CHAPTER 9

Flexographic inks

The process of printing now known as flexography originated during the

latter part of the 19th century. This process which was first called aniline
printing used simple inks that were water or alcohol solutions of coal-tar
dyes derived from aniline oil, the substrate being paper generally for bag
making.
Commercial printing started in the early part of this century and the
method was primarily used on the paper bag-making machine as a tail
end printer, the print being hand synchronized with the bag-producing
operation. Around the time of World War I press manufacturers began to
make equipment to satisfy the needs of printers and paper converters.
Since the equipment was somewhat basic at that time a number of users
manufactured their own aniline printers to link up with bag machines.
The name flexography and its adjective flexographic were adopted
much later in 1952 after the process had made considerable progress
with improved print quality, press design, inks and a much wider range
of work and substrates. The original name aniline together with aniline
inks had chemical and toxicological association with coal-tar products
which had been superseded. The process required a changed image not
tied to its old bag-making origins. The original definition of the term
flexographic became ‘a method of rotary letterpress printing which
employs rubber plates and rapid drying inks’. Since 1952 flexography
has made further rapid strides and is used to print an increasing share of
packaging and flexible packaging material to which it is ideally suited.
The range of materials for different end applications printed by the
process is extensive. The principal materials are for packaging. In addition
to the original paper bags the products include polyethylene bags and
sacks, reels of paper, board, foil and films of all types. The reels can be
converted either in-line as bags or boxes or subsequently used as slit or
trimmed reels on various packaging machines to wrap or shape around
food and other packaged items.
As well as packaging, the process is widely used to print stationery
materials, tickets, coupons, forms, paper-backed books, children’s comic
papers and newspapers. Other applications are small labels on specially
designed machines for adhesive, gummed and heat sealable types.
548 FLEXOGRAPHIC INKS

Disposable products are printed and examples of these are paper cups,
kitchen towels, cloths and toilet tissue. Wallpaper and plastic wall cover-
ings, gift wrap substrates, decorative materials, strappings and adhesive
tapes are also printed together with a number of other products.

Process fundamentals
The flexographic printing process is described in detail in Chapter 2 of this
manual. Basically similar to rotary letterpress printing it uses a raised
printing surface made of a flexible material to transfer an ink image to the
substrate. The flexible surface is able to transfer a good image even to
rough substrates. The ink is contained in a duct and metered into a thin
film often by the use of two rollers (Fig. 9.1). The first roller (A) called the
duct or fountain roller can be metal or rubber and is mounted in the duct
partly immersed in ink; this roller rotates normally at a slower speed than
the second roller (B) called the forme or transfer roller. The second roller
can be made of rubber or metal but not of the same material as the duct
roller. On modern presses the transfer roller is an engraved anilox metal
or ceramic roller and is likely to be fitted with a doctor blade for better ink
film thickness control. Originally the pressure between these two rollers
was the only means of film thickness metering.
The ink film this controlled is transferred by contact to the plate or
stereo roller (C) which in turn transfers the ink image to the substrate
web which is held against an impression cyclinder (D) normally made of
rubber.
The improvements made by a number of different methods to control
the film of ink, have over the years transformed the process. The use of
engraved rollers, of trailing and reverse blades, the ability to vary the ratio
of rotation of the duct and transfer roller, more refined engineering,
improved register control for stack presses and the use of central

Fig. 9.1 A typical flexographic printing unit.

GENERAL CHARACTERISTICS OF THE INKS 549
impression machines have all contributed. Added to these are develop-
ments in alternative stereo materials which have stimulated counter
developments with rubber stereos, inks, drying and web handling, etc.,
all of which have allowed the flexographic printing method to continue
to improve its quality and make the dramatic growth of recent years.
In general the improvements in design, particularly those which have
affected ink application and drying, have allowed the inkmaker to offer a
wider choice of inks which will print by the process and thus increase the
possibilities of making suitable inks for difficult substrates with better
end-use resistance properties. There are, however, still a number of
flexographic machines of the older type giving good service that do not
have many sophisticated features and the ink formulator should remem-
ber that some of the latest inks while perfectly satisfactory for a modern
press may cause problems on these old machines. In general press design
is as important to formulation as considerations of substrate and end use.

9.1 GENERAL CHARACTERISTICS OF THE INKS

There are a number of fundamental properties required of flexographic
inks that are determined by the nature of the printing process and
the conditions and forces met during printing; in addition there are the
requirements of the printed article and the use to which it is put.
The flexographic process did not originate and was not developed
over the course of time in isolation. Considerations of ink performance,
properties and limitations have played their part in the concept and
improvement of the process alongside other products used by the printing
industry.
Flexographic ink technology has also made considerable progress over
the years and continues to advance. Ink consists of three main constitu-
ents – colourant, binder and solvent – and the variation and choice of
these components, their properties and interactions will be covered in
detail later, but for the moment, examination of the general characteris-
tics of the ink and how these relate to the requirements of the process and
its products will assist in an understanding of the basis of ink technology.

Fluidity
A necessary property of a flexographic ink on the press is that it be a free-
flowing liquid and that it should remain in this state until deposited on
the substrate. The ink as supplied may require reduction with solvent to
adjust the viscosity for printing. On most presses the reservoir is sited
below the level of the printing unit. The ink is pumped into the duct
which is fitted with an overflow to keep the ink at a set level consistent
with the position of the inking roller. The surplus ink is thus under
constant recirculation by pumping and gravity fall, requiring a fluid
state. The action of inking rollers and nips and the doctor blades also
requires fluidity and on many presses the agitation can be considerable.
During recirculation of the ink through the unit, contact with the
atmosphere in the duct and on the rollers causes some of the solvent to
550 FLEXOGRAPHIC INKS

evaporate with a consequential increase of ink viscosity. This will cause

an increase in film weight on the stereo as will be seen later, and it
becomes necessary to replace the loss by the addition of a suitable solvent.
This can be done manually by viscosity checks during the run adding
solvent to correct or better still by the use of automatic viscosity control
equipment.
Dye-based inks satisfy the fluidity requirement best of all since the solid
content of the ink (colourant and binder) tend to be low when compared
with other inks. Moreover, evaporation of the solvent with dye inks does
not cause significant increases in viscosity (which is already close to that
of solvent) and the losses are noticed more by an increase in colour
strength of the print, due to a higher ratio of dye to solvent.
In contrast to organic solvent inks, water-based systems have the
advantage of losing little solvent by evaporation and thus require less
adjustment.

Viscosity
Ink viscosity control is important in flexography, particularly as a means
of maintaining the print density during the run. The actual printing
viscosity chosen for a particular job will depend upon a number of factors
among which are press speed, substrate, type of metering, temperature,
solvent mix and print thickness required. In practice satisfactory print can
be achieved over a wider range of viscosity than is the case with the
gravure process. The image as deposited on the substrate is faithfully
reproduced from the stereo after contact resulting, within reasonable
limits, in a satisfactory print.
Printers tend to use viscosity adjustment and the addition of solvent as
a means of controlling colour strength of the print. As solvent is added to
the ink there are two effects: first, a reduction of colour concentration due
to the increased volume, and secondly, the lower viscosity of the diluted
ink will give rise to lower sheer forces applied during metering and a
decrease in film weight will result. This second effect is more apparent
with simple roller nip metering.
Press speed will also influence the viscosity requirement of the ink. As
speed increases sheer forces will also increase and the film weight of ink
carried will correspondingly increase. A greater volume of solvent will
need to be added to maintain the same print density. This is well known
by printers and can cause problems since slow running during proofing at
the start of a job will require the use of a thicker ink than is used on the
run to give equivalent print density.
The control of colour strength and ink film weight by viscosity is a
perfectly satisfactory method but care should be taken to avoid the
extreme limits. Over-dilution may cause the print to suffer in appearance
and lose abrasion resistance and the viscosity reading is of less signifi-
cance as this moves closer to that of the solvent. At very high viscosities
print definition and dirty working on fine type can occur and viscosity
control is difficult due to wide variation as solvent is lost during the run.
The use of a medium (non-coloured ink) to weaken excessively strong inks
and the addition of a concentrated toner to a weak ink are ways of keeping
GENERAL CHARACTERISTICS OF THE INKS 551
the viscosity within the closer limits necessary for good quality printing,
particularly with halftone.

Transfer
The more sophisticated ink metering becomes with reverse angle bladed
anilox rollers, etc., the less do press speed and sheer forces affect film
weight but with more simple metering the transfer properties of ink will
alter the weight carried. Dependent upon the choice of ingredients used
in the ink, tack properties and wet adhereance to rollers, stereo and
substrate will vary extensively with each formulation and these will affect
the amount of ink transferred to the substrate. Of the ink components the
binder has the most influence on these properties and increases in con-
centration and molecular weight increase transfer.
Surface energy of the substrate can affect transfer and for good transfer
this needs to be at a higher level than that of the ink.
The transfer properties of different formulations and resins can be
compared in the laboratory by a side by side application of two inks using
a hand anilox proofer, first ensuring that the strength and viscosity are
equal. The transfer property of an ink has importance in formulation and
the use of the hand anilox applicator for colour matching can be a better
method of laboratory assessment than other hand applicators not related
to flexographic ink metering.

Colour and strength

The colour and strength of a flexographic print will be determined by the
ink film thickness applied to the substrate and the type and concentration
of colourant used in the formulation. The wet ink film thickness will, in
practice, vary over a wide range of approximately 2–15 mm, dependent
upon press, metering, substrate and, not least, the working practice of the
printer. On average the film thickness is lower than with gravure and a
stronger ink is required to obtain a satisfactory coverage.
Since ink film thickness varies widely it is difficult to be precise when
deciding colour concentration during formulation. The normal practice is
to supply an ink at higher viscosity and of greater strength than is likely to
be required on the printing press, thereby allowing solvent and reducing
medium adjustments to be made. Experience and knowledge of the
equipment and practice used by different printers can also be usefully
considered when formulating inks of suitable strength and colour.

Stereo composition
Materials used to manufacture stereos have a considerable influence on
the choice of solvent used in the ink. Those in use are various; natural
and synthetic rubbers, photopolymer compounds and occasionally plas-
tics have been utilized. In general, both water and ethanol will be suitable
for all materials but modern flexographic requirements with many
substrates and different and uses for the print lead to the use of many
552 FLEXOGRAPHIC INKS

other solvents to widen the range of resins beyond those that are soluble
in water and ethanol alone. A number of these solvents can swell or
dissolve certain stereo composition materials. Table 9.1 gives an indica-
tion of the suitability or otherwise of different solvents for some of the
more common materials in current use. The table should be only used as
a general guide since both photopolymer and rubber compounds will
vary in their solubility properties. Many inks are based on a blend of
different solvents and a particular solvent may be used in a formulation at
low concentration with no adverse effects, even though on its own it may
be aggressive to the stereo. Stereo manufacturers are usually pleased to
provide data on solvent resistance for their compounds.
The restrictions placed upon the selection of certain solvents, particu-
larly with the use of the more soluble photopolymer materials, can create
a limitation on the choice of binder for the ink. This may conflict with
requirements for adhesion on difficult substrates or end-use resistance.
These conflicting demands cannot always be simply resolved by ink
formulation.

Table 9.1 Solvent resistance of stereo materials

Solvent Natural Nitrile Butyl Photopolymer
rubber rubber rubber plate
Alcohols
Ethyl alcohol R R R R
Isopropyl alcohol R R R R
n-propyl alcohol R R R R
Esters
Ethyl acetate N N R N
Isopropyl acetate N N R N
n-propyl acetate N N R N
Ketones
Acetone C N R C
Methyl ethyl ketone N N R N
Methyl cyclohexanone N N R N
Glycol ether
Methoxy propanol R R R R
Ethoxy propanol R R R R
Aromatic hydrocarbons
Toluene N C N N
Xylene N C N N
Aliphatic hydrocarbons
SBP 3 N R N N
Water R R R R
R ¼ recommended; C ¼ caution; N ¼ not recommended.
GENERAL CHARACTERISTICS OF THE INKS 553

Print characteristics
Ink will have a basic colour requirement and in addition may need to be
glossy, matt, opaque or transparent dependent upon the design, substrate
or job. The appearance of the print with good definition for halftone and
type and good lay on solids are important considerations. The improve-
ments in the process have helped ink printability although good print
design, which takes account of the strengths and weaknesses of the
process, are equally necessary. There can be conflicts on film weight
requirements of solids and halftone and when these are on the same
stereo, difficulties can result. Ink characteristics will also affect print
quality and desirable features are good flow, wetting and good resolubil-
ity properties. Dye-based inks satisfy these needs and strong colours with
high resolubility are easy to achieve.
Dye inks have limited fastness and most inks are now based on insolu-
ble colourants and more care during manufacture and formulation is
required to make pigmented inks with good printability. This is normally
achieved but problems can be met when the formulation limits are
stretched, examples being (a) excessive pigment loading reducing flow
characteristics and (b) use of low solubility binders with high end-use
resistance properties leading to dirty working.
After deposition on the substrate the ink is required to dry very rapidly
this being most acute on a central impression multicolour press where the
gap between print units is only a few inches and at high press speeds the
time allowed for drying is a fraction of a second. Since flexography is
unsuitable for wet-on-wet printing, drying, by penetration with absorb-
ent substrates or, otherwise, by solvent evaporation has to be achieved
instantly between colours. Thus modern drying equipment with high-
velocity heated air has become normal practice.
Solvents used in the ink need to be volatile but a balance must be struck
between satisfactory drying of the print and premature drying on the
stereo which would otherwise affect print quality. Printing water-based
inks on absorbent materials will most easily satisfy these requirements.
Overprinting colour on colour causes most drying problems as there is a
tendency for solvent in the overprinting colour to resolubilize the first
down colour and become trapped into the double layer which is less easily
dried. With water-based inks overprint colour drying can also be a prob-
lem but the cause in this case is also due to the lower volatility of water.
The choice of solvent in the ink and the diluent used on the press have a
significant bearing on drying and blends of solvent may be used to achieve
the desired result. The binder used will also influence the evaporation of
solvent as resins have different solvent release properties. Some drying will
occur on the stereo and it is important that this redissolves on the next
revolution or poor image definition and dirty working could result.

Adhesion and end use

Consideration of the substrate to be printed is of fundamental importance
to formulation and this is particularly the case with non-permeable
554 FLEXOGRAPHIC INKS

substrates where ink adhesion properties are critical. With paper printing
adhesion is given by the penetration of the ink into the paper surface. In
the case of non-absorbent substrates adhesion must be achieved by other
means, therefore, and chemical and physical bonds and wetting between
the surface of the substrate and the ink are important.
Of all the ink constituents the binder is the most important for adhe-
sion, thus a suitable resin will be needed to confer adhesion to the
particular substrate. Each type of substrate will present different problems
and sometimes a combination of resins may be needed to give both
adhesion and a balance of other ink properties. In general the more
inert the substrate surface the more difficult it will be to obtain adhesion.
The end-use conditions of the print have a particular bearing on for-
mulation when making inks for packaging. There may be requirements
during the packing or processing for resistance to heat sealing, non-
adherence to reverse printed lacquers or adhesives, or for particular
surface slip characteristics. The print may have to resist packaged prod-
ucts during storage of the pack and these may contain various compo-
nents such as water, oils, fats, soap detergent, etc. Particular conditions of
storage such as deep-freeze may affect the print.
The choice of colourant will depend on the specification for bleed and
fastness, and in general, dyestuffs and soluble pigments will be excluded
from work with high requirements. The binder selected will need to have
suitable resistance properties and many packaged products will soften
certain resins resulting in a loss of adhesion or transfer of colour. Solvents
will not normally affect resistance properties although resistant binders
generally need stronger solvent mixtures for their solubility.

9.2 PHYSICAL PROPERTIES OF FLEXOGRAPHIC

INKS AND THEIR MEASUREMENT
The measurement of the physical properties of flexographic inks and an
understanding of how these properties are affected by the choice of
ingredients and their interaction is a large part of ink technology. These
measurements are ideally conducted alongside a study of ink perform-
ance on the press and in this way a relationship of properties and result-
ant performance can be built up by the ink formulator and subsequently
used to improve inks and solve problems.
Measurement of print resistance properties must also be related to the
conditions of end use, but care should be taken when setting specifica-
tions to avoid unnecessary margins of safety, particularly as this could
lead to excessive restrictions on raw materials which may result in a
lower quality of print.

Viscosity and dilution measurement

Inks are normally supplied at a viscosity which is higher than needed for
printing, for two main reasons. First, to allow for adjustment on the press
by the printer and secondly to prevent pigment settlement during storage
PHYSICAL PROPERTIES OF FLEXOGRAPHIC INKS AND THEIR MEASUREMENT 555
which might occur with a thin ink. The importance of viscosity during
printing has been discussed and the normal method for measurement is
the efflux flow cup. This is a convenient method and is satisfactory for
low viscosity liquids but can give false results with thixotropic inks. On
the press it is helpful to allow the ink to circulate in the pump for a while
before taking the final viscosity reading as this will tend to break any ink
structure.
The temperature at which the viscosity is measured is important since
the ink, in general, will decrease in viscosity with a rise in temperature.
For the ink formulator a solvent-dilution curve will yield more infor-
mation than a simple viscosity measurement of the ink after manufac-
ture. This can easily be carried out by taking readings at different dilutions
and plotting the result as a graph. The graph shown gives typical results
for some different ink types. Generally the steeper the curve the less
solvent required to reach print viscosity and the stronger will be the
resultant print (Fig. 9.2).
The tack of a wet ink can have a marked effect on printing properties
and this will be more pronounced at high press speeds. While for oil inks
it is relatively easy to take measurements with a tackmeter this is difficult
with thin volatile flexographic inks. The effect of tack can be observed,
however, using the hand anilox proofer and an ink with high tack will
give more pull-though and strength.

Colour and strength testing

The colour and strength of a formulation must first match the agreed
standard and this level must be maintained with subsequent batches. The
ink film weight carried by the stereo is the governing factor affecting
colour strength and some experience or estimation of the likely print
weight will be needed when the colour is matched. A laboratory anilox
hand applicator is normally used to simulate the printed result but less
dilution with solvent will be required by hand proofing than with print-
ing due to the relatively slower speed of hand application.
Once the colour and strength has been established maintenance of later
batches to the same colour will be a more simple task. Side by side
applications against the standard sample can be made and corrections
carried out but viscosity differentials must be minimized or this will affect
the result. Strength comparisons can be made by the ‘white reduction’
test – by diluting one part of the colour with 20 parts of a compatible
white and comparing the result with the same test on the standard
sample. In addition to colour strength, opacity must be considered and it
should be noted that opaque inks tend to look stronger than those which
are transparent.
Batch samples of flexographic inks can and do tend to deteriorate on
standing particularly when they have been opened several times. It
becomes difficult over a long period to maintain a master standard sample
and rests tend to be carried out against the last batch sample. This can lead
to colour drift and it will be necessary also to retain proofs to avoid this
problem. Colour matching and batch passing can be carried out with the
aid of a colour computer and, although it will be necessary to pay
556 FLEXOGRAPHIC INKS

Fig. 9.2 Dilution–viscosity curve: (A) polyamide-based ink;

(B) cellulose nitrate-based ink; (C) water-based ink.

attention to proofing control, the problem of deteriorating samples can

thus be overcome.

Drying tests
With solvent-based inks there are a number of factors which will
influence the drying, the most important of these being the evaporation
rate of the solvents used and the solvent release characteristics of the
binder. Some resins will release certain types of solvent more rapidly than
others dependent upon their chemical make-up. A particular resin may
release a slower evaporating solvent in preference to a faster solvent
PHYSICAL PROPERTIES OF FLEXOGRAPHIC INKS AND THEIR MEASUREMENT 557
thereby reversing the expected drying rate of each. The hardness of the
binder will also affect the point at which the ink feels dry and tack free,
even though solvent may still be present in the ink film. High concentra-
tion of pigment and extender can improve drying, keeping the ink surface
open without skinning to assist evaporation. Various additives and
plasticizers can affect solvent release.
Drying properties can be compared in the laboratory by making com-
parative drawdowns and checking the relative time for the surface to
become tack free but some solvent may still be contained in the ink.
When testing it must always be remembered that on a press heat is
normally applied, this reducing the time taken for a print to dry. Under
laboratory conditions it is difficult to record results or make comparisons
when drying is very rapid, as is the case with heat-assisted drying.
Testing of the final state of solvent retention after printing is normally
carried out by the use of gas–liquid chromatography (GLC) and the
results are expressed as the amount of solvent present in each square
meter of print. The use of this equipment can be very informative in
ink-drying research.
Prints which are poorly dried can give rise to serious problems
in printing. First, the retained solvent can cause odour problems and
secondly, the presence of solvent can leave the resin in a semi-solid
state which is prone to block to the other side of the web. On certain
coated films a ghost image may form on the unprinted side caused by
solvent attack.
Water-based inks for paper and board dry mainly by penetration of
water into the substrate and only partly by evaporation. The speed of
drying is dependent upon the substrate absorbency and the type of resin/
water dispersion used in the formulation. The inks dry too rapidly for this
to be measured easily in the laboratory although a rough comparison can
be made against an ink of known performance by testing a drawdown on
the paper with one’s finger as they dry.
With water-based inks for non-permeable substrates drying occurs by
evaporation of the water, and any solubilizing amino compound con-
tained in the formulation. Comparisons of drying can be made in the
laboratory using similar methods given for solvent-based inks but again it
should be remembered that on the press any heat applied will reduce the
time taken.

Water-based inks – special tests

The properties of water-based inks are generally measured using similar
methods to those used for solvent inks, as has already been discussed.
Due to their special nature, additional tests for foaming and pH should be
made on water-based systems.
Foaming can give rise to problems on the press, particularly when the
design is such as to cause high agitation of the ink. A simple test of
vigorously shaking or stirring a diluted sample of ink for a period of time
will quickly determine any tendency to foam. Comparisons can be made
with a satisfactory standard ink and the time taken for the foam to subside
noted in each case.
558 FLEXOGRAPHIC INKS

Conventional water-based inks are alkaline, giving pH readings above

7. Using a standard pH meter inks can be tested and the normal satisfac-
tory range will be in the region of 8–9. Problems of stability can occur
with low readings, and poor ink drying may result if the pH is too high.
The type of formulation used, however, will influence the range for a
satisfactory pH and this can be determined by experiment.

Dispersion state
Pigmented inks exist as a dispersion and the state of dispersion is depend-
ent upon the formulation and the process of manufacture. The normal
method of measurement is the grinding gauge consisting of a metal
wedge graduated from 0 to 25 mm. The ink is drawn down the wedge
with a blade until pigment particles begin to form scratches. This is then
taken as the particle size. Care should be taken that the test is conducted
prior to the addition of waxes, etc. since these will interfere with the
result.
Other indications of the dispersion state are gloss, colour development
and transparency and these are monitored. Alterations in settings con-
trolling the conditions on milling equipment will give rise to variations in
quality of dispersion and careful monitoring will be needed to avoid batch
variations. Chip-based inks are more consistent from batch to batch than
with other methods of high dispersion. Chipping can, however, induce
loss of flow due to the high dispersion state achieved.
While processing plays a major part in producing a dispersion there is
a considerable influence and interdependence between the binder, pig-
ment and solvent. All are equally important to the final result particularly
with respect to the dispersion stability. Finding the optimum conditions
and formulation balance for maximizing dispersion for a particular prod-
uct can be time consuming involving many experiments. There is little
doubt that bulk manufacture of single pigment bases, leading to fewer
products milled, is to be preferred since in this way only a few products
have to be studied.
Stability of the dispersion is important, both with neat ink as supplied
and diluted ink as used on the press. Storage stability can be assessed by
an accelerated test at 508C for one week and dilution stability can be
tested by comparing a diluted sample left overnight with a freshly diluted
sample.

Adhesion and end-use tests

The adhesion of an ink to the substrate being printed must be of a
satisfactory level for the life of the printed article. Normally the level of
adhesion will not change after printing but occasionally on some sub-
strates certain chemical type inks systems will need a short time for full
adhesion to develop. On plastic films adhesion is often improved if some
heat is applied to the film while drying; heat may also aid wetting or cause
fusion of film coatings and ink resins. Once adhesion is achieved it is
normally stable and should not deterioriate with time. On the rare
PHYSICAL PROPERTIES OF FLEXOGRAPHIC INKS AND THEIR MEASUREMENT 559
occasions when this does happen it is usually associated with a change of
state of the substrate or ink components.
The most common test for adhesion is the adhesive tape test and
although it has the virtue of being simple to carry out there are a number
of variables. Attempts have been made to standardize the tests and test
conditions but it should be remembered that the test is dependent upon
the adhesion of the tape to the ink surface as well as adhesion of the ink
to the substrate. The result should therefore be viewed alongside other
tests, i.e. scuff resistance and scratch resistance, before a final conclusion
is reached.
With most presses being reel-to-reel, prints tend to be subjected to very
high pressure after rewind. With non-absorbent substrates where the ink
remains on the surface this pressure can cause blocking and it is necessary
to ensure that film inks have good block resistance. There are a number of
tests in the laboratory to simulate reel pressures by placing a test print
under a hydraulic ram, screw clamp or weight for a period of time and
observing if the print will block. Sometimes an elevated temperature is
used and this will increase the severity of the test but the temperature
chosen must not affect the substrate of its coating otherwise the results
will be invalid. In practice, 508C with most coated films would be a limit.
Much packaging is heat sealed and sealing is often applied in the
printed area of the pack. With reverse printing there will be no direct
ink-to-heated-jaw contact but, with surface printing, ink must not melt
or stick to the heat seal jaw. Test heat sealers are available and the
formulation must be such as to give the required properties. Surface-
printed ink is also required to have good rub resistance as packaged goods
will be handled and tend to rub together in transit. There are a number of
standard rub testers available.
Flexographic printing is widely used for packaging applications and the
properties required of the print to resist packaging, packaged products
and storage conditions can be diverse. It is common for the ink to be
printed on the outside of the substrate without the protection of an
overlacquer. Many packaged products can have a powerful solvent or
chemical action on the print and not all packaging materials are good
barriers to migration or seepage of wrapped substances through to the ink
layer.
Ink manufacturers will select their raw materials and formulations to
give the necessary properties being sought, but it is important that the
inkmaker be advised of the intended use of the ink and of any special
conditions or specifications. Data will have been previously assembled by
ink technicians of the resistance properties of raw materials and particular
formulations but it is often necessary to carry out specific tests involving
the substrate and the packed product or its active ingredients. On this
basis recommendations or advice on ink selection will be made.
Tests can be devised for ink and print to simulate the various conditions
of use and under ideal circumstances a specification is drawn up between
the packer, converter and inkmaker to agree on test methods and stand-
ards which are acceptable to all. Within this specification the ink, print
and package can be tested at all stages of manufacture and problems
avoided. There are cases where the degree of resistance provided is left to
560 FLEXOGRAPHIC INKS

the judgement of only one of the parties involved. It should be remem-

bered that the final performance of the pack will be dependent upon all of
the component parts and the conditions of printing and conversion.
The measurement of the physical properties of ink are clearly of prime
consideration during batch testing of inks with quality control and assur-
ance testing. All inks will be tested for colour, strength, adhesion and
dispersion and dependent upon the ink product type specific fastness or
end-use tests can be included. The decision regarding the extent of testing
will be governed by the importance of the test, the associated risks and
the time available during the manufacturing cycle. Every ink cannot be
tested for all possible conditions and a sensible choice will need to be
made of what constitutes a reasonable cover for good control. Systematic
manufacture of a rationalized range of known specification products
makes for a satisfactory resolution of this compromise.
Testing forms very much a part of the inkmaker’s responsibility and is
carried out to ensure that mistakes during making and blending are
detected. If the final stage of manufacture is a mixing, blending, operation
on the premises of a printer similar testing will be necessary for the same
reason. Normally a simple test procedure can be recommended.

9.3 FORMULATING PRINCIPLES

As previously mentioned, flexographic inks consist of three main ingre-
dients – colourant, binder and solvent – each having a different function
but dependent on the others. Additives of various types are also used to
impart other properties and as modifiers for the basic components to
widen the range of properties available.
In considering the selection of raw materials to manufacture different
inks the properties of each raw material must be known. Manufacturers
will supply data of fastness properties, solubility, compatibility and gen-
eral chemical constitution and this will assist the selection. In practice the
properties of raw materials will be affected by the other constituents in
the ink. For example, the fastness of a pigment may be improved by the
presence of certain resins used in the formulation. It will be necessary to
compile data for different ink systems which will show modified proper-
ties from that of the raw materials themselves.
The formulation of the ink will be influenced by a large number of
factors associated with the use of the ink and the printed job. These would
include: colour standard, finish required, type of press, ink metering,
drying equipment, stereo composition, substrate, print design, end use,
after processing of print and any specification requirement. In addition
there will be considerations of ink manufacturing equipment, batch size
and cost.
It is normal to classify inks into different named product types accord-
ing to formulation, substrate usage and properties rather than all inks
being bespoke for each job. To avoid the proliferation of many ink types
held in stock most users will want the inks they use to have the widest
possible use covering several substrates and applications. Distinct
product types with known and defined performance properties and
FORMULATING PRINCIPLES 561
limitations will make the selection of the correct ink easier without mis-
understandings. Products can also be manufactured in a planned manner
and with larger batches of fewer inks, better control can be exercised both
with raw material stocks and QC testing. The printing and packaging
industry, however, is subject to rapid changes and these may require
modified ink properties. Therefore, flexibility must also be preserved.
In order to consider the principles of flexographic ink formulation an
examination of the basic raw material ingredients and their behaviour in
the inks will be covered. Details of the properties, origin and chemistry of
raw materials will be found in Chapter 4.

Colourant – dyes
The most widely used dyes in flexographic inks are the basic dyes which
are salts of cationic dye bases (commonly hydrochlorides, sulphates, etc.).
Without modification they are very soluble in water and have some
solubility in alcohol, the alcohol solubility being improved considerably
when the dyes are ‘laked’ with tannic acid or synthetic mordants. Colour
strength is improved by laking and, depending upon the choice of mor-
dant, solubility in water is greatly decreased. Laking of the dye will
improve lightfastness, although this remains relatively poor, and bleed
resistance to wax, oil, water and glycerine will also improve. Dependent
upon the choice of mordant the optimum ratio to the dye will vary to
achieve maximum colour strength development.
Price considerations are important but with wide strengths variations
the lowest-cost mordant will not necessarily be the most economic.
Phenolic and other high acid-value resins are also used to lake dyes and
these can reduce the amount of mordant required together with improv-
ing transfer properties of the ink. Other modifications are made for inks
used on kitchen paper rolls to improve resistance to domestic chemicals.
Dye inks have near Newtonian flow and give low viscosity bright
colours with high strength and, on the press, printing is clean with
good drying at high speed. The inks are used for paper bags, waxed
bread wrappers and decorative wrapping paper. Semi-pigmented inks
are made by mixing dye with white or coloured pigment. The applications
of dye inks are for prints where lightfastness is not required and their
tendency to migrate and bleed will cause no problems. Generally these
inks are not used on plastic films. The basic dyestuffs most commonly
used are:

Basic Yellow CI 37
Basic Violet CI 14
Basic Green CI 1
Basic Red CI 1
Basic Blue CI 26
Basic Violet CI 10
Basic Violet CI 1

Lightfast dyes which are mainly metal complexes are available

that have improved fastness to light, fats, water and other chemicals.
562 FLEXOGRAPHIC INKS

Solubility and strength are much lower than with the basic dyestuffs and
the manufactures’ literature must be consulted with respect to solubility
and compatibility. Inks for foil and labels are made with these dyes and
they have been used for plastic films but there is a tendency to migrate
under some conditions. It should be remembered that their lower
strength can require higher concentration of dye and being soluble the
dye will become part of the binder so that the film-forming characteristics
must be considered.
Examples of these dyes are:
Solvent Yellow CI 19
Solvent Red CI 102
Solvent Orange CI 45
Solvent Blue CI 37

Colourant – Pigments
Note that the Dyes are listed here as their CI references.
Pigments used in flexographic inks have similar specification require-
ments to those used for other processes. Irrespective of the properties
required by the end use of the print, suitable pigments will be chosen for
their wettability and dispersion characteristics in the various solvent and
resin systems which are used. Generally what is being looked for is ease of
dispersion with stability on storage, good flow at high pigment concen-
tration and maximum colour strength at reasonable cost. Properties of
gloss, opacity and transparency will be important for certain applications.
The flow and dispersion characteristics will be dependent upon pigment
type but pigments of similar chemical constitution vary considerably depend-
ing upon the processing conditions used by the pigment makers and the
various additives and treatments of the pigment during manufacture.
Flexographic inks will vary widely in the solvents used (water to
aliphatic hydrocarbon) and in the resin types for the different ink ranges.
While it is desirable to use the same range of pigments for all inks the
dispersion and rheological behaviour will differ with each solvent/binder
system. In order to optimize the properties the pigments selected will tend
to vary somewhat for each range. Other inks may contain additives and
materials which are unstable in combination with certain pigments and
these factors will also have to be considered.
The following is a list of the main pigments which are particularly
suitable for flexographic inks.

Pigments Colour index

4B toner PR 57
2B toner PR 48
Lake Red C PR 53
Lithol Red PR 49
Iron oxide PR 101
Permanent Red R PR 4
Permanent Red 2G PO 5
FORMULATING PRINCIPLES 563
Pyrazolone Orange PO 13
Diaryl Yellows PY 12, 13, 14
Monoazo Yellows PY 3, 5, 98
Phthalocyanine Green PG 7
Phthalocyanine Blue (b form) PB 15
Ultramarine PB 62
Permanent Violet PV 23
Titanium dioxide PW 6
Carbon black (furnace/channel) PB 7
PMTA pink, green, blue, violet PR 81, PG 1,
PB 1, PV 3
Copper ferrocyanide dye complexes PR 169, PG 45,
PB 62, PV 27
Extenders
Blanc fixe PW 21
Calcium carbonate PW 18
China clay PW 19

Lead chromates are not listed on grounds of toxicity. Pigments other than
those listed would be required for increased specifications, for example,
soap wrappers, so that in general the choice of pigment will be influenced
by the end use of the print. Many inks will be made using a combination
of different pigments in order to achieve the desired shade. It is important
to remember that the resistance of the resultant mixture tends to be
governed by the least resistant component.
Extenders are used in flexographic inks particularly when tints or weak
shades are required but, in general with the low film weights carried by
the process, they are not extensively used.
Bronze and aluminium powders are also used to make metallic
shades and sometimes these are blended with colourants to produce
particular effects. When aluminium powder is combined with coloured
pigments or dyes the resultant mixture is described as a polychromatic. It
is more convenient for the printer that metallic inks be supplied as
a ready made mixed dispersion but care will need to be taken with the
choice of resin, solvent and additives to avoid instability problems which,
at their worst, can involve evolution of gas and heat generation. Where
there is any doubt, inks are supplied as a two-part mixture, powder
and varnish or past and varnish, to be mixed together just prior to
printing.

Resins
The function of the resin is to act as a carrier for the pigment or dye and
bind the colourant to the surface being printed giving adhesion. There are
a large number of resins available and the main restriction is that any
resin used should be soluble in solvents which do not adversely affect
stereo materials. This can be a severe restriction with some photopolymer
stereos.
With development, the number of resins available within each chem-
ical type has increased in recent years. The ink technician needs to keep
564 FLEXOGRAPHIC INKS

up to date with these developments and to be familiar with the properties

of the variations available. In general the requirements for the resin
are solubility in flexographic solvents, adhesion to substrates, good
pigment-wetting, good solvent release, good film-forming properties,
low odour, pale colour and compatibility with other resins. All resins
vary in their fulfilment of these properties and a resin may have
good adhesion properties but be a poor film former while another may
have poor solvent release but improved pigment wetting. To overcome
these difficulties and, because the perfect resin does not exist, blends
of resins are commonly used in ink formulation and in this way
a balanced range of properties can be incorporated into the ink.
The increasing number of resins used in a formulation will, however,
increase the possibilities of incompatibility and often increase the need for
powerful solvents to bridge, the solubility requirement of all the
resins used. Compatibility and solubility tests will be essential during
formulation.

Shellac
Early inks were restricted to a very limited range of natural resins and
shellac became the principal one used. Shellac has good pigment-wetting
properties, solubility and adhesion to a large number of substrates. It is
also compatible with dyes and will make good water-based inks when the
resin is saponified with a base. Shellac has, however, slow solvent release
properties and low heat resistance and is now very expensive. The resin,
although still used, has largely been replaced by alcohol-soluble maleic
and phenolics in pigmented paper and dye-based inks, although on other
substrates the film-forming properties of these substitutes are not as good
as shellac and other resins are used.

Nitrocellulose
The most common resin employed in solvent-based flexographic inks is
nitrocellulose which is cheap and readily available and also has many
other desirable features including good solvent release, low odour, good
pigment wetting, heat resistance and very wide compatibility. This com-
patibility allows the possibility of making inks for nearly all substrates by
the addition of other resins and plasticizer to the nitrocellulose. The
properties of nitrocellulose inks can thus differ widely, dependent upon
the particular modification. In these formulations nitrocellulose will nor-
mally confer pigment-wetting, drying, heat resistance and film-forming
properties while the modifications improve gloss and adhesion. Inks
made from pigmented nitrocellulose chips give further improvements in
gloss which is necessary for film and foil printing
Nitrocellulose is available in different grades and in flexographic inks. It
is normal to choose the alcohol-soluble grade, i.e. low nitrogen/low
viscosity. This will make it possible to use less ester which is damaging
to photopolymer plates.
The main limitation of the resin is firstly a tendency to react with
bronze powders with the evolution of hydrogen and, secondly, its sensi-
tivity to water contamination which can cause blushing of the print
whilst drying.
FORMULATING PRINCIPLES 565
Ethyl cellulose
Ethyl cellulose has similar properties to nitrocellulose in respect of heat
resistance, solvent release, film formation and odour. Unfortunately
however, the resin has a number of disadvantages and among these
would be included poor flow, high cost and high viscosity. This has
resulted in the use of ethyl cellulose being mainly confined to dye systems
with which it has good compatibility and gives improved drying with low
tack.

Cellulose acetate propionate

The third member of the cellulose family used in solvent inks is cellulose
acetate propionate (CAP). It is similar to nitrocellulose in many of its
properties but compatibility is more limited and more ester is required for
solution. The primary use is in inks for PVdC coated films where it is used
or in combination with acrylic resin to give low odour, heat resistant inks
with good adhesion. There are two main versions available, one being
more alcohol soluble than the other. CAP resin has a low tack level and
this gives inks which print best at the upper speed range. Chips are
available and with careful formulation free-flowing inks with good gloss
can be made.

Polyamide resins
These are widely used in flexographic inks and they have good adhesion
to many substrates. Pigment wetting is good and glossy inks can be made
without chips by judicial selection of pigments and processing. The resin
has a slight odour and low heat resistance.
Combinations with nitrocellulose are common. Many grades are avail-
able and these vary in solubility and compatibility and in general the
more alcohol tolerant the resin is, the softer it becomes. Early polyamide
inks required the use of aromatic solvents and the resins were described
as cosolvent types. Polyamide inks can now be made with ethyl alcohol as
the main solvent and these are suitable for photopolymer plates. They dry
to give a slippery waxy surface. The resin is not suitable for laminating
inks due to the inability of adhesives to adhere to the ink surface.

Acrylates and methacrylates

These resins in recent years have found increasing use in flexographic
inks over a wider area of formulations. The range of resins in the acrylic
family is large and the diversity of properties in both solvent and water
inks is wide.
In solvent inks the resins are primarily used for their good adhesion
properties and are also suitable as binders for metallic-pigmented inks.
Acrylic resins in combination with cellulose esters or nitrate are used in
inks for PVdC lacquer applications, certain lamination inks, PVC film inks
and inks for adhesive tapes. The resin requires a careful balance of solvent
as solubility can be difficult to achieve. Solvent release properties can vary
with resin type and allowance must be made for this when formulating.
Care must be exercised with the higher molecular weight acrylics as these
tend to string causing dirty working.
566 FLEXOGRAPHIC INKS

Polyacrylic and polymethacrylic acid resins were first used in conven-

tional water-based flexographic as a substitute for shellac (which had
become too expensive). The resin is used either as a sodium or amino salt
which is soluble in water or alternatively in an emulsion form. Most inks
for paper sacks and corrugated cases are of this type.
In recent years there has been much development of water-based inks
for film substrates and particular water-soluble acrylic resins are a basis of
much of this work. With films penetration drying is not possible and the inks
dry by evaporation of water and any volatile amino compound present.
Given the lower volativity of water the inks tend to dry more slowly
than solvent-based types. With careful formulation adequate results
can be achieved, as will be explained later, although the problem is less
easy to resolve when several colours are superimposed.
Styrene acrylics are used in their solvent soluble form in nitrocellulose
overprint varnishes to provide good gloss. In water-based inks these
resins may be used either as a solution or in a non-convertible emulsion
form where their good gloss and heat resistant properties are utilized.
The use of acrylic resins in inks and varnishes has become extensive
and furthermore somewhat complex, in both solvent and water systems.
The technician may find it an advantage to catalogue properties, perform-
ance and modifications of the many different types of these important
resins in order to optimize their use in formulations.

Polyvinyl butyral
Improved polyvinyl butyral resins have become available in recent years.
These have good film-forming properties, low odour level good adhesion
to some film substrates and solubility in alcohol. These properties make
the resin suitable in formulations for a number of inks used for lamin-
ation, cold-seal packaging applications and metallic pigmented systems.
The poor resistance however to heat and water prevents the resins being
used in a wide range of applications.

Other resins
Ketone resins are used in flexographic inks to assist gloss or aid adhesion
as they have good solubility and are inert. Low-odour versions are avail-
able although the film-forming properties of ketone resin is poor.
Other resins are polyvinyl acetate, polyvinyl chloride and the copoly-
mers of these which find their main use in PVC film inks and other
speciality applications. There are also a large number of additional resins
used as minor components of inks to impart special properties.

Solvents
The two other main constituents of the ink, colourant and binder are both
solids and therefore the prime function of the solvent is to convert the ink
into the fluid form which makes it capable of being printed. The solvent is
thus a carrier for the other ingredients but must be easily removed from
the print by evaporation and by penetration into the substrate.
The choice of solvent is governed by a number of factors. The resin used
in the ink will have specific solubility characteristics and, as is often the
FORMULATING PRINCIPLES 567
case, mixed resins with different solubility parameters will demand par-
ticular solvents or solvent mixtures. With flexography there will always
be a restriction of choice of solvent determined by the nature of the stereo
materials used. Some printers may specify the use of certain solvents
which, of course, may restrict resin choice. With inks for food packaging
certain solvents may be prescribed, particularly as retained solvents in
print after drying may represent an unacceptable risk of odour or taint
even in small quantities.
Solvent choice can also be influenced by the colourant. In the case of
dye inks there is a requirement for the solvent to dissolve the dye. With
pigmented ink however, flow characteristics are affected by the choice of
solvent, and a particular pigment may have better flow in one solvent and
worse in another. An example of this is the behaviour of diarylide yellows
which while satisfactory in alcohol solvents give very poor flowing inks
when based on ester solvents. Dispersion stability and colour strength
development may also vary with the choice of solvents used in the ink.
Another property of inks which is affected by the solvent is adhesion.
On coated films or those which are soluble, certain solvents may partly
dissolve the surface of the coating or film and this will tend to assist
adhesion. With non-soluble substrates and uncoated films, solvents can
also affect adhesion by increasing or decreasing wetting of the surface.
Adhesion is normally at its best when wetting is of a high order.
The balance of solvents used in an ink will be determined by a number
of factors already mentioned above. During printing, however, more
solvent will be added by the printer to adjust the ink to a suitable
viscosity. The volume used may be equal to that contained in the
undiluted ink. Thus the total composition must be considered when
formulating and recommending diluents. Solvent will be lost by evapor-
ation from the unit during printing and depending upon factors such as
vapour pressure, temperature, resin constitution, etc., the composition of
the evaporating mixture will vary. Should the evaporating mixture be at
variance with that contained in the diluted ink an imbalance can occur
with a possible result of instability of the ink causing precipitation of
the resin and a number of side effects. This can be a particular problem
on a unit with a small area of type or halftone where the same ink
recirculates through the unit for hours without constant replenishment
with fresh ink.
Solvent added during the run should therefore be of the same consti-
tution as the evaporating mixture to avoid evaporation imbalance, parti-
cularly with inks for halftone printing (a classic case of low usage
application). The best solution in extreme situations is to simplify formu-
lation drastically and use only one solvent provided that a satisfactory ink
for the substrate and end use can be made with these restrictions.
The principal solvents used in flexographic inks are water, ethyl alcohol
(methylated spirit), isopropyl and n-propyl alcohols, ethyl, isopropyl and
n-propyl acetates, methoxy propanol and ethoxy propanol. In certain
cases aliphatic and aromatic hydrocarbon (SBP, toluene) or ketone solv-
ents (acetone, MEK, MIBK) may be used for some types of ink but the
suitability of the stereo composition must be considered when choosing
these (Table 9.1).
568 FLEXOGRAPHIC INKS

Additives
These materials are incorporated into inks at different stages of manufac-
ture to improve performance and to impart specific properties which are
essential to the requirements of use and specification. The quantity of an
additive used is normally small, and with the exception of plasticizer,
rarely exceeds 1% of the formulation. There are many additives available
and it is necessary to understand their function, limitations and any side
effects they may produce, if the best use is to be obtained.
During manufacture of ink the use of surfactants will assist the disper-
sion of pigments, which will improve gloss, colour development and
reduce the tendency of pigments to flocculate when inks are diluted.
The phenomenon of flotation (which is a tendency of different pigments
used in the same formulation to separate, causing streaks or marks on the
print) can be overcome by careful selection of surfactant. Many pigments
contain surfactants which are added by the pigment manufacturer but
some surfactants do not give good results in all ink types.
Plasticizers are incorporated into many inks particularly those to print
film and foil. Generally, plasticizers are used to give flexibility and adhe-
sion to the ink film and are essential with cellulose-based inks, otherwise
these would be too brittle. Certain resins do not require plasticizer since
they are inherently flexible by their nature. These resins however, are not
normally resistant to heat and tend to be thermoplastic. Heat resistant
inks are made using cellulose materials and, as stated, it would be difficult
to make such products without plasticizer. Excess plasticizer should be
avoided because the ink film may thus become soft which could give rise
to the risk of blocking.
With inks containing plasticizers it is possible that plasticizer, by being a
liquid, may migrate through certain film substrates which have low
barrier properties. Furthermore, studies have shown that plasticizer can
transfer by set-off from the printed side of the web to the unprinted side
during storage in the reel. Given that the pack consists simply of a single
layer of outside-printed film it can readily be seen that plasticizer could
find its way into the pack contents through the routes described. Should
the pack content be a foodstuff the contamination possibilities are obvi-
ous, and although the amounts found during the studies were extremely
small and are dependent upon many factors, this can have serious impli-
cations. Inks for food packaging should therefore only contain plasticizers
which have been well researched in respect of their toxicological proper-
ties and found to be of low toxicity. The MAFF [1] Food Surveillance
Papers No. 21 and 30 should be consulted. Finally, the responsibility of
the packer for the choice of materials and design of the pack should not be
overlooked.
Various stabilizers, which prevent reactions between ink components
and inhibit breakdown of resins and reduce corrosion of metal containers,
are also used in inks and intermediates. Anti-oxidants can also prevent
oxidation of resins such as polyamide.
The most common additives for inks are waxes, and these will be present
in most inks and varnishes, the principal exception being inks for
lamination. Waxes which are normally added as powders or compounds,
INKS AND VARNISHES FOR SPECIFIC PURPOSES 569
give improved rub, scuff and scratch resistance and also slip properties to
the print. Polyethylene and polypropylene waxes are the most popular, as
these do not inhibit drying to any great extent since they are not soluble in
solvents. One disadvantage of wax addition is a reduction of gloss.
Adhesion promoters are important additives used in certain inks, par-
ticularly those for film substrates which have surfaces that present diffi-
cult adhesion problems such as treated polypropylene. There are a
number of these materials available and some cause side effects with
the use of inks such as:
. ink viscosity build due to reaction with resin or pigment;
. loss of heat-sealing properties of some coated films;
. colouration effects with certain resins or coatings;
. odour development.
It is essential, therefore, that careful testing of these materials, in the
formulation contemplated, should be carried out prior to their use.
There are a number of other additives used in ink formulations which,
like waxes, improve scratch and rub resistance and also reduce the
coefficient of friction. Among these are fatty amides, silicone fluids and
stearates. Most of these materials also migrate to the surface of the print
and this can reduce the tendency of inks to block. It should be noted,
however, that there can be side effects under particular circumstances.
Examples of these are loss of seal properties with film, reduction of
cohesion with cold-seal adhesives, and wetting and adhesion problems
with overvarnishing and lamination.
Water-based inks may contain particular additive types. Anti-foams,
fungicides, waxes, surfactants, wetting agents, transfer aids, coalescing
agents, anti-blocking compounds and slip additives are all used to achieve
different properties. Anti-foam is usually required as foaming can be
troublesome both during manufacture of the ink and on printing presses
particularly those with high agitation. Foaming may be difficult to over-
come and there is a temptation to use excessive anti-foams agents which
can cause craters and uneven print. Some anti-foams contain hydrocar-
bons which will attack stereo rubbers and therefore care should be taken
in their choice.

9.4 INKS AND VARNISHES FOR SPECIFIC

PURPOSES
Flexography originated as a process to print packaging materials in
the form of paper bags. While the scope of the process has widened
considerably with many substrates and products being printed, packaging
has still remained the most significant area of printing for the process.
Given the relative ease and low cost of flexographic plate origination, the
possibilities of design changes at short notice and improving standards of
printing and ease of handling of flexible materials, it is not surprising
that flexography attracts an increasing share of packaging work. As pre-
viously mentioned there are, however, a large number of non-packaging
570 FLEXOGRAPHIC INKS

applications, most of these being for paper products of many kinds. In

recent years wallcoverings have been extensively decorated by flexo-
graphy and newspapers are also printed by the process.
The formulation of inks and varnishes is normally governed by the
needs of the substrates being printed and the end use of the print. Each
class of substrate and its end use will be considered in respect of the
formulation of inks and it will be seen that at present these are normally
based on pigments and organic solvents. Initially, and because of their
special nature, two types of inks will be considered: dye-based inks and
water-based inks.

Dye-based inks
The dyes can be dissolved by stirring, and solubility and laking are
improved if some heat is used. Denatured ethyl alcohol (methylated
spirit) is the solvent and dependent upon the mordant which is used
this can contain up to 6% water, thereby improving solubility although
an excess of water will precipitate the laked dye. After the inks are made
and allowed to stand at room temperature there will be a tendency for a
small deposit to settle which should be discarded as this may cause problems
on the press when printed.
Additions of resin solutions may be made, e.g. shellac or alcohol-
soluble maleic, to improve transfer properties and wax or glycerine
resistance (glycerine being used to improve the flexibility of paper for
sweet wrappers). If further resistances are required phenolic resins and
others can be used. Ethyl cellulose in small quantities is sometimes added
to reduce tack and also to increase drying speed. Glycol ethers may be
incorporated to retard the ink and because they are good dye solvents
they improve clean working on the press by keeping the type open during
printing.
A typical formulation for a paper ink is:
Basic Yellow 37 dye 8.0
Basic Blue 26 dye 4.0
Tannic acid (or other mordant) 20.0
Varnish (60% alcohol-soluble maleic) 5.0
Glycol ether 4.0
Ethanol 59.0
100.0
Most dyes require a mordant level equal to their own weight but Basic
Violet B and Basic Yellow 37 need twice this quantity to give maximum
water and wax resistance. Colour matching with dye inks is similar to
other inks but the formulator must remember that high dilution during
printing is common and proofing with the anilox hand roller is difficult
due to the low viscosities of these inks, therefore a knife-down or squee-
gee applicator gives better results dependent on the substrate and its
absorbency.
INKS AND VARNISHES FOR SPECIFIC PURPOSES 571
Dyes may be blended with white to make a semi-pigmented ink but the
use of a pigment will require more binder to stabilize the dispersion and
prevent settlement. However, simple bag machines are unable to cope
with the resulting increased viscosities and tack. Dyes can also be incorp-
orated into coloured pigmented inks to increase colour strength but the
dye may interact with some pigments and binders which can cause
instability. Pigmented water-based inks can also be strengthened using
dye solutions but the alkaline nature of the inks precludes the use of a
mordant and the print is prone to bleed under damp conditions. Some of
the dyes also have poor stability and compatibility with alkaline resin
suspensions.
Basic dyes are not normally used in inks for film printing because of
their bleed and migration properties although some early polyethylene
inks were made with dye and titanium dioxide pigment. These inks were,
however, superseded by pigmented polyamide inks which have better
fastness.
Flexographic inks based on lightfast dyes are employed for aluminium-
foil printing and these will give bright transparent effects. Inks for met-
allized substrates and coloured lacquers for overprinting silver inks are
also made with lightfast dyes. These dyes do not require a laking agent
and by consulting the manufacturer’s data a selection of suitable dyes can
be found that are compatible with several binders. Lightfastness can be
good and resistance properties are better than with basic dyes although
there is still a tendency for migration.

Disperse dye inks

Flexographic printing for the heat transfer process has decreased in
recent years although it is still carried out for particular textile applica-
tions, mainly for synthetic fabrics. The inks are printed on a carrier web
(usually paper) and are formulated with disperse dyestuffs which sublime
at high temperature onto fabric held in contact with the web. Print
quality has to be of a high standard and both solvent- and water-based
inks can be used. The print on the carrier web must not rub and the resin
used should not interfere with the subliming properties of the dyestuff.
The selection of the dyestuff and binder is influenced by the type of fabric
to be transfer-printed and the specification of the final print.

Water-based inks
Paper and board
The traditional water-based ink for paper and board consists of a pig-
mented resin system, the resin being first dispersed in water. While a
number of natural resins exist which are soluble in water such as casein
and gum arabic they will also remain soluble after printing, which is not
acceptable. It is therefore necessary that the resin is capable of being
dispersed but then become insoluble once printed. One method of
572 FLEXOGRAPHIC INKS

achieving this is to add an alkali to a suitable resin and converting this to

a soap or resin/water dispersion. Traditionally shellac was used but has
been largely superseded by carboxylated acrylics and, at times, other
resins.
Water-based inks have the advantage over solvent inks that due to
their low evaporation rate the inks are stable on the press without drying
on the stereo or in the duct giving constant viscosity. Water does not
attack stereo materials including photolymers and the inks present no fire
hazards and give economies by the use of water as a reducer and cleaning
solvent.
A problem for the printer is the disposal of waste ink and wash-up
solution which tend to be generated at a larger volume because water is
freely available. Such wastes cannot be discharged into the drains because
of pollution and have no recovery value, the alternatives being expensive
water treatment plant or the cost of dumping.
The most extensive area for use of water-based inks is for multiwall
paper sacks and corrugated case printing where non-flammability and
fast drying on the highly absorbent substrates are an advantage. Good
water resistance shortly after printing is obtained and also good level of
rub resistance essential for the case- and box-making machines.
The choice of alkali for resin solution will be made depending on a
number of factors – cost, equivalent weight, print waterfastness, press
stability and drying speed. Properties for three alkalis are given in Table
9.2 to illustrate how these may vary.

Table 9.2 Alkali properties

Alkali Cost Equivalent Water Press Drying
weight fastness stability speed
Caustic soda Low 40 Poor Good Fast
Triethanolamine Medium 149 Fair Good Slow
Ammonia Low 17 Good Poor Fast

Resins may be used in solution form. Acrylic resins are often supplied
as a resin-in-water emulsion allowing a solution to be formed instantly by
the addition of the selected alkali to the correct pH. Alternatively the
emulsion can be pigmented without alkali, making an ink which will
have faster drying and better resistance properties than the solution type.
This will be at the expense of press stability and makes press wash-up
difficult particularly when the ink is allowed to dry. Some inks are made
as a mixture of the solution and emulsion form to try to arrive at a
balance of properties. This may involve mixed acrylics and a limited
amount of alkali.
Pigments have to be selected for stability in water-based inks and those
which react in alkaline systems or show settlement must be rejected. To
give improved rub resistance the use of a wax compound will be needed.
Too much slip on inks for paper sacks may cause instability in the stack.
Water-based inks are prone to foaming problems and anti-foam additives
INKS AND VARNISHES FOR SPECIFIC PURPOSES 573
of the silicone type or organic defoamers are used although too much
may cause poor lay, wetting problems and ‘fish-eye’ effects.
The manufacture of water-based inks is relatively easy and the three
main methods are:
. milling of dry pigment into varnish;
. mixing of stabilized pigment water pastes with varnish;
. use of pigment press cakes with power mixing or milling.
A strength advantage is given by the use of pastes but the presence of
wetting aids and glycols (which are present in the pastes) may be trouble-
some. A small quantity of organic solvent incorporated into the inks
sometimes improves tack and lay but solvent content must be strictly
limited in case of fire risk. Typical water-based flexographic ink formula-
tions are as follows:
Red water-based ink:
Lithol red pigment (C.I. Pigment Red 49) 18.0
Acrylic/alkali water varnish 60.0
Polyethylene wax compound 4.0
Isopropyl alcohol 4.0
Water 13.9
Silicone anti-foam 0.1
100.0
Blue water-based ink:
50% Phthalocyanine Blue water paste 24.7
(CI Pigment Blue 15)
Acrylic emulsion 50.0
Water 20.0
Monoethylamine 2.0
Polyethylene wax compound 3.0
Organic defoamer 0.3
100.0
Extender pigments may be incorporated into the ink to reduce cost and
since many of these inks are used on natural kraft or coloured substrates,
white pigment is added to improve opacity.

Newspapers
A number of newspapers are now printed by flexography using water-
based inks. There are several reasons why the process is attractive, and
among these are:
. lower installation costs – flexo presses can be cheaper than web-offset
presses;
. less paper wastage – an ink applied via an anilox will result in less paper
waste on start up;
. reduced cost of newsprint – water inks show less strike-through so that
lower-grammage papers can be used;
. less maintenance and manpower;
. better rub resistance properties – gives a cleaner sheet to handle.
574 FLEXOGRAPHIC INKS

A major problem still associated with flexographic newsprint is plug-

ging of the polymer stereo which then leads to deterioration of print
quality. This can be caused by linting of some grades of paper and the
effect can be exacerbated by the use of tacky inks which may pull fibres
from the paper surface.
The ink requirements for printing newspapers are somewhat different
from those for other applications. The main difference is the exceptional
high speed of printing (up to 600 mpm).
High optical density is required with black ink used for printing
type and the density should generally not be less than 1.15 Status
T (USA standard – wide-band colour reflection densitometer). This
must be achieved at very low printing viscosities and a thin film of ink,
normally metered by a reverse-angle doctor blade and anilox roller.
Typically the anilox is a ceramic type with 140 lines per centimetre at a
depth of 35 microns. In order to obtain satisfactory optical density under
these conditions, pigment:binder ratios for the ink will lie between 2:1
and 3:1.
Good resolubility of the ink is essential to prevent dried ink building up
on the stereo and eventually filling-in the shadow areas of the halftone.
Resolubility can be achieved by formulating inks based on acrylic resins or
colloidal dispersions, solubilized with sodium hydroxide or liquid amines
of low volatility.
Due to the very high press speeds, rapid-drying inks are required to
avoid the problem of second impression set-off and marking on the turner
bars. However, due to the adsorbency of the substrate this is only a
problem when multicolour layers are involved. In fact the drying speed
can be made too fast and, particularly if the dried ink is fairly brittle, this
may cause the formation of a fine dust which can initiate plugging.
The way in which the inks dry is also critical. If too much tack is
developed, during the drying phase, paper fibres might be picked off
and these can swell in water and cause plugging. The correct choice of
binder and amine is the best method of controlling drying speed. The use
of alcohol should be avoided since this may soften certain photopolymer
plates.
Due to the low viscosities and high press speeds, foam control of
flexographic news ink is more critical than with conventional water-
based inks. Powerful silicone-based defoamers are usually employed but
care must be taken to choose one which does not swell the sensitive
polymer plates.
A basic formulation for a News Ink Black:
Carbon black pigment C.I. 7 23.0
Solubilized acrylic resin varnish or emulsion 38.0
Anti-foam 0.5
Surfactant 0.5
Water 38.0
100.0

Bulk storage of low viscosity, neat or diluted flexographic news inks

can give rise to settling problems. These can be overcome by the correct
INKS AND VARNISHES FOR SPECIFIC PURPOSES 575
choice of binder and pigment but a good degree of dispersion during
manufacture is also required. The level of dispersion is often so high that
microscopic methods of measurement are now replacing the traditional
grinding gauge for quality control.

Impervious substrates
Water-based inks for impervious substrates is an area of technology
which is currently being developed by ink companies. Although a num-
ber of successful commercial results have been achieved it is too early to
provide guidance on formulation for specific applications. This section
will therefore be confined to notes of the general principles which apply
to these systems.
The requirements for these inks are quite different from those which
are applicable to paper and board inks. The main problems are:
. drying
. adhesion/flexibility
. substrate wetting
. resistance properties
. printing conditions.
Because of the nature of impervious substrates ink drying is mostly by
evaporation. Water has a much higher latent heat of evaporation than the
commonly used organic solvents, meaning that it takes more heat for it to
evaporate. It is desirable to keep the water content as low as possible and
inks which contain high solids levels dry more rapidly than those which
contain more water.
Generally, high solids are achieved by using non-convertible emulsion
polymers. Emulsions when used alone, however, can give resolubility
and drying-in problems during printing. It is therefore normal to include
some resin, which has been solubilized with amine, to improve resolu-
tion. The inclusion of soluble resin will slow drying and a balanced blend
becomes necessary to achieve a compromise of properties.
Addition of alcohol can speed up drying, although the level of alcohol
will be limited to control flash point and furthermore to avoid compatibil-
ity problems with emulsions. A typical alcohol content is 5%.
The best way to speed up drying is by applying a lower film-weight of
ink. Because water inks give rapid viscosity reductions on dilution (Fig.
9.2) this will allow high solids-strength at printing viscosities without
compromising print strength.
Also important to drying is the choice of solubilizing agent (as previ-
ously mentioned) and of those available, ammonia gives more rapid
drying due to its high volatility. The choice of pigment dispersion is also
important to drying and those which contain excess glycol should be
avoided.
The adhesion and flexibility of water-based inks to impervious sub-
strates is controlled by the selection of polymer emulsion. These are
usually based on acrylic resins and there are a wide range of types avail-
able. The softer, low-Tg (glass transition temperature) polymers normally
give the best adhesion and flexibility properties when used on many film
substrates, but these polymers have poor heat resistance.
576 FLEXOGRAPHIC INKS

On uncoated substrates water-based inks are far less tolerant to vari-

ations of treatment level and the presence of surface active materials,
such as waxes, than is the case with organic solvent-based inks. Adhesion
may suffer as the result of these variations. The minimum corona dis-
charge treatment level for satisfactory adhesion to be obtained is nor-
mally 38–40 dynes/cm. Ideally, corona discharge treatment should be
carried out in-line or shortly before printing.
Alternative resin systems which exhibit good adhesion to polyolefin
films are water-based urethanes, polyamides, epoxy esters and saponified
rosin. Unlike solvent-based inks it is not common to use plasticizers to
increase flexibility.
Good substrate wetting is vital to ensure satisfactory printability. A
major problem with aqueous systems is due to the high surface energy
of water 73 dynes/cm. In contrast the surface tension of ethyl alcohol and
isopropyl alcohol is 24 and 21.7, respectively.
In order to reduce the surface tension of water-based inks which will
allow better wetting of substrates, surfactants and alcohols are used in
formulations. The use of both anionic and non-ionic surfactants may
cause problems of poor water resistance in inks and care in the choice
of these must be exercised.
A further consequence of reducing surface tension is to increase the
tendency to foam. The choice of defoamer is also critical to prevent poor
wetting which may cause reticulation of the print. Good performance on
impervious substrates using water-based inks usually involves a balan-
cing act between surfactant and defoamer.
The end-use resistance properties of prints made using water inks is
governed by the correct choice of resin/emulsion binder. With acrylic
systems, emulsions tend to give better results. Emulsion-based inks are,
however, more difficult to print due to their relatively poor resolubility
and the ultimate resistance may have to be compromised by the addition
of solubilized resins to achieve a balance.
In the past the addition of polyaziridines has been used as cross-linkers
to confer high levels of resistance properties. Their use is, however, now
in decline due to health and safety concerns.
It should be noted that, in general, water-based inks do not develop
their maximum resistance properties as quickly as solvent-based inks.
Resistance tests should therefore be only carried out after a period of
time has elapsed.
Much has been written concerning how water-based inks should be
handled on the press. Inkmakers will normally advise customers on the
best use of their products. In general, the following rules should be observed:

. use the minimum reduction with water;

. apply a thin ink film with shallow anilox and a blade;
. print at a relatively high viscosity;
. do not adjust print strength with water, use medium;
. pH of the ink should be monitored (7.5–8.5);
. wash press immediately after use
. clean anilox and stereo after printing breaks;
. use a well treated substrate, free from slip additives if possible.
INKS AND VARNISHES FOR SPECIFIC PURPOSES 577

Solvent-based pigmented inks for specific substrates

Paper and board
In formulating pigmented solvent-based inks for paper substrates the
main concerns are in producing inks having satisfactory colour and
strength with good printing properties together with good drying and
rapid solvent dilution characteristics. Adhesion to board and paper sur-
faces is not normally a problem with the possible exception of glassine
and heavily coated papers. Most inks must be dry rub resistant unless an
overvarnish is used.
Flexographic printed papers are used for labels, packaging and decora-
tive wrappers, wallpaper and other applications already mentioned.
Consequently the choice of pigment must satisfy the resistance require-
ments associated with the end use. General wrapping and bag inks do not
demand lightfast pigments except the normal avoidance of those with
poor lightfastness in pastel shades as this will reduce lightfastness even
further. Pigment used for waxed papers and soap wrappers would need to
be insoluble in the respective materials in each case.
The principal binder for these inks is nitrocellulose which has good
pigment wetting and can be pigmented either by direct grind methods or,
where increased gloss and strength are required, by using chip disper-
sions. Nitrocellulose resin gives good drying and since pigmented inks are
not absorbed as readily into paper, as is the case with dye inks, faster
drying is required. Maleic resin is often used with nitrocellulose in the
inks and the main solvent is ethanol with esters or glycol ethers to aid
solubility. Plasticizers and waxes may be incorporated to improve flexi-
bility and rub resistance, and other binders or modifiers may be used for
special applications or to give particular properties.
Typical formulation of ink for paper:

Phethalocyanine Blue (CI Pigment Blue 15:3) 14.0

Titanium dioxide (CI Pigment White 6) 6.0
Maleic resin varnish 16.0
Nitrocellulose varnish 38.0
Wax compound 4.0
Plasticizer 4.0
Ethanol 11.0
Isopropyl acetate 7.0
100.0

A formulation using chips:

N/C 2B red toner chip (CI Pigment Red 48) 24.0

Isopropyl acetate 10.0
Ethanol 40.0
Maleic resin varnish 12.0
Polyethylene wax compound 4.0
Nitrocellulose varnish 10.0
100.0
578 FLEXOGRAPHIC INKS

Film inks
Inks for films have different requirements from those for paper. There are
two main differences. First, the substrates being non-permeable will
cause the ink to lie on the surface. As adhesion is not assisted by pene-
tration as is the case for paper, it will therefore be dependent on the
physical and chemical attractions between the ink and substrate surface.
In some cases, fusion of ink and film coating or solvent attack on the base
film or coating occurs. Secondly, because the substrate is transparent it is
possible to print on the face or reverse side of the film and it is normal to
use a white underneath the colour in the former case and to back the
colour with white in reverse printing. The white is used to opacify the
film and increase the contrast of the print.
Reverse printing has the advantage that the colour is viewed through
the film which increases gloss and brightness as well as giving protection
to the print against abrasion and rub. Laminates will normally be printed
this way if the lamination is carried out after printing. Films which are
reverse printed need to be very transparent and cloudy substrates such as
extruded polyethylene are unsuitable. In recent years there has been an
almost total move away from reverse printing for non-laminated food
packaging towards face printing to avoid any possibility of contamination
contact of packaged foodstuffs by the ink or retained solvent. Reverse
printing, although still carried out, normally requires an overlacquer or
the use of an inner ply to prevent ink/food contact.
In discussing inks for films it will be assumed that these are face-printed
unless otherwise stated or dealing with laminates. With face prints,
adhesion of the white ink, if used, is paramount since this will be in
direct contact with the substrate. It may be possible to use a common
range of coloured inks on several substrates by taking advantage of the
adhesion properties of different whites which are suitable for each sub-
strate, the white being used as a key coat. The inkmaker will advise when
such possibilities exist.

Cellulose films
Regenerated cellulose films were the first packaging films used but,
although still extensively printed, they have given way to various plastic
films in many areas of use for several reasons: price considerations,
changing packaging demands and the more widespread use of deep
freezing. Cellulose film is available in three main types: uncoated, nitro-
cellulose coated and polymer coated. Some of the more common films are
listed below.

P and PF Plain cellulose films, uncoated

PS and QMS Nitrocellulose coated, semi-permeable,
sealing
MF Nitrocellulose coated, semi-permeable,
moisture proof
DMS Nitrocellulose coated one side with
moisture proof, sealable
INKS AND VARNISHES FOR SPECIFIC PURPOSES 579
MS Nitrocellulose coated both sides with
moisture proof, sealable
MXDT PVdC barrier-coated one side
MXXT/S Solvent PVdC barrier-coated both sides,
sealable
MXXT/A and MXXT/W Aqueous PVdC barrier-coated both
sides, sealable
WS PVC/PVA coated both sides, sealable

Uncoated and single-side coated films

Uncoated P and PF film has reasonable fat and grease resistance but poor
moisture resistance. It is not used to the same extent as coated films but is
used for certain applications such as twist wraps for sweets and cellulose
adhesive tapes. P film can present the inkmaker with a number of prob-
lems and among these are difficulties with adhesion at high film weights,
blocking, solvent retention by the film and bleeding of certain pigments
into glycol plasticizers contained in the film.
Inks for twist wrap may be based on nitro or ethyl cellulose (MF film is
also used for twist wrap and the same inks can be used). For adhesive
tapes polyamide inks are suitable, but care will be required with the
choice of pigments to avoid those which bleed or react with the adhesives.
Single-side coated films DMS and MXDT are primarily used for poly-
ethylene extrusion or adhesive laminates with printing being applied to
the uncoated P-side of the web. Similar ink problems to those mentioned
with P-film printing exist but adhesion to the substrate and compatibility
with adhesives is of basic importance for a good laminate. Polyamide inks
are unsuitable for adhesive lamination due to a tendency of polyamide to
interfere with two-component adhesive reactants. Polyamide/nitrocellu-
lose ink can however be used for extrusion laminates.

Nitrocellulose-coated films
There are a number of cellulose films coated with nitrocellulose most of
which are heat-sealable. PS and Q films are permeable to moisture and
are used for packaging bakery and meat products. Although the films are
sealable, it is unusual for the seal to be in the printed area. Polyamide inks
may be used which have the necessary deep-freeze resistance properties.
Pigments which are prone to migration should be avoided as these may
bleed.
MS film is designed to have heat sealing, moisture and gas barrier
properties as well as being impervious to fats and grease. The film is
used for packing products which require a moderate degree of protection
from moisture. It has also been used for many years, as unprinted film for
cigarette overwrapping. The main problem for the inkmaker is that wax
contained in the coating causes wetting problems with the ink, which
may crawl on the surface before drying. Pinholes which appear on the
printed films vary according to the source of the film. Formulations
to overcome this will contain both resins which wet the surface and
580 FLEXOGRAPHIC INKS

anti-pinhole compounds to reduce surface tension. Ethyl cellulose helps

as it sets the ink before crawling while non-alcohol solvents aid wetting.
MS films vary in their tendency to give pinholing and over reduction of
the ink with solvent will increase the problem.
Adhesion to MS film is less of a problem as it is possible to fuse the film
coating and the ink together by heating the print while drying.
Inks which are heat resistant are, however, more difficult to fuse.
Solvent retention can be a problem and alcohol solvents can be absorbed
more readily than other solvents. Heat-resistant inks are often required
for MS film if the print comes in the seal area and nitrocellulose is the
normal binder used together with a modifying resin and plasticizer. It will
be necessary to conduct tests to ensure that the formulation will not block
and has satisfactory adhesion and flexibility particularly when inks are
superimposed.
A typical formulation for an MS film ink is:
Calcium 2B pigment (CI Pigment Red 48.2) 14.0
Titanium dioxide (CI Pigment White 6) 4.0
Nitrocellulose varnish 40.0
Shellac varnish 9.0
Polyethylene wax compound 3.0
Anti-pinhole varnish 3.0
Plasticizer 3.0
Isopropyl acetate 7.0
Ethanol 17.0
100.0

Alternatively the ink could be formulated from nitrocellulose pig-

mented chips to give more gloss.

PVdC copolymer-coated film

PVdC coated cellulose film has improved gas and moisture-barrier prop-
erties compared with MS film. The film is available in two main grades
with the polymer coating being applied during manufacture from either
a solvent solution (MXXT/S) or from an aqueous dispersion (MXXT/A
and /W), the latter grade being less affected by strong solvents contained
in the ink and having better barrier properties. MXXT films are widely
used on food products which require its high barrier protection, e.g.
biscuits and some snack foods, although coated polypropylene and also
coextruded polypropylene films have replaced MXXT in many cases. The
films are heat sealable and this will affect ink formulations since the seal is
often in the printed area.
Polyamide resins have good adhesion to MXXT but poor heat resistance
and although this may be improved by the addition of nitrocellulose it is
difficult to achieve sufficient heat resistance for direct ink application in
the seal area. A number of ink additives can damage PVdC coating either
by affecting heat-sealing properties or moisture-vapour transmission
rates. Tests will need to be conducted if additives of chemical active type
are used.
INKS AND VARNISHES FOR SPECIFIC PURPOSES 581
Acrylic resins have traditionally been used to give adhesion to PVdC-
coated films and when these resins are combined with cellulose esters or
nitrate, heat-resistant inks can be formulated and since there are a large
number of acrylic resins available the selection should be made on a
balance of properties. These would include:
. high alcohol tolerance;
. low odour and a low solvent retention;
. good compatibility with cellulose-based resins;
. good pigment wetting;
. adhesion to PVdC surfaces.
The main problems with the use of these resins in flexographic inks is
the relatively high ester solvent requirement for solubility and a tendency
to string. Photopolymer plates are also difficult to use with the solvents
needed. With surface printing it is possible to formulate a white ink on an
acrylic/cellulose basis with good adhesion and use other heat resistance
inks, for example nitrocellulose colours for overprinting.
A basic breakdown formulation for heat resistant white ink is:
Titanium dioxide (CI Pigment White 6) 33.0
Cellulose acetate propionate 9.0
Acrylic resin 8.0
Plasticizer 3.0
Ethyl acetate 11.0
Normal propyl acetate 10.0
Ethanol 25.0
Polyethylene wax powder 1.0
100.0
Isopropyl acetate is avoided due to its tendency to be retained by PVdC
coatings after drying.
Pinholing of the type associated with MS film is not a feature of MXXT
films although occasionally wetting problems can be encountered which
may be a function of the coating or its components. MXXT films (as is the
case with other coated films) are subject to changes as manufacturers seek
to improve their products for storage, sealing or packaging performance
and these changes may influence ink behaviour in unpredictable ways.
The ink manufacturer will need to keep abreast of such changes by
constant liaison with filmmakers and users so that he can make necessary
adjustments or recommendations as required, thus avoiding most prob-
lems before they occur.

PVdC overlacquering
Prints on MXXT films in common with prints on coated polypropylene
and other PVdC coated substrates may be overlacquered with aqueous
PVdC emulsions to improve sealability, barrier properties or give added
protection and gloss to the print. The overlacquer can be applied in-line
or as a separate operation and will be heated to coalesce the emulsified
PVdC and to evaporate the water contained. With such applications both
582 FLEXOGRAPHIC INKS

white and coloured inks need to have an affinity for PVdC. Adhesion to
the film coating and receptivity of the print surface for the lacquer
without poor wetting and crawling are necessary attributes. Additionally
interlayer bond strength must be high to resist tape tests and possible
breakdown of heat seals.
In these circumstances the overprint colours as well as the white need
to be formulated with these considerations in mind and nitrocellulose
overprint colours, as previously described for non-lacquered surface
printing, are unsuitable. Colours similar to the white formulation given
will be more suitable and tests should be made to check the performance
of any formulation used. When considering the pigment choice for PVdC
overlacquered colours, note should be taken of the highly acidic nature of
these emulsions which may cause certain pigments to bleed.

Polyolefin films
There is a wide and expanding range of films in this group and together
they now represent the largest use of packaging films. All of these materials
are important with respect to the flexographic process. For the purpose of
covering the ink requirement they are placed into three main categories:
uncoated, co-extruded and coated. The following list gives the main films.
Uncoated polyolefins
LD polyethylene Low density polyethylene may contain
additions of ethylene vinyl acetate
(EVA) or linear low density (LLD)
polymers
HD polyethylene High density polyethylene
OPP polyethylene Orientated polypropylene
Cast polypropylene
Coextruded polypropylenes
Coextruded polypropylene Three-ply, polypropylene inner,
modified polypropylene outer
Pearlized polypropylene Three-ply, voided inner, modified
polypropylene outer (may contain TiO2 )
Coated polypropylenes
PVdC-coated polypropylene Aqueous PVdC-coated both sides
Acrylic-coated polypropylene Coated both sides
Differential-coated Acrylic one side, PVdC other side
polypropylene
Vinyl-coated polypropylene PVC/PVA-coated both sides
Coated pearlized Various acrylic or PVdC coatings
Polyethylene film together with cast and orientated polypropylene films
require to be treated by corona discharge before printing. Without treat-
ment, adhesion is difficult if not impossible with conventional inks. The
treatment may be carried out on one or both sides of the substrate.
Avoidance of ink blocking is more difficult on two-side-treated film,
particularly if the film has a different level of treatment on each side, as
INKS AND VARNISHES FOR SPECIFIC PURPOSES 583
there is a tendency of the print to be attracted towards the more highly
treated surface.

Polyethylene and uncoated polypropylene films

Treated film will normally show a surface wetting value between 36 and
40 dynes/cm. Excessive treatment can result in a print with poor water
resistance, due to improved wetting of the surface by water, which can
penetrate under the print. With polypropylene films the effect of treat-
ment is of shorter duration than with polyethylene.
There has been a steady move towards inks which are alcohol dilutable
and hydrocarbon free and these have become the most common type in
the UK. Most of these inks are still based on polyamide but of the alcohol-
soluble type which is softer than cosolvent polyamide, therefore nitrocel-
lulose is added to increase drying. Inks of this type can be formulated for
polyethylene which have all of the desirable properties of the cosolvent
systems but do not gell, are faster drying, suitable for polymer plates and
require less solvent for dilution to reach press viscosity, thus giving
stronger prints. Choice of resin, pigment and additives are all important
in achieving a good result.
Polyamide inks can be modified with rosin-based resins to improve
their adhesion and water resistance although compatibility must be con-
sidered. Waxes are used to improve scuff resistance and fatty amides may
be incorporated to adjust slip characteristics. The film itself may contain
several additives and the combination of these together with those in the
ink will need careful control to achieve the desired result. Pigments
should be chosen to give good flow in the binder and solvents used and
for other properties such as water resistance (since these are affected by
some pigments). Polyethylene is a low-barrier material and the use of
pigments which may bleed or migrate through the film must be avoided
or thoroughly tested. Some pigments may cause oxidation of polyamide
and should be used only with a suitable anti-oxidant or avoided
altogether.
Cast polypropylene film which is used for garment packaging because
of its high clarity has somewhat improved barrier properties than poly-
ethylene but because of the possibilities of lower treatment levels the
alcohol-dilutable inks may need some modification to improve their
adhesion. In other respects similar inks are used.
A typical formula for a cosolvent ink:

Organic pigment 12.0

Cosolvent polyamide resin 20.0
Maleic or phenolic resin 3.0
Normal propyl alcohol 22.0
Isopropyl alcohol 22.0
Aliphatic hydrocarbon 15.0
Polyethylene wax compound 5.0
Fatty acid amine 1.0
100.0
584 FLEXOGRAPHIC INKS

A typical starting formulation for an alcohol-dilutable hydrocarbon-

free ink:
Organic pigment 12.0
Alcohol-soluble polyamide resin 22.0
Nitrocellulose (dry weight) 4.0
Ethanol 29.0
n-propyl alcohol 18.0
n-propyl acetate 10.0
Polyethylene wax compound 4.0
Fatty acid amide 1.0
100.0
Alternatively, chips could be used with both formulations although
gloss is quite good by direct dispersion methods.
Polyethylene is also used in heavy gauges to make sacks to pack
fertilizers, animal feeds and garden and agricultural products. Polyethyl-
ene sacks are stored in the open and the inks used must resist weathering,
the chemicals which are packed, and have good lightfastness. A testing
programme will have to be conducted over many months to ensure that
both pigments and binders resist simulated weathering conditions before
such inks are used. It should also be remembered that the substrate plays
an equally important part in achieving its specified performance.

Coextruded polypropylene (COEX) film

Coextruded polypropylene films have in recent years become important
for packaging of many products including crisps, snack foods, chocolate-
coated products and confectionery. Moisture-barrier properties of these
films are similar to coated films but gas barrier is inferior. COEX film
consists of a central polypropylene core with the outside layers modified
using polyethylene or other polymer groups to melting point, thus giving
good sealing properties without film distortion.
Polyamide inks give good adhesion to the treated surface but, since the
film is heat sealable, inks resistant to heat will be required for many jobs.
Moreover, due to the nature of the products packed, grease resistance is
also desirable. Because of the difficulties in satisfying these requirements,
early systems consisted of a chemically reactive two-pot white or primer
based on polyester–isocyanate chemistry, overprinted with conventional
heat-resistant inks.
Some years ago these systems were replaced by nitrocellulose inks
modified with urethane resins and adhesion promoters. These inks give
satisfactory heat and grease resistance and have become the standard inks
for printing COEX by flexo for snack foods.
Coextruded film may be used in cold seal applications and in this case
non heat-resistant inks would be suitable; overprint varnishes may also
be used and these applications will be discussed later.
Pearlized coextruded polypropylene is another coextruded substrate
which has made fast progress in similar market areas to the plain coex-
truded films and also by the employment of special conversion methods
used for biscuit packaging. These films have a voided polypropylene
INKS AND VARNISHES FOR SPECIFIC PURPOSES 585
core which gives the pearl effect but also some loss of barrier properties
and internal film strength. As much of the film is used on cold-seal packs,
inks which have good adhesion but without heat resistance are normally
satisfactory. The main concerns for the ink and overlacquer are that they
should not adhere to the cold-seal adhesive. When heat resistance is
required, similar inks to those described for plain coextruded films are
suitable.
Pearlized films have found an increasing use for biscuit packaging
because of their attractive appearance, but due to the low barrier prop-
erties of the film a PVdC lacquer is often applied over the print to help
heat sealability; the lacquer may also be applied to the reverse unprinted
side of the web. An ink will therefore be needed to adhere to the
uncoated treated surface of the film and be receptive to the aqueous
PVdC over lacquer. Conventional flexographic inks are not suitable and
will only perform one of the functions required. One possibility is to use a
suitable print primer on the substrate, overprinted with inks of the
acrylic/cellulose ester type (already described for use with coated films)
but in view of the many layers of coatings and inks an additional layer of
primer is not desirable.
A method in use at present to solve these problems is to use a two-pot
white of the epoxy type which will adhere to the base substrate and is also
suitable for PVdC overlacquering. This gives good interlayer bond for heat
sealing. More recently various one-pot white inks have been developed
which will perform the same function, but these can have slightly lower
bond to the base substrate when measuring heat seals made from the
pack. Both the two-pot and one-pot whites can be overprinted with the
PVdC lacquerable colours as just mentioned.
It should be noted that converter-applied PVdC overlacquering
involves complex ink technology and certainly requires skills in printing
and conversion. Several printing and coating operations are needed for a
particular job.

Coated polypropylene film

PVdC-coated polypropylene was the first established and is still the most
extensively used coated plastic film. Suitable for biscuit wrappers and a
wide range of other packaging the substrate has excellent gas and mois-
ture barrier properties and in common with other polypropylene based
films has good low temperature stability.
Heat-resistant low-odour inks are used to surface print the coated film
and when the print is overcoated with aqueous PVdC lacquers the ink
must be receptive to this coating application. Inks previously discussed for
MXXT films are also suitable for printing this film, although two main
differences between the film types exist. First, coated polypropylene has
lower heat resistance than MXXT and the inks therefore need to show
good adhesion at the lower drying temperatures used during printing.
Secondly, there is a tendency for the coated polypropylene film to absorb
strong solvent such as hydrocarbons and esters and as well as being
retained in the prints these solvents can reduce the bond between the
base film and its coating.
586 FLEXOGRAPHIC INKS

Acrylic-coated polypropylene is used for similar packaging applications

to PVdC-coated films. The film is a high-barrier sealable type and ink
adhesion is not normally difficult so that more ink types can be used than
with PVdC-coated films. Solvent retention by the acrylic coating and the
possibilities of blocking do, however, demand care in the choice of solvents
used in the ink, as esters and hydrocarbons will solubilize acrylic resins.
Differentially coated polypropylene films with an acrylic coating one
side and PVdC the other have become more widely used in recent years,
and both plain film and voided-core versions are available. These films
have good barrier properties and make very good heat seals as both sides
are compatible for sealing. The manufacturer recommends that printing is
carried out on the acrylic side and similar ink recommendations are made
as for acrylic-coated films, and of course the same precautions need to be
taken with respect to solvents.

Other plastic films

Polyvinyl chloride (PVC) films
PVC films vary in their polymer composition and can be unplasticized or
contain different quantities of plasticizer. Flexography is not the main
printing process, although vinyl tapes, labels, wallcovering and some
packaging are printed by the process.
The copolymer resins of polyvinyl chloride and polyvinyl acetate are
difficult to use in flexographic inks because of the ketone and ester
solubility requirement of this resin type. Compromise formulations of
cellulose with acrylic resins or other binders have to be used and careful
formulation with comprehensive testing should be carried out to achieve
a balance of adhesion, plasticizer tolerance and non-blocking. Solvent
retention can also be a problem particularly on the unplasticized grades.
Pigments have to be chosen for non-migration into the film and
non-bleed in the film plasticizers. Adhesive tape inks should exclude
colourants which cause breakdown of latex adhesives. With inks for
wallcoverings, there are additional requirements of good lightfastness
together with high temperature stability for heat embossing work.

Nylon films
Nylon films have high strength but poor moisture and modest gas barrier
properties. They are used in laminates for thermoforming and in deep-
draw vacuum packs and various boil-in-the-bag applications. Good
adhesion is obtained with polyamide formulations (such as those already
given for polyethylene) but inks for laminates are more difficult. Boil-in-
the-bag work is also difficult as the substrate is permeable to water and
two-pack catalysed ink systems may need to be used. Much film, particu-
larly orientated nylon, is unprinted and retailers apply their own adhe-
sive labels.

Polyester films
These films are tough, heat resistant, have very good barrier properties
and are used in laminate complexes, pharmaceutical packaging, boil-
in-the-bag and liquid pouches and for carbon-copy film.
INKS AND VARNISHES FOR SPECIFIC PURPOSES 587
In its uncoated form polyamide and vinyl inks have good adhesion and
additional inks are suitable, if the film surface is corona-discharge treated
by the converter prior to printing. Primed/treated versions of these films
are available to which ink adhesion is less difficult and various modified
nitrocellulose inks can be used for surface printing or with laminates.
Polyester films are also coated with PVdC and this allows the use of
similar inks to those described under MXXT film.

Metal and metallized substrates

Aluminium foil
This material has greater light, gas and liquid barrier protection properties
than other flexible packaging materials. These properties, together with its
reflective appearance, have led to foil being chosen where such require-
ments are of a high priority.
The surface of aluminium when exposed to air oxidizes rapidly,
and once this occurs, ink adhesion becomes difficult. With virgin foil in
the reel, the surface will not readily oxidize due to the exclusion of air
and the presence of traces of lubricating oils left from the foil-rolling
process during manufacture. When foil is laminated to paper or board
however, it becomes necessary to wash-coat during lamination with a
dilute lacquer containing various resins such as nitrocellulose or shellac.
This wash coat acts as a primer for ink adhesion, in addition to preventing
oxidation.
In the virgin or washed form, adhesion with polyamide, nitrocellulose
or specialized formulations is not difficult. Inks are required to be flexible
and resistant to the packed products and with confectionery and choco-
late wrappers low odour level is essential. Resistance to blocking must be
carefully tested with virgin foil, particularly as pressure in the reel can be
severe.
Bright transparent effects can be given using dye inks (as already
mentioned) but for non-bleed results and high-resistance specifications
pigmented inks, which are also transparent, can be formulated using
selected pigments and chips.
A typical formulation for a transparent ink for aluminium foil:
Nitrocellulose pigmented chip (60% pigment) 20.0
Maleic or shellac varnish 10.0
Alcohol-soluble polyamide 4.0
Nitrocellulose varnish 10.0
Micronized polyethylene wax 0.5
Plasticizer 3.0
n-propyl alcohol 20.0
Ethanol 22.5
n-propyl acetate 10.0
100.0

Metallized substrates
A number of substrates are metallized by the vacuum metallizing process.
The metal can be deposited directly onto certain base substrates or,
588 FLEXOGRAPHIC INKS

alternatively, by the use of a primer which is applied before processing.

Among the materials which are metallized for packaging applications are
paper and board, cellulose films, polyester and coated and uncoated
polypropylene. Metallization gives the substrate a similar appearance to
aluminium foil, reduced light penetration and slightly improved barrier
properties.
When metallized substrates were first introduced, it proved very diffi-
cult to obtain satisfactory ink adhesion on to the surface of the metal.
Furthermore, as the substrate aged, adhesion problems increased, due no
doubt to oxidation of the aluminium. A number of improvements have
been made to these substrates and in general the useable period has been
extended considerably. Nevertheless, it is prudent to carry out tests, with
ink and substrate, prior to printing.
Metallized paper presents fewer adhesion problems than metallized
film. Polyamide inks will give satisfactory results, as will other formula-
tions. Depending on the specification required, it may become necessary
to test the ink on the batch of substrate which is being printed to ensure
satisfactory results.
Printing of film is invariably carried out on the metallized side of the
substrate as this gives brighter prints. Simple polyamide formulations will
be satisfactory for some substrates but if the print has to be heat resistant,
more complex specialized formulations will be required. Again tests will
be necessary prior to printing.
Because of the problems which are described above, printing on met-
allized film is often carried out using a print primer. A number of primers
are available which are suitable for different metallized films, and in
recent years water-based types have proved particularly successfully
and are widely used. The use of a primer will normally overcome many
of the problems discussed.

Inks for lamination

Laminates are formed from two or more substrates which are held to-
gether and thus combine the properties from each substrate. Although
printing may be carried out on the laminate complex this section will
cover only those laminates where the ink is sandwiched between two
layers. The possibilities of film combinations which can be laminated
together is extensive although the majority of laminates employ poly-
ethylene as the inner layer for heat sealability. There are several methods
of lamination and three main types will be considered:
. adhesive lamination
. extrusion lamination
. extrusion coating.
Adhesive lamination may be carried out using solvent-based or solvent-
less adhesives. These may be one-pot non-reactive or two-component
catalysed types. Water-based adhesives are also used. The adhesive is
normally, but not always, applied to the printed web. Any solvent or
INKS AND VARNISHES FOR SPECIFIC PURPOSES 589
water from the adhesive is first evaporated and the two webs are brought
together between nip rollers under pressure. Sometimes, dependent upon
the adhesive, these rollers are heated. Generally, a few days are required
before the bond between the laminated layers is developed.
The main concerns for the formulator is the nature of the printed
substrate, the properties of the adhesive and the laminating conditions.
Substrates which can be printed and adhesive laminated include DMS,
MXDT, MXXT, polyester, nylon and the different kinds of uncoated and
coated polypropylene. The nature of the unprinted web in the laminate
construction is generally not important to the properties of the ink.
The ink requirements are good adhesion to the substrate and compati-
bility with the adhesive. It is difficult to be too specific regarding ink
formulation because of the many substrates involved and adhesives
used, but, in general, resins which give poor bonds are polyamide, ethyl
cellulose and PVA while those which find use in formulations are acrylics,
PVB, vinyl and various combinations and modifications of nitrocellulose
and cellulose esters. The choice of plasticizer is important and often
chemical adhesion promoters are used. Wax compounds and materials
which give slip or abrasion resistance to surface prints can cause delami-
nation if used. Moreover, it is frequently found that matt inks are more
receptive to adhesives than gloss inks. Pigments are not normally a
problem although PMTA types may bleed in adhesive solvents.
With the many substrates and adhesives used there is an obvious
advantage if one ink type is suitable for several different laminates. It
becomes necessary for the inkmaker to be very specific in the recom-
mendations made regarding which substrates and which adhesives have
been tested and found to be satisfactory. Lamination bond failure is only
discovered after printing is completed and the laminate is formed. Checks
which ensure satisfactory final results are not easily made during the
production stages.
Extrusion laminates are formed from two webs which are combined by
extruding a thin film of hot polyethylene on to one web and nipping the
films together while the polyethylene is still molten. The webs may be of
the same or different composition, dependent upon requirement. Extru-
sion coating is made in a similar manner but, in this case, the molten
polyethylene is extruded onto the printed side of a single web which is
then passed over a chill roller.
Ink formulations need to have a good affinity for polyethylene. Poly-
amide and shellac inks in combination with nitrocellulose give good
results. Bond strength is generally not as high as with adhesive lamin-
ation and the inks need good solvent release properties because retained
solvent affects the strength of the bond.

Miscellaneous products
Metallic inks
These inks are made from aluminium or bronze powders mixed with a
suitable resin solution. The particle size of the metallic powders used in
590 FLEXOGRAPHIC INKS

flexographic inks are larger than pigment particles and normally are
leafing grades which give maximum reflectance and coverage. When
first mixed into a varnish, brilliance will be at its best but rub resistance
may take a day to develop to its maximum and there will be some loss of
brilliance due to ‘wetting out’ of the metal with resin and solvent. Inks
may be supplied ready mixed but the binder choice will be restricted to
those that are neutral and give storage stability. With other less stable
binders the inks will be supplied as a powder or solvent paste together
with a varnish and the mixing is carried out prior to printing.
Aluminium powders are more stable with resins than bronze powders
but gold shades can be obtained with aluminium by mixing with a
varnish which contains some dye or finely dispersed pigment. These
mixtures are, however, less bright than a bronze powder-based ink but
have the advantage of being copper free, which may be necessary for
certain food wrapper specifications. The type of resin binders for metallic
inks are dependent on the substrate and end use but good leafing of the
metal flake has to be considered. Over concentration of the powder
should be avoided as ink film strength can be affected together with the
adhesion of any overprinting colours. High powder concentration should
also be avoided in lamination inks. Suitable resins are polyamide, ethyl
cellulose, PVA, acrylics and cellulose esters. Nitrocellulose can be stable
in some aluminium-based inks but bronze powders are reactive and
care must be exercised. Stabilizers can be added to help stability in
certain cases.
Gold ink:
Bronze powder 30.0
PVA varnish (25% solids) 55.0
Wax compound 5.0
Ethanol 10.0
100.0
Silver ink:
Aluminium powder 16.0
Polyamide varnish (40% solids) 60.0
Wax compound 4.0
n-propyl alcohol 15.0
Aliphatic hydrocarbon 5.0
100.0

Halftone inks
The use of halftone and colour process printing has increased dramatic-
ally in recent years and is made possible by better printing equipment and
printing plates. Good quality inks will give satisfactory results with half-
tone, but most manufactures offer specialized inks for two main reasons:
. to ensure that each colour gives the correct hue and clean shade which
are required for process work and, moreover, as a standard for making
plates.
INKS AND VARNISHES FOR SPECIFIC PURPOSES 591
. to ensure that the ink has good solubility with few solvents (prefer-
ably one), to avoid solvent balance difficulties which can arise with
low ink usage over long periods as can be the case with halftone
printing.
High resistance specification inks with low solubility resins and complex
solvent mixtures are unsuitable and will not give clean printing, which is
essential for good reproduction.

Polyethylene-coated board
Polyethylene-coated board which is printed before extrusion has been
discussed under laminates, but when printing is carried out on the out-
side extruded layer the polyethylene is first treated by corona discharge.
Both printed forms are used extensively for milk and other liquid pack-
aging to make cartons of different types.
Flexibility of the ink is only required to facilitate folding and the main
concerns for the inkmaker are abrasion, rub resistance and adhesion
together with meeting the specification regarding resistance to the liquid
packed. Suitable inks are made from nitrocellulose which has the neces-
sary toughness and these are modified to improve adhesion and rub
properties. Pigment choice is governed by the requirements for non-
bleed in milk and other drinks.

Two-component reactive inks

The properties of prints produced from conventional evaporation-drying
inks are related to the properties of the resins employed. With flexo-
graphy the choice of resin which may be used is restricted by the limited
range of permitted and acceptable solvents. In recent years these con-
straints have become more severe. Systems which incorporate a chemical
reaction after the solvent has evaporated can give a ‘cured’ film which
shows improvements in heat, solvent and product resistances with more
gloss and adhesion than a conventional ink, thus offering the possibility
of overcoming difficult print specification problems. The principal types
are now usually based on epoxy–amine chemistry and isocyanate-cured
systems are no longer in favour.
These inks also have disadvantages:
. the need to mix two components together before printing;
. limitations of pot life after mixing which can create waste ink;
. formation of an insoluble deposit on the stereo or part of the press if
allowed to dry out;
. in certain cases odour may be a problem if the print is not properly
cured.
Given these difficulties, two-component inks are used for certain
applications where conventional inks will not satisfy the resistance or
adhesion requirements. One way of reducing the problems is to use a
two-component white overprinted with conventional colours and under
these conditions the resistance properties of the colours are also
improved.
592 FLEXOGRAPHIC INKS

Daylight fluorescent inks

Flexographic printing with daylight fluorescent inks has not increased in
recent years, although some of the problems with poor strength have
been resolved with the availability of better pigments and soluble fluor-
escent toners.
The inks can be used on paper substrates but when film prints are made
it is better to print over a white as the inks are transparent and contrast is
improved. Single-colourant formulations are best, as mixing two colours
has the effect of quenching the fluorescence. Both organic solvents and
water-based inks can be made using the binders contained in the toners
or with simple resin systems. By using the coloured inks to overprint
suitable white inks different substrates can be accommodated.

Overprint varnishes
The majority of flexographic printing on paper, foil and film is carried out
without overvarnish, since this is an additional cost and requires the
availability of a spare unit on the press. Certain work will specify or
need a varnish to enhance the print or perform a certain function.
Varnishes may also be used to increase resistance performance of the
print which cannot be achieved any other way and examples of these are
paper cups and plates and also some labels.
The most recent application need for varnishing is the increased use of
cold-seal adhesives for packaging. These adhesives are based on latex and
are applied to the reverse side of the web and function by contact. Since
adhesion to the face side of the web is to be avoided, a release varnish is
applied over the print. Although it is possible to formulate inks which
perform a similar function, total ink coverage is required because any area
left uncovered would allow the adhesive to stick to the substrate. Total
coverage is the exception and over-varnishing has thus become normal.
Polyamide resins are used in these varnishes and the aim is to achieve
good release, lowest odour and good drying. Tests will need to be made
over a period to ensure that release properties are maintained. The use of
additives for slip and abrasion resistance will need to be thoroughly tested
to ensure that they do not interfere with the properties of the adhesive.
Specialized varnishes may be used to give particular properties. Among
examples are varnishes applied over a print to aid heat sealing and barrier
varnishes which will require high resin solids to obtain maximum film
weight. Two-pot varnishes give good barrier properties.
Water-based varnishes are increasingly being used to replace organic
solvent-based systems and in many cases similar results can be obtained.
Some of the problems that are experienced using water-based pigmented
systems are easier to overcome with varnishes and it is expected that the
trend will continue.

9.5 INK-RELATED PRINTING PROBLEMS AND

POSSIBLE SOLUTIONS
A number of problems can occur during printing and these may be a
consequence of many factors including substrate, press design, ink and
INK-RELATED PRINTING PROBLEMS AND POSSIBLE SOLUTIONS 593
operating conditions. Most problems will be overcome by experienced
printers making adjustments as necessary, although sometimes it may not
be possible to do so with the equipment or materials available.
The following problems are discussed which may have an ink origin
but it should not be assumed that these are always ink related as usually
there are a number of possible causes, not all of which are discussed here.
An ink change to one with different properties may overcome a particular
problem even though the fundamental cause may lie elsewhere.

Colour and print appearance faults

Colour and strength drift may occur during a printing run. Viscosity or
machine variations may be the cause, but a badly dispersed or formulated
ink may be unstable after dilution giving rise to pigment settlement or
flocculation. Loss of gloss may be noticed and the condition may be
aggravated if the solvent balance becomes upset due to evaporation
from the duct leading to resin precipitation. Good processing, care in
selection of materials, binders with good mutual compatibility and sol-
vent blends with controlled evaporation to retain balance should avoid
such problems.
Mottle and poor lay can be the result of over-reduction of the ink but
formulations which have poor flow tend to produce prints with lay faults.
Over-pigmentation or poor pigment/vehicle wetting may be a cause and
this should be corrected during formulation. If the problem is caused by
the ink not wetting the substrate the addition of an alternative solvent or
a better wetting binder may improve the lay properties.
Inks with poor flow or bad wetting may cause a ‘ghost image’. This
is the appearance of a fainter unwanted image in a printed area and is
the result of local ink starvation on the transfer roll from the previous
impression.

Printability faults
Dirty working is probably the most common printing fault with flexo-
graphy. When the problem is due to ink, poor resolubility on the edges of
the stereo is the main reason, causing dried ink to build up, thereby
enlarging the stereo and giving it a ragged thick edge which shows on
the print. The use of a slower solvent or retarder will minimize the
problem, although binder solubility and low speed of solution are funda-
mental causes. Inks that need high resistance properties may necessitate
the use of a binder which has poor solubility in flexographic solvents and
this may give rise to dirty working.
Pinholing can occur on coated films, particularly MS film, due to poor
wettability of the surface giving rise to ink crawl after impression and
before drying. The addition of anti-pinhole compound may overcome the
problem by improving wetting and sometimes an alternative mix of a
diluent which includes a good wetting solvent will also help. Surface
properties of substrates can vary and the printer may increase the ink
film weight or pre-heat the web.
594 FLEXOGRAPHIC INKS

Pinholing or bad wetting may also be evident on overprinting colour on

colour, due to the non-wetting of the dried ink surface by the next colour.
Some ink additives and waxes can cause this problem.
Stereo swelling is normally caused by solvent attack and absorption on
stereo materials. This problem is fundamental to the choice of both
solvent and stereo composition. Changes consistent with the properties
of these are required as soon as the problem is detected.
Foaming of water-based inks may be attributable to the press recircu-
lation system causing high turbulence of the ink and thus aerating the
liquid at a faster rate than it will break down. Some resins and formula-
tions are prone to this problem, although the addition of a small quantity
of an anti-foam compound will normally overcome the foam.

Drying problems
Solvent retention of prints is of great concern with food packaging. Given
the low ink film weights deposited by flexography and the good drying
equipment available, solvent retention is not normally a problem but
occasionally on some substrates retention is encountered. A good solu-
tion is to increase the strength of the ink, as this will allow a thinner film
of ink to be carried which is more easily dried. Choice of binder and
solvents used in the ink will also determine the drying characteristics and
with film inks the type of substrate will influence the solvents choice, it is
best to avoid those which soften films or coatings.
Pick-off is a possible fault when overprinting colour, and is caused by
the first-down ink not being sufficiently dry and remaining tacky when
overprinted. Increasing the drying speed of the diluent mix on the first
colour should help to overcome the problem or, alternatively, applying a
thinner film of a stronger ink.
Screening, which is the appearance of a screen pattern on the print, can
be caused by ink which dries too rapidly giving evaporation during
transfer from the anilox to the stereo. The engraved pattern thus shows
on the print. Retardation of the ink is the obvious solution as the ink may
be formulated with solvents too fast for the press. The use of dual purpose
flexo/gravure inks can produce this problem because the choice of sol-
vents is governed by the fast solvents required for gravure.

Problems in the reel

Blocking of print in the reel is mostly a problem when printing on non-
absorbent substrates, and appears as sticking or transfer of the image to
the unprinted side of the web. Solvent retention can be a cause since this
will make the ink soft and liable to transfer under pressure. Ink formu-
lations which contain too much plasticizer or low molecular weight
binders can also be soft and sticky after drying, and these will cause
blocking. Blocking tests are a standard procedure during ink formulation
and these problems should be avoided at source.
Solvent retention may cause ‘ghosting’ in reels of printed coated films,
and this phenomenon appears as a faint cloudy image on the reverse side
 RECENT TRENDS 595
of the web due to a partial solution of the coating. The presence of traces
of slow evaporating powerful solvents in the ink or diluent is the most
common cause.
Odour in the print may be caused by the substrate or by retained
solvent, but certain resins used in ink have some odour which may be
worse in the presence of retained solvents. All materials used in ink
formulations require careful selection and screening.

9.6 RECENT TRENDS

Process developments
Notable flexographic process developments of recent times which are
widely used are reverse-angle doctor blades, ceramic anilox rollers and
improved rubber and photopolymer plates. Although in general these
changes have assisted the process by a better control of the ink film, it has
become necessary to produce stronger inks with more flow, in order to
preserve sufficient colour intensity given the lower ink film weights used.
Because of the growth of halftone printing on polyethylene and other
films, press improvements were necessary to achieve accurate impression
and good register. Inks were also developed with the better resolubility
properties which are essential to colour process printing.
Another press requirement for the future, given the likely increase in
the use of water-based inks, will be improved drying systems if existing
running speeds are to be maintained.

Substrates
There have been few fundamental changes in substrates in recent years
although variations in film coatings and laminated complexes have posed
new problems of adhesion for the inkmaker. There has also been an
increase in the use of white-pigmented films which do not require the
use of a backing white ink. Under these circumstances, and where crimp
jaw heat sealing is in the colour printed area, it has proved difficult to
avoid jaw marks on the print surface.
Water-based inks which are extensively used for paper printing will
need to have improved drying properties as the use of coated papers
becomes more commonplace.

Market changes
Changes in the market, and requirements of the market, for flexographic
printed materials have traditionally been a large stimulus for change in
inks and associated products. Market changes however, have in the past
been somewhat difficult to predict.
More predictable is the continuing increased speed of packaging
machines and the relentless search for lower cost printed packaging
materials. The former necessitates inks with higher slip, and the latter
requires inks which have lower cost or greater coverage.
596 FLEXOGRAPHIC INKS

The flexographic process continues to gain an increasing share of the

market over some other processes. One example of this is the flexo-
graphic printing of newspapers. A further example is the wider adoption
of the process to print packaging materials, given the trend towards
shorter runs and more design changes which are more economic by
flexography than by gravure.
Market changes driven by environmental considerations are likely to
affect ink requirements considerably in the future and this is discussed
later in this section.

Ink development
Raw material developments have continuously aided the progress of ink
development, and, by better communication, the suppliers now have a
greater understanding of the needs of the ink industry. Resin and pig-
ment developments have continued to make new products available to
the industry. It remains to be seen, however, if an increased priority
placed on safety and environmental requirements results in any reduc-
tion of the pace of these developments.
Many new ink products result from development work to create
improve performance products, or more rarely, from new and original
concepts. Successful new developments tend to be more rapidly con-
cluded when the work is conducted in cooperation with a converter or
end user.
Two fields of work which are being intensely studied by various ink
makers are those concerned with water-based inks and radiation-curing
inks.
Considerable progress has already been achieved with new water-
based inks for certain substrates used in particular applications, although
these products have not, as yet, been generally adopted by printers and
converters. There is much work which remains to be done if these
products are to give similar results to those achieved after decades of
development, with organic solvent-based systems.
The technology of radiation-curing inks for flexographic printing is
being studied. This research is generally being carried out in conjunction
with equipment and press manufactures because the problems to be
solved involve printing press design and UV-lamp technology as well as
ink chemistry.
UV flexographic inks are already in use for certain applications and
early indications are that more rapid progress is likely with flexography
than with the gravure process.

Environmental considerations
Society has become increasingly concerned about the impact on the
environment by industrial processes. These concerns inevitably force
governments to introduce legislation to control pollution of different
kinds. The type and the extent of legislation tends to vary from country
to country and at a higher level in the more developed part of the world.
 RECENT TRENDS 597
The printing and ink industries are not normally considered as highly
polluting industries. Nevertheless, their activities will be controlled by a
number of anti-pollution measures which, when fully enacted, will have
a severe impact on the way they operate. In the remainder of this section
three areas where regulations will directly affect ink and print technology
will be discussed. For full details of all current regulations see Chapter 17.
First restrictions on the emission of solvent into the atmosphere are
already in force or being progressed in several European countries. The
EC Directive[2] is currently at the draft stage and national regulations
such as the air pollution controls which are part of the UK Control of
Pollution Act 1990[3] are currently being enforced. Solvent emissions
from print installations will be required to be at much lower levels than
are currently the practice using solvent-based inks.
Along with other processes, flexographic printers will need to consider
the various options to reduce their emissions to such levels that will be
allowed. The following options might be considered:
. incineration
. solvent recovery
. biological treatment
. water-based inks
. radiation-cured inks.
Of the above only incineration has fully proven technology. All options
are likely to more expensive than current practice. The dilemma for the
industry is which to choose, and will any option chosen be technically
feasible within the time allowed for implementation.
Of the options given, the first three are largely the province of the
printing industry, but with solvent recovery, suitable inks will be neces-
sary dependent upon the type of equipment used. The last two options (as
has previously been stated) are currently the subject of development by
inkmakers, but as yet, these methods are not fully proven for all current
applications.
Finally, potential new regulations on waste management are currently
under debate. These are likely to have an impact on packaging and the
materials used for packaging. Re-use and recycling targets for packaging
waste are likely to be set. Furthermore, controls are likely in regard to
limits on how much packaging waste can be disposed of into landfill. As
yet, however, the final outcome is not clear.
The reuse and recycling of packaging may favour certain materials over
others. In general it is more difficult to recycle packaging made from
mixed materials, unless the mixture is compatible to enable manufacture
of a product without separating the components. Recycling often involves
extrusion and moulding and studies of ink components are being made to
see if these cause problems during the respective process. Waste regula-
tions could affect the choice of packaging materials and in turn the types
of inks with which to print them.
There is no doubt that the impact of printing ink on the environment
has become an increasing part of our thoughts and actions. It follows that
this will lead to continuing and increased development within the indus-
try, aimed at environmental improvements in the use of the ink itself.
598 FLEXOGRAPHIC INKS

BIBLIOGRAPHY
1. MAFF. Survey of Plasticiser Levels in Food Contact Materials and in Foods.
Food Surveillance Paper No. 21 (1987) No. 30 (1990), HMSO.
2. EC. Draft of Council Directive on the limitations of emissions of organic
solvents from certain processes and industrial installations.
3. UK-DOE. Environment Protection Act 1990, Part 1. (Processes prescribed for
air pollution control by Local Authorities), HMSO.