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Patent 1059704 Summary

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(12) Patent: (11) CA 1059704
(21) Application Number: 1059704
(54) English Title: PIGMENT COMPOSITION IN BEAD FORM
(54) French Title: COMPOSITION PIGMENTAIRE PERLEE
Status: Term Expired - Post Grant Beyond Limit
Bibliographic Data
(51) International Patent Classification (IPC):
  • C09C 3/04 (2006.01)
  • C09B 67/00 (2006.01)
  • C09B 67/42 (2006.01)
  • C09C 3/00 (2006.01)
(72) Inventors :
  • ROBERTSON, GEORGE H.
  • STIRLING, JOHN A.
(73) Owners :
  • CIBA-GEIGY AG
(71) Applicants :
  • CIBA-GEIGY AG (Switzerland)
(74) Agent:
(74) Associate agent:
(45) Issued: 1979-08-07
(22) Filed Date:
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): No

(30) Application Priority Data: None

Abstracts

English Abstract


PROCESS FOR THE MANUFACTURE OF A PIGMENT COMPOSITION IN BEAD
FORM
Abstract of the Disclosure
A process for the production of a pigment composition
in bead form Which comprises contacting with agitation, in
the presence of an aqueous protective colloid, 1 part
of a water insoluble carrier melting below 100°C. and an
aqueous dispersion containing 0,25 - 2,3 parts of a pigment
or Water insoluble dyestuff at a temperature above the
melting point of the carrier and allowing the aqueous phase
to become substantially free of pigment or water insoluble
dyestuff by its association with the carrier and recovering
the resulting pigmented beads which are easily dispersible in
polymeric compounds to yield even colorations.


Claims

Note: Claims are shown in the official language in which they were submitted.


THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of a pigment composition in bead
form which comprises contacting with agitation, in the presence of from
0.2% to 5% by weight based on the amount of pigment plus carrier of an
aqueous protective colloid, 1 part of a water insoluble carrier selected
from the group consisting of fatty alcohols, fatty esters, fatty amides,
phthalate esters, fatty oxazolines, water insoluble carboxylic acids,
alkylimides, alkyl hydantoins, or mixtures of the aforementioned carriers
and rosin acids or modified rosin acids, and water insoluble metal salts
of said acids or a mixture of said acids with fatty primary amines, fatty
secondary amines, or fatty imidazolines, said carrier melting below 100°C
and an aqueous dispersion of 0.25-2.3 parts of a pigment or water insoluble
dyestuff, said process being conducted at a temperature above the melting
point of the carrier and allowing the aqueous phase to become substantially
free of pigment or water insoluble dyestuff by its association with the
carrier and recovering the resulting pigmented beads, said pigmented beads
having a particle size from 0.5 to 5 mm. diameter.
2. A process as claimed in claim 1, in which the carrier is a single
compound having a melting point in the range of 40° to 100°C. or a mixture
of compounds which give a mixed melting point in the range of 40° to 100°C.
3. A process as claimed in claim 1, in which the carrier is a fatty
alcohol, a fatty ester, a fatty amide, a fatty ester of a polyol, a benzoic
acid ester of a polyol, a phthalate ester, a fatty oxazoline, a water
insoluble carboxylic acid, an alkalimide, or an alkyl hydantoin.
4. A process as claimed in claim 1, in which the carrier is a mixture
rosin acid, modified rosin acid, or a water insoluble metal salt thereof,
together with a compound as listed in claim 3, a fatty primary or secondary
amine or a fatty imidazoline.
23

5. A process as claimed in claim 1, in which the protective colloid
is hydroxy ethyl cellulose.
6. A process as claimed in claim 1, in which the pigment dispersion
is one obtained directly from an aqueous preparation, a redispersed aqueous
pigment presscake or a redispersed pigment powder.
7. A process as claimed in claim 1, in which the particle size is
from 0.5 to 2 mm. diameter.
8. A process as claimed in claim 1, in which the ratio of pigment to
carrier is from 1:1 to 1.5:1.
9. A process as claimed in claim 1, in which the protective colloid,
powdered carrier and pigment are mixed at ambient temperature, and the
mixture is then agitated at a temperature above the melting point of the
carrier.
10. A process as claimed in claim 1, in which a mixture of the protective
colloid and carrier is agitated above the melting point of the carrier, and
the pigment dispersion is added to the hot dispersion with agitation.
11. A process as claimed in claim 1, in which an aqueous mixture of
the protective colloid and pigment is heated to a temperature above the
melting point of the carrier, and the carrier as a powder is added to this
mixture with agitation.
12. A process as claimed in claim 1, in which an aid which faciliates
the subsequent association of the pigment with the organic phase and is
selected from the group consisting of a fatty amine or fatty acid which are
rendered water insoluble by pH control or salt formation in amounts of up
to 10% by weight of pigment is added to the mixture.
13. A process as claimed in claim 12, in which the amount of aid
is up to 5% w/w on pigment.
24

14. A process as claimed in claim 12, in which the aid is a fatty
amine or fatty acid rendered water insoluble by pH control or salt
formation.
15. A process as claimed in claim 12, in which the aid is formed in
the presence of an aqueous pigment dispersion.

Description

Note: Descriptions are shown in the official language in which they were submitted.


gL~5Y7~
The present invention relates to a process for the
manufacture of pigment compositions in bead form suitable
or colouring lnks, paints and plastics.
Pigments are generally produced in powder form and
are usually used as such. Powders have several
disadvantages, mainly in handling, since a large amount of
dust is produced making them unpleasant to use.
They are also dirty in manufacturing and difficult to
separate from liquor. A1SOJ powders are not always as
free-flowing as is desired. A further disadvantage
is that in order to colour a substance evenly, the
powder must be evenly distributed throughout the
substance and, particularly when colouring plastics, this
can involve prolonged and expensive mechanical working.
It has been proposed to produce pigmented polymers in bead
form which can be easily mixed with and used to colour
plastics materials. It has also been proposed to
produce pigments and other substances in the form of a
granulate by precipitating the pigment or other substancc
from an aqueous suspension in ~he presence of an organic
compound as granulating agent. It is an object of the
present invention to provide a pigment composition in a free-
flowing, non-dusting, non-aggregating, non-sticky generally
spherical form based on organic materials which are
compatible with high molecular weight organic materials such
as inks, paints and plastics, and can be readily
incorporated into same.
According to the present invention there is provided
a process for the production of a pigment composition

~IL05970~
which comprises contacting with agitation, in the presence of from 0.2% to 5%
by weight based on the amount of pigment plus carrier of an aqueous protective
colloid, 1 part of a water insoluble carrier selected from the group con-
sisting of fatty alcohols, fatty esters, fatty amides, phthalat0 esters,
fatty oxazolines, water insoluble carboxylic acids, alkylimides, alkyl
hydantoins, or mixtures of the aforementioned carriers and rosin acids or
modified rosin acids, and water insoluble metal salts of said acids or a
mixture of said acids with fatty primary amines, fasty secondary amines, or
fatty imidazolines, said carrier melting below 100C and an aqueous dispersion
of 0425-2.3 parts of a pigment or water insoluble dyestuff, said process
being conducted at a temperature above the melting point of the carrier and
allowing the aqueous phase to become substan~ially free of pigment or water
insoluble dyestuff by its association with the carrier and recovering the
resulting pigmented beads, said pigmented beads having a particle size from
0.5 to 5 mm. diameter.
The carrier may be a single compound or it can be a mixture of
compounds which give a mixed melting point in the preferred range of 40 to
100C. It is not necessary for the co~,position to have a sha~p melting
point, which of course a single compound haS, but it may melt over a r~nge
2Q of a few degrees, e.gO over 15-20 centigrade degrees.
The choice of carrier will largely be governed by the needs of the
system in which the beads are to be used to ensure adequate solubility in
and compatibility with the solvent and resin or polymer respectively.
Examples of suitable carriers include fatty alcohols, such as cetyl alcohol
and stearyl alcohol, fatty esters such as cetyl palmitate, glyceryl
tristearate, glyceryl tripalmitate, diethylene glycol distearate and tri-
ethylene glycol monostearate, fatty amides such as oleamide and palmitamide,
fatty esters of polyols such as hardened castor oil, benzoic acid esters
of polyols, phthalate esters such as dicyclohexyl phthalate, fatty
oxazolines such as stearyl oxazoline, water insoluble carboxylic acids such
as stearic acid, behenic acid,
-3-
. .

~OS97~34
N-dodecyl phthalamic acid, alkylimides such as N-dodecyl
phthalimide and N-octyl phthalimide alkyl hydantoins such as
3-stearyl-5',5'-dimethyl hydan~oin and 1-hydroxyethyl-3-
stearyl-5,5'-dimethyl hydantoin.
In addition to using single compounds, mixtures of
compounds may be used such as mixtures of those specified
above. However, mixtures of particular value are those
based on rosin acid or modified rosin acid such as wood
rosin, hydrogenated wood rosin9 Staybelite resin
(Staybelite is a Trade Marlc) and its water insoluble metal
salts such as ~inc resinate and calcium resinate with the
compounds listed above or with fatty primary amines such as
n-dodecylamine, stearylamine or fatty secondary amines
such as dicocoamine or fatty imidazolines.
The aqueous protective colloid may be used in an amount
such as will form a solution Or about 0.2 to 5~ w/~
but preferai~ly 0.5 to 2~o w~w. based on the amount of
pi~nent plus organic composition, and may be, for example,
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, polyvillyl pyrrolidone and its copolymers or mixtures
of these compounds. The preferred compounds are those of
the hydroxy ethyl cellulose type as exemplified by the
Natrosol ~ange of the llercules Powder Company. l~Then pol~ners
of the ethylelle or propylene oxide type are being used it is
advantageous to carry out the preparation above the cloud
- 4 -
~r d cl ~ r ~
.. ... . . . .. . . . . . .,, . ., . , . - - - ~ - ~ -

7~4
point ~see Kirk-Othmer's ~ncyclopedia of Chemical Technology,
Vol. l9, p. 531) of the surfactant, and at the lower levels of
concentrations.
The aqueous pigment dispersion may be one obtained
directly from an aqueous preparation, for example, an azo
coupling. In this case the dispersion may contain additives
of general application in pigment technology, but these
additives must allow or aid the bead formation and not affect
the melting point or tackiness of the beads to such an extent
that the final composition has undesired characteristics.
The pigment dispersion may also be a redispersed
aqueous pigment presscake or a redispersed pigment powder.
The aqueous presscake or powder may be redispersed into water
by stirring or by high energy dispersion.
The particle si~e o the molten carrier and of the
resulting pigmented beads may be up to 5 mm. diameter,
preferably from 0.5 to 2 mm. diameter. When the pigment or
dyestuff dispersàon is contacted with the carrier at a
temperature at which the latter is a liquid the agitation is
continued preferably until the aqueous phase is substantially
free from pigment. The ratio of pigment to carrier varies from
0~25:1 to 2.3:1, preferably from 1:1 t~ 1.5:1. I smaller
amounts of carrier are used the resulting product has inferior
dispersibility properties making it very difficult to
incorporate into the desired system.
The pigment dispersion may be contacted with the
carrie~ in the presence o a protective colloid before, during
or after heating. In one method, the protective colloid,
powdered carrier and pigment are mixed at ambient temperature,
-- 5 --

~5~7~
and the ~ixture is then agitated at a temperature above the
melting point of the carrier. In a second method, a mixture
of the protective colloid and carrier is agitated above the
melting point of the carrier, and the pigment dispersion
is added to the hot dispersion with agitation. In a third
and preferred method an aqueous mixture of the protective
colloid and pigment is heated to a temperature above the
melting point of the carrier and the carrier as a powder
is added to this mixture with agitation.
In order to assist bead formation an aid in amounts
of up to 10~ w/w on pi~ment mày be added to the mixture,
~ut preferabl)r in amounts of up to 5~. By l'aid" is
meant a compound or composition ~hich when added to,
or prepared in the presence of the aclueous pi~nent dispersion
(with or l~ithout the organio bead forming composition or
protective colloid bein~ present at this stage) facilitates
the subsequent association of the pigment with the organic
phase. The aid is a compound or composition whic~l is
initially water soluble and may be renderecl ~ater
insoluble/oil soluble by subsequent reaction. The aid may
be, for example, a fatty amine or a fatty acid rendercd
water insoluble either by plI control or salt formation, e.g.
by adjusting an amine-acetate so]ution to pl-~10.
The aid is con~eniently prepared in the presence of atl
~queous pigmcnt dispersion. ~or example, an aqueous pigmelt

l~S971~4
presscalce (20~ w/w pigment) is redispersed in an aQueOus
solution of a C18 a]kyl a~ine acetate to produce a 5~ w/~
aqueous pigment dispersion. To this dispersion is added a
solution of sodiwn oleate (or other soluble alkali metal salt
of oleic acicl) in sufficient amount to form the oleate of the
alkyl amine. The monoamine may be replaced by a related
diamine and the correspondin~ cli-oleate formed. The oleic
acid may be replaced by other carboxylic or sulphonic acid
~hich produce ~ater insoluble salts with the selected amine.
As an alternative, the sodium oleate (or other salt)
may be initially present in the pigment dispersion, and the
alkyl amine added to produce an insoluble salt.
It is also possible to produce an aid by changing the
pH vr the dispersion. ~or example, sodium oleate may be
con~erted to the substantially water insoluble oleic acid by
additions of acetic acid to a pH of 4 - 5. Alternatively,
ir a C18 alkyl amine acetate, for example~ is present,
this may be rendered insoluble by the addition of an alkali
to a pH of 10 - ll.
When highly polar pigments such as metal salts, metal
complex~s or the pigments described and claimed in German
OL 2 401 597 are used, amines at pH 4 - 5 are very effective.
i.e. pH adjustment to 9 - 10 is not necessary.
` It should also be noted that some of the above-mentioned
compounds may be present during the pig~ent preparation, for
example, Ar~e~n I` (a C18 allcyl amine from Armour I-Iess) may
be present during an azo oouplin~ qually, to those
sl;illed in the art, it will be ob~ious that ~ater solublc
forms of these aids may be used to redisperse pi~nent
presscake or powder.
~` //Y' d C/ ~ ~ a r ~ ~

~5~7019~
The pi~cnted beads may be recovered by any desired
method. They may, for example, be filtered off and
washed. This may be done on a screen to gi~e quick removal
of the water. Filtration of conventional pigment slurries
is 510w and results in a presscake having about &0 - 90~ of
water. The beads which contain only 50~ of water may then
be dried, either in a conventional oven or in an air stream.
In son~e instances it may be necessary to cool the pigmented
beads to avoid aggregation or coalescence during filtration.
Provided that the carrier used is compatible with the
desired system to be coloured, the beads are readily
incorporated therein to give an evenly coloured product.
The process of the present invention produces a good
yield of well formed free flowing beads which can be readily
dispersed into application media. By contrast, poor yields
of irregularly shaped granules having a wide distributation
and poor dispersibility are obtained when lower proportions
of carrier are used, i.e. pigment to organic composition
ratios in excess of 2.3:1. By low yield we mean that on
isolating the material from the aqueous slurry by filtration
and washing on a 100 mesh sieve a large proportion of
pigment particles is contained in the filtrate rather than in
the product on the screen.
The invention will be illustratcd by reference to the
following Examples~ in which parts by weight bear the -same
relation to parts by volume as do kilograms to litres.

~L~S~7~4
Example 1
0.75 Parts by weight hydroxyethyl cellulose CNa~rosol 250HR)
were wetted with 2 parts ~y volume m~thano~ and added to 200
parts by volume of water at 80C~ with st~rring until a solution
was obtained. 30 Parts by weight dicyclohexyl phthalate
were then added and the mixture was stirred to form a
dispersion of the dicyclohexyl phthalate. 30 Parts of
C.l Pigment Yellow 13 in 500 parts of water, obtained by a
conventional acetate buffered aqueous coupling was heated
to 85C. and added to the aqueous dispersion of
dicyclohexyl phthalate. This mixture stirred at 80 - 85C.
for 45 minutes to give yellow beads of 0.5 - 2 mm. diameter
which could be removed on a sieve of BS.100 mesh
~1.152 mm. aperture) gave a virtually pigment free
; aqueous filtrate. This product when washed salt ~ree anddried at 40C. could be readily incorporated on a 2 roll mill
in to plasticised P.V.C. When the dicyclohexyl phthalate
in the above process was reduced to 6 parts only 18 parts
of a composition containing 64% pigment was retained by the
above sieve. The filtrate contained the remainder which
analysed as practically pure pigment.
Example 2
0.75 parts of hydroxyethyl cellulose wetted out with
methanol was added to 30 parts of Cl Pigment Yellow 13 slurry as
ob~ained in Example 1. 30 parts dicyclohexyl phthalate
powder was then added to this aqueous slurry and the
mixture heated to 85C. After 40 minutes at 85C. a
product similar to that obtained in Example 1 was obtained.
_ g _

S971D4
Again i the dicyclohexyl was reduced to 6 parts only 20 parts
of a composition containing ~0% pigment was retained by the
sieve. The unretained solid material ~as again practically
pure pigment.
Example 3
A slurry containing 30 parts Cl Pigment Yellow 13 and
0.75 parts hydroxyethyl cellulose prepared as in Example 2
was heated to 85C. 30 parts of powdered dicyclohexyl
phthalate was then added to the stirred slurry. After
45 minutes yellow beads simllar to those obtained in
Example 1 were removed. The filtrate was again free of
pigment. The resultant washed and dried beads had similar
properties to those of Example 1. If the dicyclohexyl
phthalate was reduced to 6 parts and added either as a melt
or powder, 1~.5 parts o a composition containing 58%
pigment were recovered on the sieve and the remaining
pigment went through with the filtrate.
Example 4
The procedure of Example 3 was repeated except that
before addition of the dicyclohexyl phthalate powder the
pigment slurry and hydroxyethyl cellulose was adjusted to
pH10. 0.5 parts of sodium oleate was added and the pH
adjusted to 5. The beads which were similar to those
Gbtained in Example 3 werc completely formed in 20 minutes.
The application properties were also similar to those of
Example 3.
When the above procedure was repeated except that the
hydroxyethyl cellulos0 was not added and the mixture stirred
- 10 -

~i97~4
for 4 hours at 85C. 50 parts of irregularly shaped granules
were retained on the sieve. Also, if the pH was not
adjusted to 5, but left at 10, there was very little bead
formation.
Example 5
0.75 Parts by weight hydroxyethyl cellulose
~Natrosol 250 HR) were wetted with 2 parts by volume methanol
and added to 200 parts by volume of water at 80C. with
- stirring until it was all dissolved. 30 Parts by weight
dicyclohexyl phthalate were then added and the mixture was
; stirred to form a dispersion of the dicyclohexyl phthalate.
Pigment pressca~e (equivalent to 50 par~s by weight, dry
~eight) of C.I. Pigment Yellow 13, was slurried in 200 parts
by volume water with 0.5 parts by weight Armeen T which had
been predissolved in 5 parts by volume glacial acetic acid,
and heated to 86C. The slurry was added to the stirring
dicyclohexyl phthalate over 10 minutes and stirred at 80C.
for 45 minutes to give a virtually pigment free aqueous phase.
The product was separated on a BS 60 mesh sieve and
washed thoroughly with cold water. The residue was dried
in a cool oven. The yield was 78 parts by weight of yellow
beads. Dispersion on a 2 roll mill by conventional means
in polyvinyl chloride gave an evenly coloured product.
Exam~le 6
An aqueous solution of hydroxyethyl cellulose was
prepared as in Example 1, but at room temperature. To
this solution was added 30 parts by weight dicyclohexyl
phthalate and 50 parts by weight of C.I. Pigment Yellow 13,

59~
slurried as in Example 1, also at room temperature. The
mixture was heated to 80C. with stlrring, and stirring
was continued untll all of the pigment had associated with
the organic phase. The yellow beads were recovered by
the procedure set forth in Example 1.
Examples 7 - 20
The procedure set forth in Example 5 was repeated using
the substances in the Table below. In all cases the
pigment /organic composltion ~carrier) ratio is 1/l. Where
an aid is indicated, it was added to the heated pigment slurry
before it was added to ~he stirring dispersion. The amount
of aid was 10% w/w based on the dry weight of pigment.
- 12 -

~597a~L
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S971~4
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~5971)~
Examples 21 - 23
Example 1 was repeated except that the hydroxyethyl
cellulose Natrosol 250 HR used in Example 1 was replaced by an
equal amount of
21. Natrosol 250 G.R.
22. Natrosol 250 M.R.
23. Polyvinyl alcohol Elvanol* 50.42
Results similar to those in Example 1 were obtained.
Example 24
500 parts by volume of a slurry obtained directly from an
aqueous coupling containing 30 parts by weight C.I. Pigment
Yellow 12 was heated at 95C. for 1 hour and added to a
mixture of 0.25 parts by weight hydroxy ethyl cellulose,
30 parts by weight N-octyl phthalimide, 3.0 parts by weight
Imidrol* SC ~2 heptadecyl, 3 aminoethyl imida~oline) and
300 parts by volume water, and the mixture was stirred at
75 - 80C. 1.5 parts by weight of oleic acid as its sodium
salt was then added and the mixture stirred for 5 minutes.
Dilute acetic acid was ~hen added to lower the pH from 10 to 6.
The resultant yellow beads were separated off through a screen,
washed with cold water and dried in a cool ~30C.) oven.
The yield was 54.3 parts by weight.
The beads were incorporated by conventional means into
publication gravure medium to give an evenly coloured product.
* Trademark

~59~
Example 25
The procedure of Example 17 was repeated using 25 parts of
C.I. Pigment Yellow 13 and 4 parks of sodium Qleate and 15 parts
of A~meen 2C - a trade mark of Armour Hess.
The resultank 37.6 parts of yellow beads gave an evenly
coloured product when incorporated into PVC medium.
Example 26
260 parts by volume of slurry obtained directly rom an
aqueous coupling containing 15 parts by weight of C.I. Pigment
Yellow 12 was heated to 80-85C. and added over 5 minutes to a
mixture of composition formed by melting together 9.0 g. of wood
rosin and 6-0 g. C16-C18 fatty acid amide ~Armid HT - a trade
mark), 0.6 parts by weight of hydroxy ethyl cellulose
~Natrosol 250HR - a trade mark of the Hercules Powder Co.) and
150 parts by volume of water at 85C. The mixture was
s~irred at 80-85C. for 4 hours when the aqueous liquors were
substantially free of pigment. The product was separated using
a screen washed with cold water and dried in a cool oven
yielding 28.2 parts by weight of yellow beads.
The beads when incor~orated into publication gravure medium
gave an evenly coloured prod1lct.
Example 27
The procedure set forth in Example 17 was repeated using
a composition formed by melting together a 1:1 mixture of zinc
calcium resinate and oleamide in place of the wood rosin -
Armid HT mixture. The yield was 59.8 parts of yellow beads
which gave satisfactory results in publication gravure medium.
- 16 -

~Q15976~4
Ex~e~ 28
20 parts of C.I. Pigment Yellow 12 modified according
to Example 1 of German OL 2 401 597 was prepared in ~O0
parts of water in the presence of 0.5 parts hydroxyethyl
cellulose ~Natrosol 250 HR). This slurry was heated to 80C.
and 20 parts of Oleamide ~Armid 0) flake was introduced with
stirring, Stirring was continued or 60 minutes at 80C.
until tha aqueous phase was substantially free o~ pigment.
The resultant beads, 40 partsJ were recovered on a BSlOO mesh
sieveJ washed salt free and dried at 40C. The product could
be readily dispersed into a toluene/aliphatic hydrocarbon
~equal parts) solution of a phenolic modified rosin/zinc calcium
resinate ~equal parts) publication gravure media.
Example 29
Example 28 was repeated except that the oleamide was replaced
by stearyl alcohol. Very fine beads of 0,5 mm. were obtained.
When the amount of hydroxyethyl cellulose was reduced to
0.25 parts beads similar in size to those with the oleamide
carrier were obtained. When the process was carried out in
the absence of hydroxyethyl cellulose irregular beads of up to
5 mm, were obtained. The latter product was more difficult to
disperse into a publication gravure mèdia.
Example 30
The procedure in Example 28 was repeated using hydrogenated
wood rosin and oleamide premelted together in the ratio 3:2
respectively and the resultant solid used in place of oleamide.
38.3 parts of yellow beads were obtained which gave a
satisfactory product for use in publication gravure medium,

Example 31
20 parts of C.I. Pigment Yellow 13, as slurry, obtained
directly from coupling was heated to 80C. with stirring and
with 0.5 parts of hydroxyethyl cellulose ~Natrosol 250 M) at
pH 4.5 was added, followed by 20 parts dicyclohexyl phthalate.
Stirring was continued at 80C. until the aqueous li~uors were
substantially free of pigment (2 hours). The beads were
separated using a screen, washed with cold water and dried in
a cool ~35C.) oven. 39.7 parts yellow beads were obtained
which gave an evenly coloured product in P.V.C.
Example 32
Example 31 was repeated, except that the Natrosol 250 M
was replaced by Natrosol 250 GR. The yield was 40.0 parts of
yellow beads which gave an evenly coloured product in P.V.C.
Example 33
Example 28 was repeated, except that 0.5 parts of a fatty
amine ~Armeen T) as its acetate was added to the pigment slurry
before the addition of the oleamide. ~eads were formed
immediately and the aqueous phase was substantially clear
after 15 minutes as opposed to 60 minutes when no amine
acetate addition was made. The beads gave an evenly coloured
product in P.V.C. Elimination of the hydroxy ethyl cellulose
gave a low yeild of irregularly shaped beads.
- 18 -

~g)S97~4
Example 34
20 parts of C~I. Pigment Yellow 129 from a 15% w/w
aqueous presscake was dispersed in 400 parts of water at
pH5 with 0.5 parts of Natrosol 250HR. The slurry was
heated to 80C. and 0.5 parts of a fatty amine ~Armeen T)
as its acetate was added. 20 parts of dicyclohexyl
phthalate was then added with stirring. A good yield of
regularly shaped beads was obtained, which gave an evenly
coloured product in P.V.C.
E_ample 35
Example 34 was repeated, except that the pigment
used was 20 parts of CI Pigment Yellow 61. The resulting
beads gave an evenly coloured product in PVC.
Example 36
The procedure set forth in Example 1 was repe~ted,
using in place of dicyclohexylphthalate, a premelted
mixture o oleamide/cholesterol ~ The resultant
beads gave evenly coloured products in PVC and polyethylene.
Example 37
The procedure o Example 2 was repeated, using CI
Pigment Red 48 ~ca salt~ in place of CI Pigment Yellow 13
and cetyl palmitate in place of dicyclohexylphthalate.
The resultant beads gave evenly coloured products in PVC
and polyethylene.
- 19 -

~s97~
Example 38
Example 37 was repeated, except that the cetyl palmitate
was replaced by diethylene glycol monostearate. The
resultant beads gave evenly coloured products in PVC
and polyethylene.
Example 39
The procedure of Example 2 was repeated, using slightly
chlorinated alpha Pc blue in place of CI Pigment Yellow 13
and hardened cas~or oil in place of dicyclohexylphthalate.
P.V.C. and polyethylene were evenly coloured by the resultant
product.
Examples 40~~5
The procedure set orth in Example 3 was repeated
except that a non-ionic surfactant was added or replaced
hydroxy ethyl cellulose, as shown in the ollowing table.
It is seen that in terms o yield it is preferable to carry
out the preparation above the cloud point ~as described
earlier) of the non-ionic surfactant, especiallY in the
presence of hydroxy ethyl cellulose.
- 20 -

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~r ~
--~ ~ o ~
. . _ , _ _
_l ~ O
co a~
. _ _
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-o ~
~ 1 0 c~ ~J N C`l N
~1 o a~
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3 h ~ : h `-- a~
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2 1~ X U~ X
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.
- 21 -
.. . . . . . .. .. . . . . . .... .. . . . . . .

~LOS97~14
Example 46.
20 parts of C.I. Pigment Green 7 as filtercake was redispersed with
stirring in 400 parts water. 0.2 parts hydroxy ethyl cellulose was
added. The mixture was heated with stirring over 30 mins. to 80C and
0.5 parts of a C18 alkyl amine as its acetate added. 18 parts dicyclo-
hexyl phthalate were added and stirred at 80C for 17 mins. when
the aqueous phase was substantially ree of pigment. The resultant
product was isolated as in example I and dried to give 38 parts
of green beads which gave an evenly coloured product in p.v.c.
Example 47.
10 parts C.I. Pigment Red 48.2 as slurry direct from coupling was
heated with stirring to 85C wlth 0.25 parts hydroxy ethyl cellulose
and 0.5 parts of a C18 alkyl amine as acetate. 10 parts dicyclohexyl
phthalate was added and stirred until the aqueous phase substantially
clear of pigment. The resultant red beads were isolated and dried
as in example 1 and gave an evenly coloured product in p.v.c.
22 -

Representative Drawing

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Event History

Description Date
Inactive: IPC from MCD 2006-03-11
Inactive: IPC from MCD 2006-03-11
Inactive: IPC from MCD 2006-03-11
Inactive: Expired (old Act Patent) latest possible expiry date 1996-08-07
Grant by Issuance 1979-08-07

Abandonment History

There is no abandonment history.

Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
CIBA-GEIGY AG
Past Owners on Record
GEORGE H. ROBERTSON
JOHN A. STIRLING
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Abstract 1994-04-26 1 22
Cover Page 1994-04-26 1 19
Claims 1994-04-26 3 84
Drawings 1994-04-26 1 10
Descriptions 1994-04-26 21 615