Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
The present invention relates to new, valuable bis-
azomethine metal complex pigments.
Tl~e present invention provides a novel compound of the formula
Zl ~22
N ~ 0 \0 ~ - R tI)
X~ ~X
Y Y
wherein M denotes copper or nickel; R denotes alkyl containing 1 to
4 carbon atoms and phenyl, provided that both Rs are the same; X and
Y denote hydrogen and nitro, provided that both Xs and Ys are the
same or X and Y together form a fused benzene residue; Zl and Z2 denote
hydrogen, nitro, alkyl containing 1 to 4 carbon atoms, alkoxy
containing 1 to 4 carbon atoms, phenoxy and phenylalkyl wherein alkyl
contains 1 to 4 carbon atoms or Zl and Z2 together form a fused
benzene residue or a fused imidazolone residue.
It is well known in the literature that compounds of formula I
where R is hydrogen are of use as pigments.
In U.S.P. 3,132,140 is described the product of formula I when R
is hydrogen, M is nickel, X, Y, Zl and Z2 are hydrogen. This product,
as prepared by the method in U.S.P. 3,132,140, although having
good durability towards light is colouristically a weak, dull yellow
of no commercial value. However in the present invention there are
described products of h;gh tinctorial value and purity of shade with
excellent stability towards heat and light. This unpredictable result
is only achieved if R is alkyl of 1 to 4 carbon atoms or phenyl as
described hereinabove. This substantial improvement in colouristic
. ~
,, 1080~
-- 3 --
properti.es now permits the preparation of products of commercial
interest and value in both paints and plastic8.
The present invention also provides a process for producing
a symmetrical metal complex pigment of formula II comprising
reacting 2 moles of a compound having the formula:
OH
HO II
N
R
wherein R, X and Y have their previ.ous significance wlth one mole
of a 1,2-dia~ine of the formula:
æl Z2
~ III
H2N 2
and the resultant ligand of formula:
' Zl'~5~;~2
,: \ ~
~N N ~ IV
R--N )--OH HO~ N R
~Y
wherein R, X and Y, Zl and Z2 have their previous significance,
which ligand may or may not be isolated by, for example, filtration, is
then metallised to yield products of formula I.
Compounds of formula II may be synthesized by formylation
of the corresponding substituted quinolone using a modification of the
..
. : :
0~31
method of R.F.C. Brown et al. Austral. J. Chem. 7, (1954), 374.
In a furtller, one stage process, the present invention provides
a process for the production of a symmetrical metal complex pigment
comprising rea~ting 2 moles of an aldehyde of formula:
OB
X~fHO
wherein R, X and Y have their previous significance and B is
hydrogen or an alkali metal, especially sodium, with a 1,2-diamine
of formula III, as hereinbefore defined, then metallising
the product.
Examples of compounds which may be used for metallisation
iDclude the acetates, stearates, chlorides, su]phates, nitrates
and phosphates salts of, in particular, nickel and copper.
Specific examples of suitable compounds of formula III for
use in the processes of the present invention are:-
3-formyl-4-hydroxy-1-methyl-2-quinolone
3-formyl-4-hydroxy-1-ethyl-2-quinolone
3-formyl-4-hydroxy-1-n-propyl-2-quinolone
3-formyl-4-hydroxy-1-n-butyl-2-quinolone
3-formyl-4-hydroxy-1-phenyl-2-quinolone and
3-formyl-4-hydroxyl-1-benzyl-2-quinolone
5,6-benzo-4-hydroxy-3-formyl-1-phenyl-2-quinolone
6,7-ben~o-4-hydroxy-3-formyl-1-methyl-2-quinolone
7,8-benzo-4-hydroxy-3-formyl-1-methyl-2-quinolone
6-methyl-4-hydroxy-3-formyl-1-methyl-2-quinolone
6-chloro-4-hydroxy-3-formyl-1-methyl-2-quinolone
as well as the corresponding sodium salts.
,:;
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1080;~31
Of the diamines of formula III, preferred compounds are those
wherein Z] and ~2 may be the same or different and each is hydrogen,
alkyl containing 1 to 4 carbon atoms, alkoxy containing 1 to 4
carbon atoms, phenoxy, phenylalkyl wherein alkyl contains 1 to 4
carbon atoms, nitro or wherein the two radicals Zl and Z2 form a fused
benzene ring or a fused benzimidazole residue.
The following may be mentioned as examples of such preferred
diamines: 1,2-phenylenediamine, 4-chloro-1,2-phenylenediamine, 4,5-
dichloro-1,2-phenylenediamine, 4-methyl-1,2-phenylenediamine, mixtures
of 3- and 4-methyl-1,2-phenylened;amines, 4,5-dimethyl-1,2-phenylene-
diamine, 3,5-dimethyl-1,2-phenylenediamine, 4-methoxy-1,2-phenylene-
diamine, 4,5-dimethoxy-1,2-phenylenediamine, 4-trifluoromethyl-
1,2-phenylenediamine, 4-phenylisopropyl-1,2-phenylenediamine, 1,2-
diaminonaphthalene, 2,3-diaminonaphthalene, 4-phenoxy-1,2-phenylene-
diamine, 4-carboxy-1,2-phenylenediamine, 4-cyano-1,2-phenylenediamine,
4-acetyl-amino-1,2-phenylenediamine, 4-benzoylamino-1,2-phenylene-
diamine, 4-nitro-1,2-phenylenediamine, 4-methoxy-5-chloro-1,2-
phenylenediamine, 4-methyl-S-chloro-1,2-phenylenediamine, 5,6-diamino-
benzimidazol-2-one.
The processes of the present invention may be effected in solution
or in finely-divided suspension, using either water or an organic
solvent as the reaction medium. If an organic solvent is used, examples
of suitable solvents include ethylene glycol, methoxyethanol, glacial
acetic acid, dimethylformamide, o-dichlorobenzene, nitrobenzene and
carbitol. The reactions are conveniently effected at an elevated
temperature, preferably at a temperature between 50 C and the
temperature at which the reaction mixture refluxes. If water is used
then the aldehyde of formula II or V may be reacted with the diamine
of formula III at a pH of 2 to 9 using very efficient agitation
preferably at a temperature between 35 to 95 C. The resultant ligand
of formula I~, which may then be isolated or not, is then metallised
by reacting with a water soluble transition metal salt at a pH
of 4 to 9 in the presence of a suitable buffer salt for which pul-pose
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:
:
1080'~31
-- 6 --
sodium acetate iB particularly suited. The temperature of the reaction
is desirably held at 90 to 1~0C until the reaction i6 complete and
the pigment i~ then isolated by filtration. The colo~lrall~s obtained
are valuable pigments which may be used directly after production,
according to the proces6 o this invention, tha~ is after they have
been filtered off from their reQction mixture and dried. Alternatively
they may fir6t be processed using known wet or dry conditioning
techniques such as gr;nding either alone or in the presence of a
water soluble salt or other medium which can sub6equen~1y be removed
for instance by washing.
Such grinding may be optionally followed by a solvent ~restment.
A further method of proce6sing the pigments of the invention
involves the pressure treatment of an aq~eous slurry of the pigment
produced by any of the above procedures in an autoclave at
temperatures from 50 to 200C. A still further method of processing
the colourant~ entails the solvent treatment of the pigment produced
by any of the above procedures. Suitable 601vents include ethanol,
methanol, xylene, orthodichlorobenzene, timethylformamide and N-methyl-
pyrrolidone, the conditioning generally being carried out at the
boiling point of the solvent.
Because of their economical and simple mode of preparation,
combined with their excellent pigmentary properties, the compounds of
formula I are valuable as pigments in a wide variety of organic media,
for example, surface coatings, inks and polymers, paints and plastics.
The compounds of formula I are valuable pigments which in a finely
d;vided form can be used for pigmenting high molecular weight organic
materials, for example, cellulose ethers and cellulose esters such as
ethylcellulose, cellulose acetate, cellulose butyrate; natural resins or
~ynthetic re~ins, such as polymerisation resins or condensation
resins, for example aminoplasts, especially urea-formaldehyde and mela-
mineformaldehyde resins, alkyd resins, phenoplasts, polycarbona~es
t
1080Z3~
polyesters, polyamides or polyurethanes, polyolefines, polystyrene,
polyacrylonitrile, polyacrylic acid ester, rubber, casein, silicones
and silicone resins, and acrylonitrile/butadiene/styrene terpolymers,
individually or as mixtures.
The proportion of the pigment of formula I in the compositions
of the invention is preferably from 0.1 % to 10 % by weight
based on the weight of the organic material.
For these purposes it is immaterial whether the high molecular
weight compounds mentioned are in the form of plastic masses or melts
or in the form of spinning solutions, lacquers, paints or printing
inks. Depending on the end use, it may be advantageous to use the
new pigments as toners or in the form or preparations.
In addition to the pure pigment, the preparations can, for
example, also contain natural resins, such as abietic acid or its
esters, ethyluellulose, cellulose acetobutyrate, alkaline earth metal
salts of higher fatty acids, fatty amines, such as stearylamine or
rosin amine, vinyl chloride/vinyl acetate copolymers, poly-
acrylonitrile or polyterpene resins or water-soluble dyestuffs, for
example dyeYtuff sulphonic acids or their alkaline earth metal salts.
The pigments of formula I are strong in colour, clean and have
excellent light- and solvent fastness properties, combined with very
high thermal stability.
The following Examples further illustrate the present invention.
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10~ 31
Example 1
PART A. Preparation of ]i~nd
A mixture of 3-Eormyl-4-hydroxy-1-methyl-2-quinolone (6.0 g)
and 3,4-diaminonitroben~ene (2.3 g) is stirred and refluxed in ethanol
(200 ml) for 4 hours. When cool, the mix~ure is filtered, washed with
ethanol and dried at 50 to 60 C to afford the product as a yellow
solid (7.6 g) [96.8 %] of mp 265-7 C.
Analysis: C H N
Calculated for C28H21N506: 64.24 4.02 13.38
Found : 63.15 4.31 14.13
PART B. Preparation of Nickel complex
A solution of Nickel acetate [Ni(OCOCH3)2.4H20] (3.5 g) in
methyl cellosolve (50 ml) is added to a stirred suspension of the
yellow product of PART A (7.3 g) in methyl cellosolve (S0 ml) and
the mixture then heated to reflux for 3 hours. It is filtered hot,
washed with hot methyl cellosolve then ethanol and dried at 50 to
60 C to afford a red shade yellow pigment (7.5 g) 189.3 %]
which does not melt below 360 C.
Analysis C H N Ni
28 19 56 H20: 56.22 3.51 11.71 9.8
Found : 55.84 3.33 11.80 9.8
By a process similar to that described in Rxample l(A),
the carbonyl and amine components of Examples 2 to 20 (Table I)
were reacted to give the corresponding ligands.
By a process similar to that described in Example l(B).
copper and nickel complexes were prepared using the ligands obtained
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as shown in Table T; the copper complexes were prepared by substituting
copper acetate for nickel acetate.
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Example 21
PART A PRF.PARATION OF !.IGAND
Conc. Ilydrochloric acid (5.2 ml) is added to an efficiently stirred
mixture of the sodium salt of 3-formyl-4-hydroxy-1-methyl-2-quinolone
(9.0 g) and o-phenylene diamine (2.l( g) in water (300 ml) which is
then b~ated by steam inj~Lion to ~ 95 C. After 40 minutes the yellow
solid i9 filtered hot and washed with hot water (1000 ml). A weighed
sample of thefilter-cake paste is dried at 50 to 60 C to afford the
ligand as a yellow powder.
Analysis: C W N
Calculated for C26H22N404 : 70.29 4.40 11.72
Found : 69.87 4.82 11.47
PART B PRl~PARATION OF NICKEL COMPLEX
With tlle water content thus ascertained, the ligand is used in the
metallisation stage in the form of its filter-cake paste. A slurry
of the paste of Part A in water (400 ml) is efficiently stirred and
heated by steam injection to ~ 95 C. Sodium acetate trihydrate
(8.55 g) is added followed by nickel nitrate monohydrate (5.8 g).
After 3 hours the mixture is filtered hot, washed with hot water
(1500 ml) and dried at 50 to 60 C to afford a red shade yellow pigment
(8.5 g), (8g% yield) of mp not less than 360~ C.
Analysis: C H N Ni
28 20 4 4 2 60.79 3.98 10.13 10.62
Found : 60.61 3.70 10.09 10.40
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1080'~31
- 14 -
Example 22
PART A. Preparation of ligand
-
A mixture of 3-formyl-4-hydroxy-1-methyl-2-quinolone (18.3 g)
and o-phenylene diamine (4.7 g) is stirred and refluxed in methyl-
cellosolve (500 ml) for 4 hours. ~hen cool, the mixture is filtered,
washed with ethanol and dried at 50 ~o 60 C to afford the product as
a yel]ow solid (21.3 g) [99 %]
Analysis C H N
Calculated for C28H22N404 : 70.29 4.60 11.72
Found : 70.07 4.59 11.58
PART B. Preparation of nickel complex
A slurry of the yellow product of PART A (10.0 g) in water (600 ml)
is efficiently stirred and heated by steam injection to ~ 95 C
when a solution of nickel acetate [Ni(OCOCH3)2.4H20] (6.5 g) in water
(250 ml) is added. After 4 hours the mixture i8 filtered hot, washed
with hot water (1500 ml) and dried at 50 to 60 C to afford a red
shade yellow pigment (10.0 g) [95 ~].
Analysis C H N Ni
Calculated f 28 20 4 4 2 60.79 3.98 10.13 10.62
Found : 61.11 3.76 10.19 10.70
, :, '
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-` 1080,'~:31
-- 15 --
Examp1e 23
A mixture of 3-fonmyl-4-hydroxy-1-methyl-2-quinolone (10.15 g)
and o-phenylenediamine (2.7 g) i8 efficiently stirred in water
(600 ml) containing concentrated hydrochlori-~ acid (2.0 ml), for 1
hour. Sodium acetate [NaOAc.3H20] (3.4 g) is added to the yellow
suspension which is II,~u heated to ~95 C by steam ;njection and
after I 1/2 hours Nick~l acetate [Ni(OAc)2.4H20] is added. After
a further 2 hours the mixture is filtered hot, washed with hot water
(2000 ml) and dried at 50 to 60 C to afford a red shade yellow
pigment (12.0 g) (90 % yield).
Analysig C H N Ni
Calculated for C28H22NiN404 2 60.79 3.98 10.13 10.62
Found : 60.84 3.77 9.91 9.86
Example 24
Conc. Hydrochloric acid (5.2 ml) is added to an efficiently
stirred mixture of the sodium salt of 3-formyl-4-hydroxy-1-methyl-
2-quinolone (6.75 g), o-phenylenediamine (1.62 g) and Texafor B9
(a polyoxyethylene ether condensate) (0.4 g) in water (400 ml) which
is then heated by steam iniection to> 95 C . After 1 hour sodium
acetate[NaOAc.3H20] (8.55 g) is added followed by Nickel Nitrate
[Ni(N03)2.11120] (4.8 g) in water (25 ml). After a further 3 1/2 hours
the mixture is filtered hot, washed with water (2000 ml) and dried
at 50 to 60 C to afford a red shade yellow pigment (7.6 g)
(95 % yield).
Analysis C H N Ni
Calculated fo 28 20 4 4 2 60.79 3.98 10.13 10.62
Found : 61.98 4.06 9.96 10.1
F~
.
. .
: -
10~ 31
16 -
Example 25
60 parts of the product of Example 4 after comminution by
salt-grinding were ball milled with 136 parts of a solution of an
unmodified butylated melamine/formaldehyde re~in in n-butanol and
452 parts of xy]ol.
350 parts of a solu~ion of a hydroxy acrylic resin, a 1:1
mixture of xylene and n-butanol, were added gradually and ball milling
cootinued. The resulting mixture had a pigment to binder ratio of
1:5; this was adjusted to 1:10 by the addition of more resin solution
and the paint was thinned to the required viscosity for spraying.
Aluminium panels were sprayed and then stoved at 120 C for 30 minutes.
The resulting paint films had excellent fastness to light, heat and
acids; for example, spotting the panels with 0.1 N hydrochloric acid
left no discolouration after drying, and stoving the panels at
180 C for 30 minute-; had practically no detectable effect on the
colour. The resulting coated panels were a very attractive transparent
yel]ow colour.
When the stainer (with a l:S pigment to binder ratio)
wbose preparation is described above was combined with a suitable
paste of finely powdered aluminium to give a pigment to aluminium ratio
of 75:25 and the mixture was again thinned to a suitable viscosity for
spraying, very attractive greenish yellow metallic coatings were
obtained which also had excellent fastness properties.
In the same way by replacing the product of Example 4 with
the salt-ground products of any of the Examples 1 to 3 and 5 to 20
there could be obtained paint films having varying shades of
yellow to red. All were, however, characterised by having the same
excellent fastness properties.
~ ,.
' :
-- 1080Z31
- 17 -
Example 26
3-Formyl-4-hydroxy-1-methyl-2-(luinolone (22.8 g), ortho-
phenylene diamine (6.1 g), water (3.4 1) and concentrated hydro-
chloric acid (1 ml) were stirred together for 10 minutes at room
tempera~ure, using a high shear stirrer, then at 95 C for 2 hours.
Staybelite resin (2.8 g) dissolved in 50 % aqueous potassium
hydroxide (2 ml) was added followed by hydrated sodium acetate (17.2 g).
Nickel nitrate hydrate (16.8 g) was then added and the mixture heated
with high speed stirring at 95 to 98 C for 3 hours. The final
pH was 4.3. The mixture was cooled to 60 C and filtered, the solid
washed thoroughly with water and dried at 60 C in an air-circulating
oven to obtain 29.8 g resinated pigment having a nickel content of
10.66 %.
Example 27
The pigment obtained in Example 26 was incorporated at 0.1 %
into high density polyethylene by two-roll milling for 8 minutes.
The hides produced were compression moulded at 170 C for 5 minutes.
The attractive red-shade yellow plastic so produced showed, both
visually and microscopically, that the pigmeuL had readily dispersed
into the plastic medium.
Example 28
The pigment obtained in Example 26, was invorporated at 0.1 %
together with titanium dioxide at 0.5 %, into 1100 g of high density
polyethylene by two-roll milling. The hides produced were granulated
and tested for heat stability using an Injection Moulding machine.
The pigmented plastic showed no sign of degradation when held for
5 minute periods at any temperature up to 375 C.
