Note: Descriptions are shown in the official language in which they were submitted.
`` 1~8E;312
Tlle present invention relates to stabilised
phthaloc-~anines.
Phtha]ocyanine pi~nents~ especially copper phthalocyanines,
by virtue of their low cost, high strength, brillia~ shades and
outstandi~g general fastness properties are of great
commercial significance.
In paint and lacquer systems however, phthalocyanine
pigments tend to suffer from a defect, namely f`locculation.
; The defect manifests itself especially in non-aqueous systems.
If paints containing flocculating phthalocyanine pigments are
applied under different conditions of shear, widely different -~
cclour strengths can be obtained. Similarly, when paints
or prillting inks containing flocculating phthalocyanine pigments
are stored, the pigment particles tend to aggregate with
resulting loss of tinctorial strength and homogeneity of the
paint or i~c.
We have now found copper phthalocyanine derivatives
which, when --incorporated i~to a phthalocyanine pigment,
piovide a phthalocyanine pigment composition having
excell~nt flocculation resistance, when incorporated into
paint and printing ink media; moreover, the pigmented media
exhibit improved flow and other desira~le-pigmentary properties.
.. ', ' .
Accordingly~ the present invention provides a copper
phthalocyanine derivative having the forn~ula:-
;: O - .
- CuPc - [CH2- 0 - C ~ Y ~n
:;
-:~
-- 2 --
-. ~L
~,, -
~D86312
or a mixture tllereof whert~in CuPc represellts the residuc
of a copper phthalocyanine n1olecule, Y is an alkyl or
alkenyl residue each having froln 8 to 22 carbon atoms,
and each being unsubstituted or substituted by one or more
hydroxy groups or being interrupted by one or more nitrogen
atoms, or Y is an alkoxyaryl- or aralkyloxyaryl,or an
alkyl-aralkyloxyaryl residue wherein the alkoxy-,aralkyloxy
or alkyl-aralkyloxy moiety contains from 7 to 22 carbon
atoms, and n is àn integer from 1 to 8.
Preferably n is 2, 3 or 4.
Alkyl residues Y are derived from saturated acids
Y-COOH, and these acids preferably contain from 12 to 18
carbon atoms and especially from 14 to 16 carbon atoms.
Examples of suitable saturated.acids Y-COOII are n-octanoic,
iso-octanoic, n-decanoic,n-dodecanoic(lauric)~ n-tetra-
decanoic(myristic),n--hexadecanoic (palmitic), n-octadecanoic
(stearic), 12-hydroxystearic, n-eicocanoic and n-docosanoic
(behenic) acids. In view of their superior anti-flocculation
properties residues Y derived from n-tetradecanoic
and n-hexadecanoic acids are preferred.
, ~. ,.
When Y is an alkenyl residue, it is deri.ved fron an
unsaturated acid Y-COOH which preferably contains from 12 to
..
18 carbon atoms. Suitable examples of unsaturated acids
Y-COOX include n-octenoic, n-decenoic, n-dodecenoic and
olelc acids as ~ell as ethylenically unsaturated, commercially
avallable polycyclic acids such as rosin and hydrogenated rosins.
.~;
l - 3 -
.. . ~,
~, .^ /
1~81~31Z
Ex~mples of alkoxyaryl, aralkyloxy- or alkyl-aralkyloxy_
aryl residues Y are those having the ~ormula:
y~ II
wherein y1 is an allsyl residue containing from ~to 22
carbon atoms or an optiollally alkyl -substituted aralkyl
residue. Examples of suitable and preferred all~yl residues
y1 are the same as those listed hereinbefore in respect
of Y. When Y is an optionally all~yl-substituted aralkyl
residue, it may be e.g. a benzyl, methyl-, ethyl-, propyl-,
butyl-, hexyl-, octyl-, decyl-, dodecyl- or tetradecyl-
benzyl residue. Specific preferred ~xamples of alkoxy,
arall~yloxy- or all~yl-aralkyloxy residues OY are hexyloxy,
octyloxy, cetylox~y, ben~yloxy and p-dodecylbenzyloxy residues.
The present invention also pro~ides a process of
producing the compounds of formula I comprising reacting a
chloromethylated copper phthalocyan~ne of formula:-
~,'. ...
. CuPc - ~CH2Cl]n IJI
~, .
... -~
.
r wherein CuPc and ~ have their previous significance, with
, ,~ .
~ an alkali metal salt of an acid having the formula:- -
, ~ :
, . .
YCOOM IV
wh~rein Y has its previous significance and M is an alkali
... . .
- metal, preferably sodium,
~ 4 -
.
1~86312
The proccss Or the invention may be convenicntly
ef~ected by conducting the reaction in an organic solvent
e.g. xylene or toluene inert under the reaction conditions,
and optionally in the presence of a catalyst such as
cetyltrimethyl ammonium bromide. The reaction mixture may
be ~orked up in conventional tnallner e.g. by removing the
- solvent by steam distillation, filtering the conlpound of
formula I and dryillg it.
The starting~materials of formula III and IV are
lcnown compounds.
As already premised, the compounds of formula I have
value as flocculation stabilisers for phthalocyanine
pigments, and thc fl.occulation-stabilised pigment compositions
so produced impart improved flow properties into surface
coating media containing said pigment compositions.
Accordingly, the present invention further pr(~vides
a pigment composition comprising a phthalocyanine pigment
susceptible to flocculation and 2-25,especially. 5-15~ by
weight, based on the weight of the flocculating phthalocyanine,
of a compound of formula I as hereinbefore defined,
The present invention still further provides a
, composition comprising an organic material and a pigmenting
.~.`,?
. proportion of a pigment composition according to this
inven~ion,
- The phthalocyanine pigment suscept;ible to flocculation
may be a metal free or a me'cal- containing pht.halocyanine
pigment, Of these~ the latter cla~ss is more important
- 5 -
',~
.
. ,, , . .. . . . . . . . . . . ., _ .. . . ~
: ; . ' ', v ~ ,.,,, ",~ ;, , ,:, " ,, ` " ~ ,
- . .. : :. .,.: :,. .. .
1~)8631Z
for use in this invention, particularly those containing
cobalt, l~ickel or~ especially, 2 copper atom.
Pigment compositions accordin~ to this invention
may be produced by a variety of methods. Preferably~
however, the compound of formula I may be incorporated into
the flocculating phthalocyanine during the conversion of
the latter from its crude state i~to its pigmentary form
or, if the phthalocyanine is being prepared directly in
pigmentary form, during the synthesis of the pigment
Alternatively, the pigmentary flocculating phthalocyanine
and the compound of formula I may be physically blended
together before, during or after incorporation of the
pigments into an application medium e.g. a surface
coating medium.
The pigment compositions of this invention can also
contain natural reslns such as abietic acid or esters
thereof, ethyl cellulose, cellulose acetobutyrate~ alkaline
earth metal salts of higller fatty acids, fatty amines such
as stearylamine or rosinamine~ vinyl chloride/vinyl acetate
i ~ .
i< copolymers~ polyacrylonitrile or polyterpene resins.
~: .
~ Organic materials suitable for colouration by the
, 1
pigment compositions of the present invention include
~ natural or synthetic polymers or copolymers, coating
..... .
~` compositions for application to the surface of an art;cle and
~ ,.. .
~ I , . .
. ... .. . .... ~
~8631Z
printing ink media. Pre~erred organic materials ar(~
paints, lacquers and other surface coating compositions, or
tinting compositions for use in such coating cc~mpositions
and printing inks.
Pigment compositions of the in~ention containing compow~cls
of forlDula I have excellent flocculation resistance ~ihen incor-
porated into paint and printing ink media particularly gra~u~e
printing ink and paint media, whereby the flow properties of
these ~nedia are considerably impro~ed.
e following Examples further illustrate the present
invention. Parts and percentages s~own t~lereln are by weight.
;
.
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~3631Z
~X~IPL~ 1
84.5 parts of sodiuln stearate were heated i~ 1000 parts
of xylene to gi~e a thick paste which was allo~ed to cool to
room temperature be~ore the addition of 44.6 parts of cllloro-
meth~la~ed copper phthalocyanine (chlorine content 19,9%).
After the mix~ure had been stirred for 1 h~ur, 10 parts o~
GLOQUAT C ( a c~mmercially available quaternary ammonium salt)
were added, followed by 250 parts of xylene. The reaction was
heated to 120C, stirred for 5 hours at 120C and then al]owed
to cool with stirring. 12 parts of 50% aqueous acetic acid
were added, follow~d by 1000 parts of water and the xylene
was azeotroped off by distillation, water being added a~ -- ;
necessary. The solids were filtered off, reslurried in
ethanol, filtered and dried, giving 71.5 parts of a blue r
solid having a ch~orine content of 2.8%.
.''`'.. , ' - .
- ~XAMPLE 2
- 42.5 parts of behenic acid were refluxed in 390 parts of
,: ~
xylene witll 5 par~s of sodium hydroxide dissol~ed in 25 parts of
~- water~ the water being distilled off leaving a suspension of the
'J sodium salt ~f behenic acid in xylene. This was allowred to
~ cool to ~oom temperature before the addition of 2.5 parts Of
., ,.,: ~
- c~tyl trimethyl ammonium bromide and 24.7 parts of chloro-
methylated copper phthalocyanine (chlorine content 17.95%).
: The mixture was heated with stirring at 110-120~C for 8 hours,cooled, the xylene azeotroped off with water, the solids
filtered off, washed with water followed by methanol and dried
: - 8 --
'~ : , ''" , . .. .
1~3631Z
giving 57.5 parts of blue solid, ha~ing a chlorine content
of 1.5%.
EX~ll'),l~, 3
~ 0 parts of lauric acid, 8 parts of sodium hydroxide
dissol~ed in 25 parts of water~ 350 parts of methyl isobutyl
ketone and 150 parts of toluene were refluxed with stirring
until no more water was being boilcd off from the reaction.
The mixture ~as then allowed ~o cool to room temperature before
the addition of 3.6 parts of cetyl trimethyl al~ionium bro~ide
and 30 parts of chloromethylated copper phthalocyanine(chlorine
content 17.9 %). Mle reaction mixture l~as refluxed for 8 hoursO
After cooling 12 parts of 50~ aqueous acetic acid were added
followed by 500 parts o~ water and the solvent was azeotroped off.
The solid was filtered off, slurried in ethanol, flltered, washed
Wit]l water and dri~d~ giving 3~.2 parts of blue solid (chlorine
content 5. 60/o) .
, ~:
EXA~LE 4
By replacing the lauric acid in Example 3 with 45.6 parts
o~ myristic acid~ a similar product can be obtained, with a yield
of 43.3 parts~ and a chlorine content of 1.1%.
.... .
,~,.
, EX~LE 5
~:,
~}
. By replacing the lauric acid of ~xample 3 with 51.2 parts
of palmitic acid, a yield of 49.7 parts of a product having a
chlorine content of o . 7% can be obtailled.
; ,,.:-, '-" :' "' ' ',',,"' .,. '.'; ''~.. '''.,'"'',, "'"'',: ' `' ~'' ' ' " '''
~363~2
EXAMPLE 6
By replacing the lauric acid in Example 3 with 56. 8 parts
of stearic acid, a yield o~ 55.1 parts of a blue solid having
a chlorine content of nil can be obtained.
XA~IPIE 7
36.7 parts of oleic acid, 5.2 parts of sodiwn hydroxide
dissolved in 20 parts of water, and 500 parts of xylene were
refluxed until no more water was being boiled off from -the
i
~eaction. After cooling 2.5 parts of cetyl trimethyl ammonium
bromide and 22.3 parts of chloromethylated copper phthalocyanine
(chlorine content 1g.9%) were added and the reaction heated at
120-130C for 10 hours. After cooling 500 parts of water
~4
- were added followed by 15 parts of 50% acetic acid and the
xylene azeotroped off. The solids were filtered off,slurried
in éthanol~ filtered; washed with water and dried~ gI~ing a
blue solid ( chlorine content 1.8%).
, . j, .
., EXA~'LPLE 8
... .
~; 18.4 parts of undecylenic acid, l: parts of sodium hydroxide
dissolved in 25 parts of water and 300 parts of xylene were
hea~ed at 110-120C until no more water was being boiled off
from the reaction. After cooling to room temperature 1 part
of cetyl brimethyl ammonium bromide and 19.8 parts of chloro-
methylat-ed copper phkhalocyanine ( chlorine content 17.95%) were
added an~ the mixture heated to 110-120C with stirring for
_ 10 _
.
,,, ~ . .
16~8631Z
8 hours. The reaction was cooled to 50C before the addition
of 500 parts of water and the xylene was azeotroped off. The
solids were filtered off, washed with water, slurried in 500
parts of l~arm methanol, filtered, waslIed with water and dried,
giving 24.~ parts of a blue solid, having a chlorine content of
4- 'j/
EX~IPIE 9
45.1 parts of staybelite resin ( a commercially prepared
partially hydrogenated wood rosin with a carboxylic acid group
on the molecule), 7.8 parts of potassi~n hydroxide dissolved
in 20 parts of water and 750 parts of toluene wer- refluxed
~.~"
until no more water was being boiled off frotn the reaction.
After the mixture had cooled to room temperature 2.5 parts
of cetyl trimethyl ammonium bromide and 22.3 parts of chlorometh-
,.",~ .
ylated copper ~hthalocyanine ( chlorine content 19.9%) wereadded and heating continued at 100-110C for 10 hours.
After cooling to room temperature 500 parts of water were added
and the solvent azeotroped off. The s:olid was filtered off,
washed with water, stirred in ethanol, filtered, washed with -
water and dried, giving a blue solid having a chlorine content
o f 1 . 5% .
; ' ;
.
_ 11 _
.
-: .. ., :` . . . : -:;. .: .. . : . . .
1~l!36;~1Z
EX~MPI,E 10
.
14.4 parts of n-octanoic acid, 4 parts of sodium hydroxide
dissolved in 25 parts of water and 500 parts of toluene were
refluxed until no more water was being ~oiled off from the
reaction. 3 parts of cetyl-trimethyl ammonium bromide and
21.1 parts of chloromethylated copper phthalocyanine ( chlorine ;*
content 19.60/~) were then added and the mixture refluxed for
16 hours. Aft:er cooling from the boil, 500 parts of water
were then added and the toluene azeotroped off. The slurry
was drowned into 2000 parts of metllanol, stirred, filtered
and the solid washed with water and dried, giving a blue solid
having a chlorine content of 3.2/S.
I~XAMPLE 11
~ y replacing the n-octanoic acid of Example 10by 17 .9
parts of n-decanoic acid a similar product is obtained , having a
chlorine content of 2. 9/0
EXAMPLE 12
37.2 parts of 12 hydroxy-stearic acid and 5 parts of
sodium hydroxide dissolved ln 25 parts of water were refluxed
in 500 parts of toluene for 6 hours to remove all water
from the reaction. 26.4 parts of chloromethylated copper
phthalocyanine ( of chlorine content 17. 30/o) were added
~ogether with 2.5 parts of cetyl trimethyl ammonium bromlde
and the reactants were refluxed for 8 hours. 500 parts of
water were added and the toluene azeotroped off. The
blue solid was washed with methanol~ followed by water and dried~
~o give ~ product having ~ chlorine content of 7 . 40~o,
_ 12 _
~ . ' : , . ' .; '.
. ' ' ' , ': . . . ' ' ' . ., '.' ' ,, , , :. , , . ~ ' ' ' '
' " ', ' , ~, ' : ' ' '' ' "" , '; , ' ' ~' . " . ' .
312
EXA~I~IE 13
24.7 parts of chloromethyla-ted copper phthalocyaninc,
83.2 parts of a 50% solution of 3-dodecylamino-n-butanoic acid
as its sodium salt ( com-nercially l~lown as Armeen SZ), and 2.5
parts of cetyl trimethyl ammonium bromide were refluxed
in 300 parts of ~ylene to remove all of the water and then
refluxed for a further 4 hours. The xylene was then azeotroped
off with water and the blue product washed with methanol and
water. -
- - . - ,. '
EXAMPLE 14
,
128 parts of crude copper phthalocyanine were
groùnd with 248 parts of anhydrous sodium sulphate, 20
parts of anhydrous sodium acetate and 4 parts of diethyl- - -
aniline to give a salt/pigment mixture in which approximately
650~o of ~he copper phthalocyanine was in the alpha form,
the remainder being in the beta form. The salt/pigment
mixture was refluxed for 5 hours in 1100 parts of isopropanol/
water azeotrope. The slurry w~s then cool~d to 60C and
13.2 parts of the product of ~xample 6 were added, followed
by 20 parts of diethylaniline. The slurry was then stirred
for 15 minutes before the addition of 1500 parts of water
followed by 120 parts of 5N hydrochloric acid. The iso-
propanol/water azeotrope was distilled off and the pigment
filtered, washed with water and dried, giving a blue
phthalocyanine pigment in the beta form.
_ 13 -
~81Ei3~2
EX~MPLE 15
By re~lacing the 13.2 parts of the product of ExaInple 6
wlth 13.2 part~ of tl~e product of Example 7 in the procedure
of E~ample 14 a similar product can be obtaincd.
.; ~ ,
By using the process of Example 14 and replacing the
product of Example 6 by an equivalent amount of any of
the products of Examples 1-5, 8-11 and 13, samples of pigment
may be obtained which, like the productsof Examples 14 and 15
are suitable for use in gravure ink and decorative paint
coating systems wherein they exhibit superior flow and
flocculation resistance when coqnpared with phthalocyanine
pigments prepared in a similar manner but without the
addition of the respective composition of the invention.
EXAMPLE 16
45.25 parts of p-cetyloxybenzoic acid were refluxed
in 500 parts by volume of toluene with 5 parts of sodium
hydroxide dissolved in 25 parts by volume of water, until
no more ~ater was being boiled off from the reaction. 24.7
parts of chloromethylated phthalocyanine ( of chlorine content
17.3%) were then added and the reaction refluxed for 8 hours.
500 parts b~ voiume of water were added and thetoluene
distilled off. The product was filtered off, washed
- with meth~nol~ followed by water, and dried in ~he oven
at 50C, giving 55.8 parts of a blue solid having a chlorine
content of 0. 240~o.
_ 14 -
' ~ ', ,' ~, .:. . ' :''..' .,, . ~ - ' ,' :':' , ',' , . :
- , :: ' ' : : ' ' ~ . : : : ~ :
1~363~2
Ex~lrLE 1 7
500 parts of a mixture containing 160 parts of crude
copper phthalocyanine, 25 parts of anhydrous sodium acetate,
and 310 parts of anhydrous sodi~ sulphate, l~hich had been
ground in the presence of diethylaniline so that the mixture '
contained 70% of the copper phthalocyanine in the alpha form
( the remainder being in the beta form) wer,e refluxed ~ith
stirring for 5 hours in 1650 parts by volume of isoprcpanol/water~
azeotrope. 15.8 parts of the product of Exan~ple 16 ~ere
added with 25 parts by volume of diethylaniline. After 15
minutes 1900 parts by volume of ~rater were added and the
isopropanol/water azeotrope distilled off. The slurry was
then allowed to cool to 60C before the addition of 150 par-ts
of 6N hydrochloric acid. After~a further 30 mins. ~tirring
at 60C the solid product was filtered off, washed free of
sulphate ions with water, and dried at 60C giving a blue
phthalocyanine pigment in the beta form.
EXAMPLE 18
29.0 parts o~ 4(p-dodecylbenzyloxy)-benzoic acid, and
~ parts sodium hydroxide dissolved in approximately 20 parts
of water, were refluxed in 250 parts xylene until all the
water had been azeotroped off. After cooling 15.5 parts of
chloromethylated copper phthalocyanine ( of ch;orine content
12.'8~) were added and the reaction refluxed for 16 hours.
_ 15 -
., . , . ...... ,.,. ,. _.. ,.... ,.. , . ~ ... ~
~86312
Water was then addcd and the xylcne was az~otroped off.
The blue solid was fil~ercd off, washed wit}l alcohol,
followed by water and dried. The product ha~ a
chlorine content of 1, 60/o.
EXA~lPLL 19
t1.4 parts of p~benzyloxybenzoic acid a~d 2 parts
of sodium hydroxide, dissolved in 100 parts of water,
were re~luxed in 250 parts of xylene until all the water
~ad been azeotroped off. 1 part of cetyl-trimethyl
ammonil~ bromide and 10.15 parts of chloromcthylated
copper phthaiocyanine ( of chlorine content 2Q.40/~ ) were
added and the reaction mixture refluxed for 8 hours.
After co,oling 250 parts of water were added and some of
the xylene azeotroped off. The remainder was removed,
during filtration and isolation of the blue solid, by
washing with methanol, The solid had a chlorine content
of 4.150k,
:.
EXA~lPLE 20
.- .
By replacing the benzyloxybenzoic acid of Example 19
with 12.5 parts of p-octyloxy benzoic acid a similar product
was obtained. ~he product had a-chlorine content of 3.2/~.
,
_ 16 -
.: . .
;', . , :.!
3~Z
EXA~J.~ 21
~,
By replacing the bcn~yloxy~enzoic acid of Exalllple 19
with 12.1 parts of hexylo~ybenzoic acid a similar product
was obtained. The product had a chlorine content of
2.1%.
By using the process of Example 14 and replacing
the product of ~xample 6 by an equivalent amount of any
of the prod~cts of Examples 16-21, samples of pign~ent may
be obtained which are suitable for use in gravure ink and
industrial paint coating systems wherein they exhibit
superior-flow and flocculation resistance when compared with
phthalocyanine pigments prepared in a similar manner but
without the addition of the respective pigment composition
of the in~ention.
EXA~LE 22
37.2 parts of cuprous chloride and 5.4 parts of
dimethylgly~xime were added to 900 parts of dry methanol
and the mixture stirred at room ten]perature until a da k
brown complex had formed. 192 parts of 95% pure phthalo~
dinitrile, 18 parts of ammonium chloride and 6 parts of
1,2,4-trichloro-3-phenoxy copper phthalocyanine were
added and stirring continued at room temperature for 1 hour.
17.4 parts o~` sodium metal and 6 parts of p~ridine, dissolved
in 60 parts of dry methanoln are added simultaneously over
1 hour. After a further 1 hour stir at room temperature
. , .
~q~863~2
the mixture was refluxed for 8 hours, coolcd to room
temperature and treated witll 144 parts of 9~% sulphllric
acid for one hour at room temperature followed by 1 hour at
reflux. The suspension was then neutralised with aqueous
sodium hydroxide; stirred for 30 minutes and then treated
with 11 parts oi the product of Example 16 dissolved or
well dispersed in diethylaniline. Stirring at room
temperature was continued for 1 hour followed by the addition
of dilute hydrocllloric acid to adjust the slurry to pHl.
After 15 minutes stirring the.product was filtered of`f`,
washed with l!lethanol and cold dilute hydrochloric acid, and
finally with water before being dried at 50-60C to give a
blue solid which gives a red-shade blue coating in an
industrial allsyd-melamine-formaldehyde paint application
and wnich gives improved flow and flocculation resistance
when compared with the product obtained when the product of
Example 16 is omitted from the process of Example 22.
~ ' . . ' '". '' '', ' ,' " '.' ' ' . '
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