Note: Descriptions are shown in the official language in which they were submitted.
10~j9~;~'7
The invention relates to a process for the manufacture of easily iso-
latable, dustless and readily dispersible granulates of pigments and pigment
preparations.
According to the invention, there is provided a process for the manu~
facture of an easily isolatable, dustless, readily dispersible pigment granu-
late, which comprises gradually adding, at a temperature between 10 - 35C
under turbulent mixture, to a suspension of 10 parts by volume of a finely dis-
persed organic pigment or pigment preparation in 10-700 parts by volume of
water 2-22 parts by volume of an organic solvent being virtually insoluble in
water, and having dissolved 0.1-2.5 parts by volume of water-insoluble granu-
lating assistants belonging to the class of natural, synthetic or semi-synthe-
tic resins, esters of dicarboxylic acids, of arylcarboxylic acids, or arylsul-
phonic acidsJ of phosphoric and phosphorous acid, phenylsulphonamides or the
alkaline earth salts of fatty acids containing 12 to 14 carbon atoms but, in
the absence of wetting agents whereby a granulate is formed, then isolating said
granulate, which consists substantially of pigment or pigment preparation,
granulating assistant and organic solvent and removing the solvent therefrom.
The organic pigments which can be used according to the invention
can belong to the most widely different chemical classes, for example to the
class of the azo, azo-
;~B ;~
. . . ~ .
.
.. . . . .. ~
. . . -:
. . . . . . ..... .
.. - . . . . . . . .
... . . . . .
~Cui~ ~ 3'~
methine, anthraquinone, phthalocyanine, nitro, perinone,
perylene, dioxazine, thioindigo, iminoisoindolinone or
quinacridone pigments. Metal complexes, for example of azo,
azomethine or methine dyes of pigment character, are also
suitable. It is also possible to use mixtures of different
pig~ents.
Instead of pure pigments, ready for use pigments
preparations can also be used, i.e. preparations which con-
tain in addition to the pigment for example 20 to 90%, pre-
ferably between 40 and 60%, of a carrier.
The pigments are advantageously in finely divided
form, i.e. the particle size is desirably between 0.05 and
5~ as obtained, for example, by grinding per kneading the
crude pigments, optionally in the presence of solvents and
other additives, or by appropriate control of the synthesis
process. They can be used in the form of dry powders or
preferably as moist filter cakes.
Suitable granulating assistants are preferably
synthetic, semi-synthetic and natural resins. The synthetic
or semi-synthetic resins can be polymerisation, polyconden-
sation or polyaddition products In principle it is possible
to use all resins and binders commonly in use in the paint
and printing ink industry and described, for example, in
.
~ ,.
- -
~963~7
the paint and varnish raw materials tables of Karsten, 4th.
and 5th. edition, Hannover, 1967 and 1972 respectively,
andlor in Wagner and Sarx's book on paint resins, 5th. edi-
tion, Munich 1971. High molecular weight compounds with
plastic character, as described for example in the "Kunst-
stoff-Taschenbuch", Carl Hanser Verlag, Munich (18th. edi-
tion 1971), can also be used as granulating assistants. It
is preferred to use those resins which do not react further
chemically on contact with air or with themselves and pos-
sibly crosslink.
Preferred classes of resin are:
(a) colophonium and its derivatives in all forms, for ex-
ample hydrogenated, dimerised or polymerised, esterified
with monohydric or polyhydric alcohols, with resin formers,
as for example acrylic acid and butanediol or maleic acid
and pentaerythritol, modified colophonium resin, calcium or
zinc salts of colophonium, abietic acid and esters thereof;
the soluble phenolic resins modified with colophonium and
resins based on acrylic compounds, as well as other natural
resins, as for example linseed oil varnish, shellack and
other copals, and water-soluble salts of rosinamine;
(b) maleic resins, oil-free alkyd resins, styrenated alkyd
resins, vinyl toluene modified alkyd resins, alkyd resins
.
.. ~ .. 7 .. --,-- . , , ~ ..... ...... , . . ........ ._ .___ __,_ .__ _ _ .__ ____ _ __
- . , . ~ , . -
- -
., . . - . .
:. . . : .
. . , :
: . .
10~i37
with synthetic fatty acids, linseed oil alkyd resins, ri- :
cinenic alkyd resins, castor oil alkyd resins, soya oil
alkyd resins, coconut oil alkyd resins, tall oil and fish
oil alkyd resins and acrylated alkyd resins,
(c) terpene resins and terpenephenol resins;
(d) polyvinyl resins, e.g.: polyvinyl acetate, polyvinyl
chloride and polyvinylidene chloride, polyvinyl acetals,
polyvinyl ethers, copolymers and graft copolymers with dif-
ferent vinyl monomers, polyacrylic acid resins, as for ex-
. 10 ample acrylic and methacrylic esters and their copolymers;
(e) styrene polymers and copolymers;
. (f) polyolefins, polyethylene, polypropylene, polybutylene,
polyisobutylene, polyisoprene, substituted polyolefins,
halogenated polyolefins and their copolymers, as for example
ethylene and vinyl acetate copolymers and other synthetic
resins based on unsaturated hydrocarbons, e.g. low mole-
cular polystyrenes, and especially the polyolefins of aver-
age polymerisation with a molecular weight of 300-5000
(known as "petroresins"),
(g) polyamide and polyester resins, as for example linear or
. branched polyester resins based on phthalic acid, adipic
acid or sebacic acid;
(h) coumarone, indene, coumarone-indene and ketone resins,
~' S ~
.... ".
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., : ~ ` ` ,, : :
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~06963'7
(i) ceilulose derivatives, e.g. cellulose ethers, as for
example ethyl cellulose and benzyl cellulose in oxdinary
commercial orm, and also cellulose esters, as for example
cellulose acetate, cellulose acetobutyrate and nitrocellu-
lose, which can also be undernitrated.
As further granulating assistants there may also
be mentloned the alkyl, cycloalkyl or aralkyl esters of
dlcarboxylic acids, for example phthalic acld, adLpic acid
and sebacic acid, as for example dibutyl, dioctyl, di-(Z-
ethylhexyl), dicyclohexyl or dibenzyl esters of phthalic,
adipic or sebacic acid, as well as esters of phosphoric
or phosphorous acid, for example tricresyl yhosphates or
trionylphenylphosphite, arylsulphonic acid esters of phenol
or cresol, arylcarboxylic acid esters, for example tri-
methylol ethane tribenzoate, and alkaline earth metal salts
of fatty acids of 12 to 24 carbon atoms, for example
magnesium behenate and stearate.
When using pigment preparations, the carriers on
which the preparations are based can, as the case may be,
simultaneously assume the function of granulating assistant,
- 6 -
- , ... . -~
: . . - . . .. , :
,
.. . . . . ... . . . . .
. . . . .
.. . . . .
1069637
so that in these cases it is superfluous to add a granulat-
ing assistant.
Water is used in the first liquid of the two-phase
system in carrying out the process. As second liquid there
is used an o~ganic solvent or a mixture of two or more or-
ganic solvents which, under th,e given conditions, are vir-
tually insoluble in water, i.e. they have a solubility of
not more than 0.1 g/100 ml.
Examples of such organic solvents are (solubili-
ties in accordance with the literature for temperatures of
20-250C)
Aliphatic or cycloaliphatic hydrocarbons:
n-pentane 0.036 g/lO0 ml
n-hexane 0.014
n-heptane 0.005 "
petroleum ether < 0.1
cyclohexane 0.01
methylcyclohexane < 0.1 "
Aromatic hydrocarbon:
benzene 0.082 g/100 ml
toluene 0.47 "
xylene mixture 0.014
_ 7 _
-
. . .
106963'7
mesitylene 0.002 g/100 ml
ethylbenzene 0.002 "
n-propylbenzene 0.006 " (15C)
cumene < 0.1 "
Halogenated aliphatic hydrocarbons:
freon < 0.1 g/100 ml
tetrachloroethylene 0.04 "
carbon tetrachloride 0.08 "
l,l,l-trichloroethane 0.001
Halogenated aromatic hydrocarbons:
chlorobenzene 0.049 g/100 ml
o-dichlorobenzene 0.015 "
Alcohols:
n-heptanol 0.09~18C) g/100 ml
n-octanol 0.054 "
iso-octanol 0.07
2-ethylhexanol-1 0.07 "
2,2,4-trimethyl-1-pentanol 0.03 "
2,6-dimethyl-4-hep~anol 0.06 "
:
-- 8 --
' .: , : , . .. : .
- ... i .. i.. .. . . .. ,.. . . . . .. ~
~oH~9 ~ 3-7
Ketones:
diisobutyl ketone 0.05 g/100 ml
Ethers:
di-n-butyl ether 0.03 g/100 ml
Esters:
phenyl acetate 0.03 g/100 ml
2-ethylhexyl acetate < 0.03
Aromatic nitro compounds:
nitrotoluene-2 0.065 g/100 ml
10Preferred solvents are toluene, xylene mixture,
chlorobenzene, and l,l,l-trichloroethane.
. A practical guideline for choosing the solvent
.is that the boiling point of the solvent will permit it to
be removed by evaporation without detriment to the pigment.
15If appropriate, a solvent with a high boiling point which
is used for granulating can be washed out, after the granu-
; les have been isolated from the aqueous phase, by another
solvent which need not necessarily be water-insoluble but
may not dissolve out the granulating assistant and is more
;'
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.
,
1~69~3~7
easily removed by evaporation.
The pigments to be granulated can be dispersed or
suspended either in the water or in the organic liquid. In
the former case, the pigment is converted during the granu-
lation into the organic phase by a flushing procedure.
For carrying out the process there are used ap-
propriately 10 to 700 parts by volume of water to 10 parts
of pigment. The lower limit of the amount of water is de-
termined by the stirrability, but in principle there is no
- 10 upper limit. However, in certain instances the presence of
inorganic salts in the water can be advantageous. This makes
it possible, for example, to lower the solubility of cer-
tain organic solvents in water~ which in turn also makes
it possible to use those solvents that have a solubility
higher than 0.1 g/100 ml in pure water but lower than
0.1 g/100 ml in the salt-containing aqueous solution. It
can also be useful to add small amounts of organic hydro-
tropic compounds, for example to hasten the formation of
the granulates, especially if a start is made from dry pig-
~0 ment powders.
The amount of organic solvent used as second li-
quid phase depends on the amount of pigment used. It is pre-
ferably so chosen that the resultant granulate contains
.
- 10 -
.
. ,, -, ~ ' . ' .. ', ,:
: - . .
- , ~ , .
, ~
1069637
practically the entire amount of organic solvent used. Too
small an amount of solvent prevents a uniform and complete
granulate formation. If too large an amount of solvent is
used, there is the danger of lumps being formed and of the
processing being complicated.
Normally a ratio of 2 to 22 parts by volume of
solvent to 10 parts by weight of pigment proves useful.
The granulation procedure takes place without wet-
ting agents. By "wetting agents" are meant, for example,
alkali soaps, aminocarboxylic acid soaps, sulphates, sul-
phonates, fatty acid esters of hydroxyalkanesulphonic acids,
phosphate surfactants, fatty amine salts, fatty acid deri-
vatives o~ polyhydric amines or aminoalcohols, quaternised
amines, fatty acid esters of polyhydric alcohols, fatty acid
alkylol amides, alkylene oxide adducts, lignin sulphonates,
fatty acid alkylol aminoesters, amidazolyl fatty acid deri-
vatives, quaternary pyrimidino or imidazole derivatives,
~etaine derivatives, ethoxylated mercaptans, amides, amines
or polypropylene glycols.
The process according to the invention can be ex-
pediently carried out continuously or batchwise in such a
manner that the organic liquid is added dropwise to the
aqueous suspension of the pigment so as to form a multiphase
~, .
.
,
lQ6~63~7
system which is simultaneously subjected to vigorous tur-
bulence. As a rule, the process is carried out at tempera-
tures between 10 and 35C.
The granulating assistants can be added to the
water, the organic solvent, the pigment or, during the gra-
nulating process, to the multiphase system; preferably, how-
ever, they are dissolved in the organic phase.
The turbulent mixing is most easily effected by
using a stirring device. After a short time, spherical ag-
glomerates consisting of pigment, organic liquid and granu-
lating assistant then usually form.
These agglomerates, which, on account of the wa-
ter-insolubility of the organic liquid, contains practically
the entire amount of this liquid~ are isolated from the
aqueous phase in a manner which is known per se, for ex-
ample by filtering them off. The solvent-containing a glo-
merates are characterised by their very easy filterability.
Since the pigments are immersed in the organic sol-
vent, the drying procedure is easily effected. To prevent
any hardening of the pigment granules and to expedite the
removal of the organic liquid, the drying is preferably
carried out at temperatures below 80C and desirably in va-
cuo .
- 12 -
'
: - : ,: - .. - . ~ ,. - :
106~37
The solvent vapours that occur during the drying
can be separated and isolated. They do not pollute the ex-
haust air and no special ecological problems arise. It can
on occasion be advantageous initially to wash out the water-
insoluble solvent contained in the isolated granulates with
another organic solvent that is more easily removed. In
special instances, the organic liquid can be frozen and re-
moved by sublimation drying.
The granulates obtained according to the present
invention can be used of the conventional pigment applications
and have the same good dispersibility and the same coloristic
properties as the starting pigments in powder form. They are
substantially dustless and have a relatively good mechanical
strength, i.e. they do not form any dust after prolonged
storage and during transportation in containers.
The following Examples illustrate the invention,
the parts and percentages being by-weight unless otherwise
B tated.
~' ' ' .
- 13 -
, , ., . ~, . ~ :
1069637
Example 1
40 g of moist filter cake containing 25 percent by weight
of the red monoazo pigment of the formula
ii~lOC
COI~ C-
OC1~3
0.4 g of magnesium behenate and 100 ml of water are put in-
to a glass bead mill with stirrer and having a capacity of
app. 150 ml.
After stirring for 30 minutes while cooling with water to
20C, the magnesium behenate is homogeneously mixed with
the deagglcmerated pigment which is thoroughly wetted with
water. The pigment/magnesium behenate suspenion is then
flushed out of the mill with app. 250 ml of water, separated
from the glass beads and put into an agitator vessel. With
moderate stirring, 7 ml of xylene are added dropwise at
room temperature to the suspension in the course of 20 minu-
tes. The rate of stirring is so controlled that a spherical
- 14 -
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., , : . . .. . . ... - - .. ; .. . - . .
- .. . ... . . . . . . .
. .
.. , . .. ,: ~ :
.
.. . . . ..
,
..
~069637
granulate consisting of pigment, magnesium behenate and
solvent is obtained after stirring has been continued for
20 minutes at room temperature. The granulate is filtered
off by suction filtration without any mechanical action on
the filter product. The filtration proceeds very rapidly
on account of the solvent still present in the granulate.
The granulate is then dried in a vacuum drying cabinet at
60C. A spherical pigment granulate iq obtained with a par-
ticle diameter of app. 2-3 mm and a magnesium behenate con-
tent of app. 4%. When incorporated into e.g. soft PVC rol-
led sheet, it has good dispersant and coloristic properties.
Example 2
lO'g of the yellow pigment of the formula
Cl Cl Cl Cl
Cl ~ 1 Cl - ~ -Cl
= N ==N
1~ }~
.
- 15 -
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. . , . ~
, ~ .
~06963-~
are deagglomerated and thoroughly wetted by being stirred
in 130 ml of water for 10 minutes at room temperature in a
glass bead mill with stirrer and having a capacity of app.
150 ml. The pigment suspension is subsequently flushed out
of the mill with app. 250 ml of water, separated from the
glass beads and put into an agitator vessel. A solution of
0.5 g of dioctyl phthalate in 4 ml of toluene and 3 ml pe-
troleum ether is added in the course of 20 minutes at room
temperature and added to the pigment suspension with mo-
derate stirring. The rate of stirring is so controlled that
a spherical granulate consisting of pigment, zdditive and
solvents is obtained after stirring has been continued for
; a further 20 minutes at room temperature. The granulate is
collected by suction filtration without mechanical ac~ion
lS on the filter product. The filtration proceeds very easily
on account of the solvents still present in the granulate.
The granulate is then dried at 60C in a vacuum drying ca-
binet. A spherical pigment granulate is ob.f ained with a par-
ticle diameter of app. 2-3 mm. When incorporated into e.g.
PVC soft plastic rolled sheet, it has the same dispersi-
bility and the same coloristic properties as the pulveru-
lent, dust starting pigment. ~
.. . .
, .
- 16 -
.
., , . , , . . .. , , , , ' . ' ~ ' ' " ' ' . ' , , "
,'. . ' -, . ' ', ' . ' ' . .,, ., ~ ~ . ' , .' - ' .
.. '. . . . '. ' . , , , . ~ ~ . .:
;: . : .
` ' , ' ' ' ' ' ;: . ' ' ' . .
~069637
Example 3
A spherical pigment granulate of equally good quality is
obtained by using the yellow pigment of Example 2, but ad-
ding instead of the liquid dioctyl phthalate the same amount
S of solid dicyclohexyl phthalate and otherwise proceeding
according to the particulars of Example 2.
Example 4
'
A spherical pigment granulate of equally good quality is
obtained by using the same pigment as in Example 2, but
using 1.1 g of the glycerol ester of polymerised colophon-
ium (Poly Pale Ester lO) as additive instead of 0.5 g of
dioctyl phthalate and otherwise carrying out the same pro-
cedure as in Example 2,
. .
. ~ 17
, . : : - . , . -
- :,. . : . . . ~:
,' ' ~ ' . . . -.: . ' ', ' .: ' . . , ~:, ' - ':
: . .. . . . ~ . .... .
106S~63'7
Example 5
A pigment granulate of equally good quality is obtained by
proceeding as described in Example 2 but using 1.1 g of the
A pentearythritol ester of dimerised colophonium (Penta]yn K)
S as additive instead of 0.5 g of dioctyl phthalate.
Example 6
A spherical pigment granulate of equally good quality is
obtained by proceeding as described in Example 2 but using
1.1 g of an aromatic petroleum resin (Hercules~Resin HC 110)
instead of dioctyl phthalate.
.
Example 7
A spherical pigment granulate of equally good quality is
obtained by proceeding as described in Example 2 but using
.~
~ tr~ r 1~-
1f~9637
1.1 g of trimethylol ethane trlbenzoate (Benzoflex S432) in-
stead of 0.5 g of dioctyl phthalate.
Example 8
10 g of Flavanthrone Yellow containing 8.5% of colophonium
resin are deagglomerated and thoroughly wetted by being
stirred for 10 minutes at room temperature in 130 ml of
water in a glass bead mill with a stirrer and a capacity of
app. 150 ml. The pigment suspension is subsequently flushed
out of the mill with app. 250 ml of water, separated from
the glass beads and put into an agitator vessel. Then a
solution of 0.5 g of magnesium behenate in 7 ml of xylene
is added at room temperature in the course of 20 minutes
to the pigment suspension with moderate stirring. The rate
of stirring is so controlled that a granulate consisting of
pigment, resin, magnesium behenate and solvent is obtained
after stirring has been continued for 20 minutes at room
temperature. The granulate is isolated by suction filtration
without any mechanical action on ~he filter product. The
filtration proceeds very easily on account of the solvent
,
- 19 -
x f ,.~ J~
'- ' . ;~' ~ ' ' ', ': '
.
1~9~;3~7
,...
still present in the granulate. The granulate is subse-
quently dried in a vacuum cabinet at 60C and the solvent
removed. A spherical pigment granulate with a particle size
, of app. 2-3 mm is obtained which has the same dispersibility
and the same coloristic properties as the dusty yellow pig-
ment in powder form when incorporated into soft PVC rolled
sheet.
Example 9
A pigment granulate of equally good quality is obtained by
proceeding as in Example 8 but using the resin-free yellow
pigment of the formula -
Cl Cl Cl Cl
Cl ~ Cl Cl- ~ Cl
, ~ O ~ O
1~ }~
instead of Flavanthrone Yellow.
i
- 20 -
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~ ~ '` ' ' -.
,
. ~ .
~069~3'~'
Example 10
A pigment granulate of equally good quality is obtained by
proceeding as in Example 8, but without the addition of
magnesium behenate and replacing xylene by a solvent mix-
ture consisting of 4 ml of xylene and 4 ml of cyclohexane
in which the resin contained in the pigment is slightly
soluble.
Example 11
10 g of Flavanthrone Yellow, 0.5 g of magnesium behenate and
130 ml of water are put into a glass bead mill equipped with
stirrer. After the mixture has been stirred for 30 minutes,
with water cooling, to app. 20C, the magnesium behenate
is homogeneously mixed with the deagglomerated and thor-
oughly wetted pigment. The suspension is then flushed out
15 . of the mill with about 250 ml of water, separated from the
glass beads and put into an agitator vessel. With stirring,
a solvent mixture consisting of 4 ml of xylene and 4 ml of
- 21 -
- : . . ..
- - - ,. . : - : , .
-: . .
~. . . . , ~ :
1069637
cyclohexane is added dropwise in the course of 20 minutes
and a granulate consisting of yellow pigment, magnesium be-
henate, solvent mixture and resin is obtained. Immediately
after the dropwise addition of the solvent mixture, the
granulate is isolated from the water by suction filtration
without mechanical action on the filter product. The fil-
tration proceeds very easily on account of the solvents pre-
sent in the granulate. The granulate is dried in a vacuum
cabinet at 50C and the solvents removed. A spherical granu-
late with a particle size of app. 2-4 mm is obtained. When
incorporated e.g. into soft PVC rolled sheet, it has dis-
persant and coloristic properties analogous to those of the
dusty pigment in powder form.
' .
.
Example 12
A pigment granulate of equally good quality is obtained by
proceeding as in Example 11, but using instead of the fla-
vanthrone pigment a red pigment of the formula
.
~ .
- - 22 -
'
- . ' ' ~ ' ' ' .
:' ' ' "" ~ ' ' ' ' ' . ' , " '' ' ' ~ . '
- . ~ . ' ' . ' '
''~ " ' ' , . . ~:
1()69637
,~ ,~Cl
~ C0~ NI~OC~
Cl
adding dropwise a solvent mixture consisting of 3.5 ml of
xylene and 4.5 ml of cyclohexane instead of that consisting
of 4 ml of xylene and 4 ml of cyclohexane, and, after addi-
tion of the solvent mixture, stirring for a further 20 minu-
tes at room temperature.
Example 13
The yellow pigment of the formula
. C1~3
CO ~0
C1l3 ~ -~H0~ Cl. Cl C0~ CH3
CH3 C
- 23 -
.. . . . . . .
106963~7
obtained by coupling tetraazotised 3,3'-dichloro-4,4'-di-
aminodiphenyl-l-aceto- with acetylamino-2,4-dimethylbenzene,
is granulated by adding dropwise, with stirring, at room
temperature in the course of app. 15 minutes a solution of
0.2 g of the petroleum resin Hercules Resin HC 110 in 15 ml
of l,l,l-trichloroethane to 300 ml of a suspension, obtained
- direct from the synthesis, containing app. 8 g of pigment.The rate of stirring is so controlled that a spherical granu-
late consisting of pigment, resin and solvent is obtained
after stirring has been continued for 5 minutes at room tem-
perature. The granulate is isolated, without mechanical ac-
tion, by suction filtration from the aqueous phase which
still contains water-soluble impurities resulting from the
synthesis and washed with 400 ml of water. The filtration
and washing procedure is effected very rapidly on account
of the solvent still present in the granulate. The granu-
late is subsequently freed from solvent and dried in a vac-
uum cabinet at 60C. A spherical pigment granulate with a
particle size of app. 1-3 mm is obtained When incorporated
e.g. into various paint and varnish systems it exhibits good
d~spersant and coloristic properties.
, ~
..
:.
.
' ` ,: '
'
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~06963'7
Example 14
.
Using a toothed disc stirrer, 27 g of a moist press cake
containin~ 3% of colophonium resin and 37% of the violet
dioxazine pigment of the formula
NIICOC~13
-CON~I ~ O ~ ,N ~ OCH2C~I3
CH3CH20 ~ ~N'~ ~ ~0 ~ ~N~IOC_
.
are deagglomerated and homogeneously mixed in 130 ml of wa-
ter in a 500 ml glass beaker in the course o~ 20 minutes at
room temperature. The pigment/colophonium resin suspension
is then put into an agitator vessel. With moderate stirring,
7.5 ml of xylene are then added dropwise to the suspension
at room temperature in the course of app. 15 minutes. The
rate of stirring is so controlled that a spherical granulate
consisting of pigment, resin and solvent is obtained after
stirring has been continued for 5 minutes at room tempera-
ture. The granulate is isolated by suction filtration with-
out mechanical action on the filter product. The filtration
proceeds very rapidly on account of the solvent still pre-
sent in the granulate. The granulate is subsequently freed
. . , - - . .. ~ : :-: .:, ,: .
. . . .. . .
~069637
from sclvent and dried in a vacuum cabinet at 60C. A spheri-
cal pigment granulate is obtained with a particle size of
app. 1-3 mm and a colophonium resin content of app. 8%.
When incorporated e.g. into soft PVC rolled sheet, it ex-
hibits good dispersant and coloristic properties.
Example 15
Using a toothed disc stirrer, 30.1 g of a moist press cake
containing 33.2% of the yellow disazo pigment of the formula
_ _ CH3
CH3 ,_~N = N~C-COHN
~1 ~ NHOC ~ ~ Cl CH ¦ ~
are deagglomerated in 200 ml of water in a 500 ml of glass
beaker in the course of app. 20 minutes at room temperature.
The pigment suspension is then put into an agitator vessel.
With moderate stirring, a solution of 0.5 g of cellulose
acetobutyrate in 12 ml of l,l,l-trichloroethane is added
dropwise to the suspension in the course of app. 20 minutes
- 26 -
.. .
, -- - . ' ' ' ' '. , ~
.
~06963'7
at room temperature. The rate of stirring is so controlled
that a spherical granulate consisting of pigment, cellulose
acetobutyrate and solvent is obtained after stirring has
been continued for 5 minutes at room temperature. The granu-
late is isolated by suction filtration without any mechani-
cal action on the filter product. The filtratio-n proceeds
very rapidly on account of the solvent still present in the
granulate. The granulate is subsequently freed from solvent
and dried in a vacuum cabinet and dried, A spherical pig-
ment granulate with a particle diameter of app. 1-2 mm is
obtained. When incorporated into e.g. soft PVC rolled sheets,
it exhibits good dispersant and coloristic properties.
Example 16
A spherical pigment granulate of equally good quality is
obtained by using the yellow pigment of Example 15, but re-
placing the 0.5 g of cellulose acetobutyrate by a solution
of 0.2 g of a polystyrene in 10 ml of xylene and otherwise
carrying out the procedure as described in Example 15.
- 27 -
.
' ' ' . .
- .: . ... ~ .... , :, :........ :
.: - , : : . -
~L06963'7
Example 17
A spherical. pigment granulate of equally good quality is
obtained by using the same yellow pigment as in Example 15,
I but replacing cellulose acetobutyrate by the same amount of
the benzenesulphonic amide Dellatol MMA (Bayer) as granulat-
ing assistant and otherwise proceeding in the same manner
as in Example 15.
Example 18
..
A pigment granulate of equally good quality is obtained by
carrying out the procedure of Example lS, but replacing
cellulose acetobutyrate by the same amount of tricresyl
phosphate.
; Example 19
A pigment granulate of equally good quality is obtained by
- 28 -
f r~
,-
. ~ :
.
~069637
carrying out the procedure of Example 15, but replacing cel-
lulose acetobutyrate by the same amount of a terpene resin
A (Terpalyn A3, Hercules).
Example 20
-
A pigment granulate of equally good quality is obtained by
carrying out the procedure of Example 15, but replacing cel-
lulose acetobutyrate by the same amount of a maleic resin
(Hobimal P 65, NV Zaanochemie, Holland).
. Example 21
10 g of the orange pigment of the formula
.' ,
- 29 -
~r~ t~&kS
, .. ~ .. , . , - ~ . .
.: , ' : ,
', ., ' ' ' . ' , : . ' ' , . ~ ' . .: - '
~069637
C113 N=N - ~ -N---N ~CH3
N~ ~ o Cl Cl ~ /
CH3 H3
are deagglomerated and thoroughly wetted by being stirred
for 10 minutes at room temperature in 130 ml of water in a
glass bead mill with stirrer and a capacity of app. 150 ml.
The pigment suspension is subsequently flushed out of the
mill with app. 250 ml of water, separated from the glass
beads and put into an agitator vessel. Then a solution of
1.1 g of dicyclohexy phthalate in 5 ml of l,l,l-trichloro~
ethane and 3 ml of xylene is added, with moderate stirring,
to the pigment suspension at room temperature in the course
of 20 minutes.
The rate of stirring is so controlled that a spherical granu-
late consisting of pigment, dicyclohexy phthalate and sol-
vents is obtained after stirring has been continued for 20
minutes at room temperature. The granulate is isolated from
the water by suction filtration without mechanical action
on the filter product. The filtration proceeds very rapidly
30 -
:.
~06963~7
on account of the solvents still present in the granulate.
The granulate is subsequently freed from solvent and dried
in a vacuum cabinet at 60C. A spherical pigment granulate
with a particle diameter of app. 1-3 mm is obtained, When
S incorporated e.g. into different varnish and paint systems,
it has the same dispersant and coloristic properties as the
dusty starting pigment in powder form.
Example 22
A granulate of equally good quality is obtained by proceed-
ing in analogous manner to Example 21, but using a ~-Cu-
phthalocyanin pigment instead of the orange pigment, 1.1 g
of dioctyl phthalate instead of 1.1 g of dicyclohexyl phtha-
late, and only 6 ml of toluene as solvent.
.; .
Example 23
""'
A granulate of equally good quality is obtained by proceed-
:~ ..
, .
~ 31 -
- . .: .~ .
- .
.... ''' . " "' ', .. ~'. :''', ~,, , ' ~,: ,
,: ,- ,' . .. ,,... , :. : :
9637
A ing as in Example 22, but using instead of dioctyl phthalate
the same amount of a viscous polyisobutylene (Oppanol~B3,
BASF) and instead of 6 ml of toluene a solvent mixture of
4 ml of cyclohexane and 3 ml of toluene.
Example 24
A granulate of equally good quality is obtained by proceed-
ing as in Example 23, but using instead of polyisobutylene
1,1 g of the colophonium resin of Example 4.
Example 25
. .
A granulate of equally good quality is obtained by proceed-
ing as in Example 23, but using instead of polyisobutylene
; the same amount of an epoxidised soya bean oil (Rheoplast
3g).
,
- 32 -
r~ kJ
, , ' ' : '
-.' ' ' ' '
~, . ~, :,, ,
': , .
~06963~
Example 26
10 g of the red disazo pigment used in Example 12 and
130 ml of water are put into a glass bead mill with stirrer
and with a capacity of app. 150 ml. After it has been stir-
red for 10 minutes at room temprature, the pigment is deag-
glomerated and thoroughly wetted by the water. The suspen-
sion is then flushed out of the mill with app. 250 ml of
water, separated from the glass beads and put into an agi-
tator vessel. With moderate stirring, a solution of 0.5 g
of a polyisobutylene (Oppanol B3) in a solvent mixture of
3.5 ml of xylene and 4.5 ml of cyclohexane is then added
in the course of 20 minutes at room temperature. The rate
of stirring is so controlled that a spherical granulate
consisting of pigment, polyisobutylene and solvents is ob-
tained after stirring has been continued for 20 minutes at
room temperature. The granulate is separated from the wa-
ter by suction filtration without mechanical action on the
filter product. The filtration proceeds very easily on ac-
count of the solvent still present in the granulate. The
~ranulate is subsequently freed from solvent and dried in
a vacuum cabinet at 60C. A spherical pigment granulate
with a particle diameter of app, 2-4 mm is obtained. When
.
;
- 33 -
, .. ... .. ~ ..... . ~ .. ,.. ~ , .
~06963~7
incorporated into e.g. soft PVC rolled sheets it has the
same dispersant and coloristic properties as the very dusty
starting pigment in powder form.
Example 27
10 g of a pigment preparation in powder form consisting
50% of ~-Cu-phthalocyanin and 50% of ethyl cellulose are
deagglomerated and thoroughly wetted by being stirred for
10 minutes at room temperature in 130 ml of water in a
glass bead mill with stirred of app. 150 ml capacity. The
resultant blue suspension is subsequently flushed out of
the mill with app. 250 ml of water, separated from the glass
beads and put into an agitator flask. A solvent mixture
consisting of 4 ml of chlorobenzene and 2 ml of methyl ethyl
ketone in which the ethyl cellulose is slightly soluble is
then added in the course of 20 minutes at room temperature
to the pigment suspension, with moderate stirring. The rate
at which the batch is stirred is such that a spherical gra-
nulate consisting of pigment preparation and solvents is
obtained after stirring has been continued for 20 minutes.
;
.
... .
. . . :
.: :.. ~ ' - . , . .. : .
. ~ .i , . . .. ...
.
106963t7
The granulate is isolated from the water by suction fil-
tration with mechanical action on the filter product. The
granulate is subsequently freed from the solvents and dried
at 60C in a vacuum cabinet. A spherical granulate with a
particle diameter of app. 2 mm is obtained. Its behaviour
in application is as good as that of the dusty starting pro-
duct in powder form.
Example 28
A pigment preparation granulate of equally good quality is
obtained by proceeding as in Example 27, but using instead
of the ethyl cellulose preparation the same amount of 50%
~-Cu-phthalocyanin preparation which contains a vinyl chlo-
ride/vinyl acetate copolymer as carrier resin and 7 ml of
trichloroethane and 1 ml of petroleum ether as solvent mix-
ture (b.p. 50-60C).
~ ~ 35 ~
., ' .
. . , - ,, ~ . , . .: .
. ~ . . . . ~. .. . . :
. - . .- ' : : ~',' . . . ~ '
, . . .
. ~ .
:106963'7
Example 2~
A pigment preparation granulate with a particle diameter of
app. 1-4 mm which yields colourations of as good quality as
the very dusty pigment preparation powder is obtained by
proceeding as in Example 27, but using instead of the ethyl
cellulose preparation a 50% ~-Cu-phthalocyanin preparation
which contains magnesium behanate as carrier and only 5 ml
of toluene as solvent.
- 36 -
- . ~ : . . -. . . -
- .. ... ..
.
. ~ . . . : ... -
