binder pre-
cursors. Kela and co-workers described a water-based UV-curing
ink composition with substituted hemicellulose as binder com-
ponent [35]. Pudas and co-workers successfully applied acrylated
ethylcellulose as UV-curable binders that allow for the viscosity
control of ceramic inks [45]. But also other contributions with pos-
sible applications as printing ink ingredients have been made. As
an early example cellulose acetate butyrate has been used as an
additive for UV-curing flexographic inks [46]. Also photoinitiators
from renewable resources have been described [47].
But again in most of these examples acrylate containing com-
pounds are utilized as crosslinking agents. Even though acrylates
can be produced from renewable resources [48], they are to date not
economically compatible with acrylates from petrochemical feed-
stock. As a result, the acrylate components in UV-curing inks are
rarely derived from renewable resources.
Because of that and the health concerns outlined above, finding
alternatives to acrylates from renewable resources is a challenge
for both academic and industrial research and would be of high
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5
industry.
3. Concluding remarks
This work aimed to give an overview on renewable resources
in the manufacturing of printing inks and recent research activities
in this field. There is a clear trend in industry as well as academia
nomic reasons, driven by a growing demand of consumers for more
sustainable technologies. This resulted in the commercialization
of several new renewable inks. Despite this progress, there is still
further room for improvement. At the moment renewable binder
precursors are almost exclusively made from vegetable oils. How-
ever, the use of these oils directly competes with food production.
Therefore the identification of renewable alternatives that can be
employed in the production of printing inks is of great importance.
Special emphasis should be placed on the utilization of “waste”
materials, such as products from side streams of established indus-
trial processes or secondary ingredients from the production of
food or fodder. These include lignin, (hemi)cellulose or polyphe-
nols to name but a few. Despite a considerable amount of research
amount of materials of this type are to date commercially avail-
able. However, the examples outlined in this article using these
compounds already showed their potential and applicability as raw
materials in printing inks.
In the field of UV-curing inks, only a few examples based on
renewable resources have been described so far. With the mar-
ket potential of these inks in mind, further research is of great
importance. Due to the disadvantages of the UV-curing inks that
are currently used (see Section 2.2), acrylate-free as well as inks
with little or no reactive diluents would be desirable. This could
be achieved either by using cationic polymerization methods or by
identifying alternative materials that can be used in radical poly-
merization reactions.
It is important to keep in mind that the increasing utilization
of renewable resources does not only contribute to more resource
security and a higher degree of sustainability within the indus-
try. It might also lead to the identification of new materials having
properties that cannot be achieved by materials derived from petro-
chemical feedstock.
References
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[2] Based on an internet search in 2014.
[3] H. Kipphan, Handbuch der Printmedien, Springer Verlag, Heidelberg, 2000.
[4] (a) H.E. Adams, P.O. Powers, Ind. Eng. Chem. 36 (1944) 1124–1127;
(b) P.O. Powers, J. Am. Oil Chem. Soc. 27 (1950) 468–472.
[5] R. Leach, R. Pierce (Eds.), The Printing Ink Manual, 5th ed., Springer Verlag,
Heidelberg, 1993.
[6] (a) J.T. Moynihan, Printing Ink, American Newspaper Publishers Association,
1983, US04419132;
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