Note: Descriptions are shown in the official language in which they were submitted.
t~
3-10464/~A 1660
TREATMENT OF PHATH~LOCYANINE PIGMENTS
The present invention relates to a process of pigment
treatment, particularly a phthalocyanine pigment.
In our British Patent No. 1,263,684 there is described
and claimed:
.
A process in which a pigment is treated comprising .
contacting a metal phthalocyanine blue pigment, in dry pigmentary form,
with a polar aliphatic solvent which is at least partially water-
miscible, and separating the solvent from the treated pigment, in
which process there is added to the metal phthalocyanine blue ~ -
pigment before it is contacted with the solvent, during the contacting, ~
or after it has been separated from the solvent, a minor proportion .
of a copper phthalocyanine derivative having the formula: `.
/ 2 l)y -:
CuPc \ . -,
(S03 H2~NRRl)x :
"~
wherein CuPe represents the copper phthalocyanine residue, either
chlorinated or unchlorinated, R represents a cyclic or acylic alkyl ; :
group having from 1 to 20 carbon atoms or an aryl group, and R~
represents hydrogen or a cyclic or acyclic alkyl group havin~ from
1 to 20 carbon atoms or an aryl group,the alkyl or aryl groups being
either unsubstituted or substituted by hydroxyl, amino, alkylamino
or amide substituents, and x and y each represent l, 2 or 3 with the
proviso that the sum of ~ and y is 2, 3 or 4.
~ :,
,
; ~3 ' ' ' - ~ .` ~:
5()
--2--
The pigment so treated shows improved brightness
when incorporated into inks.
- We have now found,surprisingly, that by adding a ~ .
different phthalocyanine derivative to a phthalocyanine pigment in
a similar process treatmen~ before or during contact with a polar
aliphatic solvent, the resulting treated pigment composition has
improved properties with regard to strength and rheology when ~.
incorporated into inks and paints, when compared with the treated :~
pigment composition described in B.P. 1,~63,684. ~ -
. .: .
. According to the present invention there is provided .~ :
a process in which a pignlent is treated by contacting a phthalocyanine
pigment, in pigmentary form, with a polar aliphatic solvent which is at .
least partial~y water-miscible, and separating the solvent from the :~
treated pigment, in which process there i5 added to the phthalocyanine
pigment before it is contacted with the solvent or during the contacting
a minor proportion Qf a sulphonated phthalocyanine-amine derivative .
of the formula
~ / 2
Pc ~SO - N - R
' ,~
wherein Pc represents a phthalocyanine residue, R2, R3 and R4 each
represents an alkyl, alkenyl or alkapolyenyl group, R6 represents
hydrogen, or an alkyl, alkenyl, alkapolyenyl cr aralkyl group and x
is the average number of sulphonic groups per phthalocyanine molecule :.::
and is from 1 to 4.
g~lslo
Compounds of formul.a I may be formed by reacting
a phthalocyanine dyestuff having the formula
Pc(S03M)~ II
wherein Rc and x have their previous significance and M represents
hydrogen or an alkali metal, with a tertiary amine having the general
formula
R2 ~ N - R3 III
4 ~.
or a quaternary ammonium salt having the formula `
R2 ~ N - R B(-) IV
I ,
wherein R2, R3 and R4 have their previous significance, R6 represents
an alkyl, alkenyl alkapolyenyl or aralkyl group and B represents :~
an anion, the total number of carbon in the tertiary amine or cationic ;~ :
portion of the quaternary ammonium salt being from 20 to 60, and at :~
least one of the groups R2, R3, R4 and R6 having a backbone of at
least 12 consecutive carbon atoms.
:`
When the dyestuff of formula II is reacted with a
tertiary amine of formula III, R5 in formula I is hydrogen and when
the dyestuff of for~ula II is reac~ed with the quaternary ammonium :
salt of formula IV, R5 in formula I cannot be hydrogen. : ."
.
9~o
Preferably two of the groups R2, R3, R4 and R6 have backbone of at least
12 consecutive carbon atoms, and the totaL number of carbon atoms
on the nitrogen atom is pre,erably from 25 to 45. The anion B( is
preferably halide, acetate or hydroxide. i ;
The phthalocyanine dyestuff of formula II may be
metal free, or it may be a zinc, copper, cobalt, nickel or other
transition metal phthalocyanine and may contain halogen, especially
chlorine, in the phthalocyanine molecule.
Halogen free copper phthalocyanine dyestuffs of
the formula:
cuPc (S03H?x v
are preferred where CuPc represents a copper phthalocyanine residue -~
and x has its previous significance.
The phthalocyanine dyes~uff of formula II may be
prepared by any of the methods in common use, for example by
reacting the phthalocyanine with chlorosulphonic acid or oleum
at elevated temperature for several hours, then dr~wing out into an
aqueous solution of sodium chloride prior to recovery as a presscake
by filtration.
.
The phthalocyanine pigment may be metal free or it `
may be zinc, copper, nickel or other transition metal phthalocyanine,
and may contain up to 50% by weight of chlorine. The preferred pigment
is a copper phthalocyanine, which may be in either the alpha or beta ~-~
crystalline form, or a mixture of the two. ~ ;
.
The ratio of phthalocyanine pigment to phthalocyanine
deystuff of formula II may be from 88:12 to 99:1 by weight, but
preferably from 92:8 to 96:4. -
. ':
While x can be from 1 to 4, compounds of formula I
are preferred in which x is 1-2.5.
Compounds of formulae III and IV may be based on
specific alkyl, alkenyl or alkapolyenyl amines but are more conveniently
derived from the mixtures of hydrocarbon residues of naturally occuring ..
oils and fats such as tallow, corn oil, fish oil, or whale ail. Among
such suitable tertiary amines there may be mentioned dimethyl tallow,
dimethyl hydrogenated tallow, dimethyl soya, dimethyl octadecyl, `~
` dimethyl eicosanyl, dimethyl docosanyl, monomethy~ di eicosanyl, .
monomethyl di(dodecyl), monomethyl di(hydrogenated tallow), monomethyl
di docosanyl, tri dodecyl andtri octadecyl amines or mixtures thereof.
: The quaternary ammonium salts are conveniently
formed from such tertiary amines by reaction with methyl chloride or
dimethyl sul?hate to form the methyl quaternary ammonium salt or with ~: -
benzyl chloride to form the appropriate benzyl quaternary ammoium
salt.
~.
The sulphonated phthalocyanine-amine derivati~es :~-
of formula I formed by the combination of ~ompounds of formula II
with a compound of formula III and/or I~, may be produced, for example ~;
by reacting a phthalocyanine compound containing x sulphonic acid
groups with a sufficient quantity of one or more amines and~or
quaternary ammonium salts to substantially neutralise the free sulph- :~ :
onic acid groups~
` ,i: '..
, -
l~V~ ~t~V ,
--6--
The sulphonated phthalocyanine-amine derivative of
formula I may be prepared in aqueous solution, providing the nitrogen
compounds of formulae III and IV are watersoluble or are capable of
forming a solution in aqueous mineral or organic acids. Alte~natively,
the derivative may be prepared in a suitable solvent and recovered
by precipitation, e.g. with water, or by removal of the solvent by
distillation, optionally with the addition of wat~r. Such preparation
in solvent is particularly useful for compounds of formulae III and IV
which do not readily form solutions in water or aqueous acidic media. ~;~
Among suitable solvents there may be mentioned acetone, ethylmethyl-
ketone, ethanol and methanol, but isopropanol is particularly preferred. -
The polar aliphatic solvent with which the pigment
composition is treated is one which is at least partially miscible
with water. Suitable solvents are described in B.P. 1140~36 and include
alkanols having from 1 to 4 carbon atoms in the alkyl chain, for
example, methanol, ethanol, n~propanol, isopropanol and n-butanol;
alkyl monocarboxylates having from 1 to 4 carbon atoms in the alkyl
chain, for example alkyl esters of alkanoic acids especially ethyl
acetate; dialkyl ketones having from 1 to 4 carbon atoms in each
alkyl chain, for instance acetone, methyl ethyl ketone or dlethyl
ketone; alkoxy alkanols having from 1 to 4 carbon atoms in each
of the alkyl chains of thealkoxy and alkanol components for instance,
2-methoxy ethanol or 2-ethoxyethanol; or alkylene glycols having from 2
to 6 carbon atoms in the alkylene chain, for e~ample, ethyl~ne glycol
or diethylene glycol.
The solvent may~ if desired, contain disolved
water in a proportion insufficient to cause separation into two phases,
and may thus be, for example, aqueous ethanol(for instance industrial
methylated spirits), an aæeotropic mixture of ethanol and water or
an azeotropic mixture of isopropanol and water, the alkanol in each
.
~ case being the major cons~ituent.
9~
--7--
The pigment to be contacted with the dyestuff/amine
derivative may be added to the solvent as a powder or aqueous presscake.
The pigment may be in a full pigmentary state or in a hyghly aggregated
state, as formed during a dry grinding process. The pigment thus may
be in the Eorm of a mixture of phthalocyanine with a salt, especially
a mixture resulting from a preparation of the colouring matter in
pigmentary form by grinding with the salt; the mixture of the organic
solvent and the pigment is then preferably treated by mixing it with a
proportion of water, sufficient to dissolve the salt present.
As noted in BP. 1,140,836 such solvent treatments
lead to products of improved rheology, brightness, and dispersibility:
the present process gives improvements in properties in addition to
those from such a solvent treatment of the pigment alone. The process
of contacting dyestuff/amine derivative with the pigment may then be
combined with the process of such a solvent treatment. Such solvent
treatments of the pigments, as noted in PB. 1,140,836, may be effected
under a wide variety of conditions, the particular temperature and
pressure at which the treatment is effected and the time during
which the pigment and solvent are contactled, being dep~ndent on the
nature of the pigment and of solvent in order to secure the optimum
improvement in pigmentary properties.
Although the pigment is preferably contacted with
the solvent at a temperature in the range from 10C.to the boiling
poi~t of the solvent at the pressure applied, a temperature of from
50C to the boiling point is particularly preferred when the treat~
ment is carried out at atmospheric pressure. Although a superatmospheric
pressure may be applied, if desired, for example when the solvent used
is highly volatile at the treatment temperature chosen, it is generally
convenient to treat the pigment with the solvent at atmospheric or
substantially atmospheric pressure. `
~- .
,:: ~ . . . :: . . .. .~,.:. , - . . .
The proportion of solvent with which the pigment
is treated in the process, relative to the pigment is preferably
in the range of from 0.5 to 20 parts by weight of solvent per part by
weight of pigment, the proportion of l to 15 c~nd especially 5 to lO
parts by weight of solvent per part by weight of pigment being
particularly preferred. If the proportion of solvent to pigment is
above that of the preferred range, no further significant improvement
i7a the pigmentary properties of thetreated pigment is achieved. If
the proportion of solvent to pigment is below that of the preferred
range, the strength and brightness of the treated pigment is inferior
so that of the same pigment when treated with a proportion of solvent
within the preferred range.
Sulphonated phthalocyanine amine derivative may
be added at any point during this treatment but it is preferred
that the pigment and derivative are contacted for at least lO minutes
at the reflux temperature of the preferred solvent, i.e. isopropanol
or the water isopropanol azeotrope mixture. Although the sulphonated
phthalocyanine amine derivative may be preformed, as in the case
above, and then contacted with the pigme7at, it is a further advantage
of this process that the derivative can be formed in the selected
solvent in the presence of the pigment. 5uch an approach avoids the
separation of dyestuff/amine preparation. This is especially advan-
tageous in the use of the preferred dialkyl amine d~:rivatives which
are substantially water insoluble but readily react with sulphonated
phthalocyanine dyestuff in such solvents.
The pigment composition may be isolated from the
solvent by filtration, preferablyafter dilution with water. The more
volatile solvents may be removed by direct distillation but it -
is preferable that water is added, solvent is removed by distillation
and the pigment is then left dispersed in essentially an aqueous
phase; isolation from water is then by the conventional techniques of
B~ .
45~3
g
filt~ation and drying. In all c~ses the com~ositions are washed free
of any inorganic salts.
The pigment compositions prepared by the process
of the inven~ion may be used for pigmenting various media.
They can be used in decorative paint, in publication
gravure inks, nitrocellulose, alkyd~ and acrylic-MVF systems, but
are particularly suitable in those media containing a high proportion
of hydrocarbons in the solvent.
In Belgian Patent 833,518 there is described and
claimed a composition which comprises:
i) a finely divi~ed solid with a mean grain size of less than
20 microns
ii) a polymer or resin dis?ersi?.g agent
iii) a fluidifying agent which is an ammonium salt substituted by an
acid colorant in which 16 to 60 atoms of carbon are contained
in at least three chainsbo~ded to the nitrogen atom of the
substituted ammonium ion, and
iv) an organic liquid. ~
' ~:
We have found that phthalocyanine pigm~nt compositions
prepared by the process of tile present inven~ion in which the pigment
and dyestuff amine derivative is contacted with a polar aliphatic
solvent~ show superior properties with regard to strength and
rheology when incorporated into ink and paint media, over the pigment
compositions claimed in Belgian Patent 833,518 which have not been
contacted with a polar aliphatic solvent.
. ' ~:
~ ` '
1~ 5V
--10--
It can be seen in the following Examples that the
sulphonated derivatives promote good flow and flow stability in
systems which would otherwise be thick and/or thixotropic, and
also accelerate the rate of dispersion.
The invention is illustrated by the following
Examples in which parts and percentages are expressed by weight
unless otherwise stated. Parts by weight bear the same relationship
to parts by volume as do kilograms to litres.
; .
Example 1: 175 parts of crude copper phthalocyanine were ground
with 23 parts of inorganic salts, 1.6 parts diethyl aniline and
0.8 parts glycerol mono-oleate until the phthalocyanine was in
pigmentary fxom.
103 parts of this mixture, corresponding to 90 parts
of copper phthalocyani11e, were added to 600 parts of isopropanol
and heated under reflux conditions with good agitation for 5-L~2 ;
hours. 4 parts of the compound of formula V
CuPc(S03H)
x ~ ~
wherein x is 2, in presscake form, were added and reflux continued. ~;
After 15 minutes, 6 parts of an amine (Kemamine T.9701 ~ , Humko
Chemical Products)of formula III where R4 is a methyl group and
R2, R3 are hydrogenated tallow residues, were added as a solution
in hot isopropanol. A further 15 ~inutes later, 600 parts of water
were added and the isopropanol removed by distillation. Agitation
was stopped and the pigment composition filtered from clear liquors,
washed salt free to neutral pH, and dried at 50-60C. The yield
~as 99.1 parts. ;
A publication gravure ink of 6% pigmentation and
1:5 pigment: binder ratio was prepared by ball milling, the pigment
composition of this Example in a phenolic resin varnish with toluene
solvent, according to the method of ~xample 10 of British Patent
No. 1,501,184. I~en compared with a similar ink prepared from un-
treated beta-copper phthalocyanine, the ink prepared from the
product of this Example had a very much more fluid millbase and was
15% stronger, cleaner and brighter.
Example 2: Example 1 was repeated using 3.4 parts of the compound
of formula V
t 3 )x '
where x is 2~4, and 5.6 parts of the hydrogenated tallow amine. The
publication ~ravure ink derived from this composition was approximately ~
10% stronger than the corresponding ink prepared from untreated ~;
~~copper phthalocyanine and had a more fluid millbase. `
Example 3: -
- ~
A) 20 parts of the compound of formula V ~ ~
. :
CUPC SSO3H)X
in which x is 2, in presscake form, were stirred in 200 parts of
isopropanol and the temperature raised to reflux. 29.2 parts of
the amine of formula III, where R4 is a methyl group and R2, R3
are hydrogenated tallow residues, were dissolved in 200 parts
hot isopropanol, and added over 5 minutes. After a further 30
minutes at reflux, 400 parts of water were added over 60 minutes, and
the isopropanol simultaneously distilled off at the same rate. ~-
Stirring was stopped and the blue-green product of the reaction
isolated by iltra~ion from clear liquors, l~ashed with warm
wat~r, and dried at 60C to give a yield of 48.1 parts.
' ~.
..
B! 175 parts of c~ude copper phthalocyclnine were ground by the method
of Example 1. 103 parts of this mixture, corresponding to 90
parts of copper phthalocyanine, were added to 600 parts of isopropanol
and heated under reflux conditions for 5-1/2 hours with good agitation.
I0 parts of the product of Part A of this example were added as a
solution in hot isopropanol and reflux continued for 30 minutes. 600
parts of water were run in and the isopropanol removed by distillation,
after which agitation was stopped.
The pigment composition was filtered from clear
liquors, washed salt free to neutral pH, and dried at 50-60C.
The yield was 99.3 parts.
A publication gravure ink prepared from the product
of Part B of this example by the method of Example 1 had similar
properties to the ink derived from the product of Example 1.
Comparative Example: ;
C) Example 3B was repeated except that the 10 parts of product of
Part A of this example was omitted. To ~he resultant 90 parts
o~ ~-copper phthalocyanine pigment powder, 10 parts of the powder
product of Part A was then added and the two components intimately
mixed. A publication gravure ink prepared from this mixture was
10% weaker and had inferior rheology to that achièved with a sample
of Example 3B.
Example 4: Example 3B was repeated using 108.6 parts of the ground
mixture, corresponding to 95 parts copper phthalocyanine, ~ogether
with 5 parts of the product of Example 3A. The pigment composition
so obtained, when incorporated in the publication gravure ink
medium was 10-15% stronger than the corresponding ink derived from
untreated ~-copper phthalocyanine.
-13-
Example 5:
A) 90 parts of a substantially alpha-form copper phthalocyanine,
containing 1.8% w/w peripheral~Tbound chlorine, were added as
a 30% aqueous presscake, to 500 parts of isopropanol, and heated
to reflux with agitation. 4.8 parts of the compound of formula V
CuPc(S03}1)
in which x is 2, in presscal.;e form were added and reflux continued
for 15 minutes. 5.1 parts of technical di(dodecyl)methylamine were
then added as a solution in hot isopropanol.
After 15 minutes, 500 parts of water were added
and the isopropanol removed by distillation. Agitation was stopped
and the pigment composition filtered from clear liquors, washed
salt-free to neutral pH with warm water and dried at 50-60C. The
yield was 99.L parts.
The pigment composition of this Example was ~
incorporated in a glycerol coconut oil alkyd resin in xylene/n-bu~anol ~ `
solvent by ballmilling and subsequently reduced to 6% pigmentation
and 1~6.6 pigment: binder ratio with an unmodified isobutylated
melamine/formaldehyde (M/F) resin solution. The initial mill base
dispersion was fluid, in contrast to a similar dispersion prepared
from alpha-copper?hthaloc'yani~e pigment untreated by dyestuff and
amine, which was thixotropic and only pourable after agitation.
Blue tint alkyd-MVF paints were prepared from the reduced dispersions
by admixture with white alkyd-M/F paint and stoving. The paint derived
from the pigment of this Example was approximately 10-15% stronger
than the paint derived from the pigment not so treated.
When this pigment composition was dispersed into a
long oil soya alkyd decorative paint by a "Red Devil" technique
and then reduced into a ~hite base paint at a 1:25 reduction, that ls,
ratio of phthalocyanine pigment composition to titanium dioxide,
this product was 20~ stronger than the untreated a-copper
,~..
~89~50
-14-
phthalocyanine dispersed and assessed by an identical technique. The
initial dispersion of the treated pigment in the alkyd medium exhibit
superior flow p~operties to the dispersion from the untreated
pigment.
Co~R___tive Example
B) A pigment composition was prepared by intimately mixing as dry
powder, 9 parts of the above ~-copper phthalocyanine and 1 part
of the dyestuff-amine composition as used in Example 5R. The
composition was then tested in the short oil alkyd and long oil alkyd
media used for Example SA. In both paint systems the composition of
Example 5A, prepared via contacting in isopropanol, showed superior
strength (10-15% stronger) and rheology.
Example 6:
A) A phthalocyanine dyestuff-amine composition was prepared by the
method of Example 3A, us~ng 21.7 parts of the amine of formula III,
where R4 is a methyl group and R2, R3 are dodecyl residues.
B) The method of Example 5 was repeated with the addition of 10 parts
of the product of Part A of this example in place of the separate
additions of dyestuff and amine. There was obtained~a paint of sub-
stantially similar application properties to those of the paint
derived from the pigment composition of Example 5.
Example 7:
A) A phthalocyanine dyestuff composition was prepared by the method
of Example 3A using 32.6 parts of the amine of formula II, in which
the group R2, R3 are each eicosanyl or docosanyl residues, and R4 is
a methyl group.
B) 150 parts of a pigmentary phthalocyanine green pigment powder
of 47.1~ chlorine content were added with efficient agitation to
800 parts of acetone and the temperature raised to reflux. After
10 minutes, 15 parts of the product of part A of this Example were
~ ~.
:.- . : :.:, . . . :. : : , , : . ~
.:: -, :- ~ - . . ; - . . : : , . :
5~D
-15-
added as a slurry in acetone, and reflux continued for a further
15 minutes, after l~hich 800 parts oE water ~ere added and the acetone
removed by distillation. A mixture of lS parts concentrated
hydrochloric acid and 15 parts water was then added evenly over 2
minutes. After 30 minutes, agitation was stopped and the product
isolated by filtration from clear liquors, washed with warm water
and dried at 50-60C. The yield was 163.2 parts. The pigment
composition was incorporated in a nitrocellulose varnish by
ball milling and subsequently reduced to 11.7% pigmentation at 1:1,38
pigment: binder ratio by the addition of a mixture of nitrocellulose
and maleic condensate varnishes. The resulting dispersion had
equivalent colouristic properties, but markedly superior millbase
flow, compared to a similar dispersion prepared from untreated
phthalocyanine green.
Example 8: 95.2 parts of the ~-form copper 2hthalocyanine of
Example S were added, as an aqueous presscake, to 900 parts of ethyl
acetate and heated to reflux with stirring. After 30 mins., 7.5
parts of the product of Example3A were added, and stirring at
reflux continued. A further 15 mins. later, lO00 parts water were
added and the ethyl acetate removed by distillation. The mixture
was acidified with 15 parts 25% aqeuous hydrochloric acid and
stirred 15 mins. Agitation was then stopped, and the pigment
composition filtered from clear liquors, washed to neutral pH
with warm water and dried at 50-60C. The yield was 98 parts.
::
The pigment composition of this Example was
incorporated in an alkyd-M/F paint medium by the method of Example 5.
The mill base was very 'luid and the corresponding blue tint ~ ;
paint 15-20~ stronger, cleaner and sligthly redder than the paint
derived from the a-form copper phthalocyanine starting material.
Example 9: The m~thod of Example 8 was repeated with the use of
9.15 parts a-form CP?e~ phthalocyanine~ 8.5 parts of the product
'~
'` ' ' . ' ' ' : . . ' ' ' ` ` ' . ' :, . ' . ' ~, ' ! . , ,
-16-
of Example 3A, and m~thanol as solvent. There were obtained 98 parts
of pig~eQt co~position.
The alkyd-~F paint prepared from this pigment
composition was similar to that of Example 8, being 10-15% stronger,
cleaner and slightly redder than the corresponding paint prepared
from the ~-form copper phthalocyanine starting material.
Example 10: The method of Example 8 was repeated with the use of
90.5 parts ~-form copper phthalocyanine, 9.5 parts of the product of
Example 3A and ethanol as solvent. The resultant pigment composition,
which was obtained in a yield of 99 parts had similar properties
to the product of Example 9 when incorporated in the alkyd-MVF
paint medium by the method of Example 5.
The pigment composition of this Example was also
incorporated in a long oil soya penta alkyd based decorative paint
medium by baLl milling. A 1:25 reduction, prepared by admixing the
mill base with white decorative alkyd paint, was approximately i
20% stronger than the corresponding reduction prepared from the
untreated ~-form copper phthalocyanine starting material, and
moreover had substantially improved resistance to flocculation.
The mill base containing the pigment composition
of this Example was also very much more fluid than the mill base
derived from the untreated ~-copper phthaloc7anine starting material.
Example 11: 89 parts of ground copper phthalocyanine were stirred
in 500 parts n-butanol. The temperature was raised to reflux and
maintained for 5 hrs. 11 pa~ts of the product of Example 3A were
added and reflux continued for 15 mins. 1000 parts water at 55C
were run in and the n-butanol removed by distillation. The mixture
was acidified with 15 parts 25~ aqeuous hydrochloric acid. 15 mins.
after, the stirring was stopped and the pigment composition filtered ~;
from clear liquors, washed to neutral pH whith warm water and dried
at 50-60C. The yield was 9~ parts.
'~ ` ' ' : ' ~. '.
39f~
.,
-17-
The publication gravure ink prepared from the
product of this Example by the method of Example 1 was 15-20% stronger,
and slightly greener than the corresponding ink prepared from the
ground copper phthalocyanine starting material, and moreover, was
derived from a considerably more fluid mill base.
Example 12: The method of Example 11 was repeated using 87.5 parts
s
ground copper phthalocyanine, 12.5 parts of the product of Example 3A
and ethyl methyl ketone as solvent. The pigment composition was -
obtained in a yield of 97 parts. The publication gravure ink prepared
from this pigment composition was similar to that of Example 11,
being 15% stronger than the corresponding ink prepared from the ground
copper phthalocyanine starting material.
,
Example 13:
~ ?
A) 59 parts of the amine of formula III, where R3 and R4 are methyl
groups and R2 is a soya oil residue, commercially available as
Kemamine T.9972.~, ~ (Humko Chemical Products) were added to 1800
parts boiling water containing 13 parts glacial acetic acid, and
stirred until a solution was obtained. The solution was allowed to
cool and diluted to 2000 parts with water.
" i.,~.~,
60 parts of the compound of formula V
CUpc(s03H)
where x = 2, in the form of inorganic salt-containing aqueous presscake,
wera dissolved with stirring in 4000 parts water. The pH was adjusted
to 5.0 with aqueous sodium hydroxide solution and 1650 parts of the
above amine acetate solution run in evenly over 30 mins.,maintaining
stirring throughout. The mixture was stirred for a further 1 hr.
then filtered, washed free of inorganic residues with warm water and
recovered as presscake. ,;
', .
': ~ ' `,"':'
s~ ~
.
B) The method of Example 11 was repeated using 86.5 parts ground
copper phthalocyanine in the form of an aqueous presscake 13.5
parts of the product of part A of this Example, also in presscake
form, and isopropanol as solvent. The pigment composition, which
had similar properties to that of Example 11 was recovered in a yield
of 97 parts.
Example 14: Example l was repeated except that the 6 parts of
amine used in that Example were replaced by 8.6 parts of an amine of
formula III ~n which R2, R3 and R4 are hydrogenated tallow residues
(Adogen 340 ex Ashland Chemicals). Results in publication gravure
were similar to those obtained from the product of Example l.
Example 15: Example 1 was repeated except that the 6 parts of the
amine used in that Example were replaced by 4.0 parts of an amine
of formula III in which R2, R3 and R5 areisooctyl residues (Adogen
381 ex Ashland Chemicals). Results in publication gravure were
similar to those obtained from the product of Example l.
Example 16:
A) The procedure of Example l was repeated except that the 6 parts
of amine were replaced by 6.6 parts an ammonium salt of formula IV
- with R2 = R3 = methyl and R4 = R6 = hydrogenated tallow and B = Cl.
(Kemamine Q.9702.C ) Results in publication gravure were similar
to the product of Example 1. ;
.
Comparative Example 16.~:
A dyestuff amine composition was prepared according to the procedure
of example 3A but replacing the amine used there by 32.5 parts
of the ammonium salt used in Example 16.A. The dry mixing of 9 parts
of the ~-copper phthalocyflnine pigment and l part of the dyestuff~
amine derivatiYe of ~his Example gave a produkt which when tested
in publication gravure was irfe ior in strength and rheology to
.
. ~ ` '~ ' ~
~ :~
1~ 0'
-19-
the product of Example 16.A.
Example 17: The procedure of Example 16.A was repeated except that
.
the 6.5 parts of ammonium salt was replaced by 4.0 parts of an ammon~
ium salt w th R2 = R3 = methyl R4 = dodecyl and R6 = benzyl (Kemamine
BQ.6502.C ) Results in publication gravure were similar to those
obtained from the product of Example 16.A.
Example 18: 2,143 parts of crude copper phthalocyanine peripherally
chlorinated to the extent of 1.8% by weight were milled for approxi-
mately 14 hours with 6,857 parts of inorganic salts. 4,200 parts of
this mixture, corresponding to 1,000 parts pigment were stirred
into 1,900 parts of isopropanol-water azeotrope containing 25 parts
of the dyestuff-amine composition of Example 6.A. The mixture was
refluxed for 2 hours with stirring. 25 parts of diethyl aniline
were added and refluxed with stirring for 30 mins.
~hile continuing agitation, 2500 parts of water ;
were added in 500 parts aliquots while isopropanol-water azeotrope
was removed by destillationto a vapour temperature of 84C. The
mixture was acidified by adding 800 parts of 1:1 concentrated
hydrochloric acid: water over 10 mins., then stirred for 1 hr.,
filtered hot, washed salt free to neutral pH with hot water and
dried at 60C. -~
The product of ~his Example, when incorporated
in a decorative alkyd paint medium was 15% stronger and brigh~er
than a pigment similarly prepared, but from which the dyestuff
amine composition had been onmitted.
S(~
-20-
Example 19: A pigmentary a-form copper phthalocyanine, prepared
by acid pasting of crude copper phthalocyanine, was treated with the
product of Example 6.A in isopropanol~water azeotrope and subsequently
recovered from water by the method of the previous Example.
The produ~t of this Example was incorporated in a
hydroxy-acrylic resin in 4:1 xylene: n-butanol solvent by ball
milling and subsequently reduced to 6% pigmentation and 1:5 pigment:
binder with an unmodified isobutylated melamine-formaldehyde resin
in n-butanol. The resulting dispersion was considerably more fluid
than a similar dispersion prepared from the a-form copper phthalocyan-
ined starting material.
Blue tint acrylic paints were prepared from these
dispersions by admixing with white acrylic paint and StOVillg. The
paint incorporating the dyestuff-amine treated pigment was 15%
stronger, redder and brighter than the paint derived from the i~;
untreated a-form copper phthalocyanine starting material.
