CA1080907A - Pigment compositions - Google Patents

Abstract

PIGMENT COMPOSITIONS

Abstract of the Disclosure A phthalocyanine pigment composition comprising a phthalocyanine pigment and a sulphonated phthalocyanine derivative formed from sulphonated phthalocyanine dye-stuffs having the formula wherein R represents a C1 - C22 cyclic or acyclic alkyl group, aryl, aralkyl group or a dehydrvabietylamine residue; and R1 represents hydrogen or a C1 - C22 cyclic or acyclic alkyl group, an aryl or an aralkyl group;
the alkyl, cycloalkyl, aryl or aralkyl groups, R and R1 may be optionally substituted with one or more hydroxyl groups; x is from 1 to 4, y is 0 or from 1 to 3 and the sum of x and y is from 1 to 4, and, when y is 0 to 3, a sufficient quantity of dehydroabietylamine of the formula to substantially neutralise the free sulphonic acid groups, when y is O, a tertiary amine having the general formula or a quaternary ammonium salt having the formula:

wherein R2, R3 and R4 each represent an alkyl or alkylene group, R5 represents an alkyl, alkylene or aralkyl group and B(-) represents an anionic species, the total number of carbon atoms 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 R5 having a backbone of at least 12 consecutive carbon atoms, gives printing inks and paint media having improved tinctorial strength, gloss and especially improved rheological properties.

- 1a -

Description

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-:, . ' ', ' .:- ': -:

.

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.
, ,~ ~

~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 \./ . '''. ' ' 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 , :
.

,:

-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 .: .

,~, .

, , , .. ,.... , . .. , .,, 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.

.::

:

- : .: . . .. . .

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.

.
. '. ' , ' .:: ' ' : ' . ~ ~ . .: . ' . :
., ' '' . : ' :, . ~'' .. . .. .

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.

, . .

... : - . . . . :: ~ : . .: . . - . . ,: ,:
:: .. .. , ".:. :-.. ... .. .. ..

, , . ,, ., . . : , :, .. .
.. ~ ,: : . : . ..
, ... .. .. ., : .. , , . ,. :,.. , . ,.. ,,, , ., .. .~ , . .

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 .

, ~ . . , :. . . : .~ , .;......... . :
:: ., :-- , , , : , : .

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 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 .

- : . . . :. . . . .
, . '. ~ . , " ' ' ' ' ' ' ' , ~ ' '' ~ . ' 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 :.

.

.. :.. .. . . . , .. : . ,.,.: ,. , ., .. , . . .. ., . :: . .. ... , . .. ; ., . : .. . :

: , : - . . , . . , . . .. : .. : , :: . . :
. . . . . : . . ;~ ,: ,. .
: ........ : .. . : :, . , : . . .,,. : :.
: ., . ' . , ' ,, , . . , . , . .:. ., :... .

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 , , : . . .. : . : - .
: ', ' ' . . ' ,, ,' , ' ; : :., ~ ',' '~, ' " . . :

., . , . . . . : :
.:-, . . .. ~ ~ . . :
, . . ~. - :: . . .. ~: . .. . , : :

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~

:, ' ' -, ~ : . , , ., ; : . : :

. .

~ . .

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 .- . - ,. . ............... .-: . . .. ., :

. . : : . .: : . .. . :
,: , . .: ': : ,: . .,. .. ,. .... :.. . . .

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.

.
. ' :.~ . :

. . . ; : , . : , .: . .

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 . . . .. . . . .. . . .

. ' ~ , , ' '. , ' '. ' ' ., ,. ,' . '.
'' ' ' "' ',`' ' ~ ;' ' ,"'' 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 '.',; .' ~ ,, '. ; ' ', '~,' "', '. .' ',, " ". ,' 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 .

, !
. .

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.

: :. . . :: . ~ . .

- : . . .
~, . ... . . ~ .
:,, :
. .
., ~

9~7 .. :
. . . ' _ - . .
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 - :

.: . .

, ., .
::

: . .:. : : : . , :. ,., : . . . ., : :; . :; .. ;

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 _ ~ , .

:
. ~ . ..
, ~
', ' '. . "' ' ' . ' : . .
:: . ....... ::. . ~ ~, . . ..
'. ~ ' ,~ ~ .,. .,:

, . ' -' . .

~ o o tq ~: h ~1 .
. C~ ~1 ~ ~ ~
~ O U~

O.) ~ O h . ,C ~ O
_ . ...
~ ~ ,1 ~ ~ . - .
~ ~ O ~ ~ . . .
rY t~ O ~ S~ o, O ~
H ~:: ~ O ~ O ~ ~0 ~1 10 ~ O O U~ ~) . O +) ~ C.) ~1 1` U~

a .~ ~o ~ \
dP U~ ~ ~ ~D I~
U~ .. .. ..
a) ~ I_ I~ co : ,, . ~ ~
~ m a N _ ~ . V O :"' o a) ~ ~
Z ~q ~.q u~ . .
O ~ O f~ ~
__. .. _ .. : . ' h S~ ~7 rq ~ ~ rq a) ~ o c~ ~ ~ o ~ \ z a~ ~ a) a .~ 3o Q~ ~n O ~ ul ~ ,1 :~ ~ O O oo c~ ~_ C) E~ ~: ~1 ': :' ., ' ~, ~; _ _ ' ~ -~ a~ Q
~-1 t~ - _, 1~ ' ~ ~ _ ~1 ~

- 44 - :
. . ~
.

; ' - ' '' .' ' ,' ~ ' '' . ' : ' .. -, , .
- . . . ~ :, . - .:. . :

- ~ - -0 o o rol ~ o ~ :
o ~ ~ ~ ~ 0~
`:
-~ ~s~ ~o s~ ~ ~o ~ ~ ~ h ~ ~~
C 0~ U ~ ~ U
. _ 0 U~ O O
. ~C ~ 0~ ~0 0~ 0~ q~,~
C ~ In~ O
~' ~0~
~-1 0 C~ ..
~ ~ ~ ~ r~, 1~. 1~, 1~, 1~, ~D ' ~ rl ~ r~ I~ ~o o~ 1-0 0 0 0 0 ~ ' ~ ~ . . . . .
0 0 ~ 0 o Q 0 æ 0 Iq 0 u~ u~
: . 3 ~ ~ D ~ ~ O
1~ _ .
.~ . . ~.~ ',.' 0 . o ~1 ~ 0 0 ~1 ~ ' . .
. ~ O ~ ,~ C~ ~ ,C: ~d 3 O æ~ 0 o 5~ 0 0 o ~
~ ~1 ~ . o o ~ ~ o o u~ ~ ~ o~ E~ ~ ~ ,~ E~ ~
-~-; 1.. ,.~ _ .~ . .
s~

I x o o ,~ ~ .
.

.. , , .. . .. " . . . . .

- - ~
~! O ~J ~1 ~ ~I h h h P .~ o ~ o ~ a) o o ~3 ~ a) h ~ ~: ~:
u ~ ~ ~ a) ~ ~ ~ ~ ~ a) ~ ~ ~,1 o ~1 o a~ a~ h O
P ~d ~ O~I h ~I h h h G) h

5~ ~r; , u~ O u~ U) to ~ ~ ~ ~), ~ a) ~ ~ ~
g~ ~ ~: h u~
H ~:: ~) .-1 h ~ ~ P~ O
E~ ~ ~ o rd bl S~ ~ ~ O ~ ~1 f:~ ~ h ~, O ~:: ta ~ Lr) ~ O u~ ~: ~1 u~
~ It~ Q) ~) ~ O ~ O ~ O ,J ~ O I
O ~`1 h ~ O I h S~ I h i ~I h ~ h n~
c.) . ~ o o u~ ~ o ~ o Y o (~ ~, o ~ a) ~1 ~1 u~ ~ co V~ a~ u~ cs~ cn ~ ~1 ~ 3 P _ _ _ .
U~:
~- ~ ~ t` I~ I~ i` I~
~ a) .. .. .. .. .. ..
~1' ~ r~ 1_ 1~ 1`
~ ~ ~ .. .. .. . .. .. ..
rl ~ Q) ~ o~ OD a~ ~o oo a~
H ~ __~5~ ___ P~ t~ ~ ~
pil ~ ~ O ~r~ _ t4 ~ ~-~ ~ I O
u~ c,~_ ,s:: (d o ,l L~
H 3~ ~ ~ X Q ~ . cr~ O
a o~: O h ~1 0 co .-1 1:4 .'d O O O ~) ~) ~ ~; E~ ~ _ _ _ __ _ __. . : .
a ~ ~ ~D
r~ ~ ~ ~ ~ O~
O P~ l ~ In ~_ . ~
H _ ::
O ~
p~_ O
~, ~n u~
O E~ _~ ~ .9 oo O O
-, ~ P~ ~ ~
~Z ~ ~ : '' '' " ' ~ ~ O ~9 ~l ~ O O
H O O a~ c~ Cl~ t~ c~

C2 _ __ _ _ _ _ _ _ : . ' ;
IJ ~ _ __ ___ __ ' O ~ .
~ ~1 ~ 00 ~1 t~l a) ~ o ~r .. .. . ..
O .. .. ~r ~ O O ..
~n rl O ~9 cr ~ ~ oo .~ o __ , .
~ ~ _ ._ P . ~ ~
~ ~ o _ _ E~ X Z ~ ~ ~r L~
~ . ~ ~ ~ ~ ~ ~ . . .
._I _~_ ._ ~ :, ' ' , , : ~ . , , . . ,, .. . ., .,. . .: .
-. ~ . - . . ' ' . ' , ' : '. ' : ' ' ' ~ ; ' ',' ' ' ', . '' ' . ' .. . ~ , . .
.::
'': ~ ' '' ~

.. .. ... . ...

.

~1 ~ ~ ~ ~1 ., . o ~ ~ ~ a ~ ~ a) .
~ o ~ ~ ~ a) ~ ~ ~ a) 1~-,1 (d ~ rl tL) ~1 tL) ~1 tU
~4 ~) ~ O ~J ~1 r-l ~J ~ l $1~ U~ O U~O U~ U~ t~
~,~ 0 . 0 $ 5~ ~1 tn tn Q~
~ ~ ~1 ~ Q~
,1 ,~ ~ O Q~ 1~ S~ t~ O
u~ ~ ~ ~: O ~
"' U~ tl,) ~ O ~ O Q, O ~ O
S~ ~O 1 S~ ~ I
a ~ o ~ o ~ ~ U~ tO-- ~ U~ Ci~ U~ c~ U~
~_ _ I __ .
t ~ ~ ~ a) ~ t~ ,~
.. .. .. ..
~r ~ r- t_ - - - -O X ~ 00 o~ 0~ ~0 _ .. __ ., ..
_ rlC~ ~ .~ ' tn ~ I 1: .
S~Q. ~n ~ ., a) 3 ~~ u ~
tQn O O ,~ ~ ~ ~o O
,~ ~ ~: ~ S~
~ ~O OO . :' . _ t~ Z E~ ~ . . ~ - -._ a ~: I~ ,~ ~r, :: ~
.~ I_ ~ ~r n_ ~.-',-tn Q~ t ~n l o~ o~ tx ô ~ ID
~: - ... _ ~ l tJ' ~ C) O ~ ~3 t~l ,~ ~ P~ 0~ ~n ~ ~ .' ~ ~ ~ .. , ~ O _ ~ ~ . ~
~ . ,~
4~ 0 ~
~D Z O U~ t~ .
~ _ _ _ _ __ 1 ¦ ~-1 A
~ ~ O ~
3 Z t~l t~3 r~ _~

-- 47 -- :
: .

''..
". '~ ' ' - ~ ' ~ ' ' '.
'. , ' ~ ' ~ ' ' , . .
,: : ,, , ,j, ' ' ': '~ ' ' ' ' . . ' : ~ ' :
' , , : ', .
,

Claims (10)

WHAT WE CLAIM IS:

1. A phthalocyanine pigment composition comprising a phthalocyanine pigment and s sulphonated phthalocyanine derivative formed from sulphonated phthalocyanine dyestuffs having the formula wherein R represents a C1-C22 cyclic or acyclic alkyl group, aryl, aralkyl group or a dehydroabietylamine residue; and R1 represents hydrogen or a C1-C22 cyclic or acyclic alkyl group, an aryl or an aralkyl group; the alkyl, cycloalkyl, aryl or aralkyl groups, R and R1 may be optionally sub-stituted with one or more hydroxyl groups; x is from 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 dehydroabietylamine of the formula to substantially neutralise the free sulphonic acid groups, when y is O, a tertiary amine having the general formula or a quaternary ammonium salt having the formula:

wherein R2, R3 and R4 each represent an alkyl or alkylene group, R5 represents an alkyl, alkylene or aralkyl group and B(-) represents an anionic species, the total number of carbon atoms 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 R5 having a backbone of at least 12 consecutive carbon atoms.

2. A pigment composition as claimed in claim 1 comprising a phthalocyanine pigment and a sulphonated phthalocyanine derivative formed from sulphonated phthalocyanine dyestuffs having the formula:

and a sufficient quantity of dehydroabietylamine having the formula to substantially neutralise the free sulphonic acid groups, wherein R, R1, x and y have their previous significance.

3. A pigment composition as claimed in claim 2, in which x is 1-2.5 and y is 0-3.

4. A pigment composition as claimed in claim 1 comprising a phthalocyanine pigment and a sulphonated phthalocyanine derivative formed from sulphonated phthalo-cyanine dyestuffs having the formula:

Pc(SO3H)x wherein x has its previous significance, and a tertiary amine having the general formula:

or a quaternary ammonium salt having the formula:

wherein B(-), R2, R3, R4 and R5 have their previous significance.

5. A pigment composition as claimed in claim 4, in which x is 1-2.5.

6. A pigment composition as claimed in claim 1, 2 or 3, in which the sulphonated phthalocyanine is a copper phthalocyanine.

7. A pigment composition as claimed in claim 1, 2 or 3, in whiGh the pigment is a copper phthalocyanine.

8. A pigment composition as claimed in claim 1, in which the ratio of phthalocyanine pigment to sulphonated phthalocyanine dyestuff is from 88:12 to 99:1 by weight.

9. A pigment composition as claimed in claim 8, in which the ratio is from 92:8 to 96:4.

10. A pigment composition as claimed in claim 1, 2 or 3 which also contains a urethane compound having two or more urethane groups and contains no significant proportion of basic amino groups.