SEPTEMBER 1980 PIGMENT AND RESIN TECHNOLOGY 11

Pollution-free
printing inks
Dr. C. A. Smith, M.Sc.

A general review of the factors involved. (3) To transfer to relatively small harm solvent, i.e., to
use paraffin line hydrocarbon.
Part I considers some of the more recent
Prior to the study of these three points in
developments. detail, the following general comments are necessary:
Offset ink is composed of pigment (20%)
Introduction
resin ( 3 0 % ) , drying oil ( 3 0 % ) , and solvent ( 2 0 % ) .
Probably the most dramatic development in
The solvent evaporation temperature on the press is
printing inks in recent years is the formulation of
240°-340°C generally. On the other hand, what w i l l
pollution-free inks that polymerize under UV light and
become of gaseous material which is generated when
enable printers to meet pollution control regulations
the drying oil undergoes oxidation polymerisation on
by eliminating the release of solvents to the atmos-
the paper? Such gaseous material sometimes reaches
phere. Conventional inks contain anything from 2 5 %
the boiling point of achrolain or toluene. In the case
solvent, (letterpress and " l i t h o " inks) to as high as
of web offset printing, 20-30% solvent is used in the
7 5 % solvent (certain gravure inks). It is these solvents
ink and this solvent is either absorbed by paper or
that are driven off and vented to the atmosphere dur-
evaporated into the atmosphere.
ing process at about 150°C that contribute to the pol-
Ink, except for pigment has the viscosity of
lution problem. Pollution-free ink in a strict sense
approximately 150 poises (and one of the elements
must be pollution-free in all respects. It must be pollu-
accountable for this low viscosity is the solvent), and
tion-free not only in the manufacturing and printing
to increase the ink viscosity rapidly so as to quicken
processes but in the product printed w i t h it also.
the drying of ink, the 20-30% solvent is evaporated
Commonly, however, the judgement as to
in a moment. This means that the whole ink viscosity
whether the ink is pollution-free or not is made in a
increases to tens of thousands of poises and makes
narrow sense, i.e., after the printing process and
the ink dry. In this case, a great volume of solvent
especially in the drying process during printing.
vapour is released from the duct, and here arises a
Actually, the manufacture of such ink that makes the
serious problem w i t h regard to web offset ink.
printed product contain no heavy metal like lead must
be the basic requirement for pollution-free ink. One idea to prevent this is to make web offset
The development of ink and printing systems ink high-solid. Actually, however, this is impractical
which can minimize the dispersion into the atmos- though the balanced heat-set process answers the
phere of organic solvent contained in the printing ink purpose to a limited extent.
is urgently required. This fact especially holds true to The idea of using water in the place of solvent
web offset printing and metallic printing that use the also seems to be impractical for offset ink, consider-
hot air (or direct fire) dryers and to gravure printing ing the volatility of water. If it can be so devised that
that releases a large quantity of low boiling point the ink w i l l not discharge moisture, water may be used
organic solvent. as solvent. A n d , even so, the fact that offset printing
Another way to prevent atmospheric pollution itself uses the damping water possesses a deterrent.
by printing ink is to make it possible somehow or The feasibility of the water for solvent idea exists
other to dry multicolour prints at a time instead of only when what may be called reverse offset can be
drying one printed colour after another. The apparent realised.
decrease of dryers that are needed presumably serves Experimental data shows that the dry plate
that purpose. which has been developed (in which the non-printing
area is silicon treated) can operate even w i t h water
Pollution-free ink development ink to some extent. Actually, however, unless the
To consider pollution-free printing is, after a l l , method to prevent the moisture evaporation is dis-
to study how to make printing ink pollution-free. For covered, such a dry plate method cannot be used for
this purpose, three things can be considered from the offset printing. At present, water ink is mainly used
printing ink component ratio. They are: for gravure printing of publications. When used for
(1) To eliminate the solvent completely, i.e., to make gravure printing of packages, water ink does not settle
printing ink 100% solid or, should this be impractical, well on the package film. The printed gloss also is not
to decrease the solvent to the possible m i n i m u m , i.e. as rich as desired.
to make high-solid printing ink. As regards the use of paraffin line hydrocar-
(2) To use completely harmless water in place of bons, the oxygen containing ketone or alcohol type
solvent, i.e., to make water-based ink. has come to be less and less used for reason of its
12 PIGMENT AND RESIN TECHNOLOGY SEPTEMBER 1980

photochemical reaction. Solvent makers are trying to Methylol melamines

introduce new products but their development re- When CH 2 OH consists of six hexametnylol
search is not exactly proving successful. melamines the reaction to alcohol is rapid. However,
when the printing speed is as fast as to print 80-100
100% Solid, high solid inks sheets per minute, the ink drying speed cannot be as
Of all types of printing ink drying, the drying fast as required.
by solvent evaporation and the drying by solvent Another big question is that melamine without
osmosis are rapid in drying speed and therefore effec- acid catalyst is slow to react. For example, when P-
tive. The fact is that the solvent, compared with other toluene or sulphonic acid is used as acid catalyst, the
ink components, is of extremely low viscosity so that acid density must be increased so that the aluminium
its use even in a small quantity changes, i.e., lowers, plate cannot be used and even the trimetal plate
the ink viscosity greatly, but in the process of drying chrome layer blackens. Further, such ink that contains
its evaporation or osmosis even in a small quantity acid catalyst gelatinizes during preservation.
causes the ink viscosity to increase rapidly, leading to On the other hand, a study is being made in
speedy drying of the ink film. Therefore, to make the which the acid catalyst to be previously added be
ink 1 0 0 % solid or high-solid without deteriorating its blocked w i t h molforine or weak base in order to repro-
drying speed, it becomes necessary to have the ink duce acid after heating. However, even in this
viscosity increased somehow or other to match the attempt, since the catalytic reaction begins only after
viscosity due to solvent evaporation or osmosis. the release of a c i d , too much time is required to meet
However, there are few methods (chemical up w i t h ink drying in printing.
reactions) to increase the ink viscosity easily in a The popular practice among paint makers is
short time of one second or so while the printed paper to have high methylol melamine or benzo guanamine
goes through the dryer as in web offset printing. Fol- resin react w i t h the aid of acid catalyst, to the
lowing are the cases of relatively rapid reactions hydroxyl group containing resin. However, this reac-
which are often used as the printing ink drying tion is in no means applicable to high speed printing.
method: The treatment of formalin as a by-product and the
a) Reaction between isocyanate group and ammonia effect of acid catalyst on the printing plate must also
or a c i d / h y d r o x y l group. be considered.
b) Reaction between methylol melamines and hydroxyl (To be continued)
group via acid catalysis.
c) Ion-catalyzed polymerisation.
d) Radical polymerization. BAYERTITAN R-SE 44
Some of them are introduced here. Bayer U.K. Ltd., Bayer House, Richmond,
Surrey T W 9 1SJ, have issued details on a new pig-
Isocyanate group and others ment from their Inorganics Division. Bayertitan R-SE
The isocyanate group reacts rapidly to the 44 is a micronised rutile pigment produced by the
hydroxyl group containing active hydrogen and car- sulphate process. It is coated w i t h aluminium com-
pounds and also organically treated.
boxil. Therefore, when this group pendant to the poly-
mer is heated, the reaction is extremely rapid and the Technical Data
solidification is believed to take place immediately. TiO 2 content approx. 9 5 %
To be regretted, however, NCO presents so quick a Additional components A12O3
reaction to water that it cannot be used for the offset Density (DIN 53 193) approx. 4.1 g / c m 3
ink that uses water. The alternative is to utilize the Refractive index 2.75
dry plate that uses no water but this alternative, too, Oil absorption (DIN 53 199) 20
is not as easy to realize as is considered to be because Relative light scattering power
NCO reacts to the pigment and its moisture also. (DIN 53 165; at PVC of 15%,
Thus, to utilize NCO for printing ink drying, it R-KB-2 = 100) 112
is necessary to have isocyanate blocked previously Sieve residue DIN 53 195 < 0.01 %
w i t h phenol or alcohol. Ethyl alcohol as a blocking Properties
agent, for instance, makes isocyanate de-blocked at Owing to its high light scattering power,
160°C or sometimes at as low as 5 0 ° C . De-blocking Bayertitan R-SE 4 4 is distinguished by a very good
at too low temperature makes the printing ink gela- hiding and brightening power. It disperses most
tinize during preservation. At any rate, it is difficult to readily and possesses a good stability to flocculation.
maintain the optimum blocking and de-blocking rela- Bayertitan R-SE 4 4 is recommended for the
tionship. The question also arises in that this chemical pigmentation of binders w i t h poor wetting characteris-
reaction, however rapid, can never keep abreast of the tics, especially nitro-cellulose and polyamide-based
ink drying speed in web offset printing wherein the printing inks having to come up to exacting require-
ink gets dry in not more than one second or so. ments with regard to gloss and hiding power.