Note: Descriptions are shown in the official language in which they were submitted.
ilO~07
.
The present invention relates to pigment composi-
tions coneaining a phthalocyanine pigment.
In our British Patent No. 1 263 684 there is des-
cribed 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~
/ ( S02NRR l )y . . : . '
CuPc .
~ S03 H ~ RRl)x
wherein CuPc represents the copper phthalocyanine residue7 ..
either a chlorinated or unchlorinated, R represents a
cyclic or acyclic alkyl group having from 1 to 20 carbon
atoms or an aryl group, and Rl represents hydrogen or a
cyclic or acyllc alkyl group having from 1 to 20 carbon
atoms or an aryl group, the alkyl or aryl groups being
either unsubstituted or substituted by hydroxyl7 amino,
alkylamino or amide substituents, and x and y represen~
-2- ~ : :
.. : ~ . :, :. ,, , - , . . ..
. . : . . . . . . , : :: . .. . . . . .. ..
1, 2 or 3 with the proviso that the sum of x and y is 2,
3 or 4.
We have now unexpectely found that by introducing.
dehydroabietylamine, a tertiary amine or a quaternary
ammonium salt in the mentioned copper phthalocyanine
derivative the resulting compositions have supexior flow,
strength and gloss in paint and ink to those previously
known.
Accordingly the present invention provides a
phthalocyanine pigment composition comprising a phthalo~
cyanine pigment and a sul~honated phthalocyanine deriva--
tive formed ~rom sulphonated phthalocyanine dyestuffs
having the formula
/(S02NRRl ) y
Pc (I)
(S03~)x
wherein
R represents a Cl-C22 cycllc or acyclic alkyl group, aryl,
aralkyl group or a dehydroabietylamine residue; and Rl
represents ~ydrogen or a Cl-C2~ cyclic or acyclic alkyl
gxoup, an a.yl or an aralkyl group; the alkyl, cycloalkyl,
aryl or aralkyl groups, R and Rl may be opt10nalli sub-
stituted with one or more hydroxyl groups; x is Crom 1 to
4, y is O or from 1 to 3 and the sum of x and y is from
1 to 4, and when y is O to 3~ a sufficient quantity of
dehydroabi.etylamine of th2 formu~a: .
-- 3 - ~
. , .:
.
. . ~ . , ~ . . ,., ~ - ,
.. .. - . ,. : ,
. . ,, ., .'' , ~ . . : ' '
H2NCH~ 3
\~/ " :~'
I i ~ , I ~ (II~
C~3 \~ \CH/ 3
\CH
to substantially neutralise the free sulphonic acid groups,
when y is 0, a tertiary amine having the gereral formula
R ~ 3
2 R4 (III)
or a quaternary ammonium salt having the formula:
B (IV)
~ 4
whereln R2, R3 and R4 each represent an alkyl or alkylene
group, R5 represents an alkyl, alkylene or aralkyl group
and B~ )represents an anionlc species, the total number
of carbon atoms in the tertiary amine or ca'ionic portion
of the~quaternary ammonium salt heing from 20 to 60, and
at least one of the groups R2, R3~ R4 and R5 having a
backbone of at least 12 consecutive carbon atoms. Pre-
ferably there are two R groups having a backbone of at
least 12 consecutive carbon atoms, and the total number
of carbon atoms in the tertiary amLne is preferably from
25 to 45. The anionic species B is preferably hallde,
aoetate or hydroxide.
The phthalocyanine dyestuff of formuIa I may be
metal free, or it may be a zinc, copper, cobalt, nickel or
other transition metal phthalocyanine and may contain
halogen, especially chloride, in the phthalocyanine mole-
cule. Halogen free copper phthalocyanine dyestuffs of the
formula:
CuPc(S03H)x (V)
are preferred where CuPc represents a copper phthalo-
cyanine residue and x has its previous significance.
The phthalocyanine dyestuff may be prepared by
any of the methods in common use; for example by contac-
ting the phthalocyanine with chlorosulphonic acid or
oleum at elevated temperature for several hours, then
drowning 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 a zinc, copper, nickel or other transition meta]
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 sulpho-
nated phthalocyanine dyestuff of formula I may be fxom
88:12 t¢ 99:1 by weight, but preferably from 92:8 to 96.~.
While Y can be from 1 to ~ and y from 0 to 3 in
~:: , ' .'' ' ''
'' .. , . ':
- :: - . . . ,, ,~ , . ..
.. . . . , .: .
:: . . . : . . .. . ... . . . :
, ........ . . .... ,. . : . ..
, ., ., ~, -, '-,': ~,. ' . i , ,.
G~
the sulphonatea phthalocyanine derivatives which are
formed by the combination of compounds of formula I and II,
compounds Gf formula I are preferred in which x is 1 to
2.5 and y is O to 3.
. While x can be from 1 to 4 and y is O in the sul-
phonated phthalocyanine derivatives which are formed by
the combination of compounds of formula I and compounds of
formula III or IV, compounds of formula I are preferred
in which x is 1 to 2.5.
Compounds of formula III may be based on specific
alkyl or alkylene amines but are more conveniently derived
from the mixtures o~ hydrocarbon residues of naturally
occurri.ng cils and fats such as tallow, corn oil, fish oil, .
or whale oil. Among such suitable tertiary amines there . .
may be mentioned Dimethyl Tallow, Dimethyl Hydrogenated
Tallow, Dimethyl Soya, Dimethyl Octadecyl, Dimethyl
Elcosanyl, Dimethyl Docosanyl, MonomethyI di(dodecyl),
Monomethyl Dl(Hydrogenated Tallow), Monomethy1 Di Eicosa-
nyl, Monomethyl Di Docosanyl, Tri Dodecyl and Tri Octade-
cyl amines or mixtures thereof.
When the substituents R and Rl of the sulphonated
phthalocyanine dyestuff I represent a ~l-C22 cyclic or
acyclic alkyl, aryl or an aralkyl group, each may be for ~:
example a methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, ~ ;
octyl, decy~, hexadecyl, octadecyl, eicosyl, phenyl,
.
,
.
': : ' ,' ' ' ' ' . ' ' . ' . ' ':" '' . '
.; ' . ' ' ~ ,,' . ': . ,.
benzyl and dodecylphenyl or 2-hydroxye-thyl group.
The sulphonated phthalocyanine derivatives which
are formed by the combination of compounds, for formula
I and II may be produced, for example by reacting a copper
phthalocyanine compound containing x sulphonic acid groups
and y sulphonyl chloride or sulphonamide groups with a
sufficient quantity of dehydroabietylamine to substantially
neutralise the free sulphonic acid groups, and to react
with the sulphonyl chloride groups if present.
The sulphonated phthalocyanine derivatives which
are formed by the combination of compounds of formula I
and III may be produced, ~or example by reacting a phthalo-
cyanine compound containing x sulphonic acid groups with a
sufficient quantity of one or more amines io substantially
neutralise the free sulphonic acid groups.
The sulphonated phthalocyanine-amine derivative
may be prepared in aqueous solution, providing the amine
of formula III is capable of forming a solution in aqueous
mineral or organic acids. Alternatively, it may be prepa-
red in a suitable solvent and recovered by precipitation,
e.g. with water, or by removal of the solvent by distilla-
tion, optionally with the addition of water. Such prepara-
tion in solvent is particularly useful for amines which do
not readily form solutions in aqueous acids. Among Sllit-
able solvents there may be mentioned acetone, ethylmethyl-
7 --
:, . ' ', ' .:- ': -:
.
ketone, ethanol and methanol, but isopropanol is parti-
cularly preferred.
The sulphonated phthalocyanine-amine derivative
may also be prepared in aqueous solution using water
soluble compounds of formula IV.
The sulphonated phthalocyanine derivativ~ may be
incorporated into the pigment at various stages in the
preparation, treatment or use of the pigment. It may be
added to an aqueous slurry of the pigment or during
treatment of the pigment with solvent, such as the solvent
treatment described and claimed in British Patent Specifi-
cation No. 1 140 836. In these two cases the sulphonated
derivative may be preformed and then added as a powder,
presscake, slurry or solution, or it may be formed in situ,
within the aforesaid limitations on solubility and amine ~.
type. Alternative1y, it is a feature of these compositions
that the preformed sulphonated derivative may be added
during milling of the pigment in an application system,
or example, in a bead mill, or it may be simply mixed
with the pigment powder before use.
The preferred methods of incorporation are (a) to
add the phthalocyanine dye and amine separately to the '
aqueous pigme~t slurry, orming the sulphonated derivative
in situ, (b) forming the derivative in situ during solvent
treatment o' the pigment according to the procedure
.
-- 8-- .
,
:,: -, .
, ~ . , . . . ~
, . , ~ , , ; ! '
": :: ' ' ' , ', ' ".' : " ' '' ' .' : ' ', ' " , :, ., ' '
' , , ' ' ~' ' ' ' ' , ' , ' .' ', ', ' ' ': " . ',.'. :'
described in British Patent Specification No. 1 140 836,
and (c) adding the preformed derivative to the pigment
during treatment of the pigment according to the proce-
dures described in our British Patent Specification
No. 1 140 ~36.
The pigment compositions of the invention may be
used for pigmenting various media. They can be used in
decorative paint, in publication gravure inks, nitro-
cellulose, alkyd-M/F and acrylic-M/F systems, but are
particularly suitable in those media containing a high
proportion of hydrocarbons in the solvent.
A further feature of the pigment compositions of
the presen~ invention is their ability to be milled into
hydrocarbon solvents in the absence of resins to give
fluid dispersions at high pigment loadings and excellent
strength when subsequently incorporated in ink and paint
media. In his feature of the invention those dyestuff
amine compositions are preferred in which the amine has
one or more alkyl or alkylene chains containing at least
20 carbon atoms.
It can be seen in the following E~amples that the
sulphonated derivatives promote good flow and rlow sta-
bility in systems which would otherwise be thick and~or
thiY.otropic, and also accelerate the rate of dispersion.
They are o particular value in the preparation of high
_ g _
,. .~ '
~ i ' ' :'
'~ ' ' .' ': .'
'' ' ' ' ~ ` '. ~, ' '~' ,
.: ' , ' ~
~ ' ' .
''
pigment content dispersions of good rheology when used in
combination with the urethane compounds as claimed, in
German OLS No. 2 350 454. The urethane compounds are water
insoluble compounds which contain two or more urethane
groups and which contain no signi~icant proportion of
basic amino groups.
These urethane compounds preferably have either
the formula:
O O
Il , 11 :,: ' '
R - O - C - NH - R7 - NH - C ~ OR8
wherein R6 and R8 are derived from monohydroxyl compounds
or the formula:
O O
Il 11 .
Rg - NH - C - O - R7 - O - C - NH - Rlo
wherein Rg and Rlo are derived from monoisocyanate com-
pounds, and wherein R7 is an organic bridging residue. The
preferred solvent in such dispersions are the aromatic and
aliphatic hydrocarbons.
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.
- 10 - ' .
~.. __ _. _ .. .. , . .. _ ~ . .. , . ~ . _ _., .. _, . .. . ~ .. __.. _ _ . _, . .. r __ 7_. _ .. ~. _ .. _~ .. __ .. ~_ ._ . .. _ . , ,.. _ _ .. _ ., ~,~ .
, .. __ _ ., . . ~ _ .. ,. ~_.
' . , ' , ' ' ,. ' ' . ~ ' ~ ' '' ', , ' . ' ' ' ,' ' .. ' " ' ", ' '
" ' "' "''' " '" ' ' ' '" ~ " ' ', ~ '' ;' ,','' ~".,' '' ,'' '.; ' ' ', ' " ', ' '"' " ' ' ', ', , , ' ' "
' "" " .'',',.' , ' , ' ' ' ' .' ' . . ' .''.. ' '" .' ' ' ',"" ,- . ' .' ,", ' ',.. , ',.' ' ', '' ,' ' " ,. ."'. .', ' ' ,
The Tables which follow the Examples show the
properties of compositions containing the treated pigments
of the Examples indicated.
,
-- 11 --
,~ ~
~8~
. .
Example 1
92 Parts of pigmentary beta-copper phthalocyanine were dis- `
persed by high speed stirring in 3000 parts water, with
the aid of 0.05 part Lissapol* NX (anonyl phenol/ethylene
oxide condensate).
` ::
8 Parts of a compound having the formula
CuPc (S03H)2 (VA)
were stirred in. The pH was adjusted to 5.0 by the addition
of dilute hydrochloric acid or sodium hydroxide solutions
as required.
7.2 Parts of a compound having the formula
H2NCH2 CH3
\./ . '''. ' '
C~3 ~/ \CH/ 3
~ CH3
known as Rosin Amine D were added in the form of its 0.2M
aqueous acetate solution over a period of 30 minutes. The
slurry was stirred a further 30 minutes, then filtered
from clear liquors, washed salt~free wjth water to neutral
pH, prior to drying at 50C.
.
* Trademark
'
.~ .
': .
.- : ., .. -. .. :. . .. . .. , , . . : ~ .,: .. : : .. -.
. ': . : ~ ' . . . , , ; ' . , ., : , : ' ,, . ., ,:
103 Parts of a blue pigment composition were obtained.
Example 2
a) in a 1/2 litre vessel containing 250 parts of 3/8"
steatite balls, 30 parts of the product of Example 1 were
milled for 16 hours with 52 parts white spirit and 18 parts
of the urethane compound VI, prepared according to German
OLS No. 2 350 454, by reacting 3 moles of tolylene diiso-
cyanate (a commercial mixture of 2,4 and 2,6 isomers~ with
2 moles of ethylene glycol and 2 moles oleyl alcohol ln
ethylmethylketone at 80C. for 10 hours, and removing the
::
ethylmethylketone by distillation.
:
.
The resulting fluid dispersion had an efflux time through
a~No. 3 Zahn Cup of 8.5 seconds, and moreover retained this
fluidity with time. 2.33 Parts of this dispersion were
~added with slow speed (~500 rpm) paddle stirrlng to 70
~parts of a white paint of the following compositions:
TiO2 (R - CR2) 25% ~
Beckosol* P. 470 56.7%
White Spirit 16.3%
Driers solution 2
`~ (Beckosol P. 470 is a long oil soya alkyd, 70% in white
spi~lt).
* Trademark
- 13 -
,
:
.
,:
-
Example 3
a) A paint stainer was prepared from the product of
Example 1 by charging to a half litre vessel
16 parts product of Example 1
32 parts Beckosol P.470
31 parts White Spirit
250 parts 3/8" steatite balls
This was ground for 16 hours. Then there were added
40 parts P.470, milled for 30 minutes, folla~ed by
37 parts P. 470 and 3.84 parts driers solution.
The mixture was milled a further 30 minutes and discharged.
7 parts of this stainer were used to prepare a blue paint
according to the method of Example 2(a).
:: '
b) The method of 3 a) above was followed, except that 16
parts of an untreated beta-phthalocyanine blue pigment
were substituted for the product of Example 1.
.
Example 4
: .
100 parts of the compound of formula VA in Example 1 were
stlrred in 3000 parts water. The pH was adjusted to 5.0
with dilute hydrochloric acid or sodium hydroxide as re-
quired. 90 parts of the compound of formula II were added i~
in the form of its 0.2M aqueous acetate solution over a
.: .
- 14 - -
,~, .
, , , .. ,.... , . .. , .,, i : . ,. , , - ., . .. .. ; ... .- i .. : ~ ..
:, : . : . , : . : ,
a~
period of 30 minutes.
The slurry was stirred a further 30 minutes, then filtered
from clear liquor, washed salt-free with water to neutral
pH, prior to drying at 50C.
182 parts of a blue powder were obtained.
Example 5
~he method of Example 2 a) was repeated, except that 30
parts of the product of Example 1 were replaced by 25.7
parts of untreated beta-copper phthalocyanine and 4.3
parts of the product of Example 4.
Example 6
: '
The method of Example 3 a) was repeated, except that 16
parts of the product of Example 1 were replacad by 13.7
parts of untreated beta-copper phthalocyanine and 2.3
parts of the product of Example 4.
Example 7
,' ,:
100 parts of crude copper phthalocyanine were ground wlth
200 parts of inorganic salts until the phthalocyanine was
in pigmentary form.
- 15 ~
- . ~
., . : .
: . . . , . . ~. . . , . . i ! . : '
' , , ~ ' ' . ' ' ~ ,~ ' ' , ': ': , ' . ' , ' ', . : ' '" " . ' ' ' . ' . ' .
276 parts of the mixture (=92 parts copper phthalocyanine)
were added to 900 parts of isopropanol and heated under
reflux conditions for 4 hours.
900 parts of water and 8 parts of the compound of formula
VA of Example 1 were added to the mixture, and the isopro- .
panol remo~ed by distillation. The pH was adjusted to 5.0
with dilute hydrochloric acid and 7.2 parts of the compound
of formula II were added, in the form of its 0.2M aqueous
acetate solution, over 30 minutes.
The slurry was stirred a further 30 ~inutes, then filtered
from clear liquors, washed salt-free with water to neutral
pH prior to drying at 50C.
102 parts of a blue pigment composition were obtained.
Substantially similar results were obtained when the
compounds VA and II of this example were replaced by the
addition of 15.2 parts of the product of Example 4, either
before, during or after the isopropanol treatment stage.
'''' ' '"
Example 8
':
The method of Example 2 a) was repeated, using 30 parts
of the product of Example 7 in place of 30 parts of the
product of Example 1.
- 16 -
.::
:
- : .: . . .. . .
Displays of the paints ol the foregoing Examples were
prepared using a No. 7 wire wound laboratory coating rod
(k-bar) on Astralux* card. Observations on comparisons as
to flow, strength and shade are shown in Tables 1 and 2.
The results demontrate the improved characteristics of
paint compositions using the pigment compositions of this
invention in contrast to results using untreated phthalo-
cyanine.
Example 9
The following were charged to a bead mill
lCO parts glass beads
25.7 parts crude copper phthalocyanine
4.3 parts of the product of Example 4
6 parts urethane compound VI
38 parts white spirit
Milling was carried out for 4 hours until the vlscosity
of the mixture increased. The following were then added:
12 parts urethane compound VI
14 parts white spirit
Milling was continued for a further 6 hours at room
temperature. The resulting dispersion had an efflu~ time
through a No. 3 Zahn Cup of 12 seconds, and retained this
fluidity with time.
* Trademark - 17 -
- . . . :,
A blue tint decorative alkyd paint was prepared from this
dispersion according to the latter part of the method of
Example 2(a).
A second dispersion prepared by the method of this example
in which 25.7 parts of crude CuPc and 4.3 parts of the
product of Example 4 were replaced by 30 parts of crude
CuPc was found to increase in viscosity to a greater degree
than the dispersion incorporating the product of Example 4
which remaind fluid. A long oil alkyl decorative paint
prepared from this dispersion by the latter part of the
method of Example 2 a) was lO~ weaker and redder relative
to the corresponding paint incorporating the product of
Example 4. :
Example lO
a) To a half litre ball mill were charged the following: :
Steatite balls (lO mm) 400 parts
Phenoli.c varnish* 96 parts
Toluene 80 parts
Product of Example l 24 parts
Milling was carried out for 16 hours, then there were
added to lO0 parts of the rnillbase with agitation
Phenolic varnish 72 parts :
,
" : , - . ~ :
:
.. ". . , ~ , . . . . ... . ..
-
.: , : .. . .. :
Toluene 28 parts
Thus was formed a rotogravure ink of 6% pigmentation and
1:5 Pigment : Binder ratio.
Phenolic Varnish consisted of:
Alsynol* RL.30 50 parts
Toluene 50 parts
(Alsynol RL.30 is a modified phenolic resin, pentaerythri- :
tol esterified). :
b) Example 10 a) was repeated, except that the product of
Example 1 was replaced by an equal weight of untreated ~ -
beta-copper phthalocyanine pigment. .
Example 11 . .
a) In a half litre vessel, containing 250 parts of 3/8"
steati-te balls, 30 parts of the product of Example 1 were
milled for 16 hours, with 55 parts or hydrocarbon solvent
.,
SBP3::tShell-Mex*) and 15 parts of the urethane compound VI
of Example 2. The resulti.ng fluid dispersion had an efflux
time through a No. 3 Zahn Cup of 9 seconds, and retained ~ .
:this fluidity with time. .
20 parts of this fluid disperslon were added to ÇO:parts ..
of pheno].ic varnish with stirrlng, followed by 20 parts
of SbP3. After 10 minutes stirring, the 6~ pigmentation
*Trademark 19
.. .
.
. . ~ , , ~ ;. . ~, ,
ink was discharged.
b) Example 11 a) was repeated, except that the product
of Example 1 was replaced by an equal weight of an un-
treated beta-copper phthalocyanine pigment.
Illustrations were prepared on newsprint from the inks
of Examples 10 a) - 11 b~. Observations on comparisons as
to flow, strength and gloss are shown in Tables 3 and 4.
Example 12
Example 1 was repeated, except that 8 parts of the com-
pound VA were substituted by 8 parts of the compound of
formula:
CuPc (S2NHcH2cH2H)2 (S3 ~2
and 7.2 parts of the compound II by 5.4 parts of the
compound II.
Example 13
Example 4 was repeated, except that the compound of for-
mula VA was replaced by an equal amount of the compoun~ of
formula VII of Example 12, with 68 parts of the compound II
instead of 90 parts. The yield was 165 partc.
- 20 -
.
. '. ' , ' .:: '
' : ' . ~ ~ . .: . ' . :
., ' '' . : ' :, . ~''
.. . .. .
Example 14
Example 2 a) was repeated, except that 30 parts of the
product of Example 1 were replaced by 25.7 parts of an
untreated betacopper phthalocyanine blue and 4.3 parts o
the product of Example 13.
Example 15
' .'
Example 2 a) was repeated, except that 30 parts of the
product of Example 1 were raplaced by 30 parts of the
product of Example 12.
~' , ' .
Example 16
: .
Example 10 a) was repeated, except that the product of
Example 1 was replaced with an equal weight of the product ~:
of Example 12. .
Example l?
Example 11 a) was repeated, except that the product of
Example 1 was replaced with an equal weight of the product
of Example 12.
- 21 -
, . .
... : - . . . . :: ~ : . .: . . - . . ,: ,:
:: .. .. , ".:. :-
.. ... .. .. ..
, , . ,, ., . . : , :, .. .
.. ~ ,: : . : . ..
, ... .. .. ., : .. , , . ,. :,.. , . ,.. ,,, , ., .. .~ , . .
Example 18
The compound of formula:
CUpc(so2NHc2oH29)y(so3 H2NC20 29 x (VIII)
where C20H29 represents a dehydroabietyl residue and in
which x + y~ 2.5 was prepared by treating crude CuPc with
chlorosulphonic acid at 110 - 113C. for 5 1/2 hours, and
subsequently drowning out lnto an ice/salt/water mixture.
The.filtered, washed, presscake was reslurxied i.n more
ice/salt/water, the pH adjusted to 5.0 and Rosin Amine D
acetate solution added dropwise. After 1 hour at 80-85C.
sufficient HCl was added to give no blue bleed, and the .: .
slurry filtered, washed salt-free and dried at 60C. ~ -
Example 19
a) The following were stirred at high speed for 30 minutes:
63 parts untreated beta-copper phthalocyanine
pigment
7 parts compound VIII of Example 18
158.4 parts toluene :
237.6 parts medium*
*The medium consisted of
Alsynol Rl.30 25 parts
. - 22 -
. ~ : ' . ' ' :'. : . , - : ::
.
:
,"', ,,,, ', ' ' , '
Zinc/calcium resinate 25 parts
Toluene 5G parts
250 Parts of the stirred slurry was transferred ~o a half
litre ball mill and milled for 10 hours. The final ink
(6~ pigmentation) was obtained by reducing 60 parts of
mill base with 77.4 parts medium and 12.6 parts toluene.
b) Example l9 a) was repeated, except that the compound
VIII was omitted, and the quantity of untreated beta-
copper phthalocyanine pigment used was 70 parts.
:
Illustratlons of Examples l9 a) and b) were prepared on
newsprint. ObservaLions on comparisons as to flow strength
and gloss are shown in Table 4.
'
Example 2 a) was repeated, except that 30 parts of the
product of Example l were replaced by 25.7 parts of
untreated betacopper phthalocyanine and 4.3 parts of the
compound VIII.
. . .
~ Example 21
:: .
.. .
Example 3 a) was repeated, except that 16 parts of the
product of Rxample l were replaced by 13.7 parts of un-
.
~ 23 - - ~
: ~ -;:
treated beta-copper phthalocyanine and 2.3 parts of com-
pound VIII. Illustrations of Examples 10-21 were prepared
as described above. Observations on comparisons are shown
in Tables 1-4.
Examples 22-25
Pigments with various pigment: dyestuff ratios were prepa-
red according to the method of Example 1, and the amounts
of Rosin Amine D adjusted to substantially neutralise the
sulphonic acid groups of the dyestuff. F1uid dispersions
and decorative alkyd paints were prepared from these
pigments by the method of Example 2 a). The compositions
and results are given in Table 5, from which it can be
seen that an excellent ~alance of dispersion fluidity and
strength can be obtained from a pigment: dyestuff ratio
of 94:6.
Examples 26 and 27
- '
Pigments were prepared according to the method of Example
1, with 8 parts of the compound
CuPc (S02NH CH2CH20H)2 (S03H)X with x = 1 and 1.5 re-
placing 8 parts o~ CuPc (S03H)2.
' '
The amounts of Rosin Amine D used were adjusted to sub-
stantially neutralise the free sulphonic acid groups of
- 24 -
.
, ~ . . ,
:. . . : .~ , .;......... . :
:: ., :-
- , , , : , : .
the dyestuff.
Fluid dispersions and decorative al~yd paints were prepa-
red from these pigments by the method of Example 2 a). The
results are compared in Table 6, from which it can be seen
that the most strongly tinted paints are obtained using
compounds havirlg from 1-1.5 sulphonic acid groups, when
sulphonamide groups are also present on the dyestuff.
Example 28
A substantially a-form copper phthalocyanine containing
1.8~ by weight of peripherally substituted chlorine and
10% by weight on pigment of compound VIII of Example 18
were incorporated in a glycerol coconut oil alkyd resin
solution in xylene/butanol solvents by ballmilling, and ~ -
subsequently reduced to 5.9% pigmentation at 1:6.6
plgment:binder by the addition of an unmodified isobuty-
lated melamine-formaldehyde (M/F) resin solution. The
resulting dispersion had a Hegman gauge reading of 8:7:7
and a Zahn Cup Mo. 4 reading of 11 seconds.
A dispersion prepared at the same pigmentation and pigment:
binder levels, but in the absence of compound VIII, had a
di~perslon of 8:5:3 and was thioxotropic and only pourable
after agitation.
Blue tint alkyd-M/F paints prepared from these dispersions
.' ' ~ -
.~
' .
. , ~ ', ` ' ' : .. : ' ~, ,': , . ". .. .
by admixing with white alkyd-M/F paint and stoving, had ;
similar strength.
Example 29
The product of Example l 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 M/F
resin in n-butanol solvent. The resulting dispersion had
a Hegman ~auge reading of 8:7:7 and was very fluid, having
a Zahn Cup No. 4 reading of 8 seconds. In contrast, a
similar dispersion prepared from untreated ~-copper
phthalocyanine pigment was thixotropic and had a poorer
dispersion.
Blue tint acrylic paints were prepared from these disper-
sions by admixing with white acrylic paint and stoving.
The paint derived from the pigment of Example l was found
to be of similar strength and greener than the paint
derived from the pigment not so treated.
Example 30
The pigment of Example 26 was incorporated in a nitro- -
cellulose varnish by ballmilling an subsequently reduced
to 11.7% pigmentation at 1:1.38 pigment:binder by the ~ -
addition of a mixture of nitrocellulose and maleic conden- ;-
,. .
: :
sate varnishes.
The resulting dispersion was found to have superior flow,
strength and gloss compared to a similar dispersion prepa-
red from an untreated ~-copper phthalocyanine pigment.
Example 31
95 parts of a substantially alpha-f~rm copper phthalo-
cyanine containing 1.8~i w/w peripherally bound chlorine,
were added, as powder, to 2500 parts water containing 0.2
parts of a nonyl phenol/ethylene oxide condensate
~Synperonic* NX, I.C.I. Ltd.) and dispersed by high speed
stirring. 5 parts of the compound of formula VA CuPC
(S03~)2 were added, in a presscake form, and stirred for
15 minutes. The pH was adjusted to 4.5 with dilute aqueous
sodium hydroxide solution, and 6 parts of dimethyl-di
~dodecyl) quaternary ammonium chloride, as a solution in
200 parts water run in evenly o~er 30 minutes, with good
stirring. The slurry was stirred for a further 30 minutes,
and the product filtered from clear liquors, washed salt
free to neutral pH, and dried at 50-60C.
The pigment composition of thls Example was incorporated
in a hydroxy-acrylic resin in ~:1 xylene: n-butanol sol-
vent by ballmilling and subsequentiy reduced to 6% pig-
mentation and 1:5 pigment:binder ratio with an unmodified
isobutylated melamine/formaldehyde resin in n-butanol. The
* Trademark - 27 -
~, . .
.
' "', :'. ' ''. " '' ~: .', . - '
initial m-ll base dispersion was fluid, in contrast to
a similar dispersion prepared from alpha-copper phthalo-
cyanine pigment untreated by dyestuff and amine, which
was thixotropic and only pourable after agitation. Blue
tint acrylic paints were prepared from the reduced disper-
sions by admixture with white acrylic paint and stoving.
The paint derived from the pigment of this Example was
approximately 10~ stronger than the paint derived from the
pigment not so treated, and, moreover, had improved
resistance to flocculation.
Example 32
95 parts of pigmentary beta-copper phthalocyanine, in
presscake form, were dispersed by high speed stirring in
3000 part~ water. 5 parts of the compound of formula VA
CuPc(S03H)~ were stirred in, and the pH adjusted to 5.0
with dilute sodium hydroxide solution. 4.2 parts of an
amine (Kemamine* T-9972D, Humko Chemical Products) of
formula
R N / R12 IX
11 R13
where Rll, R12 are methyl groups, and ~13 is a soya oil
residue, were added in the form of a O.lM aqueous acetate
solution over 30 minutes. Stirring was continued for a
further 3G minutes and the product isolated by filtration
: .
from clear li~uors, washing salt free to neutral pH with
* Trademark - 2 a - :
. . ............... .
.. . .
water r and drying at 50-60C.
103.1 parts of a blue pigment composition were obtained.
The pigment composition was incorporated in a nitrocellu-
lose 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 conden-
sate varnishes. The resultiny dispersion was found to be
approximately 5~ stronger, with superior flow and gloss
properties, compared to a similar dispersion prepared from
an untreated beta-copper phthalocyanine pigment.
Example 33
Example 32 was repeated using 90 pa~ts of pigmentary beta-
copper phthalocyanine, 6.55 parts of the compound of
formula V CuPC(S03H)x where x is 1.2, and 3.45 parts of
the soya oil amine. When incorporated in nitrocellulose
varnish, flow and colouristic properties were substan-
~tially simllar to those of the product of Example 3~.
Example 34
175 parts of ~rude copper phthalocyanine were ground with
23 parts of inorganic salts, 1.5 parts diethyl aniline
and 0.8 parts glycerol mono-oleate until the phthalo-
cyanine was in pigrnentary form.
103 parts of this mixture, corresponding to 90 parts of
-
.~, .
.
copper phthalocyanine, were adaed to 600 parts of iso-
propanol and heated under reflux conditions with good agi-
tation for 5 1/2 hours. 4 parts of the compound o~ for-
mula VA CuPc(S03H)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 IX
where R13 is a methyl group and Rll, R12 are hydrogenated
tallow residues, were added as a solution in hot isopropa-
nol. A further 15 minutes later 600 parts of water were
added and the isopropanol removed by distillation. Agita-
tion was stopped and the pigment composition filtered from
clear liquors, washed salt free to neutral pH, and dried
at 50 - 60C. The yield was 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 Example 10. When compared with a similar ink prepared
from untreated beta-copper phthalocyanine, the ink prepa-
red from the product of this Example had a very much more
fluid millbase and was 15~ stronger, cleaner anfl brighter.
Example 35
Example 34 was repeated using 3.4 parts of the compound
of formula V CuPc(S03H)x- where x is 2.4, and 5.4 parts of
- 30 -
.
- : . . . :. . . . .
,
. '. ~ . ,
" ' ' ' ' ' ' ' , ~ ' '' ~ . '
the hydrogenated tallow amine. The publication gravure
ink derived ~rom this composition was approximately 10~
stronger than the corresponding ink prepared from untre-
ated ~-copper phthalocyanine and had a more fluid millbase.
Example 36
a) 20 parts of the compound of formula VA CuPc(S03H)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 IX, where R13 is a methyl group and Rll,
R12 are hydrogenated tallow residues, were dissolved in
200 parts hot lsopropanol, 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 filtra-
tion from clear liquors, washed with warm water, and dried
at 60C to give a yield of 4~.1 parts.
. .
b) 175 parts of crude copper phthalocyanlne were ground by
the method of Example 34. 103 parts of this mixture,
corresponding to 90 parts of copper phthaloxyanlne, were
added to 600 parts of isopropanol and heated under reflux
conditions for 5 1/2 hours with good agitation. 10 parts
of the product of part a of this example were added as a
solution in hot isopropanol and reflux continued for 30
:.
- 31 -
.
.. :.. .. . . . , .. : . ,.,.: ,. , ., .. , . . .. ., . :: . .. ... , . .. ; ., . : .. . :
: , : - . . , . . , . . .. : .. : , :: . . :
. . . . . : . . ;~ ,: ,. .
: ........ : .. . : :, . , : . . .,,. : :.
: ., . ' . , ' ,, , . . , . , . .:. ., :... .
minutes. 600 parts of water were run in and the isopropa-
nol 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 rom the product of
part b of this example by the method of Example 34 had
similar properties to the ink derived from the product of
Example 3~.
Example 37
Example 36 b was repeated using 108.6 parts of the ground
mixture, corresponding to 95 parts copper phthalocyanine,
together with 5 parts of the product of Example 36 a. The
pigment composition so obtained, when incorporated in the
pu~lication gravure ink medium was 10 - 15% stronger than
the corresponding ink derived from untreated ~-copper
phthalocyanine.
Example 38
90 parts of a substantially alpha-form copper phthalo
cyanine, containing 1.8% w/w peripherally bound chlorine,
were added, as powder, to 500 parts of isopropanol, and
heated to reflux with agitation. 4.8 parts of the compound
of formula VA CuPc($03~)2, in presscake from, were added
- 32 -
, , : . . .. : . : - .
: ', ' ' . . ' ,, ,' , ' ; : :., ~ ',' '~, ' " . . :
., . , . . . . : :
.:-, . . .. ~ ~ . . :
, . . ~. - :: . . .. ~: . .. . , : :
and reflux continued for 15 minutes. 5.1 parts of tech-
nical 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 99.1
parts.
The pigment composition of this Example was incorporated
in a hydroxy-acrylic resin by the method of Example 31 to
produce a very fluid millbase. The blue tint acrylic paint
derived from this millbase was 5-10~ stronger than the
paint derived from alpha-copper phtha~ocyanine pigment
untreated by dyestuff and amine.
... .. ..
Example 39
a) A phthalocyanine dyestuff-amine composition was pre-
pared by the method of Example 36 a, using 21.7 parts
of the amine of formula IX, where R13 is a methyl group
and R11, R12 are dodecyl residues-
b) The method of Example 38 was repeated with the additionof 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 substantia]ly similar
application properties to those of the paint deri~ed fro~
33 -
:, ' ' -
, ~ : . , , ., ; : . : :
. .
~ . .
pigment composition of Example 38.
Example 40
90 parts of a substantially alpha-form copper phthalo-
cyanine, peripherally chlorinated to the extent of 1.8%
w/w, was dispersed by high speed stirring in 1500 parts
water, with the aid of 0.5 parts of Synperonic NX (I.C.l.
Ltd.). With ef~icient agitation, 10 parts of the product
of Example 39 a were added as a solution in hot iso-
propanol over 15 minutes. After a further 15 minutes
stirring, the pigment composition was recovered by fil-
tration, washing and drying.
When incorporated in a long oil soya penta alkyd based
decorative paint system by ballmilling, the product of
this example was approximately 25% stronger than an equal ~ -
weight of untreated alpha-form copper phthalocyanine
pigment and moreover had substantially improved re-
sistance to flocculation.
Example 41
90 parts of a substantially alpha-fo-m copper phthalo-
cyanine, containiny 1.8~ by weight of peripherally
substituted chlorine, together with 10 parts of the pro-
duct of part a of Example 39, were incorporated in a
- 34 -
.- . - ,. . ............... .-: . . .. ., :
. . : : . .: : . .. . :
,: , . .: ': : ,: . .,. .. ,. .... :.. . . .
s
~ . .
glycerol cGconut oil alkyd resin solution in xylene/butanol
solvents by ballmilling, and subsequently reduced to 5.9%
pigmentation at 1:6.6 pigment:binder by the addition of an
unmodified isobutylated melamine-formaldehyde resin solu-
tion. The resulting dispersion had a Hegman gauge reading
of 8:7 1/2:7 1/2 and a flow of 9 seconds, measured by a
No. 4 Zahn Cup. A similar millbase dispersion prepared
from 100 parts of the alpha-form copper phthalocyanine
pigment, was thixotropic, and only pourable after agi-
tation. The subsequently reduced paint prepared according
to the above procedure has a Hegman gauge reading of
8:5:3 and still exhibited thixotropy.
Blue tint alkyl-M/F paints were prepared from these
reduced dispersions by admixing with white alkyd-MVF
paint and stoving. The paint containing the product of
Example 39 a was 10% stronger, redder and brighter than
that from which the product of Example 39 a had been
omitted. Similar results were obtained by the use of the
dyestuff compositions of Example 36 a, 42 a and 43 a.
'. ..
Example 42
a) a phthalocyanine dyestuff composition was prepared by
the method of Example 36 a, using 32.6 parts of the amine
of formula IX, in which the groups Rll R12 are each
eicosanyl or docasanyl residues, and R13 is a methyl yroup.
- 35 -
.
. '
:.~ . :
. . . ; : , . : , .: . .
b) 90 parts of halogen free substantially alpha-form
copper phthalocyanine pigment used in Example 39, together
with 10 parts of the product of part a of this Exa~nple
were incorporated in a hydroxy-acrylic resin by the method
of Example 31. The resulting reduced fluid dispersion had
a Hegman Gauge reading of 8:7 1/2:7 and a Zahn Cup No. 4
reading of 10 seconds. A similar dispersion prepared from
100 parts of untreated alpha-copper phthalocyanine pigment
was thixotropic and poorly dispersed at the mill base
stage and remained so on reduction ~ith resin. The acrylic
paint derived from the dispersion incorporating the
dyestuff composition was approximately 20~ stronger than
that derived from the untreated alpha-copper phthalo-
cyanine dispersion and, moreover, was cleaner and of
superior flocculation resistance.
Use o~ the dyestuff compositions of Examples 36 a, 39 a
and 43 a in the method of this example gave substantially
similar results.
xample 43
a) 20 parts of the compound of formula VA CUPc(S03H)2,
Ln presscake form were stirred in 600 parts of wa~er, and
the pH adjusted to 5.0 with dilute sodium hydroxid~ solu-
tion. 16.8 parts of the soya oil amine used in Example 32
were added in the form of its aqueous acetate solution
- 36 -
. . . .. . . . .. . . .
. ' ~ , , ' '. ,
' '. ' ' ., ,. ,' . '.
'' ' ' "' ',`' ' ~ ;' ' ,"''
over 30 minutes'. Stirring was continued for a further30 minutes and the product isolated by filtration, washing
and drying to yield 36.1 parts of a blue green dyestuff
composition.
bl A nitrocellulose ink was prepared from 90 parts of an
untreated phthalocyanine green pigment powder of 47.1%
chlorine content and 10 parts of the product of part a of
this example according to the method of Example 32. When
compared with a similar ink prepared from 100 parts of
untreated phthalocyanine green pi~ment, the ink incorpo-
rating the dyestuff composition was found to be of equal
strength, but of superior flow and considerably superior
gloss and transparency. :
.
Example 44
'''
150 parts of a pigmentary phthalocyanine green plgment
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 Example 42 a were added as a slurry in acetone,
.
and reflux continued for a further 15 minutes, after which
800 parts of water were added and the acetone removed by ~;
distlllation. A mixture of 15 parts concentrated hydro
chloric acid and 15 parts water was then added evenly over
~ .
- 37 ~ ~
' .
.
- , , .~ ~ ... . .. ..
.,
g~7
.
2 minutes. After 30 minutes, agitation was stopped and
the product isolate~ by filtration from clear liquors,
washed with warm water and dried at 50 - 60C. The yield
was 163.2 parts.
When incorporated in a nitrocellulose medium by the method
of Example 32, the product of this example had equivalent
colouristic properties, but markedly superior millbase
flow, compared to a similar dispersion prepared from un-
treated phthalocyanine green.
.
Example 45
18 parts of a pigmentary beta-coppex phthalocyanine powder,
prepared by conventional salt milling followed by solvent
treatment in isopropanol, were added to a glass jar of
280 parts by volume containing 2 pa~ts of the product of
Example 42 a, 80 parts of toluene and 250 parts of 10 mm.
steatite balls. The jar was sealed and the contents milled
for 16 hours. A fluid, well deflocculated, dispersion was
obtained. In contrast, a similar dispersion prepared in
the absence of the product of Example 42 a was undiScharge-
able. A 6% pigmentation ink was prepared by stirring the
dispersion incorporating the product of Example 42 a intv
a phenolic resin medium in toluene solvent to give a pig-
ment:binder ratio of 1:5. (The product of Example 42 a was
regarded as pigment). The ink was found ~o be rheologically
- 38 -
'.',; .' ~ ,, '. ; ' ', '~,' "', '. .' ',, " ". ,'
9~7
and colouristically similar to the ink of Example 34with excellent gloss and transparency.
Substantially similar results were obtained by substitu-
tion of the product of Example 42 bY the products of
Example 36 a, 39 a and 43 a.
Example 46
175 parts of crude copper phthalocyanine were ground by
the method of Example 34. 103 parts of this mixture,
corresponding to 90 parts of copper phthalocyanine were
added to 3000 parts water and dispersed by high speed
stirring with the aid of 0.2 parts "Synperonic NX". 5.7
parts of the compound of formula VA CuPc(S03H)2, were
added in presscake form, and stirred for 15 minutes.
The pH was adjusted to 5.0 with dilute sodium hydroxide,
and 4.3 parts of trimethyl - hydrogenated tallow quater-
nary ammonium chloride, (Kemamine Q.97038 a 49~ active
quaternary salt supplied by Humko Chemical Products~
diluted with 200 parts water, run in evenly over 30
minutes, with good agitation. The slurry was stirred for
a further 30 minutes, and the product filtered from
clear liquors, washed salt free to neutral pH, and dried
at 50 - 60C.
The publication gravure ink prepared from this product
.
- 39 -
, !
. .
by the method of Example 3~ was 5 to 10% stronger than
the corresponding ink prepared from untreated ~-copper
phthalocyanine and had a very much more fluid mill base.
Example 47
The method of Example 46 was repeated using 4.7 parts of
the compound of formula VA CuPc(S03EI)2, and 5.3 parts of
dimethyl- benzyl- dodecyl ammonium chloride in the for~
of a 20% aqueous solution.
The publication gravure ink derived from the product of
this example by the method of Example 34 was 10% stronger
than the corresponding ink derived from untreated ~-copper
phthalocyanine and had excellent gloss and transparency.
'
Example 48
92 parts of crude copper phthalocyanine and 8 parts of
phthalimide were ground in a ball mill until the propor-
tion of alpha-type phthalocyanine was in the range of -
45 - 75% alpha.
22.5 parts of 50% aqueous potassium hydroxide solution~
and 10 parts of hydrogenated wood resin (Staybeli-te*,
Hercules Powder Co. Ltd.) were stirred with 100 parts
wate~ ~t 50C until a smooth dispersion was obt~ine~.
9.2 parts o the product of Example 3~ a were stirred in
* Trademark - 40 -
: ' ,
. . : ,, -, .:::, . : : , . : :. : :.: .
~, - : . . . . . . . .
.-: . :, , :, ~. ~ : , .:
...... .. . . . . .
. . ..
. , , , ,-, : :: , ., . ., ' , .:: . . . :
18.7 parts of N,N-diethylaniline then added to the resin
dispersion and high speed stirred until a smooth, stable
emulsion was formed. 100 parts of the aforementioned
ground copper phthalocyanine mixture and 200 parts of
water at 50C were added to the emulsion with high speed
stirring and the stirring continued until, by microscopic
examination, the average particle size of the pigment in
the emulsion was less than 1 micron.
A solution of 5 parts of calcium chloride in 450 parts of ;
water at 50C was added, whereupon the emulsion became
destabilised and the resin precipitated. The pigment
slurry was stirred for 30 minutes and 70.8 parts of -~
concentrated hydrochloric acid in 60 parts of water at
50C added to give a final pH of between 1.0 and 1.5.
The pigment composition was recover-d by filt ation,
washing with water, until the filtrate was salt free and
at neutral pH, and finally drying at 50 - 60C.
The publication gravure ink derived from this pigment
composition by the method of Example 34 was slightly
stronger than the ink of Example 34 and had similar mill-
base flow.
- 41 -
: :. . . :: . ~ . .
- : . . .
~, . ... . . ~ .
:,,
:
. .
., ~
9~7
TABLE 1
.. :
. . . ' _ - . .
Example No. Stainer 1:25 White Reduction
. .. . . .. . ._ ._ . ...
Flow Fineness Strength Shade
_ . Of Grind .. ._ _
No. 3 Zahn Hegman
. Cup (secs) Gauge . _
2 (a) 8.5 8:7:7 90-95 pts. Greener :
..... _ . . _ .. _
2 (b) ~oo thick- 8:4:2 Control Control
no reading
(100 parts)
. . . . _ .. _ ... _ _ . ,," :
9 8:7:7 Equal : Slightly
. . .... ... _
8 14 8:7:7 Equal Slightly
Greener . .
~. . . ,.. _ ... : ~ .... .
14 18 8:7:7 Equal Slightly
: : Greener
. , .. . . ... _ .... __ ....
8:7:7 95-100 pts. Slightly
: strong Greener
. r _ . _ . . _ _ . . . _ _ . _
: 20: 62 8:7:7 85-gO pts. Slightly
_ _ _ Str~ny Cre~er
~: -
~: : ' ~'
42 - :
.: . .
,
., .
::
: . .:. : : : . , :. ,., : . . . ., : :; . :; .. ;
TABLE 2
Example No. Stainer 1:25 White Reduction
_
Fineness Flow Strength Shade
of Grind
Hegman I.C.I
Gauge CPlateand _
3 (a) 8:7:7 3.7 poise strong Greener
3 (b) 3:1:1 Too thicX Control Control
_ (100 parts) _ _
6 8:7:6 7 poise Equal Slightly
21 8:7:7 7.5 poise 80-85 pts. Greener
Strong _
- 43
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:
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