CA1089450A - Treatment of phthalocyanine pigments - Google Patents

Abstract

TREATMENT OF PHATHALOCYANINE PIGMENTS

ABSTRACT OF THE DISCLOSURE

Process for treating a pigment by contacting a phthalocyanine pigment 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 phthalocyanine pigment before it is contacted with the solvent or during the contacting, a minor proportion of a sulphonated phthalocyanine-amine derivative.

Description

t~

3-10464/~A 1660 TREATMENT OF PHATH~LOCYANINE PIGMENTS

The present invention relates to a process of pigment treatment, particularly a phthalocyanine pigment.

In our British Patent No. 1,263,684 there is described and claimed:
.

A process in which a pigment is treated comprising .
contacting a metal phthalocyanine blue pigment, in dry pigmentary form, with a polar aliphatic solvent which is at least partially water-miscible, and separating the solvent from the treated pigment, in which process there is added to the metal phthalocyanine blue ~ -pigment before it is contacted with the solvent, during the contacting, ~
or after it has been separated from the solvent, a minor proportion .
of a copper phthalocyanine derivative having the formula: `.

/ 2 l)y -:
CuPc \ . -, (S03 H2~NRRl)x :
"~
wherein CuPe represents the copper phthalocyanine residue, either chlorinated or unchlorinated, R represents a cyclic or acylic alkyl ; :
group having from 1 to 20 carbon atoms or an aryl group, and R~
represents hydrogen or a cyclic or acyclic alkyl group havin~ from 1 to 20 carbon atoms or an aryl group,the alkyl or aryl groups being either unsubstituted or substituted by hydroxyl, amino, alkylamino or amide substituents, and x and y each represent l, 2 or 3 with the proviso that the sum of ~ and y is 2, 3 or 4.
~ :, , ; ~3 ' ' ' - ~ .` ~:

5() The pigment so treated shows improved brightness when incorporated into inks.

- We have now found,surprisingly, that by adding a ~ .
different phthalocyanine derivative to a phthalocyanine pigment in a similar process treatmen~ before or during contact with a polar aliphatic solvent, the resulting treated pigment composition has improved properties with regard to strength and rheology when ~.
incorporated into inks and paints, when compared with the treated :~
pigment composition described in B.P. 1,~63,684. ~ -. .: .
. According to the present invention there is provided .~ :
a process in which a pignlent is treated by contacting a phthalocyanine pigment, in pigmentary form, with a polar aliphatic solvent which is at .
least partial~y water-miscible, and separating the solvent from the :~
treated pigment, in which process there i5 added to the phthalocyanine pigment before it is contacted with the solvent or during the contacting a minor proportion Qf a sulphonated phthalocyanine-amine derivative .
of the formula ~ / 2 Pc ~SO - N - R

' ,~
wherein Pc represents a phthalocyanine residue, R2, R3 and R4 each represents an alkyl, alkenyl or alkapolyenyl group, R6 represents hydrogen, or an alkyl, alkenyl, alkapolyenyl cr aralkyl group and x is the average number of sulphonic groups per phthalocyanine molecule :.::
and is from 1 to 4.

g~lslo Compounds of formul.a I may be formed by reacting a phthalocyanine dyestuff having the formula Pc(S03M)~ II

wherein Rc and x have their previous significance and M represents hydrogen or an alkali metal, with a tertiary amine having the general formula R2 ~ N - R3 III
4 ~.
or a quaternary ammonium salt having the formula `

R2 ~ N - R B(-) IV
I , wherein R2, R3 and R4 have their previous significance, R6 represents an alkyl, alkenyl alkapolyenyl or aralkyl group and B represents :~
an anion, the total number of carbon in the tertiary amine or cationic ;~ :
portion of the quaternary ammonium salt being from 20 to 60, and at :~
least one of the groups R2, R3, R4 and R6 having a backbone of at least 12 consecutive carbon atoms.
:`
When the dyestuff of formula II is reacted with a tertiary amine of formula III, R5 in formula I is hydrogen and when the dyestuff of for~ula II is reac~ed with the quaternary ammonium :
salt of formula IV, R5 in formula I cannot be hydrogen. : ."

.

9~o Preferably two of the groups R2, R3, R4 and R6 have backbone of at least 12 consecutive carbon atoms, and the totaL number of carbon atoms on the nitrogen atom is pre,erably from 25 to 45. The anion B( is preferably halide, acetate or hydroxide. i ;

The phthalocyanine dyestuff of formula II may be metal free, or it may be a zinc, copper, cobalt, nickel or other transition metal phthalocyanine and may contain halogen, especially chlorine, in the phthalocyanine molecule.

Halogen free copper phthalocyanine dyestuffs of the formula:

cuPc (S03H?x v are preferred where CuPc represents a copper phthalocyanine residue -~
and x has its previous significance.

The phthalocyanine dyes~uff of formula II may be prepared by any of the methods in common use, for example by reacting the phthalocyanine with chlorosulphonic acid or oleum at elevated temperature for several hours, then dr~wing out into an aqueous solution of sodium chloride prior to recovery as a presscake by filtration.
.
The phthalocyanine pigment may be metal free or it `
may be zinc, copper, nickel or other transition metal phthalocyanine, and may contain up to 50% by weight of chlorine. The preferred pigment is a copper phthalocyanine, which may be in either the alpha or beta ~-~
crystalline form, or a mixture of the two. ~ ;

.

The ratio of phthalocyanine pigment to phthalocyanine deystuff of formula II may be from 88:12 to 99:1 by weight, but preferably from 92:8 to 96:4. -. ':
While x can be from 1 to 4, compounds of formula I
are preferred in which x is 1-2.5.

Compounds of formulae III and IV may be based on specific alkyl, alkenyl or alkapolyenyl amines but are more conveniently derived from the mixtures of hydrocarbon residues of naturally occuring ..
oils and fats such as tallow, corn oil, fish oil, or whale ail. Among such suitable tertiary amines there may be mentioned dimethyl tallow, dimethyl hydrogenated tallow, dimethyl soya, dimethyl octadecyl, `~
` dimethyl eicosanyl, dimethyl docosanyl, monomethy~ di eicosanyl, .
monomethyl di(dodecyl), monomethyl di(hydrogenated tallow), monomethyl di docosanyl, tri dodecyl andtri octadecyl amines or mixtures thereof.

: The quaternary ammonium salts are conveniently formed from such tertiary amines by reaction with methyl chloride or dimethyl sul?hate to form the methyl quaternary ammonium salt or with ~: -benzyl chloride to form the appropriate benzyl quaternary ammoium salt.
~.
The sulphonated phthalocyanine-amine derivati~es :~-of formula I formed by the combination of ~ompounds of formula II
with a compound of formula III and/or I~, may be produced, for example ~;
by reacting a phthalocyanine compound containing x sulphonic acid groups with a sufficient quantity of one or more amines and~or quaternary ammonium salts to substantially neutralise the free sulph- :~ :
onic acid groups~

` ,i: '..

, -l~V~ ~t~V , The sulphonated phthalocyanine-amine derivative of formula I may be prepared in aqueous solution, providing the nitrogen compounds of formulae III and IV are watersoluble or are capable of forming a solution in aqueous mineral or organic acids. Alte~natively, the derivative may be prepared in a suitable solvent and recovered by precipitation, e.g. with water, or by removal of the solvent by distillation, optionally with the addition of wat~r. Such preparation in solvent is particularly useful for compounds of formulae III and IV
which do not readily form solutions in water or aqueous acidic media. ~;~
Among suitable solvents there may be mentioned acetone, ethylmethyl-ketone, ethanol and methanol, but isopropanol is particularly preferred. -The polar aliphatic solvent with which the pigment composition is treated is one which is at least partially miscible with water. Suitable solvents are described in B.P. 1140~36 and include alkanols having from 1 to 4 carbon atoms in the alkyl chain, for example, methanol, ethanol, n~propanol, isopropanol and n-butanol;
alkyl monocarboxylates having from 1 to 4 carbon atoms in the alkyl chain, for example alkyl esters of alkanoic acids especially ethyl acetate; dialkyl ketones having from 1 to 4 carbon atoms in each alkyl chain, for instance acetone, methyl ethyl ketone or dlethyl ketone; alkoxy alkanols having from 1 to 4 carbon atoms in each of the alkyl chains of thealkoxy and alkanol components for instance,

2-methoxy ethanol or 2-ethoxyethanol; or alkylene glycols having from 2 to 6 carbon atoms in the alkylene chain, for e~ample, ethyl~ne glycol or diethylene glycol.

The solvent may~ if desired, contain disolved water in a proportion insufficient to cause separation into two phases, and may thus be, for example, aqueous ethanol(for instance industrial methylated spirits), an aæeotropic mixture of ethanol and water or an azeotropic mixture of isopropanol and water, the alkanol in each .
~ case being the major cons~ituent.

9~

The pigment to be contacted with the dyestuff/amine derivative may be added to the solvent as a powder or aqueous presscake.
The pigment may be in a full pigmentary state or in a hyghly aggregated state, as formed during a dry grinding process. The pigment thus may be in the Eorm of a mixture of phthalocyanine with a salt, especially a mixture resulting from a preparation of the colouring matter in pigmentary form by grinding with the salt; the mixture of the organic solvent and the pigment is then preferably treated by mixing it with a proportion of water, sufficient to dissolve the salt present.

As noted in BP. 1,140,836 such solvent treatments lead to products of improved rheology, brightness, and dispersibility:
the present process gives improvements in properties in addition to those from such a solvent treatment of the pigment alone. The process of contacting dyestuff/amine derivative with the pigment may then be combined with the process of such a solvent treatment. Such solvent treatments of the pigments, as noted in PB. 1,140,836, may be effected under a wide variety of conditions, the particular temperature and pressure at which the treatment is effected and the time during which the pigment and solvent are contactled, being dep~ndent on the nature of the pigment and of solvent in order to secure the optimum improvement in pigmentary properties.

Although the pigment is preferably contacted with the solvent at a temperature in the range from 10C.to the boiling poi~t of the solvent at the pressure applied, a temperature of from 50C to the boiling point is particularly preferred when the treat~
ment is carried out at atmospheric pressure. Although a superatmospheric pressure may be applied, if desired, for example when the solvent used is highly volatile at the treatment temperature chosen, it is generally convenient to treat the pigment with the solvent at atmospheric or substantially atmospheric pressure. `

~- .

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

The proportion of solvent with which the pigment is treated in the process, relative to the pigment is preferably in the range of from 0.5 to 20 parts by weight of solvent per part by weight of pigment, the proportion of l to 15 c~nd especially 5 to lO
parts by weight of solvent per part by weight of pigment being particularly preferred. If the proportion of solvent to pigment is above that of the preferred range, no further significant improvement i7a the pigmentary properties of thetreated pigment is achieved. If the proportion of solvent to pigment is below that of the preferred range, the strength and brightness of the treated pigment is inferior so that of the same pigment when treated with a proportion of solvent within the preferred range.

Sulphonated phthalocyanine amine derivative may be added at any point during this treatment but it is preferred that the pigment and derivative are contacted for at least lO minutes at the reflux temperature of the preferred solvent, i.e. isopropanol or the water isopropanol azeotrope mixture. Although the sulphonated phthalocyanine amine derivative may be preformed, as in the case above, and then contacted with the pigme7at, it is a further advantage of this process that the derivative can be formed in the selected solvent in the presence of the pigment. 5uch an approach avoids the separation of dyestuff/amine preparation. This is especially advan-tageous in the use of the preferred dialkyl amine d~:rivatives which are substantially water insoluble but readily react with sulphonated phthalocyanine dyestuff in such solvents.

The pigment composition may be isolated from the solvent by filtration, preferablyafter dilution with water. The more volatile solvents may be removed by direct distillation but it -is preferable that water is added, solvent is removed by distillation and the pigment is then left dispersed in essentially an aqueous phase; isolation from water is then by the conventional techniques of B~ .

45~3 g filt~ation and drying. In all c~ses the com~ositions are washed free of any inorganic salts.
The pigment compositions prepared by the process of the inven~ion may be used for pigmenting various media.

They can be used in decorative paint, in publication gravure inks, nitrocellulose, alkyd~ and acrylic-MVF systems, but are particularly suitable in those media containing a high proportion of hydrocarbons in the solvent.

In Belgian Patent 833,518 there is described and claimed a composition which comprises:

i) a finely divi~ed solid with a mean grain size of less than 20 microns ii) a polymer or resin dis?ersi?.g agent iii) a fluidifying agent which is an ammonium salt substituted by an acid colorant in which 16 to 60 atoms of carbon are contained in at least three chainsbo~ded to the nitrogen atom of the substituted ammonium ion, and iv) an organic liquid. ~
' ~:
We have found that phthalocyanine pigm~nt compositions prepared by the process of tile present inven~ion in which the pigment and dyestuff amine derivative is contacted with a polar aliphatic solvent~ show superior properties with regard to strength and rheology when incorporated into ink and paint media, over the pigment compositions claimed in Belgian Patent 833,518 which have not been contacted with a polar aliphatic solvent.

. ' ~:

~ ` ' 1~ 5V

It can be seen in the following Examples that the sulphonated derivatives promote good flow and flow stability in systems which would otherwise be thick and/or thixotropic, and also accelerate the rate of dispersion.

The invention is illustrated by the following Examples in which parts and percentages are expressed by weight unless otherwise stated. Parts by weight bear the same relationship to parts by volume as do kilograms to litres.
; .
Example 1: 175 parts of crude copper phthalocyanine were ground with 23 parts of inorganic salts, 1.6 parts diethyl aniline and 0.8 parts glycerol mono-oleate until the phthalocyanine was in pigmentary fxom.

103 parts of this mixture, corresponding to 90 parts of copper phthalocyani11e, were added to 600 parts of isopropanol and heated under reflux conditions with good agitation for 5-L~2 ;
hours. 4 parts of the compound of formula V

CuPc(S03H) x ~ ~
wherein x is 2, in presscake form, were added and reflux continued. ~;
After 15 minutes, 6 parts of an amine (Kemamine T.9701 ~ , Humko Chemical Products)of formula III where R4 is a methyl group and R2, R3 are hydrogenated tallow residues, were added as a solution in hot isopropanol. A further 15 ~inutes later, 600 parts of water were added and the isopropanol removed by distillation. Agitation was stopped and the pigment composition filtered from clear liquors, washed salt free to neutral pH, and dried at 50-60C. The yield ~as 99.1 parts. ;

A publication gravure ink of 6% pigmentation and 1:5 pigment: binder ratio was prepared by ball milling, the pigment composition of this Example in a phenolic resin varnish with toluene solvent, according to the method of ~xample 10 of British Patent No. 1,501,184. I~en compared with a similar ink prepared from un-treated beta-copper phthalocyanine, the ink prepared from the product of this Example had a very much more fluid millbase and was 15% stronger, cleaner and brighter.
Example 2: Example 1 was repeated using 3.4 parts of the compound of formula V

t 3 )x ' where x is 2~4, and 5.6 parts of the hydrogenated tallow amine. The publication ~ravure ink derived from this composition was approximately ~
10% stronger than the corresponding ink prepared from untreated ~;
~~copper phthalocyanine and had a more fluid millbase. `

Example 3: -- ~
A) 20 parts of the compound of formula V ~ ~
. :
CUPC SSO3H)X

in which x is 2, in presscake form, were stirred in 200 parts of isopropanol and the temperature raised to reflux. 29.2 parts of the amine of formula III, where R4 is a methyl group and R2, R3 are hydrogenated tallow residues, were dissolved in 200 parts hot isopropanol, and added over 5 minutes. After a further 30 minutes at reflux, 400 parts of water were added over 60 minutes, and the isopropanol simultaneously distilled off at the same rate. ~-Stirring was stopped and the blue-green product of the reaction isolated by iltra~ion from clear liquors, l~ashed with warm wat~r, and dried at 60C to give a yield of 48.1 parts.
' ~.

..

B! 175 parts of c~ude copper phthalocyclnine were ground by the method of Example 1. 103 parts of this mixture, corresponding to 90 parts of copper phthalocyanine, were added to 600 parts of isopropanol and heated under reflux conditions for 5-1/2 hours with good agitation.
I0 parts of the product of Part A of this example were added as a solution in hot isopropanol and reflux continued for 30 minutes. 600 parts of water were run in and the isopropanol removed by distillation, after which agitation was stopped.

The pigment composition was filtered from clear liquors, washed salt free to neutral pH, and dried at 50-60C.
The yield was 99.3 parts.

A publication gravure ink prepared from the product of Part B of this example by the method of Example 1 had similar properties to the ink derived from the product of Example 1.

Comparative Example: ;
C) Example 3B was repeated except that the 10 parts of product of Part A of this example was omitted. To ~he resultant 90 parts o~ ~-copper phthalocyanine pigment powder, 10 parts of the powder product of Part A was then added and the two components intimately mixed. A publication gravure ink prepared from this mixture was 10% weaker and had inferior rheology to that achièved with a sample of Example 3B.

Example 4: Example 3B was repeated using 108.6 parts of the ground mixture, corresponding to 95 parts copper phthalocyanine, ~ogether with 5 parts of the product of Example 3A. The pigment composition so obtained, when incorporated in the publication gravure ink medium was 10-15% stronger than the corresponding ink derived from untreated ~-copper phthalocyanine.

Example 5:
A) 90 parts of a substantially alpha-form copper phthalocyanine, containing 1.8% w/w peripheral~Tbound chlorine, were added as a 30% aqueous presscake, to 500 parts of isopropanol, and heated to reflux with agitation. 4.8 parts of the compound of formula V
CuPc(S03}1) in which x is 2, in presscal.;e form were added and reflux continued for 15 minutes. 5.1 parts of technical di(dodecyl)methylamine were then added as a solution in hot isopropanol.
After 15 minutes, 500 parts of water were added and the isopropanol removed by distillation. Agitation was stopped and the pigment composition filtered from clear liquors, washed salt-free to neutral pH with warm water and dried at 50-60C. The yield was 99.L parts.

The pigment composition of this Example was ~
incorporated in a glycerol coconut oil alkyd resin in xylene/n-bu~anol ~ `
solvent by ballmilling and subsequently reduced to 6% pigmentation and 1~6.6 pigment: binder ratio with an unmodified isobutylated melamine/formaldehyde (M/F) resin solution. The initial mill base dispersion was fluid, in contrast to a similar dispersion prepared from alpha-copper?hthaloc'yani~e pigment untreated by dyestuff and amine, which was thixotropic and only pourable after agitation.
Blue tint alkyd-MVF paints were prepared from the reduced dispersions by admixture with white alkyd-M/F paint and stoving. The paint derived from the pigment of this Example was approximately 10-15% stronger than the paint derived from the pigment not so treated.

When this pigment composition was dispersed into a long oil soya alkyd decorative paint by a "Red Devil" technique and then reduced into a ~hite base paint at a 1:25 reduction, that ls, ratio of phthalocyanine pigment composition to titanium dioxide, this product was 20~ stronger than the untreated a-copper ,~..

~89~50 phthalocyanine dispersed and assessed by an identical technique. The initial dispersion of the treated pigment in the alkyd medium exhibit superior flow p~operties to the dispersion from the untreated pigment.

Co~R___tive Example B) A pigment composition was prepared by intimately mixing as dry powder, 9 parts of the above ~-copper phthalocyanine and 1 part of the dyestuff-amine composition as used in Example 5R. The composition was then tested in the short oil alkyd and long oil alkyd media used for Example SA. In both paint systems the composition of Example 5A, prepared via contacting in isopropanol, showed superior strength (10-15% stronger) and rheology.

Example 6:
A) A phthalocyanine dyestuff-amine composition was prepared by the method of Example 3A, us~ng 21.7 parts of the amine of formula III, where R4 is a methyl group and R2, R3 are dodecyl residues.

B) The method of Example 5 was repeated with the addition of 10 parts of the product of Part A of this example in place of the separate additions of dyestuff and amine. There was obtained~a paint of sub-stantially similar application properties to those of the paint derived from the pigment composition of Example 5.

Example 7:
A) A phthalocyanine dyestuff composition was prepared by the method of Example 3A using 32.6 parts of the amine of formula II, in which the group R2, R3 are each eicosanyl or docosanyl residues, and R4 is a methyl group.
B) 150 parts of a pigmentary phthalocyanine green pigment powder of 47.1~ chlorine content were added with efficient agitation to 800 parts of acetone and the temperature raised to reflux. After 10 minutes, 15 parts of the product of part A of this Example were ~ ~.

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

5~D

added as a slurry in acetone, and reflux continued for a further 15 minutes, after l~hich 800 parts oE water ~ere added and the acetone removed by distillation. A mixture of lS parts concentrated hydrochloric acid and 15 parts water was then added evenly over 2 minutes. After 30 minutes, agitation was stopped and the product isolated by filtration from clear liquors, washed with warm water and dried at 50-60C. The yield was 163.2 parts. The pigment composition was incorporated in a nitrocellulose varnish by ball milling and subsequently reduced to 11.7% pigmentation at 1:1,38 pigment: binder ratio by the addition of a mixture of nitrocellulose and maleic condensate varnishes. The resulting dispersion had equivalent colouristic properties, but markedly superior millbase flow, compared to a similar dispersion prepared from untreated phthalocyanine green.

Example 8: 95.2 parts of the ~-form copper 2hthalocyanine of Example S were added, as an aqueous presscake, to 900 parts of ethyl acetate and heated to reflux with stirring. After 30 mins., 7.5 parts of the product of Example3A were added, and stirring at reflux continued. A further 15 mins. later, lO00 parts water were added and the ethyl acetate removed by distillation. The mixture was acidified with 15 parts 25% aqeuous hydrochloric acid and stirred 15 mins. Agitation was then stopped, and the pigment composition filtered from clear liquors, washed to neutral pH
with warm water and dried at 50-60C. The yield was 98 parts.
::
The pigment composition of this Example was incorporated in an alkyd-M/F paint medium by the method of Example 5.
The mill base was very 'luid and the corresponding blue tint ~ ;
paint 15-20~ stronger, cleaner and sligthly redder than the paint derived from the a-form copper phthalocyanine starting material.

Example 9: The m~thod of Example 8 was repeated with the use of 9.15 parts a-form CP?e~ phthalocyanine~ 8.5 parts of the product '~

'` ' ' . ' ' ' : . . ' ' ' ` ` ' . ' :, . ' . ' ~, ' ! . , , of Example 3A, and m~thanol as solvent. There were obtained 98 parts of pig~eQt co~position.
The alkyd-~F paint prepared from this pigment composition was similar to that of Example 8, being 10-15% stronger, cleaner and slightly redder than the corresponding paint prepared from the ~-form copper phthalocyanine starting material.

Example 10: The method of Example 8 was repeated with the use of 90.5 parts ~-form copper phthalocyanine, 9.5 parts of the product of Example 3A and ethanol as solvent. The resultant pigment composition, which was obtained in a yield of 99 parts had similar properties to the product of Example 9 when incorporated in the alkyd-MVF
paint medium by the method of Example 5.

The pigment composition of this Example was also incorporated in a long oil soya penta alkyd based decorative paint medium by baLl milling. A 1:25 reduction, prepared by admixing the mill base with white decorative alkyd paint, was approximately i 20% stronger than the corresponding reduction prepared from the untreated ~-form copper phthalocyanine starting material, and moreover had substantially improved resistance to flocculation.

The mill base containing the pigment composition of this Example was also very much more fluid than the mill base derived from the untreated ~-copper phthaloc7anine starting material.

Example 11: 89 parts of ground copper phthalocyanine were stirred in 500 parts n-butanol. The temperature was raised to reflux and maintained for 5 hrs. 11 pa~ts of the product of Example 3A were added and reflux continued for 15 mins. 1000 parts water at 55C
were run in and the n-butanol removed by distillation. The mixture was acidified with 15 parts 25~ aqeuous hydrochloric acid. 15 mins.
after, the stirring was stopped and the pigment composition filtered ~;
from clear liquors, washed to neutral pH whith warm water and dried at 50-60C. The yield was 9~ parts.
'~ ` ' ' : ' ~. '.

39f~
., The publication gravure ink prepared from the product of this Example by the method of Example 1 was 15-20% stronger, and slightly greener than the corresponding ink prepared from the ground copper phthalocyanine starting material, and moreover, was derived from a considerably more fluid mill base.

Example 12: The method of Example 11 was repeated using 87.5 parts s ground copper phthalocyanine, 12.5 parts of the product of Example 3A
and ethyl methyl ketone as solvent. The pigment composition was -obtained in a yield of 97 parts. The publication gravure ink prepared from this pigment composition was similar to that of Example 11, being 15% stronger than the corresponding ink prepared from the ground copper phthalocyanine starting material.
, Example 13:
~ ?
A) 59 parts of the amine of formula III, where R3 and R4 are methyl groups and R2 is a soya oil residue, commercially available as Kemamine T.9972.~, ~ (Humko Chemical Products) were added to 1800 parts boiling water containing 13 parts glacial acetic acid, and stirred until a solution was obtained. The solution was allowed to cool and diluted to 2000 parts with water.
" i.,~.~, 60 parts of the compound of formula V

CUpc(s03H) where x = 2, in the form of inorganic salt-containing aqueous presscake, wera dissolved with stirring in 4000 parts water. The pH was adjusted to 5.0 with aqueous sodium hydroxide solution and 1650 parts of the above amine acetate solution run in evenly over 30 mins.,maintaining stirring throughout. The mixture was stirred for a further 1 hr.
then filtered, washed free of inorganic residues with warm water and recovered as presscake. ,;

', .
': ~ ' `,"':' s~ ~
.

B) The method of Example 11 was repeated using 86.5 parts ground copper phthalocyanine in the form of an aqueous presscake 13.5 parts of the product of part A of this Example, also in presscake form, and isopropanol as solvent. The pigment composition, which had similar properties to that of Example 11 was recovered in a yield of 97 parts.

Example 14: Example l was repeated except that the 6 parts of amine used in that Example were replaced by 8.6 parts of an amine of formula III ~n which R2, R3 and R4 are hydrogenated tallow residues (Adogen 340 ex Ashland Chemicals). Results in publication gravure were similar to those obtained from the product of Example l.

Example 15: Example 1 was repeated except that the 6 parts of the amine used in that Example were replaced by 4.0 parts of an amine of formula III in which R2, R3 and R5 areisooctyl residues (Adogen 381 ex Ashland Chemicals). Results in publication gravure were similar to those obtained from the product of Example l.

Example 16:
A) The procedure of Example l was repeated except that the 6 parts of amine were replaced by 6.6 parts an ammonium salt of formula IV
- with R2 = R3 = methyl and R4 = R6 = hydrogenated tallow and B = Cl.
(Kemamine Q.9702.C ) Results in publication gravure were similar to the product of Example 1. ;
.
Comparative Example 16.~:
A dyestuff amine composition was prepared according to the procedure of example 3A but replacing the amine used there by 32.5 parts of the ammonium salt used in Example 16.A. The dry mixing of 9 parts of the ~-copper phthalocyflnine pigment and l part of the dyestuff~
amine derivatiYe of ~his Example gave a produkt which when tested in publication gravure was irfe ior in strength and rheology to .
. ~ ` '~ ' ~
~ :~

1~ 0' the product of Example 16.A.

Example 17: The procedure of Example 16.A was repeated except that .
the 6.5 parts of ammonium salt was replaced by 4.0 parts of an ammon~
ium salt w th R2 = R3 = methyl R4 = dodecyl and R6 = benzyl (Kemamine BQ.6502.C ) Results in publication gravure were similar to those obtained from the product of Example 16.A.

Example 18: 2,143 parts of crude copper phthalocyanine peripherally chlorinated to the extent of 1.8% by weight were milled for approxi-mately 14 hours with 6,857 parts of inorganic salts. 4,200 parts of this mixture, corresponding to 1,000 parts pigment were stirred into 1,900 parts of isopropanol-water azeotrope containing 25 parts of the dyestuff-amine composition of Example 6.A. The mixture was refluxed for 2 hours with stirring. 25 parts of diethyl aniline were added and refluxed with stirring for 30 mins.

~hile continuing agitation, 2500 parts of water ;
were added in 500 parts aliquots while isopropanol-water azeotrope was removed by destillationto a vapour temperature of 84C. The mixture was acidified by adding 800 parts of 1:1 concentrated hydrochloric acid: water over 10 mins., then stirred for 1 hr., filtered hot, washed salt free to neutral pH with hot water and dried at 60C. -~

The product of ~his Example, when incorporated in a decorative alkyd paint medium was 15% stronger and brigh~er than a pigment similarly prepared, but from which the dyestuff amine composition had been onmitted.

S(~

Example 19: A pigmentary a-form copper phthalocyanine, prepared by acid pasting of crude copper phthalocyanine, was treated with the product of Example 6.A in isopropanol~water azeotrope and subsequently recovered from water by the method of the previous Example.

The produ~t of this Example was incorporated in a hydroxy-acrylic resin in 4:1 xylene: n-butanol solvent by ball milling and subsequently reduced to 6% pigmentation and 1:5 pigment:
binder with an unmodified isobutylated melamine-formaldehyde resin in n-butanol. The resulting dispersion was considerably more fluid than a similar dispersion prepared from the a-form copper phthalocyan-ined starting material.

Blue tint acrylic paints were prepared from these dispersions by admixing with white acrylic paint and StOVillg. The paint incorporating the dyestuff-amine treated pigment was 15%
stronger, redder and brighter than the paint derived from the i~;
untreated a-form copper phthalocyanine starting material.

Claims (15)

WHAT WE CLAIM IS:

1. A process in which a pigment is treated by contacting a phthalocyanine pigment , in 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 phthalocyanine pigment before it is contacted with the solvent or during the contacting, a minor proportion of a sulphonated phthalocyanine-amine derivative of the formula I

wherein Pc represents a phthalocyanine residue, R2, R3 and R4 each represents an alkyl, alkenyl, or alkapolyenyl, group, R5 represent hydrogen or an alkyl, alkenyl,alkapolyenyl or aralkyl group, and x is the average number of sulphonic groups per phthalocyanine molecule and is from 1 to 4.

2. A process as claimed in claim 1 in which the sulphonated phthalocyanine-amine derivative of formula I is formed by reacting a phthalocyanine dyestuff having the formula:

Pc(S03)M)x II

wherein Pc and x are as defined in claim 1 and M represents hydrogen or an alkali metal, with a tertiary amine having the general formula:

III
or a quaternary ammonium salt having the formula IV

wherein R2, R3 and R4 have their previous significance, R6 represents an alkyl, alkenyl,alkapolyenyl or aralkyl group and B(-) represents an anion, the total number of carbon 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 R6 having a backbone of at least 12 consecutive carbon atoms.

3. A process as claimed in claim 1 or claim 2 in which x in the compound of formula I is from I to 2.5.

4. A process as claimed in claim 2 in which two of the groups R2, R3, R4 and R6 have a backbone of at least 12 consecutive carbon atoms, and the total bumber of carbon atoms on the nitrogen atom is from 25 to 45.

5. A process as claimed in claim 2 in which the compounds of formula III are derived from mixtures of hydrocarbon residues of tallow, corn oil, fish oil or whale oil.

6. A process as claimed in claim 2 in which the compound of formula III is dimethyl tallow, dimethyl hydrogenated tallow, dimethyl soya, dimethyl octadecyl, dimethyl eicosanyl, dimethyl docosanyl, monomethyl di(dodecyl) 9 monomethyl di(hydrogenated tallow), monomethyl di eicosanyl, monomethyl di docosanyl, tri dodecyl or tri octadecyl amine or a mixture thereof.

7. A process as claimed in claim 2 in which the phthalocyanine dyestuff of formula II is a halogen free copper phthalocyanine dyestuff of the formula:

CuPc(S03H)x V

where CuPc represents a copper phthalocyanine residue and x has its previous significance.

8. A process as claimed in claim 1 in which phthalocyanine pigment is copper phthalocyanine.

9. A process as claimed in claim 2 in which the ratio of phthalocyanine pigment to sulphonated phthalocyanine dyestuff of formula II is from 88:12 to 99:1 by weight.

10. A process as claimed in claim 2 in which the ratio of phthalocyanine pigment to sulphonated phthalocyanine dyestuff of formula II is from 92:8 to 96:4 by weight.

11. A process as claimed in claim 1 in which the solvent is an alkanol having from 1 to 4 carbon atoms in the alkyl chain;
an alkyl monocarboxylate having from 1 to 4 carbon atoms in the alkyl chain; a dialkyl ketone having from 1 to 4 carbon atoms in each alkyl chain; an alkoxy alkanol having from 1 to 4 carbon atoms in each of the alkyl chains of the alkoxy and alcohol components;
or an alkylene glycol having from 2 to 6 carbon atoms in the alkylene chain.

12. A process as claimed in claim 1 in which the solvent is isopropanol.

13. A process as claimed in claim 1 in which the process is effected at a temperature from 50°C to the boiling point of the solvent, and at atmospheric pressure.

14. A process as claimed in claim 1 in which the proportion of solvent to untreated pigment is from 5 to 10 parts by weight per part by weight of pigment.

15. A process as claimed in claim 1 which the phthalo-cyanineamine derivative is formed in the solvent in the presence of the pigment.