Note: Descriptions are shown in the official language in which they were submitted.
~16810
-- 2
~ he present invention relates to a process for the preparation
of dustless, readily-dispersible pigment or dyestuff granules.
The preparation of pigment granules by a process which comprises
stirring together an aqueous pigment dispersion and a solution of a
water-insoluble organic carrier in a water-immiscible organic liquid is
known. However, in the known processes the resulting product contains
some solvent, and it is necessary to remove the organic solvent from
the product by distillation. We have now discovered a process in which
the product is obtained directly in a solvent free condition.
According to the present invention there is provided a process
for producing a pigment or dyestuff composition in the form of dust-
less readily-dispersible granules which process comprises contacting,
with agitation, an aqueous dispersion of a pigment, and 0,1 to 2 parts
by weight per part of pigment of an aniline compound which is liquid
at temperatures below 100C, insoluble in water at pH values above 7,
and soluble in water at pH values below 7, the pH value being above 7,
maintaining the temperature above the melting point of the amine com-
pound, and reducing the pH to below 7 to render the amine compound
soluble in water, and recovering the resulting granules.
As anilines come into consideration mono- or di- alkyl anilines
in which each alkyl group has 1 to 8 carbon atoms or a derivative there-
of, such as aniline, N-methyl aniline, N-ethyl aniline, N-propyl
aniline, N-butyl aniline, N,N-dimethyl aniline or N,N-diethyl aniline,
N,N-dipropyl aniline, N-cyclohexyl aniline, N-cyclohexyl N-hydroxy-
ethyl aniline, N-octyl aniline, N-methyl-o-toluidine, N-ethyl-p-
toluidine, N-butyl-m-toluidine, N,N-diethyl-m-toluidine, N,N-dimethyl-
m-toluidine, methyl anthranilate, but is preferably N,N-diethyl aniline.
' '~; 2
~4
llif~810
-- 3 -
The amount of amine compound used is from 0.1 to 2 parts,
preferably 0.3 to 0.6 parts by weight per part of pigment.
The process may also be carried out in the presence of from 0,05
to 2 parts per weight per part of pigment of an organic carrier The
organic carrier may be any organic compound which is soluble in, or
at least softened by, the amine compound, and is insoluble or can be
rendered insoluble in water throughout the pH range used in the
process. The carrier can be a liquid if the ratio of pigment to
carrier is high, for example at or above 90:10; at lower proportions
of pigment it is preferably to have a compound having a melting point
above 40C as carrier.
Suitable carriers include, for example, carboxylic acid esters
derived from alkyl, aryl, aralkyl or cycloalkyl carboxylic acid or
polyacids and alkyl, aryl, aralkyl, or cycloalkyl mono- or poly-
hydroxy compounds, such as the fatty acid esters cetyl palmitate,
glycerol tristearate, glycerol monostearate, glycerol tripalmitate,
glycerol trioleate, ethylene glycol dilaurate, ethylene glycol di-
stearate, diethylene glycol distearate or the benzoic acid esters,
such as ethylene glycol dibenzoate, neopentyl glycol dibenzoate
trimethylol ethane tribenzoate, trimethylol propane tribenzoate
or the dicarboxylic acid esters, such as dibenzyl phthalate, dibutyl
phthalate, dioctyl phthalate, dicyclohexyl phthalate, and similar
esters of adipic, sebacic or azelaic acids; amides from the above
carboxylic acids and ammonia, or alkyl aryl, aralkyl or cycloalkyl
mono- or poly-amides, such as stearamide, oleamide, palmitamide, N-
alkyl stearamides or oleamides, ethylene bis stearamide; phosphate
esters such as triphenyl or tricresyl phosphate, resins such as hy-
drocarbon resins, xylene-formaldehyde resins, coumarone, coumarone-
indene and ketone resins; vinyl polymers, such as polyvinyl chloride
~116810
-- 4 --
and vinyl chloride copolymers, acsylate and methacrylate palymers and
copolymers, polyvinyl acetate and vinyl acetate copolymers; styrene
homo and copolymers; polyolefines such as polyethylene, polypropylene
and polyisobutylene; fatty alcohols which are water insoluble, such as,
cetyl alcohol and stearyl alcohol; and fatty amines which themselves
do not give water soluble salts, such as didodecyl amine and distearyl
monomethyl amine; and fatty oxazolines; water insoluble carboxylic
acids, for example C12 and greater fatty acids, such as lauric acit,
stearic acid, behenic acid and the rosin derivatives, such as wood
rosin or its hydrogenated or disproportionated versions. These acids
may also be added to the pigment as their alkali metal or ammonium salt
dissolved in water: in this case the process is preferably carried out
in the presence of water soluble inorganic salts, e.g. sodium chloride
or calcium chloride.
These acids are applied as their soluble salts and may also be
combined with the non-water soluble carriers, especially the sorbitan
esters as defined in British patent specification No. 2,008,601;such
combinations give granules which are extremely useful for pigmentation
of PVC.
The weight ratio of pigment or dyestuff to carrier may be up
to 33.3:66.7, preferably from 95:5 to 50:50, more preferably from
90:10 to 6Q:40.
When the process is carried out in the presence of an organic
carrier, the amount of amine compound used is that which will form a
solution of or at least soften the carrier. When using high ratios
of pigment to carrier or when using a carrier which is poorly soluble
in the amine compound, higher proportions of the amine compound may be
needed to form satisfactory granules.
The pigment and dyestuffs that can be used are those which
are water insoluble and stable in the pH range required for granule
~ .
~16810
-- 5 --
formation and isolation. Suitable pigments are azo, azomethine, an-
thraquinone, phthalocyanine, nitro, perinone, perylene, dioxazine,
thioindigo, isoindolinone, quinacridone, azo or azomethine metal salts
or complexes; mixtures of pigments may also be used. Water insoluble
dyestuffs are those such as the solvent soluble azo and phthalo-
cyanine dyes. These dyes can also be used as mixtures and in admixture
with the pigment.
The organic carrier may be added with the amine compound,
either dissolved or dispersed in the amine or both may be added prior
to any heating or at any point during the heating cycle. The carrier
may also be added in the form of an aqueous dispersion, for example,
an aqueous dispersion of a polymer or resin such as polyvinyl
chloride, vinyl chloride copolymer or low molecular weight (oxidised)
polyethylene.
As well as using pure pigments or dyestuffs, ready-for-use pig-
ment preparations may be used i.e. preparations which contain, in
addition to the pigment, for example S to 90 per cent, preferably
from 10 to 40 per cent by weight of a carrier.
Preferably a protective colloid is added to the mixture to
assist in the formation of granules and the production of granules
of a more uniform size distribution. When used it is preferably mixed
with an aqueous pigment slurry or an aqueous dispersion of the amine
compound before the pigment and amine compound are brought together.
Suitable protective colloids include cellulose derivatives such as
hydroxy ethyl cellulose, hydroxy propyl cellulose, polyvinyl alcohol,
polyethylene oxide, polypropylene oxide, copolymers of ethylene oxide
and propylene oxide, adducts of ethylene oxide or propylene oxide,
polyvinyl pyrrolidone and its copolymers or mixtures of these com-
pounds. The preferred compounds are those of the hydroxy ethyl cellu-
lose type as exemplified by the Natrosol range of the Hercules Powder
Company.
;810
- 6 -
The amount of protective colloid may be up to 15 per cent, but is
preferably less than 5 per cent by weight of the pigment.
The process may be carried out at a selected temperature,
at which the carrier is at least softened, but preferably dissolved in
the amine derivative at the temperature used.
:~ '
The mixture is originally formulated at or adjusted to a pH
of at least that at which the amine compound is insoluble in water.
The mixture is stirred at least until the pigment has migrated from
the aqueous phase to the organic phase. Sufficient stirring is used to
keep the droplets (or granules) in suspension. The size of granule is
controlled to ~ome extent by the speed of stirring. Increased stirring
or turbulence gives a reduction in granule size. High turbulence and
therefore small granules can be obtained by use of the modified mixed/
emulsifier outlined in 8ritish patent specification No. 2,008,601.
The granules may be from 0.1 to 5 mm. in diameter, but preferably from
O.S to 2 mm. in diameter.
The time of the process can be varied depending on the pigment
used and the desired properties of the product. For example some
pigments, particularly azo pigments, are susceptible to crystal growth
when maintained in contact with the aniline compound, the amount of
growth being dependent on the time of contact and the temperature.
Increased crystal size gives a pigment having higher opacity. There-
fore, in these cases and if a product with good opacity and improved
rheology in the application system is required, the time of contact of
the pigment with the amine compound can be increased. If, on the other
hand, a pigment of this type is used but a product having good trans-
parency is required, the process time can be shortened to that which
is sufficient for the pigment to migrate into the organic phase. In
these cases the addition of a carrier assists robust granule forma-
tion, thereby further shortening the process time. Selection of amine
can also affect the opacity/transparency: aliphatic amines have less
~ '
~ ' .
~ B
i5 16~
crystallising effect than aromatic amines and thus produce more
transparent compositions.
With those pigments which show little or no tendency to crystal
growth in the process, there is no benefit from increased time of
contact of the pigment wieh the amine compound beyond that required
to form granules. Granule formation in such instances is substantially
assisted by the use of a carrier. In these cases granule formation
is further assisted by the use of inorganic salts dissolved in the
water during the contacting process. Especially typical of such pig-
ments are those which have been treated with a crystallising solvent
during a previous process stage, e.g. halogenated copper phthalocyanine
(green).
The pH of the mixture is then reduced to below 7, preferably
below 5, by the addition of an acid which will form a water-soluble salt
with the amine compound. The preferred acids are hydrochloric acid
and acetic acid. This causes the amine compound to dissolve in the
water as a salt, leaving the organic carrier if used, and pigment
granules in suspension. If necessary, e.g. to promote solution, or if
desired for handling or product performance, the temperature of the
mixture may be increased or decreased. The granules are then recovered
by sieving, washing and drying. Any granules that are too small to be
recovered in this way may be filtered off and re-used in a subsequent
batch.
To recover the solvent, the pH of the filtrate is raised,
to a pH above 7, e.g. 10, whereupon the solvent becomes
insoluble, separates from the water and can be recovered fo sub-
sequent use by decantation for example. The aniline derivative may be
further purified, if necessary, by steam distillation.
~6810
It is also possible to combine the granulation process of the
present invention with a pigment solvent treatment process, to im-
prove those pigment properties known to be improved by a solvent
treatment. The solvent treatment can be carried out before or during
the granulation step. For example, a phthalocyanine in a highly
ag8regated state of an ~/~ crystal form mixture, as produced by dry
grinding may be de-aggregated and converted substantially to the ~-
form using the amine compound as the solvent in a solvent treatment
process.
The granules, especially those of < 1 millimetre diameter can
be improved in free flowing nature initially and during storage by
the addition of a small percentage for instance up to 2% by weight,of
a finely divided inorganic or modified inorganic material conven-
tionally used for imparting such properties, such as a finely divided
silica or silicate; such materials may conveniently be added to the
granules by simple mixing. Especially advantageous materials of this
type are the finely divided silicas with surface modifications by
organic groups such as the Aerosil R 972 ex. Degussa.
The products of the invention may be used for the pigmentation
of any system, such as surface coating media, e.g. paint and ink,
or plastics. The carrier used will normally be selected so as to be
compatible with the system to be pigmented. The product, when in-
corporated into the system, releases the pigment from the granule to
colour the material.
The invention is illustrated by the following Examples,
wherein parts are parts by weight.
11~6~
Example l: 25.5 Parts C.I. Pigment Yellow 93 from a 30% w/w aqueous
presscake were stirred with 600 parts water containing 0.5 parts
hydroxyethyl cellulose for 10 minutes at room temperature. 13 Parts
by volume diethyl aniline were added and the pH raised to 10.0;
1.5 parts sorbitan tristearate and 3.0 parts dicyclohexyl phthalate
were added and the temperature raised to 85C. After stirring for a
further 30 minutes at 85C the pH was lowered to 1.0 by the addition
of 5N hydrochloric acid.
Stirring was continued for a further 60 minutes and the granules
so formed were recovered by passing the mixture through a B.S. 60
mesh sieve and washing with, alternately, water at 50C and water
at room temperature until chloride free. The granules, after drying
at 40C in a drying cabinet with circulating air, gave a clear yellow
film on incorporation in polyvinyl chloride and polyethylene.
Example 2: The procedure of Example 1 was repeated, except that
3.0 parts hydrocarbon resin under the trade mark Hercules A80 replaced
the 3.0 parts dicyclohexyl phthalate. Similar results were obtained.
Example 3: The procedure as of Example 2 was repeated, except that
19 parts by volume diethylaniline were used as solvent. Similar re-
sults were obtained. Temperature was raised to 85C and maintained for
30 minutes then 9.6 parts of hydrocarbon resin,(trade mark Hercules
A80) was added. After a further 30 minutes stirring, the pH was lowered
to 1.0 and, after stirring for a further 4 hours, the product was
separated as in Example 1. The product could be incorporated into a
thin lithographic ink to give a satisfactory dispersion.
~ "
~116810
-- 10 --
Example 4: To 18.0 parts C.I. Pigment Yellow 13 in 600 parts water,
obtained by a conventional acetate buffered aqueous coupling, was
added 0.36 parts hydroxyethyl cellulose. The pH was raised to 10.0
by the addition of 2N sodium hydroxide and 2.4 parts sorbitan tri-
itearate and 10 parts by volume diethylaniline were added.
Example 5: 0.2 Parts hydroxyethyl cellulose were dissolved in 200 parts
water. 18 Parts C.I. Pigment Blue 15.3 slurried with 120 parts water
were added with 3.7 parts in 200 parts water of the salt formed be-
tween C.I. Direct Blue 86 and Rosin Amine D. To this mixture was
added 10 parts diethylaniline and the pH adjusted to 10.0 by the
addition of 2 N sodium hydroxide. The temperature was raised to 85C
and held at this temperature for 30 minutes. 20 Parts of a melt of
a hydrocarbon resin under the trade mark Hercules A80 and cetyl
alcohol in the ratio 2:1 were added and after a further 60 minutes the
pH was lowered to 1.0 by the addition of 5 N hydrochlorid acid.
Stirring was continued for a further 6Q minutes and the resulting
granules recovered as in Example 1. The pigmented granules thus
produced could be readily dispersed in publication gravure medium.
Example 6: 0.2 Parts hydroxyethyl cellulose were dissolved in
200 parts water and to this was added 27 parts copper phthalocyanine
(previously ground with 12~ w/w calcium chloride to an o/~ ratio of
60:40) in 150 parts water and 7.5 parts in 300 parts water of the
salt formed between C.I. Direct Blue 86 and monomethyl di (hydro-
genated tallow) amine. 10 parts diethylaniline were added and the pH
of the mixture then raised to 10.0 as in Example 5, and the process
and quantities thereafter were again as in Example 5. The pigmented
granules thus produced could be readily dispersed in publication
gravure medium.
~, ^,
111tj810
Example 7: To a stirred aqueous slurry of 100 parts of pigment
- C.I. Pigment Yellow 13 - there were added 2 parts of hydroxyethyl
cellulose. The temperature was raised to 80C and the pH adjusted
to 10 by the addition of 2 N sodium hydroxide. A solution of 20 parts
dicyclohexyl phthalate in 50 parts diethyl aniline was then added
and the mixture stirred until the pigment had migrated from the
aqueous phase into the organic phase. The pH was then adjustad to 1
by addition of hydrochloric acid. Stirring was maintained at pHl for
a further 15 minutes. The pigment composition - 120 parts - was then
removed by sieving (60 mesh) and washed initially with water + acid
(pH3) and then with water alone. The product was dried at 60~C. The
resultant non-dusting composition was satisfactorily incorporated into
a lithographic varnish.
Example 8: To a stirred aqueous slurry of 40 parts C.I. Pigment
Blue 15.3 in 800 parts of water at pH10 there was added 10 parts of
low molecular weight oxidised polyethylene in the form of a 20% w/w
emulsion. 0.2 parts of hydroxyethyl cellulose was then added and the
mixture agitated on a high energy mixer at 85C. The high energy mixer
was then removed and a paddle stirrer inserted. 20 parts of diethyl
aniline was addet and the mixture maintained for 30 minutes. The pH
was then adjusted to pHl by the addition ofHCl over 2 - 3 minutes
and the mixture stirred for a further 30 minutes. The resultant
granules were sieved off on a 60 mesh (B.S.) sieve, washed with dilute
acid and then water, and then dried at 60C to give 50 parts of a
product which could be dispersed into polyethylene.
Example 9: 10 Parts of hydrogenated wood rosin (trade mark Staybelite
resin) and 22.5 parts of 50% aqueous potassium hydroxide solution
were high speed stirred using a cavitation mixer in 100 parts of
water at 50C until a smooth dispersion had formed (approximately
20 minutes).
f--
lil681~
- 12 -
In a separate vessel, 15 parts of dicyclohexyl phthalate
were dissolved in 30 parts of diethyl aniline with heating and 10 parts
of the compound of average formula:
CuPc ~ S03 NCH3 (C12H25)2 ]
the preparation of which is described in Example 6 of British patent
specification 1,541,599, added with stirring to form a smooth paste
at 50-60C. This paste was added to the dispersion of Staybelite resin
(trade mark for hydrogenated wood rosin) with the aid of a further
10 parts of diethyl aniline, and the whole high speed stirred until
a smooth blue emulsion had formed (approximately 15 minutes).
92 Parts of crude copper phthalocyanine and 8 parts of phthalo-
imide were ground in a ball mill until 55~ of the copper phthalo-
cyanine was in the ~-crystal form. 97.8 Parts of this mixture, corres-
ponding to 90 parts of copper phthalocyanine, were stirred in 200
parts of water at 50C until thoroughly weeted out. With high speed
stirring, the above blue dispersion was poured into the wetted pigment
and stirring maintained for 30 minutes, using external cooling as
required to maintain the temperature of the mixture between 50 and
55C.
A paddle stirrer was substituted for the high speed stirrer.
While stirring at approximately 150 r.p.m., a solution of 5 parts
calcium chloride and 71 parts concentrated hydrochloric acid in
500 parts of water was run in over 5 minutes. After a further 30
minutes stirring, the pigment composition thus formed was isolated
by filtration, washed salt and acid free with warm water and dried
at 50 - 60C.
There were obtained 120.8 parts of small, non-dusting granules
having excellent rheology and colour strength in toluene based
publication gravure inks.
- 13 -
Example 10: 20 Parts of a ~-copper phthalocyanine pigment and 0.3 partsof a nonyl phenol-ethylene oxide condensate (trade mark Synperonic NX)
were stirred in S00 parts of water until the pigment had thoroughly
wetted out. The pH was raised to 11 with dilute sodium hydroxide solu-
tion and 0.5 part hydroxyethyl cellulose added prior to raising the
temperature to 50C.
5 Parts of a coumarone-indene resin (trade mark Escores 11028)
were dissolved in 10 parts of diethyl aniline with heating.
This solution was added to the pigment slurry while stirring with
a paddle stirrer at approximately 150 r.p.m. and the mixture stirred
at 50C for 30 minutes. While maintaining stirring, the pH was re-
duced to 1 by the addition over 5 minutes of hydrochlorid acid.
After stirring for a further 30 minutes, the pigment composition
so formed was recovered by pouring the reaction mixture onto a 100
mesh sieve, washing salt and acid free with warm water, and drying
at 50 - 55C.
There were obtained 22.3 parts of evenly sized spherical granules
of approximately 1 mm diameter, suitable for the preparation of
lithographic inks.
Example 11: 48.9 Parts of the ground copper phthalocyanine mixture
of Example 9, containing 45 parts of copper phthalocyanine, were
stirred for S hours at reflux in 250 parts of isopropanol-water azeo-
trope. 250 Parts of water were added and the isopropanol-water azeo-
trope removed by distillation. A further 250 parts of water were added
to reduce the temperature to 50C. 12.5 Parts of a hydrocarbon resin
(trade mark Hercules A80) were dissolved in 25 parts of diethylaniline
with heating and added to the stirring pigment slurry. 15 minutes
later, S parts of the copper phthalocyanine sulphonic acid-tallow
amine compound of Example 6 were added and the mixture stirred a
111~;81{)
further 15 minutes. The reaction mixture was acidified by adding
30 ml of concentrated hydrochloric acid in 30 ml of water.
The pigment composition so formed was recovered on a 60 mesh
sieve (B.S.), washed with hot water and dried at 50-55C.
There were obtained 58.2 parts of spherical granules 78% of
which were in the range of 0.21 - 0.32 mm diameter.
Examples 12 - 18: 0.2 Parts of hydroxyethyl cellulose was added to
20 parts of C.I. Pigment Yellow 17 as present in an aqueous slurry
from an azo coupling. The temperature was raised to 80C and the pH
adjusted to 10. 10 Parts of the alkyl aniline and varied amounts of
di-isooctyl phthalate tDiOP) as shown in the Table below, were then
addad. The mixture was stirred for 20 minutes at which time beads of
1 - 2 mm diameter had formed, the pH was then atjusted to ~ 1 with
hydrochloric acid and stirring continued for 5 minutes. The beads
were then filtered off, washed and dried at 50C. The resulting pro-
ducts were evenly sized granules which could be incorporated into
plasticised PVC to give a clear yellow film.
~1681~
Example AlkylanilineParts of DiOP
_ ,
12 N,N-Diethyl aniline 2
13 N,N-Diethyl aniline 4
14 N,N-Diethyl aniline 6
lS N-ethyl aniline 2
16 N-butyl aniline 2
17 N-cyclohexyl aniline 2
18 N-hydroxyethyl-N- 2
cyclohexyl aniline .
Examples 19 - 23: 0.2 Parts of hydroxyethyl cellulose (trade mark
Natrosol 250HR) was added to 20 parts C.I. Pigment Yellow 17 as present
in an aqueous slurry from an azo coupling. The temperature was raised
to 80C and pH adjusted to 10 by the addition of 2 N sodium hydroxide.
10 Parts of NN-Diethyl aniline and 2 parts of a carrier, as shown in
the table below, were added. The mixture was stirred for 6Q minutes
at which time granules of 1-2 mm had formed. The pH was then adjusted
to 1 with hydrochloric acid and stirring continued for 5 minutes.
The granules were then filtered off, washed free of salts and dried
at SOC. The resulting products were dispersed into lithographic ink
media to give a printing ink concentrate.
_ .
Exa~ple Carrier
19 Hercules A80 (trade mark for a hydro-
carbon resin)
Cetyl palmitate
21 Crodamide O (oleamide)
22 Cellulose acetate proprionate
23 Kemamine 19701 (trade mark for monomethyl di-
hydrogenated tallow amine)
I
....~.
~116810
- 16 -
Example 24: ~0 Parts o~ C.I. Pigmen~ Yellow 17 as present in an aqueousslurry from an azo coupling and 0.2 parts hydroxyethyl cellulose (trade
mark Natrosol 250HR) were adjusted to pH10 by the addition of 2 N
sodium hydroxide. 2 Parts of hydrogenated wood rosin (trade mark Stay-
belite resin) as an aqueous solution of its potassium salt were added
to the pigment slurry. After stirring for 10 minutes 1 part of calcium
chloride dihydrate in 10 minutes 1 part of calcium chloride dihydrate
in 10 parts of water was added and the temperature raised to 85C.
10 Parts of NN-diethyl aniline were then added and stirring continued
for 1 hour at 85C. The pH was adjusted to 1 with hydrochlorid acid
and the granules removed by filtration. They were then washed and
dryed. The product was easily dispersed into lithographic varnish.
Example 25: To the pigment slurry as used in Example 24 were added
0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250 HR) 2 g
stearic acid and 0.6 parts calcium chloride dihydrate; the pH was ad-
justed to 10 by the addition of 2N sodium hydroxide, the temperature
raised to 85C and 10 parts l~N-diethyl aniline added. After stirring
for 1 hour the pH was adjusted to 1 by the addition of 5 N hydro-
chloric acid and the granules removed by filtration. They were then
washed and dryed. The product could be dispersed into polyvinyl
chloride.
Example 26: An aqueous slurry of 100 parts of C.I. Pigment Yellow 13
as formed in a conventional azo coupling and 2 parts of hydroxyethyl
cellulose (trade mark Natrosol 250 HR) were stirred together for 20
minutes at 15C. The slurry pE was adjusted to 10 by the addition of
2 N sodium hydroxide, and a mixture of 10 parts dioctyl phthalate
and 100 parts diethyl aniline were added. Stirring was continued for
90 minutes at 15C until granule formation was complete. The pH
was then adjusted to 1 by the addition of hydrochloric acid and the
resultant granules, 100 parts, recovered by separation on a 60 mesh
11168~0
sieve, washing and drying at 50C. The product could be dispersed
into lithographic ink media.
Example 27: 20 Parts of C.I. Pigment Green 7 in the form of a 30% w/w
presscake were dispersed into 600 parts of water in which there was
dissolved 30 parts sodium acetate and 10 parts sodium chloride. After
raising the temperature to 85C 10 parts of NN-diethyl aniline were
added and stirring continued for 2 hours at 85C. The pH was then
reduced to just below 1 by the addition of 5N hydrochloric acid.
20 Parts of granules were removed on a 60 B.S. mesh sieve and after
cax~fully washing to eliminate inorganic salts and acids, the product
was dried at 55C. The resultant non-dusting granules could be dis-
persed into lithographic ink media.
Example 28: 16 Parts of C.I. Pigment Green 7 in the form af a 30%
w/w presscake were dispersed into 300 parts water. To this dispersion
were added 3 parts hydrogenated wood rosin (trade mark Staybelite
resin) as an aqueous solution of its potassium salt. This mixture was
stirred for 2 hours, then 0.2 parts of hydroxyethyl cellulose (trade
mark Natrosol 250HR) and 3 parts sorbitan tristearate were added. This
mixture now at pH 9 was heated to 85C, the pH was adjusted to 6 with
5N hydrochloric acid and 24 parts sodium acetate, 8 parts sodium
chloride and 16 parts NN-diethyl aniline added. The mixture was stirred
at 85C for 5 minutes, and the pH was then adjusted to just below 1
by the addition of 5N-hydrochloric acid. The resulting granules were
filtered on a 60 B.S. mesh sieve, washed free of inorganic salts and
acids and dried at 55C. The resulting product, 22 parts, could be dis-
persed into plasticised P.V.C.
11~ti8~0
- 18 -
Examples 29 - 34: A series of bisarylamide azo pigments were prepared
according to convention~ azo coupling techniques. To 20 parts of ehe
various pigments as S~ w/w aqueous suspensions, as shown in the
table, were added 0.2 parts hydroxyethyl cellulose (trade mark Natro-
sol 250HR) and, after adjusting to pH 10 with 2N sodium hydroxide,
10 parts of NN-diethylaniline.
In each case the temperature was raised 85C and stirring con-
tinued at this temperature for 2 hours; the pH was then adjusted to
just below 1 by the addition of 5N hydrochloric acid and the granular
product isolated by washing free of inorganic salts and acids followed
by drying at 60C. The resulting products disper~ed into lithographic
oil ink media.
Example Pigment
29 C.I.Pigment Yellow 13
C.I.Pigment Yellow 12
31 C.I.Pigment Yellow 14
32 C.I.Pigment Yellow 17
33 C.I.Pigment Yellow 55
34 C.I.Pigment Yellow 63.
Example 35: 20 Parts of C.I. Pigment Yellow 13, as a 5% w/w aqueous
slurry prepared in a conventional aqueous azo coupling and 0.2 part
hydroxyethyl cellulose (trade mark Natrosol 250 HR) are heated to
85C at pH 6. 10 Parts of NN-diethyl aniline were then added and
stirring continued for a further 30 minutes. The pH was adjusted to
just below 1 with 5N-hydrochloric acid and the granular product iso-
lated by filtration, washing free of inorganic salts and acids and
drying at 55C. The properties of this product were similar to those
of Example 29.
.. ....
11168~)
Example 36: lO0 Parts of an aqueous slurry of C.I.Pigment Yellow 13,
prepared as for Example 35, was adjusted to pH 11 with 2N sodium hy-
droxide and 1 part of hydroxyethyl cellulose (trade mark Natrosol
250HR) and 30 parts hydrogenated wood rosin, as an aqueous solution of
its potassium salt, were added. The mixture was raised to 85C and
held at this temperature for 15 minutes. The pH was then adjusted to
6.2 and 50 parts of NN-diethyl aniline added. Stirring was continued
for 15 minutes and the pH was then reduced to just below 1 by the
addition of 5 N hydrochloric acid. The regular spherical granules were
recovered by filtration, washing free of inorganic salts and acids and
drying at 55C. The resultant granules were dispersed into lithographic
oil ink media to gi~e excellent gloss as a print.
Example 37: The procedure and quantities of Example 36 were repeated
but the amount of hydrogenated wood rosin was reduced to 10 parts.
A similar product with like properties was obtained.
Example 38: 20 Parts of a 5% w/w aqueous suspension of a C.I.Pigment
Yellow 13 composition, formed by treatment with a sulphonic acid dye-
stuff and Rosin Amine D according to Example 109 of B.P. 1,356,253,
was adjusted to pH 10 by the addition of 2N potassium hydroxide;
0.2 parts hydroxyethyl cellulose (trade mark Natrosol 250HR) and 2
parts hydrogenated wood rosin (trade mark Staybelite Resin), as
aqueous solution of its potassium salt, were added and the mixture
heated to 85C. 10 Parts of NN-diethyl aniline were then added and
the mixture stirred for 1 hour at 85C before adjusting to just
below pH 1 by the addition of 5N hydrochloric acid. The resul~ing
spherical granules were filtered, washed free of inorganic salts and
dried at 50C. This product could be dispersed into lithographic
oil ink and showed greater transparency than the product of
Example 37.
B
ill~i81(~
- 20 -
Example 39 The procedure and quantities of E~ample 37 were repeated
but the amount of wood rosin was increased to 6 parts. A product
similar in appearance and performance to that of Example 12 was ob-
tained.
Example 40: 20 Parts of a 5% w/w aqueous slurry of C.I. Pigment Yellow
13, prepared as for Example 9, and 0.2 part hydroxyethyl cellulose
(trade mark Natrosol 250~R) was adjustet to pH 10 by the addition of 2N
sodium hydroxide. 20 Parts of NN-diethyl aniline and 2 parts dioctyl
phthalate were added and the mixture stirred for 45 minutes at 20C.
The pH was then adjusted to just less than 1 by the addition of 5N
hydrochloric acid. The granule composition was isolated by filtration,
washing free of inorganic salts and acid and dried at 55C. The re-
sultant granular product could be dispersed into lithographic ink.
Ecample 41: 20 Parts of C.I. Pigment Yellow 74 as a 5% w/w aqueous
slurry, as prepared by conventional aqueous azo coupling, and 0.2
part hydroxyethyl cellulose (trade mark Natrosol 250HR) were adjusted
to pH lO by the addition of 2N sodium hydroxide. 2 Parts hydrogenated
wood rosin (trade mark Staybelite Resin), as an aqueous solution of
its potassium salt, was then added, the temperature raised to 85C
and 10 parts NN-diethyl aniline added. Stirring was continued at 85C
for 2 hours, the pH adjusted to just less than 1 by the addition of
5N hydrochloric acid and the product isolated by filtration on a 6Q
B.S. mesh sieve, washed free of inorganic salts and acid and dried
at 55C. The resulting generally Apherical granules could be dispersed
into lithographic ink or decorative paint; in the latter application
a very desirable opaque film could be achieved.
Example 42: 30 Parts of C.I. Pigment Yellow 83 as a 5% w/w aqueous
slurry, as produced in a conventional aqueous azo coupling, was ad-
justed to pH 7 by the addition of 2N potassium hydroxide, and 3 parts
hydrogenated wood rosin (trade mark Staybelite Resin) were added as an
~116~0
- 21 -
aqueous soLution of its potassium salt. 0.3 Parts hydroxyethyl cellu-
lose (trade mark Natrosol 250~R) was then added and the slurry now
at pH 10 hea~ed to 85C and held at 85C for 10 minutes before ad-
justing to pH 6 with 5N hydrochloric acid. 30 Parts of NN-diethyl
aniline were then added and stirring continued at 85C for a further
10 minutes. The pH was then adjusted to less than 1 by the addition of
SN hydrochlorid acid and the granules isolated by filtration on a
60 B.S. mesh sieve, washed free of inorganic salts and acid ant dried
at 60C. The resulting product could be dispersed into oil ink to give
a strong transparent ink film. In a nitrocellulose binder - alcohol
solvent liquid ink excellent rheology was obtained and the resultant
film showed excellend gloss and brightness.
Example 43: 30 Parts of an aqueous slurry of C.I. Pigment Yellow 83,
as produced for Example 42, and 0.3 parts of hydroxyethyl cellulose
(trade mark Natrosol 250MR) were atjusted to pH 7 and heatet to 85C.
30 Parts of NN-diethyl aniline were addet with stirring and contacting
continuet for 3 hours at 85C. pH was then atjusted to just below 1 by
addition of 5N hydrochloric acid and the generally spherical granules
isolated by filtration on a 6Q B.S. mesh sieve, washed free of in-
organic salts and acid and dried at 60C. The dry granules were free-
flowing and robust to applied pressure. Incorporation into a lithogra-
phic ink gave a film slightly more opaque than the product of
Example 42; a nitrocellulose binder - alcohol solvent ink again
exhibited goot rheology and a final film of excellent gloss as for
Example 42.
Example 44: A mixture of 30 parts of an aqueous slurry of C.I. Pigment
Yellow 83 as protuced for Example 42 and 0.2 parts of hydroxyethyl
cellulose (trade mark Natrosol 250HR) was adjusted to pH 11 and 15
parts NN-diethylaniline added. The temperature was raiset to 95
and maintained at this temperature with constant stirring for 6 hours.
The pH was then retuced to 0.5 by the addition of 5N hydrochloric acid.
The product was then recovered by filtration on a 60 B.S. mesh sieve,
, ~ ,j.
8~(~
- 22 -
washed free of inorganic salts and acid and dried at 55C.The resultant
product was generally spherical granule of 0.5 - 1 mm average diameter.
Example 45: The procedure of Example 44 was repeated with an identical
formulation and stirring conditions but omitting the hydroxyethyl
cellulose: the resuleing product was granules of 3-5 mm diameter.
Example 46: 15 Parts of C.I. Pigment Red 38 in the form of a 5~ w/w
aqueous slurry, ob~ained by a conventional aqueous coupling, was added
to 400 parts water and the pH raised to 6.3.; 0.2 parts hydroxyethyl
cellulose was added and heating commenced. When a temperature of 70C
was reached, 15 parts N,N-diethylaniline were added and the tempera-
ture was raised to 80C. After stirring at 80C for a further 3 hours,
the pH was lowered to just below 1.0 by the addition of 10 N hydro-
chloric acid and the product separated and dried as in Example 45.
The resulting spherical granules could be readily dispersed in litho-
graphic ink medium.
Example 47: 18 Parts of a ~-copper phthalocyanine pigment and 2 parts
bis-cetyloxy-sulphanilide of copper phthalocyanine tthe preparation
of which is described in US-patent specification 4,199,509) in the
form of a 10~ w/w aqueous slurry were dispersed into 500 parts water
in which there was dissolved 40 parts sodium chloride. To this dis-
persion was added 0.2 parts hydroxyethyl cellulose (trade mark Natro-
sol 250HR) and heating was commenced with stirring. At 70C, 5 parts
dicyclohexyl phthalate dissolved in 15 parts N,N-diethyl aniline were
added and the temperature taken to 80C and the stirring continued
for 2 hours. The pH was then reduced to just below 1.0 by the addi-
tion of lON hydrochloric acid. The rPsulting granules were separated
by filtration and washed chloride free with water and dried at 40C
in a drying cabinet with circulating air. The product could be disper-
sed into lithographic and publication gravure media.
B
1~16~
- 23 -
Example 48: 200 Parts of the aqueous pigment slurry of Example 47 were
added ~o 500 parts water in which there was dissolved 20 parts sodium
chloride. To this dispersion was added 0.5 parts of a primary fatty
(tallow) amine (trade mark Crodamine IT) as the acetate in aqueous
solution and 1.5 parts of an hydrogenated wood rosin (trade mark
Staybelite Resin) as an aqueous solution of its potassium salt and 0.1
parts of hydroxyethyl cellulose. Heating was commenced and, at 70C,
15 parts N,N-diethyl aniline were added and the temperature taken to
80C and stirring continued for a further 80 minutes. The pH was then
reduced as in Example 21 and the resulting product, which was composed
of generally spherical granules, were separated on a B.S. 60 mesh
sieve, washed free of chloride ions and dried at 40C as in Example 47.
Example 49: 27 Parts of copper phthalocyanine (previously ground to an
o/~ ratio of 60:40) and 30 parts sodium chloride were dispersed into
700 partswater. 0.1 part hydroxyethyl cellulose was added and heating
commenced. When a temperature of 70C was reached, 1.5 parts of a
secondary fatty (coconut oil) amine (trade mark Armeen 2C) dissolved
in 11.2 parts N,N-diethyl aniline were added. The temperature was
raised to 80C and, 1 hour after the addition of the diethylaniline,
6 parts of a hydrogenated wood rosin (trade mark Staybelite Resin)
as an aqueous solution of its potassium salt was added. This was
followed by 3 parts of the bis-cetyloxysulphanilide of copper
phthalocyanine of Example 21. After stirring for a further 15 minutes,
the pH was lowered to just below 1.0 by the addition of lON hydro-
chloric acid and the resulting generally spherical granules separated
as in Example 28. The granules thus obtained could be readily dis-
persed in lithographic ink medium.
Example 50: 30 Parts of copper phthalocyanine (previously ground to
an o/~ ratio of 55:40) and 30 parts sodium chloride were dispersed
into 700 parts water and 0.1 part hydroxyethyl cellulose added.
Heating was commenced and 7.5 parts of an hydrogenated wood rosin
(trade mark Staybelite Resin) as an aqueous solution of its potassium
- 24 -
salt added. At a temperature of 75C, 15 parts N,N-diethylaniline
were added and the mixture stirred at 80C for a further 2 hours. The
pH was lowered as in Example 47 and the resulting granules, after being
separated and dried as in Example 48, could be readily dispersed in
lithographic ink medium.
Example 51: ôl.O Parts of the pigment of Example 24, 90 parts sodium
chloride and 9.0 parts of the bis cetyloxysulphanilide of copper
phthalocyanine of Example 47 were dispersed in 1500 parts water.
Heating was commenced and 2.25 parts of a primary fatty (tallow) amine
(trade mark Crodamine IT) as the acetate in aqueous solution and 20.25
parts of an hydrogenated wood rosin ( trade mark Staybelite Resin) as
an aqueous solution of its potassium salt were added. Stirring was con-
tinued for 1 hour and 70 parts N,N-diethylaniline were added to the
slurry at 80C. After a further 15 minutes the pH was lowered as in
Example 27 and the resulting granules, after being separated and dried
as in Example 48 could be readily dispersed in lithographic and publi-
cation gravure ink media.
Example 52: 24 Parts of C.I. Pigment Orange 34 in the form of a 5%
W/'d aqueous slurry, obtained by a conventional acetate buffered
aqueous coupling was dispersed with 100 parts water and the pH raised
to 7.0 by the addition of 2N potassium hydroxide solution. 12 parts
N,N-diethylaniline were added and the temperature raised to 80C over
45 minutes. After stirring at 80C for a further 15 minutes, the pH
was lowered to just below 1.0 by the addition of lON hydrochloric acid.
The resulting granules were separated by filtration and washed
chloride free and dried as in Example 47. The granules of 0.5-4 mm
diameter could be readily dispersed into lithographic ink medium.
Example 53: 120 Parts of C.I. Pigment Orange 34 in the form of 5% w/w
aqueous slurry, obtained by a conventional acetate buffered aqueous
coupling was added to 500 parts water and the pH raised to 8.0 by the
additicn of 2M sodium hydroxide solution; 0.6 parts hydroxyethyl
11~681~:)
- 25 ~
c~llulose was added and heating commenced. When a temperature of 60C
was reached 120 parts N,N-diethylaniline were added and the temperature
raised to 80C. After stirring at 80C for 2 hours the pH was lowered
to just below 1.0 by the addition of lON hydrochloric acid and the
product separated and dried as in Example 48. The resulting spherical
granules of 0.3 - 1 mm diameter could be readily dispersed into litho-
graphic ink medium.
Example 54: 15 Parts of C.I. Pigment Red 3 in the form of a 5% w/w
aqueous slurry, obtained by a conventional aqueous coupling, was dis-
persedwith 400 parts water and the pH raised to 8.0 by the addition of
2N sodium hydroxide. 0.3 Parts hydroxy ethyl cellulose was added and
heating commenced. When a temperature of 80C was reached 10 parts
N,N diethylaniline was added and the mixture stirred for a further
2 hours at 80C. The pH was then reduced to 1.0 by the addition of
lON hydrochloric acid and the product separated and dried as in
Example 47. The resulting granules could be readily dispersed into
lithographic ink medium.
Examples 55-6Q: The procedure of Example 36 was repeated except that
the N,N'-diethyl aniline was replaced by an equal amount of the amines
listed below. Product appearance and performance was equivalent to
that of Example 36.
Example Amine
N,N'-dimethyl-3-methylaniline
56 N,N'-dipropyl-aniline
57 N-ethyl-2-methylaniline
58 N,N'-dibutylaniline
59 2,5-dimethylaniline
methyl-anthranilate
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C r1 0 ~ C ~
3 ~ ~ 1 o
z ~ e P~ I
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3 3 3 ~4
.5
C C ~ C
Oao P~ ~ ~ ~ ~ ~ ~'
.~ C~ i
_ C
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a ~
X ~ O ~ O `O ~
Example 70: 20 parts of CI Pigment Yellow 13 as an aqueous slurry
as prepared according to Example 35, 0.2 parts hydroxyethyl cellulose
(trade mark Natrosol 250HR) and 5 parts dicyclohexylphthalate were
heated at pH 8 from 15C to 85C and 15 parts of 2 ethyl hexylamine was
then added. The mixture was maintained at 85C for 1 hour, then ad-
justed to pHl.5 with lON hydrochloric acid and the granules covered by
filtration, washing and drying at 55C. The product could be dispersed
into a lithographic varnish.
Example 71: 10 parts of Solvent Yellow 48 was dispersed in 200 parts of
water and 0.1 parts potassium resinate and 0.1 part hydroxyethyl
cellulose (trade mark Natrosol 250HR). The mixture was adjusted to
pH7 and 5 parts N,N'-diethylaniline added. The mixture was heated to
80 and held for 30 minutes, before adjusting to pH 1 with lON hydro-
chloric acid. The resulting granules were recovered by filtration
washing and drying at 30C.
Example 72: An aqueous slurry of 20 parts of a CI Pigment Red 57:
resin composition (16:4 part ratio by formation of tha pigment metal
salt in the presence of Staybelite resin, (trade mark) 0.5 parts
hydroxyethyl cellulose (trade mark Natrosol 250HR) and 3.3 parts
abietyl amine, added as its water soluble acetate salt, were heated
to 95C at pH 10. 10 parts N,N'-diethylaniline were then added the
pH adjusted to 7 and stirring continued for 2 hours at 95C. The pH
was then adjusted to 3.2 by the addition of glacial acetic acid.*
The granules were isolated, washed and dried at 90C. The product could
be dispersed into lithographic ink varnish.
*Adjustment to pH 1 with concentrated hydrochloric acid is to be
avoided as it results in a product of poor performance, presumably
due to breakdown of the metal salt at this pH.
Example 73: 100 parts of C.I. Pigment Green 7 as a 35% parts by
weight presscake were dispersed i~ 2000 parts of water using a modi-
fied mixer/emulsifier head as described in the text. After 20 minutes
"~
~,
, ,~,
111681V
- 28 -
mixing a solution of 30 parts of Staybelite resin as its a~monium salt
was added and ~i~ing continued for a further 60 minutes. 0.4 parts
hydroxyethyl cellulose (trade mark Natrosol 250 HR) and 20 parts sorbi-
tan tristearate were then added and the temperature raised to 85C.
~ith continued mixing 30 parts of N,N'-diethylaniline, dispersed in
100 parts ofwater and 0.5 parts of dissolved potassium resinate, was
added. ~he modified mixer/emulsifier stirring was continued for
1 minute, the pH adjusted to 6 ant stirring continued for a further
5 minutes before adjusting to pH 1 by the addition of 5N hydrochloric
acid. The granules were removed by filtration on a 200 mesh BS sieve,
washed free of acid and salts and dried at 45C. The resultant
granules, all of < 0.5 mm diameter could be readily dispersed into a
plasticised P.V.C. compound.
The addition of 1~ by weight of Aerosil R 972 (trade mark) to
the above granules gave a product of improved free 1Owing properties
especially after storage.
Example 74: The procedure of Example 73 was repeated except that
the solution of Staybelite resin was replaced by a solution 30 parts
of Ennesin A 100 (trade mark) as its potassium salt. A product of
similar properties was produced.
B
