RESEARCH ARTICLE

Producing Food Packaging Printing Ink via Green

Emulsion Aggregation Method
PREFACE API 2015
Maryam Ataeefard Shohre Rouhani
Institute for Color Science and Technology Institute for Colour Science and Technology
[email protected] [email protected]

ABSTRACT

Digital printing will become more and more important in the packaging industry. Digital printing
technology is growing because it allows the print suppliers to improve the level of service they offering
to their customers, as well as, it opens new opportunities and helps them to make more money. Additives,
dyestuffs, resin and other chemicals in packaging printing ink may influence safety of the food.
Therefore, choosing suitable materials are very important in food packing ink. Over the last years, many
printing ink manufacturers moved toward more sustainable inks. Drivers for this development, besides
the resource scarcity and a higher legislative burden, are an increasing environmental awareness
throughout the population and as a result a growing demand for inks with a small ecological footprint.
In this regard, in this research due to the importance of electrophotographic printing in the printing
industry, for the first-time we try to produce food packing ink for electrophotographic printing called
toner by an eco-friendly EA method. The results show that, within the design of the toner, choosing
suitable raw materials resulting in a toner with various color and appropriate toner properties.

KEY WORDS Printing, Packaging, Food-grade dyes, Toner

1.0 INTRODUCTION printing. Therefore, the printing ink market is

growing by 3% per year leading to an increasing in
In spite of the increasing importance of digital demand for traditional as well as new printing inks.
media over the last decades, printing still plays an In addition, resource scarcity, increased legislative
important role in our daily lives and, for example, burden, and rising environmental awareness force
more than one million tons of ink is annually ink manufactures to develop more sustainable inks
produced in Europe (EuPIA 2012). Even though particularly for special applications such as packing
the market for printed media is declining, there is (Robert 2015).
an increasing demand for inks in other areas of the Printing inks are used to print on many differ-
printing industry, such as packaging and digital ent kinds of food packages (Leach 2007). During

Producing Food Packaging 23

the last years, very intense studies were carried out has been acceptable for use in foods (Innovateus).
to evaluate the potential of using digital printing There are many aspects in food safety. The toxi-
techniques for packaging applications (Rosenberger cology of the toner components plays an impor-
and Boensch 2001). The reasons for doing this were tant role as well. However, with migration being
so obvious and they still are due to achieve an eco- a pivotal concern, dry toner does have an intrinsic
nomically affordable potential of making a short run advantage over other digital technologies. Migra-
for the test-sales. Having the opportunity of printing tion depends on several factors, a major one is the
fully variable information can be used for produc- size of the potential migrant molecule: The larger
ing more different consumer packaging or labels, in the molecule, the lower its mobility, and the less its
order to satisfy (and promote) the collector’s mania tendency to migrate from one layer to another. The
of especially children (Deprez and Rosenberger potential migrants differ depending on the digital
2003). Among all digital printing, the only technol- print technology. In toner, the pigment particles are
ogy that can deal with the desired printing speeds encapsulated in a high molecular weight polymer,
and image quality is electrophotography (Rosen therefore the migration decreases (Deprez 2012).
and Ohta 2006). C.F. Carlson (Pell 1999) invented Although, it is very important to choose appro-
Electrophotographic printing in 1938 as a copying priate component and integrant for food packag-
technology. This technology currently is in a high ing ink. The European Printing Ink Association
demand, and can be considered as the latest genera- (EuPIA) (EUPIA 2011) regulates the use of printing
tion of publishing and printing industry (Marshall inks for food packaging. Even only allowed mate-
1997). This method has attracted a lot of attention rials can be used in the manufacture of food pack-
in the recent years as one of the major technologies aging inks such as additives, colorants, (pigments,
for document printing and a wide range of market dyes), pigment additives, polymeric resins, solvents
applications (Galliford 2008). Today, the total cost of or photo-initiators (Aznar et al. 2015).
ownership, convenience and quality, favor this tech- In a previous work, author investigated the
nology over other alternatives in many applications effect of mixing time, agitation speed, monomers
(Ataeefard and Saeb 2015). Toner considered as the ratio, carbon black content, surfactant concentra-
ink in digital electrophotographic printing, is poly- tion, magnetite and colorant on toner properties
meric particles compose of a polymeric resin as the produced with various methods (Andami et al.
main component, and various ingredients. The toner 2016; Ataeefard 2015). Authors also produce toner
particles comprise at least one coloring substance with special applications such as antibacterial,
such as black and/or other colored substances, such fluorescence and ceramic toner (Ataeefard 2016;
as colored pigments (Bazrafshan et al. 2015). Ataeefard and Arabi 2014; Ataeefard and Nourmo-
In order to apply electrophotographic tech- hammadian 2015). In the current work, we report
niques for food packaging, the ingredients of the an environmentally friendly fabrication method
toner need to satisfy the particular standards that called emulsion aggregation (EA) for producing
are not generally required for other applications. For electrophotographic food-grade printing toner. The
example, although various materials may be used to recently developed technique, known as emulsion
coat or mark pharmaceutical products, such mate- aggregation (EA), was a chemically controlled
rials would not necessarily be acceptable for food process with the ability to yield toners exhibiting
products (Pedersen et al. 2012). By “food-grade”, in small particle size with narrow distribution and
reference to a component, means that the component uniform shape. The importance of this method is

Journal of Applied Packaging Research 24

indeed because of being environmentally friendly Table 1: Characteristics and structures of food
of both the process and resulting product. grade dyes used for packaging toner preparing
In this regard, for the first time, 12 various
kind of food-grade dyestuffs were used to prepare
monodisperse semi-spherical composite with poly
(styrene-co-acrylic acid) by using an eco-friendly
EA method, which can be used as the food packing
electrophotographic printing ink.

2.0 MATERIAL AND METHODS

2.1 Materials
The polymer used in this study was a styrene-
acrylic ;latex (R579; ResinFam Co., Iran) with a
pH value of around 9, and Tg (glass transition tem-
perature) of 51°C, and mean particle size of 220
nm, according to the specification provided by the
supplier. A polyethylene emulsion wax was pur-
chased from Kala Kar (EE 95, Kala Kar Co., Iran).
Polyaluminum chloride from Merck Company was
used as a coagulating agent. All the mentioned
materials were used as received.
The characteristics of 12 food-grade dyes used
for toner preparing in this study has been illustrated
in Table 1.

2.2 Preparation of Packaging Printing Toner

Toner particles were produced via a stepwise
procedure, in accordance with previous studies
(Ataeefard and Saeb 2015; Bazrafshan et al. 2015).
First (step a), a 1 L beaker was filled with 24.5 g
styrene-acrylic latex, 2 g carbon black, 3 g wax,
and 120 g deionized water and the contents were
manually mixed at room temperature for about 15
min. In step b, the resulting suspension obtained in
a, mixed using a homogenizer for 5 min. Next step,
c, was started by continuous mixing of ingredients
at room temperature for about 1 h followed by the of the mixture to 2. In this manner, forming a gel
addition of a solution of 0.6 g coagulation agent in was observed, as a result of a change in the visco-
nitric acid over 10 min until reaching the pH value elastic nature of the suspension from a Newtonian

Producing Food Packaging 25

 Figure 1: Schematic of toner preparing method Table 2: Image of food-grade dyes and produced
toners
water-like fluid to a shear-thinning paste-like gel. In
step d, the temperature of the mixture rose to 50°C
for about 30 min while the gel was continuously
mixed. The mixture was held at this temperature
for another 60 min in step e, where the temperature
of the mixture increased to 96°C for 30 min. The
last step, denoted as g, was started by holding the
product of step f, at 96°C for a further 60 min. Fig
1 shows the schematic of toner preparing method.
The ultimate mixture was neutralized with
sodium hydroxide solution and cooled down to
25°C, then the produced microparticles were
isolated from the water, washed to remove divalent
ions, filtered, and dried using a frizzed dryer.
Table 2 shows food-grade dyes and produced
packaging toners.
The obtained toner were printed in a controlled
environment [23°C, 50% relative humidity (RH)]

Journal of Applied Packaging Research 26

using a monochrome laser-jet printer (HP 1100, toward yellow; and a negative ∆b* indicates a color
Laser-jet printer). This printer was changed; in shift toward blue (Fairchild 2005).
order to only have hot roll fusing system contain- The obtained color toners were centrifuged
ing two metal rolls covered with silicone rubber and and dispersed in water followed by a sonication
was heated from inside the rolls. for about two minutes in order to break aggrega-
tions. The dispersions were prepared for analyses of
2.3 Characterization of food grade dyes and
particle size and the measurements of particle size
food grade printing toner
distribution by using particle size analyzer (PSA,
The reflectance measurement of the dye and Malvern Rasterizer 2000, England) in the range of
toner was performed in the range of 380 -780 nm 0.02-2000μm. The evaluation of the particle size
with 10 nm intervals using a GretagMacbeth Color distribution (PSD) was normally achieved through
Eye 7000A spectrophotometer (USA), an instru- the span parameter, as follows:
ment with 8/d geometry in a specular component Where D50 denotes the diameter (μm) at which
including (SCI) mode. Then it transformed into half of the particles have a size below this value.
CIE LAB colorimetric coordinates (L*, a*, b*) by Similarly, D90 and 10 were defined.
using CIE standard illuminant D65 and a CIE 1964 Morphology of the pigmented composite toners
standard colorimetric observer. All measurements was studied by scanning electron microscopy (SEM,
were carried out on five different positions of each KYKY-EM3200, China).
sample, and the average value was reported. An Thermal behavior of the toner was conducted
increase in L* indicates the lightening of a sample. on a differential scanning calorimeter (DSC, Perki-
A positive ∆a* signified a color shift toward red; a nElmer USA). Approximately 5 mg of each sample
negative ∆a* signifies a color shift toward green. was loaded onto a pan and sealed with a covering
Similarly, a positive ∆b* signifies a color shift lid. The measurements were performed over a

Figure 2: (A) the colorimetric coordinates (L*, a*, b*) of the food grade dyes (D1 to D12) and toners (T1 to
T12) and (B) 2D projection of them

Producing Food Packaging 27

temperature range of 0-150 °C at a heating rate of
10 °C/min in an atmosphere of nitrogen.

3.0 RESULT AND DISCUSSION

Fig 2A shows the colorimetric coordinates

(L*, a*, b*) of the food-grade dye (D1 to D12) and
packaging toner (T1 to T12) and 2D projection of
it (Fig 2B).
Although, we tried to choose color in the various
range of color contain blue and brown. The results
showed that the most of food packing toner colors
located in the yellow and red region of the CIE
LAB color space due to its large positive amount
of b and a. Colors often have different meanings in Figure 3: The color difference between food grade
various cultures. And even in Western societies, the dyes (D1 to D12) and toners (T1 to T12)
meanings of various colors have changed over the
years .While blue is one of the most popular colors (L*) due to using white acrylic resin with a high
it is one of the least appetizing. Blue food is rare amount of lightness.
in nature. Food researchers say that when humans In general, the physical properties of the toner
searched for food, they learned to avoid toxic or particles including shape, particle size and particle
spoiled objects, which were often blue, black, or size distribution play a vital role in determining the
purple. When food dyed blue is served to study quality of digital printing created by photocopiers
subjects, they lose appetite. Green, brown, and red and laser printers (Kmiecik-Lawrynowicz 2003).
are the most popular food colors (Johnson 2007). Fig 4 shows the SEM micrographs of the three
The color difference results between toners selected packaging toner particles (T9 as cyan toner,
and dyes showed that introducing the dye into T11 as magenta toner and T7 as yellow toner). It
the resin to produce toner would change the color can be seen that the toner particles formed from a
characteristics. Fig 3 results show that almost completely spherical shape to an almost spherical
all samples have shown an increase in lightness shape or potato shape. Moreover, SEM images of

Figure 4: SEM image of three selected packaging toner particles (T9 as cyan toner, T11 as magenta toner
and T7 as yellow toner)

Producing Food Packaging 28

toners show that the particles have a rough surface. direct effect on the fixing properties of toners onto
This phenomenon can be attributed to the particu- the paper substrate. A moderate Tg value is gen-
lar surface tensions of the toner’s constituents that erally required for the toner to have appropriate
have resulted from the migration of the dyes from fixing properties. A too high Tg would result in a
the inner part of the particle to the surface (Baz- large-scale energy consumption during the printing
rafshan et al. 2014). Therefore, as the compatibility process, and a too low Tg causes the toner to stick to
of a polar dye with the toner medium is high, the the printer cartridge. For an industrial toner, to have
dyes migration to the surface and the toner surface suitable fixing properties for an energy-efficient
roughness have reduced. laser printing, Tg should normally be in the range
With Regard to the difference in the obtained of 50 to 70°C (Einarsson 2002). The results of DSC
SEM micrographs and toner particle shapes and analysis show a packaging toner between 60-80°C.
roughness (Fig), D11, is more polar than two others The results show that the Tg (endothermic event in
dyes, and revealed a better compatibility with the the DSC diagram) is in an appropriate range. There-
toner medium. Consequently, toner with desired fore, changing the dyes did not affect the thermal
spherical particles could be obtained. A compari- properties of toner.
son between toner with T7 and T9 dye showed that Fig 5 shows the decomposition (TGA and
D7 is more compatible with the toner medium and DTG) diagram of packaging and original toner. All
caused to produce a toner with more spherical shape toner has followed one main decomposition step
than D9. In the previous study (Bazrafshan et al. at around 400 °C confirmed by derivative thermo-
2014; Bazrafshan et al. 2015), the authors showed gravimetric (DTG). Packaging and original toner
that the physicochemical properties (polarity and also show almost different decomposition rate, and
compatibility) of pigments do not affect the toner starting decomposing temperature (Tonset). Among
shape, while the physicochemical properties of dyes all toners, the fastest rate of decomposition and the
significantly affect the toner shape. lowest Tonset belong to the produced toner with D7
The thermal characteristics of the packaging dyes, and the slowest rate of decomposition and the
toners, namely Tg (glass transition temperature), highest Tonset belong to the original toner.
are important. This importance is due to having a After the thermal decomposition of organic

Figure 5: TGA and DTG image of three selected packaging toner particles (T9 as cyan toner, T11 as magenta
toner and T7 as yellow toner) and original toner

Producing Food Packaging 29

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4.0 CONCLUSION acrylic co-polymer: Investigation on
the effect of variation in components J
The aim of this work was to produce packag- Compos Mater 49:1553-1561
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