4 PIGMENT AND RESIN TECHNOLOGY NOVEMBER 1978

Progress in
water based
printing inks*
by G. H. Hutchinson**

Introduction
The trend towards a greater use of water as
the solvent in flexographic and gravure printing inks
has been influenced by a number of factors — the
growing attention to environmental pollution pro-
blems, health and safety aspects, elimination of
residual print odour in food packaging printing and
conservation of organic solvents.

Historical
For many years ink manufacturers have
investigated the use of water as a component of
various types of printing inks. Even before any
extreme pressures were brought about by anti-
pollution legislation and problems of raw materials
shortages, the economies that could be achieved
through using water as a major solvent component
were attractive. Earlier investigations, however,
showed that there were technical restrictions on the
use of water, except in minor proportions in letter-
press and offset lithographic printing inks. However
there was an obvious potential for more extensive
use in flexographic and gravure inks. This can be
illustrated by outlining the essential mechanics in-
volved in the four major printing processes. Fig. 1
is a simplified schematic outline showing the
different inking systems.

Letterpress and offset lithographic printing inks

Examination of Fig. 1 shows that in letter-
press and lithographic printing processes, the ink is
carried to the plate by means of a train of rubber
rollers which means a thin film of ink is distributed
over a large surface area. Both letterpress and offset
lithographic printing processes preclude the use of
volatile organic solvents in the inks because of the
swelling effect or attack on the rubber rollers and
blankets and because of their high evaporation rates
which would lead t o premature drying or tack deve-
lopment of the ink film on the rollers, plates and
blankets. Water is also evaporated more rapidly
than the high-boiling aliphatictype solvents normally
used in letterpress and offset lithographic inks, by
the heat that can be developed (30°C or more) in
the rollers after a period of running. Several different
types of drying mechanism may be used in the *Presented at the OCCAA Pacific Paint Convention, Can-
printing of offset lithographic and letterpress inks, berra, 1977 and First published in Australian OCCA
Proceedings and News, December 1977.
depending on the particular print application and **Croda Ink Ltd., Edinburgh, Scotland.
NOVEMBER 1978 PIGMENT AND RESIN TECHNOLOGY
substrate which dictate the type of ink formulation
to be used. Excluding inks that are cured by ultra-
violet radiation, these mechanisms could involve
penetration (absorption), oxidation and evaporation
or combinations of some of these methods. A n ink
used for rotary letterpress printing of newspapers
dries mainly by absorption into the pores of highly
porous newsprint stock. A combination of surface
absorption into t h e paper or board substrate and
subsequent oxidation-polymerisation of the pig-
mented oleoresinous surface layer is a method by
which many offset lithographic and letterpress inks
are dried.
In heatset web offset lithographic printing,
the ink films on the last-moving paper w e b are dried
rapidly by evaporation of the high boiling solvent
component of the inks, using a drying oven w i t h
gas flames or hot air impingement. In the water
miscible type of letterpress ink used, e.g. for prin-
ting corrugated boards, the vehicle may be a glycol
solution of an alkali soluble resin — maleate or
shellac resin incorporating appropriate quantities of
alkali (alkanolamine) t o saponify a sufficiency of
carboxyl groups, thereby rendering the ink water-
miscible. In this system, the basic method of ink
drying comprises absorption of some glycol solvent
into the surface fibres of the board promoting gela-
tion of the pigment: resin-soap complex on the
surface and subsequent transformation of the water-
soluble complex t o the water-insoluble form. The
transformation is aided by evaporation of the amine
a n d / o r decomposition of the soap complex by the
acidity in the board when the surface pH of the
latter is sufficiently low (pH 4 - 6 ) . The dried ink film
on the board has a degree of w e t rub resistance yet
the printer can wash rollers and plates and water
because on these non-absorbent surfaces the ink
film remains 'wet' for a long period, retaining
adequate water miscibility. It is of course practic-
able to use water in the vehicle of water-miscible
letterpress inks, replacing a proportion of glycol as
both the resin soaps and glycol solvent are water-
soluble. The proportion used must take into account
the particular end-use application, which has a bear-
ing on the quantity of ink t o be carried by the rollers
and the length of the print run; these are factors
influencing the stability of the ink on both the roller
train and printing plate. Furthermore, too high a
water content replacing glycol can give inks of poor
flow and transfer, hence inferior printing properties.
In the early 1960s there was some interest in
waterbased news inks, which dried by absorption of
water into the highly porous newsprint. Unfortu-
nately, the high water content of the inks and the
tackiness of the ink film after printing caused paper
fibres to be deposited on the printing plate. There
was little further progress in this field. Emulsion
5
news inks in which the water can be incorporated
as the disperse phase in a predominantly mineral oil
vehicle are still attracting attention and there has
also been a renewed interest in using water in a
similar manager in some types of web-offset printing
inks. W i t h offset lithographic inks, water can be
incorporated only in such a w a y that it does not
interfere w i t h the separation of the image and
non-image areas when the ink reaches the litho
plate. This separation of ink-receptive (water-repel-
lant) and water-receptive (ink-repellant) areas is
aided by application of fountain (dampening) water
t o the plate. Lithographic inks must not emulsify so
as to give ink-in-water emulsions, otherwise tinting
and scumming problems could arise. Choice and
quantity of the surfactant used for these products
is very important. However one views the potential
use of water as a major solvent component in letter-
press or offset lithographic inks, the evaporation and
instability problems are not likely to be eliminated
on existing, large fast-running printing presses and
quantities of water incorporated in suitably formu-
lated inks w o u l d seem t o be limited to minor
amounts, say less than 20 per cent.
Flexographic and gravure inks
The ink distribution systems on flexographic
and gravure printing presses are quite different from
those of letterpress and offset lithographic printing
machines. There are no long ink roller trains, and
the solvents used in conventional flexographic and
gravure inks must be volatile since the drying pro-
cesses depend mainly on evaporation. It is not sur-
prising, therefore, that recent interest has been in
water-based inks for flexographic and gravure print-
ing. Attention may be drawn to the following re-
views on progress in water-based inks 1 and on
water-based and water reducible flexographic inks 2 .
THE REASONS FOR CONTINUING RESEARCH
The printing ink industry has become in-
creasingly dependent on petrochemical sources for
its ink-making materials, pigments, synthetic resins
and solvents, therefore the availability of appro-
priate feedstocks for these products is of prime
interest t o the industries concerned w i t h their manu-
facture. In 1974 the worldwide shortages and rising
prices of petroleum made it essential for industry to
economise in the use of expensive organic solvents
and there was an upsurge of interest in water-based
printing inks, w i t h water-based gravure inks attrac-
ting particular attention. Then followed a period of
economic recession during which there have been
no major problems in the availability of organic
solvents and from this aspect no pressing needs for
users to investigate water-based materials. A great
deal of uncertainty in the future economics (price
6 PIGMENT AND RESIN TECHNOLOGY
and availability) of petrochemical derivatives and
the real possibility of a period of shortages coincid-
ing w i t h increased demand indicate that there
could be an urgent need for alternative water-based
products replacing their organic-solvent based
counterparts.
Availability of appropriate feedstocks for
organic pigments, resins and solvent manufacture is
not the only consideration. Ecological pressures cal-
ling for more expensive manufacturing plant and
reduced incentive in the investment area can lead
to a lack of manufacturing capacity for any of these
groups of products.
Advances in printing inks including the
'solvent-free' ultraviolet curing inks, low odour and
low emission heatset inks and water-based inks have
been stimulated by the growing attention t o environ-
mental pollution problems. Research has been par-
ticularly active in the USA where the need to control
solvent emissions led t o the well-known Los Angeles
Rule 66 legislation. This limits the use of certain
photochemically-active solvents because of their
'smog' producing tendencies. In the particular
climate and environment, ultraviolet light from the
sun promotes the interaction of certain of these
solvents and the components of motor car exhaust
gases t o produce eye irritating smog. While the
conditions of this type of smog development are
NOVEMBER 1978
more likely to occur in areas such as Los Angeles
where climate, environment, industrial and traffic
densities produce the worst possible circumstances,
the trend will inevitably be t o legislate for a cleaner
atmosphere in our major cities and industrial com-
plexes.
In the UK the requirements of the Health
and Safety at Work etc. A c t 1974 have far-reaching
implications for the development of printing inks
and coatings that are free from noxious and irrita-
ting solvents and there is a provision in the A c t for
controlling certain emissions into the atmosphere.
Thus in Section 5 (1) " i t is a duty . . . to use the
best practicable means for preventing the emission
into the atmosphere of noxious or offensive sub-
stances . . .". This requirement alone should attract
increasing interest in water-based inks and coatings
for flexographic and gravure printing. Looking at
other printing processes, there has been significant
progress in the development of low odour heatset
w e b offset inks and in ultraviolet curing inks based
on substantially involatile systems. The A c t imposes
duties on ink manufacturers to ensure that so far as
is reasonably practicable their products are safe
and without risk to health when properly used. There
seems little doubt t h a t inks and coatings i n which
water is the major solvent component w i l l help to
increase safty in use because of the reduced fire
NOVEMBER 1978 PIGMENT AND RESIN TECHNOLOGY
hazard and in addition to the benefits of less pollu-
tion to outside atmosphere, help to produce a
cleaner environment in the press-room. A further
practical advantages of suitably formulated water-
based gravure inks and water-based gravure over-
print varnishes is their m a r k e d l y reduced residual
print odour in food-packaging printing compared
w i t h wholly organic solvent-based equivalents. This
aspect is receiving increasing attention.
REVIEW OF DEVELOPMENTS IN WATER-BASED
PRINTING INKS
Flexographic inks
Water based flexographic inks have been
used commercially for some time mainly for printing
corrugated boxes, paper bags and multi-wall sacks
and w i t h these absorbent substrates the require-
ments have been for low cost inks producing a
serviceable print finish, w i t h no demand for a high
gloss or special resistance properties. For these inks
there has been a trend away from the conventional
vehicles based on aqueous solutions of alkali-
solubilised shellac and rosinmaleates t o the use of
resin media derived from petrochemical sources. In
recent years the chemistry and technology of poly-
meric materials PVA, PVDC and acrylic copolymers
used for water-based paints has been exploited by
resin manufacturers in the development of special
media for use in printing inks. There were early
problems for the ink makers in the use of these
water dispersible polymers, including foaming ten-
dencies, unacceptable odour and instability during
storage but w i t h increasing knowledge of the be-
haviour of these media in pigmented systems and
the availability of improved polymers, many of the
initial problems have been overcome.
The newer types of water-based flexo inks
have advantages over the conventional inks chiefly
in their faster drying and improved dry and w e t rub
resistance, properties which are essential for appli-
cations such as wallpaper printing. They are also
superior to the aqueous shellac/maleate types, in
solvent (water) release properties and this is mani-
fested by faster setting and the absence of the
intervening sticky stage, characteristic of many of
the conventional types of aqueous inks. Water-
based flexo inks formulated on acrylic type copoly-
mers have found increasing applications for wall-
paper printing and an expanding field is for printing
heat transfer papers, the designs on which are
subsequently transferred in the vapour phase to
synthetic textile fibres. The dispersions of sublim-
able dyes must have good printability properties,
fast drying and good rub resistance of the printed
papers.
7
Water reducible flexographic inks
Water-based flexographic inks are usually
reducible w i t h water or mixtures of water w i t h
minor amounts of polar solvent (alcohols).
A new group of products are recently deve-
loped by the author's company t o help printers
exercise economy in the use of polar organic
solvents that are required to reduce inks t o printing
viscosity. The new products contain no water but
can be thinned at the press w i t h a reducer based
substantially on water containing a minor amount
of glycol ether solvent. Another major advantage
of these inks is that they have a flashpoint in excess
of 32°C and are therefore exempt from the UK
Highly Flammable Liquid and Liquefied Petroleum
Gases Regulations 1972. The inks are dyestuff con-
centrates of high colour strength yielding prints of
good holdout on paper and a brilliance similar to
alcohol reducible dyestuff concentrates. Uses are for
printing envelopes, stationary and pool coupons.
Water-based gravure inks
Early attempts to formulate water-based
gravure inks were not very successful and there
were some formidable problems for printers. One
was distortion or a 'cockling' of the paper and an-
other the insolubilisation of inks in the cells of the
engraving when the press was stopped for a short
period of time. The latter was very serious because
i t was impossible to remove the early types of ink
from the cells and t h e engraving was ruined. Since
then such progress has been made and these t w o
problems have been largely overcome, although
there are others which require further attention. A
programme of development carried out in Croda
Inks laboratories led t o the 'Aquavure' series of
water-based gravure inks and overprint varnishes.
It is useful t o compare the properties of these inks
w i t h conventional solvent based inks under head-
ings of Cost, Drying and Printability.
1. Cost — Despite t h e fact that the solvent
component of water-based gravure inks is water or
water w i t h minor amounts of alcohol solvent, the
cost can be higher than that of conventional inks of
equal colour strength and light fastness. Factors
influencing this are the selection of suitable pigments
and polymers for the water-based media so as to
produce optimum printability properties and ade-
quate shelf life of the finished inks. The thinners
used at the press w i t h water-based gravure inks w i l l
of course be much cheaper than organic solvents as
t h e y consist of water, or water w i t h about 30 per
cent. isopropanol, giving a thinned ink in the duct
containing approximately 13 per cent. organic
solvent. It would be difficult to predict the future
economics of water-based gravure inks and much
will depend on future developments in water-based
8 PIGMENT AND RESIN TECHNOLOGY
polymers to increase the range available for use in
inks and ensure competitiveness w i t h resin systems
based on organic solvents. Even so the ability to
economise in the use of reducing solvents may well
compensate for the higher price of water-based
gravure inks and more experience in their use will
establish the extent of these economies.
2. Drying — On absorbent papers and
boards the running speed of modern water-based
gravure inks compares favourably w i t h that of
conventional solvent based inks due to the water
wetting the paper fibres more rapidly than does the
solvent. The modern types of water-based ink set
rapidly to a tack-free state and the high running
speed achieved on gravure presses w i t h normal
drying facilities is due to this property rather than
the water being completely evaporated by the
dryer. This however leaves the water content of the
substrate higher than normal and it may be advan-
tageous in some cases to use radio-frequency
drying prior to re-reeling or sheeting so as to remove
excess water. Early trials w i t h 'Aquavure' inks on
various machines using coated papers have achieved
running speeds of 500 f t / m i n u t e on a full depth solid
print w i t h water-based ink followed by water-based
gloss over-print varnish showing no signs of set-off
on the cold water roller and no modifications were
made t o the machine drying system. In other trials
using MG paper, running speeds of 350 f t / m i n u t e
were achieved, again w i t h no set-off problems or
alterations to the drying system.
Once printed and dried on the substrate the
inks become quite insoluble in water. Modern water-
based gravure inks should re-dissolve in themselves
if they have been allowed to dry in the engraving
but if trouble is experienced in this respect, a little
toluene or MEK solvent w i l l remove the ink com-
pletely. On non-absorbent surfaces where the drying
is not assisted by penetration it has to be taken into
account that water is much less volatile than, say,
ethylene glycol monoethyl ether which is usually
regarded as an ink retarder. Here again one has to
take into account the effects of solvent retention as
well as solvent volatility. If solvent release is slow
the ink goes through the sticky stage, a problem
associated w i t h the rosin-maleate and shellac-based
aqueous inks. The modern water-mased gravure
inks based on water dispersible acrylic copolymers
have better 'solvent' release properties which meet
the conditions for 'tack-free' inks w i t h no 'set-off'
on the cold water roller.
Experience has shown that some presses are
deficient in drying power, caused by an insufficient
volume of air. To remove water vapour effectively
t w o or four times the volume of air is needed w i t h
conventional organic solvent vapours and this calls
for larger, more powerful fans to be fitted to the
NOVEMBER 1978
exhaust side of the drying hoods. It has been found
that radio frequency dielectric heating is very effec-
tive in drying water-based inks. In this connection
experience has shown that this type of dryer must
be provided w i t h adequate air circulation to be
effective.
3. Printability — it has been stated 3 that
w i t h aqueous gravure inks, optimum printability
w i t h maximum press speeds will not be obtained
using a conventional 150-line screen. Cylinders w i t h
175 to 250-line screen and a relatively shallow etch
are required to achieve press speeds and printability
approaching organic solvent based gravure inks.
These requirements are essential because water-
based inks are transferred in greater volume from
the cells than are organic solvent based inks. Fur-
thermore, in water-based vehicles w i t h adequate
hold-out properties on absorbent papers there is
less inherent flow and penetration of the paper sub-
strate, resulting in a tendency for the inks to
'screen'. The paper or board substrate has an
important influence on printability properties, the
absorbency and smoothness characteristics, affec-
ting speed of setting and gloss properties of the
inks. On coated label papers the 'Aquavure' inks
give a higher finish to the ink film than on news-
print. There are continuing investigations t o obtain
improvements in gloss properties through choice of
suitable water-based media t o give optimum pig-
ment dispersion and Theological properties, balanc-
ing ink flow-out on the paper, or board surface, w i t h
adequate speed of ink setting and drying. Much
more practical experience in the use of water-based
gravure inks is needed to investigate the extent of
paper distortion or 'cockling' due t o water uptake
In a trial on a Regina machine using a newsprint
quality of paper there were slight signs of paper
distortion on the reverse side corresponding to the
heavier solids areas but this did not cause any
subsequent difficulties. However, some water-based
inks do cause paper distortion, possibly through
prolonged solvent (water) retention of the resin
component, meaning that there is more time for the
water to be soaked up especially by the more
porous uncoated papers. W i t h coated papers exces-
sive water absorption by the body stock fibres may
be prevented by the coating acting as a barrier
although there must be sufficient absorbency in the
coating to allow initial penetration 'setting' t o take
place. In a recent informative paper on water thinn-
able acrylics for printing inks, Knightly 4 ascribes
defects in the printing of water-based publication
gravure inks on a clay/starch/latex coated paper,
to the hydrophilic character of the clay coating caus-
ing distortion of the cell presumably by capillary
action producing a blurred print lacking the depth
and clarity of a solvent-based ink. There was a
NOVEMBER 1978 PIGMENT AND RESIN TECHNOLOGY
misregister problem, due to 'cockling' of the paper,
particularly on solid areas of colour, which later
gave set-off problems, due to lack of drying capa-
city. It is suggested that these problems could be
overcome by the development of papers and paper
coatings specifically designed for aqueous printing
inks, high velocity air-hoods to drive off the water
and gravure cylinders w i t h shallower etch depths to
allow less ink of higher solids t o be applied. The
defects mentioned were related to wholly water-
based gravure inks and no doubt the requirements
of existing papers and printing machines w o u l d be
more nearly met by the use of water-based gravure
inks containing some alcohol solvent. One desirable
effect that water-based gravure inks have on the
paper substrate is to remove completely any static
electricity from the w e b thus rendering the subse-
quent handling of paper much easier.
4. Lower residual print odour — The advan-
tages of the lower residual print odour which can
be achieved using water-based gravure inks have
been exploited in inks and overprint varnishes for
confectionery wrappers. These printed wrappers
and cartons (e.g. chocolate boxes) are required t o
be completely free from odour and tainting of the
confectionery product. Finished print has to meet
stringent specifications and testing is by gas liquid
chromatography and by odour 'panels' (subjective
testing by smelling the print and tasting t h e con-
fectionery products).
5. Adhesion and printability on impermeable
substrates — 'Aquavure' water-based inks f o r m u -
lated on vehicles prepared from alkali soluble acrylic
copolymers w i t h ca. 13 per cent. isopropanol solvent
in the finished ink were printed on various cellu-
losics, plastic films and aluminium foils. W i t h the
exception of M.S. film which exhibited pin-holing,
printability and adhesion was satisfactory on coated
and uncoated cellophane and on treated polyethy-
lene, polyester and PVC film. However on the PVC
substrate the degree of w e t rub resistance was not
up to the standard required for vinyl wallcoverings.
When considering inks for impermeable substrates,
water-based inks unfortunately have t w o principal
shortcomings when compared w i t h their organic
solvent-based counterparts. During drying, water
requires much more heat energy t o evaporate it by
comparison w i t h organic solvents of similar boiling
point, and, despite the fact that prints of water-
based inks on papers and boards can achieve a good
level of w e t rub resistance, the inks yield less resist-
ant films on plastic substrates; their chemical and
product resistance is also generally inferior t o that
obtainable from the types of organic solvent based
inks normally used for printing plastic substrates.
Although modern water-based gravure inks set and
dry well on papers and boards, an effective source
9
of heat energy is required t o evaporate the water
when such inks are applied to impermeable substra-
tes or when a thick film is deposited (as in superim-
position of several colours). Radiofrequency energy
in the form of microwave or the less costly RF
dielectric heating is an effective form of volume
heating by virtue of the penetrative effect and
stimulation of polar molecules such as the water
'solvent'. The highly polar water molecules are vola-
tilised throughout the film rather than initially at the
surface as is the case in conventional hot air heating.
More uniform heating therefore produces less
chance of surface hardening of the film and of
residual solvent being trapped in the film. Some
applications of microwave and RF dielectric heating
have been reviewed in a recent paper 5 . In a test using
a gravure proof press in line w i t h a 27 MHz RF dry-
ing unit, it w a s demonstrated that a blue water-
based gravure ink formulated on phthalocyanine blue
pigment and alkali soluble acrylic copolymer resin
system could be printed and dried effectively on
treated polyethylene film, yielding a smooth print
free from reticulation of other imperfections. Print
abrasion resistance and adhesion by Scotch take
test was good although after water-soaking, the
print was much inferior in rub and scratch resistance
to that obtained w i t h a conventional solvent-based
ink formulated on nitrocellulose/polyamide resins.
The problem of inferior w e t rub resistance and
chemical resistance will be given further discussion
in the section on chemistry and technology of water-
based inks.
In spite of some current limitations in the use
of water-based flexographic and gravure inks the
advantages to be gained from the very considerable
reduction in atmospheric pollution, benefits of
reduced fire hazard and reduction of solvent vapour
concentrations in working areas, whether in the ink
factory or print shop, provide considerable incentive
for continued research and development towards
improved products. More recent developments in
water-based inks w i l l be discussed in the concluding
section of this paper.
FURTHER APPLICATIONS FOR WATER-BASED
INKS AND COATINGS
W i t h continuing advances in the chemistry
of water dispersible polymers leading to improve-
ments, for example in gloss properties, there is likely
t o be a revival of interest in water-based overprint
varnishes for application 'wet on w e t ' t o sheet fed
litho printed papers or boards. In this technique the
application is via the dampening system on the press
or by a single coating unit attached to the press. A
US patent 6 advocates the use of microwave energy
to cure aqueous varnish systems that are applied
directly over freshly printed lithographic and letter-
10 PIGMENT AND RESIN TECHNOLOGY NOVEMBER 1978

press ink films. The varnished sheet is passed

through the dryer where the varnish is dried rapidly
to give a transparent protective film. This prevents
the ink setting off in the stack while the underlying
ink films can still dry by the normal oxidation pro­
cess. Water-based coatings for the metal decorating
field are attracting attention and can utilise cross-
linking systems in which water dispersible resin
components can be interacted at high temperature
and for longer periods than are practicable for plastic
films or paper and board substrates.

SOME ASPECTS OF THE CHEMISTRY A N D

TECHNOLOGY OF WATER-BASED INKS
Advances in the field of water-based inks
and coatings for the printing and packaging indus­
tries will depend to a great extent on the contribu­
tions of pigment and resin manufacturers working
in co-operation w i t h each other and w i t h ink manu­
facturers. This joint co-operation w i l l be essential
to get a better understanding of pigment dispersion
problems, rheology of the inks, stability, drying and
film formation mechanisms. Studies on water-based
paints will continue to contribute to developments
in the printing ink field although the problems are
different and particularly so in the methods of appli­
cation. For example on high speed printing machines
copolymer emulsions which are dispersions of small
spheres of polymers (0.2 to 1μm) tend to coalesce
when the water content becomes less than 26 per
cent.
Attention may be drawn to informative
papers by Sauntson 7 and Knightley 4 on acrylics for
water-based printing inks. Another useful contribu­
tion on the use of synthetic resin dispersion in
acqueous printing inks in by Firmin 8 .
Sauntson 7 describes the preparation of water
soluble polymers — the alkali soluble type of acrylic
copolymer made by copolymerising a suitable acid
monomer in the polymer. The deposited films are
still water soluble but become water insoluble when
the alkali is removed. If volatile amines are used to
increase pH, the polymer salt can revert to
the water insoluble form by a combination of
mechanisms. The main ones are volatilisation of the
amine and neutralisation by acids in the paper
stock 4 . Alkali-soluble emulsion polymers, when con­
verted to alkaline salts, become soluble in polar
solvents — alcohols and glycols — as well as in
water. Solution takes place when the carboxyl
groups in the long polymer chain become ionised.
Repulsion of like charges then causes the chains to
separate and solubilise; there is a similarity w i t h the
dissolving of solid polymer in organic solvent except
that in this case the solvent is alkaline water. This
indicates that pH of the system is a very important
factor influencing the final properties and form of
the polymer.
The two-dimensional diagrams of Sauntson's
paper 7 are shown in Fig. 2, to illustrate the convers­
ion and the changes that take place when the pH is
raised. The pipe cleaner models of Fig. 3 illustrate
the three-dimensional form.
Raising pH causes the chains in the polymer
emulsion t o separate and the polymer dissolves.
Viscosity increases w i t h the solubilisation and there
is a transition from a milky white emulsion to an
almost clear solution. There is an intermediate
'colloidal dispersion' stage of partially neutralised
polymer. In the process of neutralisation, the visco­
sity of the system increases to a maximum due to
chains opening t o a rod-like configuration. As more
alkali is added the concentration of ions (e.g.
NH4 + ) builds up and has a repressive effect on
the ionisation of the polymer chain. This results in
some chain curling and a reduction in solution vis­
cosity when neutralisation is complete. These solu­
tions from emulsions have several advantages for
use in flexographic and gravure inks. Pigments can
be ball milled into them and the partially dried ink
film is re-soluble in the ink. Pigment wetting and
dispersion properties are good and the deposited
films which w e t most surfaces do not go through a
sticky stage during drying 4 . The intermediate col­
loidal dispersion stage formed during neutralisation
of the emulsion copolymer has interesting proper­
ties; these partially neutralised dispersions are still
redispersible in the ink media and on film formation,
development of w e t rub resistance is faster than
w i t h the solutions because there is less amine to be
volatilised or neutralised for reversion to the acidic
form. Also, drying rate is speeded up because the
colloidal dispersions are less water-retaining than
are the solutions. There are, however, some prac­
tical problems, in that the viscosity is very depend-
12 PIGMENT AND RESIN TECHNOLOGY
ent on pH at higher solids, making viscosity control
very difficult. The use of organic co-solvent in the
preparation of the water-soluble copolymers affects
viscosity, drying rate, stability, pigment dispersion
ability and flow. For example, addition of an alcohol
(isopropanol) w i l l speed up drying rate, reduce
foaming tendencies and give lower viscosity at
equal solids. Although in some cases alcohol addi-
tions can cause rise in viscosity, the effect is gene-
rally t o move the inflexion of the viscosity/pH curve
t o the left so that viscosity stability is obtained at
lower pH values. Concerning the type of base for
the neutralisation of the acid-modified polymer, the
most volatile, such as ammonia, produce rapid
development of water resistance in the film but
press stability is minimised. Using less volatile bases
such as medium-to-high boiling alkanolamines from
monoethanolamine (BP 170°C) to triethanolamine
(BP 3 6 0 ° C ) , the press stability is improved but
water resistance of the ink film is reduced as long
as they remain in the film. Compared to conven-
tional emulsion polymers having molecular weights
ca 250,000 to 1,000,000, the alkali soluble copoly-
mers used for printing inks have generally low
molecular weights (10,000 t o 25,000). It appears
that t o obtain a balance of good printability and film
forming properties t w o separate types could be
used: 'colloidal dispersion' or solution to give
adequate pigment dispersion properties and possibly
the addition of a polymer emulsion to upgrade the
film properties and give a low viscosity/high solids
product.
Behaviour with pigments
It is seen that in the formulation of water-
based flexographic and gravure printing inks, visco-
NOVEMBER 1978
sity, flow, drying speed and film forming properties
are greatly influenced by the type of copolymer, pH
conditions, character of neutralising base and the
type of quantity of co-solvent. These factors also
influence choice of pigments to be used. Because
the predominant solvent is alkaline water it will be
appreciated that even traces of acidity in a pigment
can influence pH in such a way that the stability is
affected by viscosity changes. In studies in the
author's laboratories, for example, it was found that
some grades of Prussian Blue gave a hard precipita-
t i o n due to the residual acidity. In contrast, other
grades containing a proportion of nickel ferro-
cyanide gave quite stable dispersions w i t h the same
water-based media.
Problems due to residual acidity have also
been encountered w i t h the bright pigments derived
from lakes of basic dyes w i t h complex phosphomo-
lybdic acid ( P M A ) or phosphotungstomolybdic acid
( P M T A ) . On the other hand a suggested range of
organic pigments 9 used in water-based inks includes
copper ferrocyanide complexes of basic dyes in red,
blue, green and violet shades. The list of organic
pigments embraces a fairly wide choice in the
yellow, orange, red and blue/green areas. It is
emphasised, however, that care should be taken
when using Red 4B Toners (Pigment Red 57) and
toner pigments in general. The acidic nature of these
pigments may well result in some interaction be-
tween the pigment and the alkaline varnish system
which could result in de-metallisation of the pig-
ment, giving inks or concentrates of poor flow and
colouristic stability. The dispersibility of organic
pigments of different chemical classes in three
different types of aqueous binder, namely, saponifi-
ed shellac, ammonium salt of vinyl acetate/crotonic
acid copolymer, and rosin maleate, has been
investigated 10 .
There was a marked difference in the dis-
persibility of the three binders and it appears that
interactions of the polarity of the pigment and bind-
ing agents are influential; thus it would be difficult
to find an optimum binding agent for the dispersion
of all classes of pigments. The superior effect of the
rosin maleate during dispersion of powder pigment
was attributable t o its good wetting on account of
high polarity at relatively low molecular weight.
In the aforementioned study pre-dispered
pigment preparations were also investigated and it
was found that best results in terms of maximum
colour intensity were achieved w i t h the copolymer
resin. It is suggested that the less polar copolymer
resin which, however, had a much higher molecular
weight than the aqueous shellac or aqueous rosin
derivatives, could stabilise very fine dispersions of
the pigment preparation through steric effects.
NOVEMBER 1978 PIGMENT AND RESIN TECHNOLOGY
WATER-BASED INKS, PRESENT A N D FUTURE
No doubt increasing attention w i l l be given
to improving water-based inks for printing on
impermeable substrates, particularly plastic films
used in packaging. For these applications the devel­
opment of water-based flexographic and gravure
inks w i t h properties equal t o the best obtainable
w i t h organic solvent-based systems is in the future.
No doubt the use of reactive water soluble cross-
linking resins w i l l be a principal route but there are
difficulties in balancing reactivity and stability. Bear­
ing in mind the limitations in temperatures that
could be used when drying inks on plastic films and
the high speed of printing machines, it would seem
that adequate cross-linking using, for example,
melamine-formaldehyde or epoxide type resins could
only be achieved using t w o - p o t systems. Cross-
linking of water-based inks by interaction w i t h
multivalent metal ions, for example zinc/ammonia
complexes as in zinc ammonium carbonate has been
investigated. Given a suitable pH the addition of
these compounds to water-based acrylic copolymer
systems can give a stable one pot ink of good
storage life. Cross-linking takes place during the
drying at ambient temperature leading t o some
improvement in film hardness and water resistance.
Unfortunately the cross links so formed are broken
by the action of ammonia so there are limitations
in this technique. Despite the difficulties in formula­
ting satisfactory water-based inks for printing on
plastic substrates, there have been reports of pro­
gress in the USA 1 1 towards water-based flexo­
graphic inks for printing some grades of polye­
thylene and polyethylene coated board. Also
commercial development of water-based flexo­
graphic inks for lamination purposes which could be
modified to give moderately heat-resistant (150°C)
surface inks and special grades for printing polys­
tyrene and aluminium foil substrates. A contribu­
tion 1 2 reviewing the advances in water-based flexo­
graphic inks that have resulted from improvements
in pigments, vehicles waxes and anti-foam additives,
stresses that when printing non absorbent substrates
the temperature control of drying ovens on presses
is particularly important. Because of the higher
colour strength of water-based inks compared to
solvent-based counterparts it is possible to print
thinner films which therefore print more clearly,
improving trapping of one colour over another, and
achieve high press speeds. It is recommended that
when using water-based inks for printing plastic
films, the highest count Anilox roller w i t h the hardest
rubber fountain or wipe roll which w i l l produce
acceptable colour density should be used.
There should be continuing improvements in
drying techniques through the more extensive use
of RF dielectric heating and further progress in the
13
field of high velocity hot air-jets, helping to widen
the scope for water-based inks. There is also a
revival of interest in the use of infrared radiation to
dry water-based inks The use of so-called infrared-
responsive resins in water-based inks on the basis
of tuning the vehicle and ink system to the radiant
energy of the infrared emitter, has been advocated 3 .
Thus an emitter which has its point of maximum
radiant energy emission nearest t o the wave length
of maximum absorption of the ink to be dried
should produce the most efficient transfer of energy.
For the resins used in these studies absorption
efficiencies were 98 per cent. at peak wave length
in the band 2.8 to 3.5 μ and this gave an excellent
match t o the peak wave length (3.0 μ) of the emitter
operating at temperatures 1100 to 1500°F (593°C
to 8 1 6 ° C ) .
Looking to the future, some attention will
need t o be given to investigations of agricultural
sources of raw materials for synthesis of water-
based resins, as alternatives to the petrochemical
derivatives. In this context it is interesting to note 3
the development of a new type of resin for aqueous
inks which utilises resin and other tall oil derivatives
as essential raw materials. The technology involves
metal co-ordinate bonding to complex acidic resins
in acqueous solutions
A s w i t h the acrylic copolymers, progress in
this field will influence both the technical versatility
and future economics of water-based inks. There
seems little doubt that interest will be maintained
in the use of water as a major solvent particularly
for flexographic and gravure inks and w i t h the
co-operation of all those involved in manufacture of
raw materials, the ink makers, the paper manufac­
turers, the printers, and not least those involved in
the design of drying equipment and presses, con­
siderable progress should be made in the coming
years.
References
1. Hutchinson, G. H. PIRA Seminar Notes, January 1975,
PIRA Seminar Notes, March 1976.
2. Hutchinson, G. H., PIRA/EFTA Conference on Flexo­
graphic Technology, London, 1976, Section 17.1
3 Burke, R. E., Am. Ink Maker 1976, 54, No. 6, 29, 60.
4. Knightley, J., Chemistry in Industry — the way ahead
Conference, Wembley, November 1976
5 Hutchinson, G. H., PIRA Seminar Notes, January 1975,
Radio Frequency drying for the future.
6. Ulrich, F. S., USP. 3,506,467.
7. Sauntson, B. J., British Ink Maker, 1975, 18, No. 1, 26
8 Firmin, D. M. Polymers Paint Col. J , 1975, 165, 577.
9 Clarke, R. G., Private Communication, Ciba-Geigy
10 Kaiser, W., Farbe & Lack, 1974, 9, 825.
11. Gilbert, S. B., PIRA/EFTA Conference on Flexographic
Technology, London, 1976 Section P19 1.
12. Pollock, R. L., Paper, Film & Foil Converter, 1975
(September) p49, 92.