Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
3 12760 +
1:1 Nickel complexes of isoindolinazines, process for
their preparation and use
-
The invention relates to 1:1 nickel complexes of
isoindolinazines of the formula
N--NaC~ qEI
ao/ ~ \ ~ 1)
NC/~R ' .
in which Ri is a cyano, carbamoyl, benzylcarbamoyl or
thiocarbamoyl group, an alkylcarbamoyl or alkylthiocar-
bamoyl group having 2 - 22 C, an alkoxyalkylcarbamoyl
group having 4 - 23 C or a group of the formula
C-N~ 2) or _. ~ ~ 3)
in which Z is an oxygen or sulfur atom, V is an oxygen
or sulfur atom or the radical -NH-, X1 is an H, chlorine
or bromine atom, a nitro, trifluoromethyl, carbamoyl or
sulfamoyl group, a.n alkyl, alkoxy or alkylsulfamoyl
group having 1 - 22 C, an alkanoylamino or alkylcarbamoyl
group having 2 - 2.2 C, or a phenoxy, phenylcarbamoyl,
.
55~z
benzoylamino or phenylsulfamoyl group which is unsubstitu-
ted or substituted by chlorine or bromine atoms or methyl
groups, and X2 is an H, chlorine or bromine atom or an alkyl
or alkoxy group having l - 4 C, R2 is an H or chlorine atom
or a methoxycarbonyl group, Rl is a H or chlorine atom, a
sulfamoyl group, a phenoxy, phenylmercapto, benzoylamino or
phenylsulfamoyl group which is unsubstituted or substituted
. by halogen, atoms or alkyl or alkoxy groups having l - 22 C,
or an alkanoylamino group having 2 - 22 C, and, in the case
where Rl and R2 are H or chlorine atoms, methyl groups or
alkoxy groups having l - 4 C, R' is an alkylcarbamoyl or
alkylthiocarbamoyl group having 7-22 C, an alkoxyalkylcarb-
amoyl group having 7 - 23 C or a radical of the formula 2)
in which Xl is an alkyl, alkoxy, alkylsulfamoyl or alkanoyl-
amino radical having 6 - 22 C or an alkylcarbamoyl radical
having 7 - 23 C.
Nickel complexes of the formula l) in which Rl is
a radical of the formula
-C-NH~ 1 2a)
. O 2
are very fast pigments with a particularly pure colour
shade and are therefore preferred. Xl and X2 are as
defined above.
Nickel complexes of the ~ormula l) in which Rl is
an alkylcarbamoyl or alkoxyal~ylcarbamoyl group are distl.n-
guished by being particularly easlly accessible.
Preferred Ni complexes are those of the formula
NC CONHQ
.... , .. ~
'
:~
'.
., '
l~S5iZZ
in which Q is an alkyl or alkoxyalkyl group having 8 - 22 C
or a group of the formula
. ~ ~ 3
in which Y3 is an alkoxy, alkylsulfamoyl or alkanoylamino
group having 8-22 C.
The formulae 1) and 4) represent only one of the
possible isomeric or tautomeric forms.
The nickel complexes according to the invention
are obtained by
a) treating an azine of the formula 1) with nickel donors
or
b) heating a hydrazone of the formula
H 2 N - N =
HO ~N \. ~
R2
in which Rl and R2 are as defined, with an isoindolinone of
the formula
.~ ~./ \
! 11 /NH 6)
~'b
NC R'
in which R' is as defined, in the presence of nickel donors,
ln a polar organic solvent.
The azines of the formula 1) are obtained, for
example, by the process described ln British Patent Speci-
flcation 1,467,595, wherein a hydrazone of the formula 5)
ls condensed with an imino-isoindoline of the formula
. ~
:
..
lZZ
-- 4 --
.
. I!
.~ \./
!~ ,1!, jN~ 7
-
in which R' is as defined above.
The imino-isoindolines of the formula 7) are in
turn obtained by condensing l-amino-3-imino-isoindolenine
with the acetonitrile of the formula NCCH2R', in which R'
is as defined. Examples are the acetonitriles men-
tioned on page 7 of British Patent Specification 1,467,595
and also cyanoacetic acid hexylamide, 2-ethylhexylamide,
2-ethylhexyloxypropylamide, dodecylamide or stearylamide,
cyanoacetic acid octylthioamide, cyanoace-tic acid p-dodecyl-
phenylamide, cyanoacetic acid p-octyloxy-phenylamide,
cyanoacetic acid m-octylsulfamoyl-phenylamide, cyanoacetic
acid p-stearylcarbamoyl-phenylamide, cyanoacetic acid p-
stearoylami~o-phenylamide or dodecylsulfamoyl-acetonitrile.
However, the azines of the formula 1) can also be
obtained by condensing an acetyl compound of the formula 9)
with a hydrazonoisoindoline of the formula 8)
N-N~72
i ~ 8)
~-'b
N~ ~'
in which R' is as defined above. The compounds of
the formula 8) required for -this prupose are obtained by
reacting imino-isoindolines of the formula 7) with
hydrazine hydrate.
1: l5512Z
-- 5 --
The hydrazones of the formula 5) are obtained by
the known process of condensing the quinoline of the
formula
: . OH
C~3Co\.~
! '! ! 9)
HO~ ~ \-~
in which R1 and R2 are as defined, with hydrazine hydrate.
Examples are the following quinolines: 2,4-dihy-
droxy-3-acetyl-7-carbomethoxy-quinoline, 2,4-dihydroxy-3-
acetyl-7-carbamoyl-quinoline, 2,4-dihydroxy-3-acetyl-7-
methylcarbamoyl-quinoline, 2,4-dihydroxy_3-acetyl-6- or
-7-phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6-phenoxy-
8-chloroquinoline, 2,4-dihydroxy-3-acetyl-6-p-chloro-
phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6-p-methyl-
phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6-p-methoxy-
phenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6- or -7-benzoyl-
amino-quinoline, 2,4-dihydroxy-3-acetyl-7-phenylcarbamoyl-
quinoline~ 2,4-dihydroxy-3-acetyl-6- or -7-phenylsulfamoyl-
quinoline, 2,4-dihydroxy-3-acetyl-6-methyl-7-phenylsul-
famoyl-quinoline, 2,4-dihydroxy-3-acetyl-6-methyl-7-benzo~-
amino-quinoline, 2,4-dihydroxy-3-acetyl-6-methoxy-7-ben-
zoylamino-quinoline, 2,4-dihydroxy-3-acetyl-6-p-chloro-
benzoylamino-quinoline~ 2,4-dihydroxy-3-acetyl-6-p-methyl-
benzoyla~ino-quinoline, 2,4-dihydroxy-3-acetyl-6-p-
methoxybenzoylamino-quinoline, 2,4-dihydroxy-3-acetyl-6-
or -7-acetylamino-quinoline, Z,4-dlhydroxy-3-acetyl-6- or
-7-stearoylamino-quinoline, 2,4-dihydroxy-3-acetyl-6-(2'-
ethyl-hexanoyl)-amino-quinoline, 2,4-dihydroxy-3-acetyl-6-
or -7-p-toluenesulfonylamino-quinoline, 2,4-dihydroxy-3-
acetyl-6- or -7-nitro-quinoline, 2,4-dihydroxy-3-acetyl-6-
p-dodecylphenoxy-quinoline, 2,4-dihydroxy-3-acetyl-6- or
-7-phenylthio-quinoline, 2,4-dihydroxy-3-acetyl-6-sulfamoyl-
quinoline, 2,4-dihydroxy-3-acetyl-6-methylsulfamoyl-quin-
oline, 2,4-dihydroxy-3-acetyl-6-phenylsulfamoyl-quinoline,
2,4-dihydroxy-3-acetyl-7-stearylcarbamoyl-quinoline,
, . . . .
- . ., -
- - .
1~L55i2Z
-- 6 --
2,4-dihydroxy-3-acetyl-7-(2'-ethylhexyl)-carbamoyl-
quinoline and 2,4-dihydroxy-3-acetyl-7-phenoxycarbonyl-
quinoline.
The nickel donors used are preferably nickel
formates, acetates or stearates. The reactions take
place in a polar solvent, in particular one of a hydro-
philic nature, for example an amide, such as dimethyl-
formamide, formamide, dimethylacetamide or N-methyl-
pyrrolidone, or also dimethyl sulfoxide, acetonitrile or
an alcohol, for example ethylcellosolve. It is also
possible to use a mixture of polar solvents.
m e reaction temperature is advantageously between
100 and 200C.
m e metal complex obtained is isolated in the
customary manner by filtration. The material on the
suction filter is washed thoroughly with solvent. It is
obtained in good yield and purity and can be used without
further purification, in finely divided form, for colour-
ing high-molecular organic material, for example cellulose
ethers and esters, such as ethylcellulose, acetylcellulose
and nitrocellulose, polyamides, polyurethanes or polyesters,
and natural resins or synthetic resins, for example amino-
plasts, in particular urea/formaldehyde and melamine/
formaldehyde resins, alkyd resins, phenoplasts, polycarbon-
ates, polyolefins, such as polystyrene, polyvinyl chloride,
polyethylene, polypropylene, polyacrylonitrile and poly-
acrylic acid esters, thermoplastic or curable acrylic
resins, rubber, casein, silicone and silicone resins,
individually or in mi~tures, The high-molecular com-
pounds mentioned can be in the form of plastic masses or
melts or in the form of spinning solutions, surface coat-
ings or printing inks. Depending on the intended use,
it proves advantageous to use the novel pigments as
toners or in the form of preparations.
The pigment can be employed in the form in which
it is obtained in the synthesis, or in a lightly ground
form, in which case it produces opaque final colourations.
.
-- --
: ;' ' ~ . ,
1~S~l2Z
However, it can also be subjected tomoreintensive grinding,
in which case transparent final colourations, for example
intensely coloured metallic-effect coatings, are obtained.
Pastes of the pigments in surface coatings are
distinguished by favourable flow properties.
The colourations obtained, for example in plastics,
fibres and surface coatings, are distinguished by
colour intensity, high purity of colour shade, good dis-
persion of the pigment and good fastness to overcoating,
migration, heat, light and weather, and also by a good
gloss.
Those pigments which possess an alkyl radical
having 6 or more C atoms in the radicals R' or R2 of the
formula 1) have a particularly high tinctorial strength
and easy dispersibility, especially in plastics. In
addition, final colourations of these pigments already
have an unexpectedly high transpar~ncy in the crude state
in plastics.
In the following examples, percentages are by
weight and degrees a~e degrees centigrade. In each case,
only one of the possible isomeric and tautomeric forms is
indicated.
Example 1: A suspension of 24.8 g (0,09 mol) of the
hydrazone of 3-acetyl-7-carbomethoxy-2,4-dihydroxyquinol-
ine and 23.6 g (0.0945 mol) of nickel acetate tetrahydrate
in 1,400 ml of N-methylpyrrolidone is warmed to 60 and
treated with 26 g (0.09 mol) of 1-(cyano-N-phenylcarba-
moylmethylene)-isoindolin-3-one, The mixture ls heated
to 150 in the course of one hour and stirred for 3 hours
at this temperature. The product precipitates out in
the form of orange needles. It is filtered off at 100,
washed thoroughly with N-methylpyrrolidone, methanol and
acetone and dried at 80 in vacuo. ~ weight of 38.1 g
of the metal co~plex of the composition C30H20N6NiO5 is
obtained, which still contains 2% of water.
,
.
' : ' , . ~
::
llSS12Z
-- 8 --
The microanalYsis:
C H N Ni
% calculated 58.54 3.50 13.65 9.45
% found 58.4 3.6 14.0 9.79
confirms the formula:
oa c~3
COOC ~ NC CON~
Only one of the possible tautomeric formulae has been
considered.
, ,
Exampl~ _51: Equally valuable pigments;are obtained
in an analogous procedure by condensing a hydrazone of
the formula
o~ j 3
- ~H2
~-/ ~ ~0~ ~
in which R1 and R2 are as defined in columns 2 and 3 of
Table 1 below, with an isoindolinone of the fo~mula
o
NC~ ~CONH-~
in which X1 and X2 are as defined in columns 4 and 5, in
the presence of nickel acetate. When finely dispersed
in plastics, sheets and surface coatings, the 1:1 nickel
complexes produce very brilliant and fast final colour-
ations, the colour shade of which is represented in
column 5.
..
. .
: ' ~ . ' . ' ' , ~
' :
.
'
1:l551ZZ
_ g _
Table 1
.
ample¦RI l R2 xl ¦ shade .
2 H -COOCH3 2-Cl H orange
3 H do 3-Cl a orange-red
4 H do 4-Cl H ditto
H do 2-Methyl H ditto
6 H do 3-~ethyl H ditto
7 H to 4-~ethyl H red
8 H do 2-MethoxyH red
9 H do 4-OCX3 . H orange-red
H to 4-Phenylazo H red
11 H do 4-Benzoylamino H . red
12 H do 4-Car~amoyl H red
13 a do 3-CF3 H orange
14 H to 4-N02 H ditto .
15. H do 4-Phenoxy H red
16 H do 2-Cl 4-Cl orange
17 H do 2-Cl 5-Cl ~ ditto
18 H: do 3-Cl 4-Cl ditto
19 H do 3-Methyl 4-Methyl orange-red
H do do 5-~Iethyl red
21 H -COOCH3 3-Cl 4-C~3 orange
22 H to 2-~ethoxy 5-OCH3 orange-red
23 H to 4-Sulfamoyl H r~d
24 H do 4-Carbamoyl 3-Cl orange-red
8 to 4-Dimethyl- H ditto
maleinimido
26 H do 4-p-Methoxy- 2 ~ s-di-oca3 red
phenoxy
27 H do 4-Phthal- H orange-red
imido
28 H to 4-o-Methyl- 2-CH3 ditto
. :. _ phenylazo
,
:.
-''
,. . .. .
~15512
_ 10 -
Table l
= Rl R2 ~ --- ~ -- Colour
No. _ . _ . .
29 H -COOCH 4-p-Aceeyl- a orange-red
3 aminophenyl-
carbamoyl
H do 2-Cl S-CF3 ditto
31 yl~amino H 2-Cl H orange-red
32 do H 3-Cl H red
33 do H 4-Cl H red
34 do H 4-oCH3 H red
do a 4-Carbamoyl H red
36 do H 3-CF3 H orange-red
37 do H 4-Acetyl- H red
amino
38 do H 4-CH3 H red
39 H -COOCH3 3-CF3 4-Cl red
H do 3-CF3 6-Cl red
41 Phenoxy H H H red
42 do H 2-Cl H orange-red
43 do H 3-Cl a ditto
44 do H 4-Cl H red
do 3-CF3 ~1 orange-red
46 do 4-CH3 H red
47 p-Meth- 2-Cl H red
phenoxy
48 do 3-Cl H red
49 do 4-Cl H red
do 3-CF3 H red
51 do amino H red
~.. . . . . _
11~5~22
Example 52: 1.52 g (0.007 mol) of 2,4-dihydroxy-3-
acetylquinoline-hydrazone and 1.84 g (0.0074 mol) of
nickel acetate tetrahydrate are warmed to 60 in 80 ml of
N-methylpyrrolidone. The brown suspension is treated
with 4.0 g (0.007 mol) of 1-(cyano-N-p-stearoylamino-
phenyl-carbamoylmethylene)-isoindolin-3-one, heated to
155-160 and stirred for 4 hours. During this process,
the product precipitates out as red needles. It is isol-
ated by filtration at 100, washed with dimethylformamide,
methanol and acetone and dried at 80 in vacuo. 2.8 g
of the metal complex of the formula
I 1 3
i.l/~i ' , .
~ \CON~ ~COC17~35
are obtained.
Microanalysis:
C H N Ni
% calculated 66.83 6.46 11.86 7.10
% found ~ 66.8 6.6 11.6 6.83
The product colours surface-coatings, sheets and
plastics in strong bluish red shades with excellent fast-
ness to light, weather, heat and migration.
Examples 53-64: Equally valuable pigments are obtained
starting from a hydrazone of the formula
OH CH3
~ 2
R ~ ~t~ ~ \OH
in which R1 to R3 are as defined in columns 2-4 of Table 2,
and an isoindolinone of the formula
.,
1~55~2
- 12 -
.~-\./-\
11 NH
.~ \./
N~ CONH-Q
in which Q is as defined in column 5, following an analo-
gous procedure to that of Example 52. The colour shade
of final colourations in PVC is represented in column 6.
1Y ~5~ZZ
Table 2
~ R3 _ Cohouder ¦
,
53 H H H -~CH2) l7Ca3 orange~ed
54 H H H 2 t 2 ;)(CX2)3C~3 orang~red
Cl H Cl -(CX2)17CH3 orange
56 H COOCH3 ~ -(CH2)17CH3 orange
;7 CH3 H H ~ Hco(cH2)l6cH3 reldiSh
8 ~:1 a C1 ditto ditto
9 a COOCH3 H ditto ditto
¦;Q ¦H ~ --(CIIz 11C~I3 ~ed
~1 H El EI \ , / 8al7 red
. So2Na(cH2)7cH3
3 H H H --~ C0OC H red
64 H H H \ /--CONHC18H37 ~ed
.~
i~5~1Z2
- 14 -
Example 65: 2.75 g (0.01 mol) of the hydrazone of 3-
acetyl- 7-carbomethoxy-2,4-dihydroxyquinoline and 2.6 g
of nickel acetate tetrahydrate (0.0105 mol) are suspended
in 60 ml of N-methylpyrrolidone and the suspension is
warmed to 60. 3.03 g (0.01 mol) of 1-(cyano-N-benzyl-
carbamoyl-methylene)-isoindolin-3-one are added to the
brown suspension. The mixture is warmed to 155 and
stirred for 3 hours. After cooling to 100, it is
filtered and the material on the filter is washed with
N-methylpyrrolidone and methanol. By drying at 80
in vacuo, 2.7 g of a red pigment of the composition
C31H22N6Ni5 are obtained.
Microanalysis:
C H N Ni
% calculated 60.32 3.59 13.62 9.51
% found 59 9 3.6 13.8 9.50
In PVC sheets and stoving lacquers, a sample of the pig-
ment converted into a fine form by grinding with salt
produces intense, brilliant orange final colourations
with very good fastness to migration, light and weather.
Exanrple 66: An equally valuabIe pigment is obtained from
(cyano-N-methylcarbamoylmethylene)-isoindolin-3-one,
following the procedure indicated in Example 65.
Example 67: 25 parts of the pigment prepared according
to Example 1, 100 parts of finely ground sodi~m chloride
and 30 parts of diacetone-alcohol are initially intro-
duced into a laboratory kneader with a capacity of 250
parts by volume. The mixture ls kneaded for 5 hours,
with cooling, and then inl;roduced into 4,000 parts by
volume of water. The sodium chloride and diacetone-
alcohol dissolve and the pigment precipitates out. The
suspension is filtered and the material on the suction
filter is washed thoroughly with water and dried in a
vacuum drying cabinet at 80.
Example 68: 56.5 g (0.5 mol) of ethyl cyanoacetate and
64.6 g (0.5 mol) of 2-ethylhexylamine are stirred for
l hour at 130-140 and the ethanol Iiberated is distilled
., : ~ ' ,'~ .
~L~lr55~ 2Z
- 15 ~
off. 61.6 g of the acid amide of the following
formula:
2 2IH(CH2)3CH3
C2 5
' CllH20N2
are obtained from the reaction mixture by distillation
at 130/0.1 mm Hg.
calcuiated 67.3 ~0 C 10.3 % H 14.3 % N
found 67.~ % C 10.4 % H 14.1 % N
19.6 g (0.1 mol) of this acid amide, 18.2 g (0.1 mol)
of 1-imino-isoindolin-3-one hydrochloride and 11.1 g
(0.135 mol) of sodium aceta-te are stirred in 100 ml of
ethylcellosolve for 4 hours at 110. This suspension
is left to cool, with stirring, and diluted with 100 ml
of isopropyl alcohol. By filtration, washing with iso-
propyl alcohol and water and drying, 19.5 g of a product
melting at 121 to 122 are obtained, the microanalysis of
which agrees with the methine-isoindolinone of the follow-
ing formula:
o
, jNH 19 23 3 2
NC c0NHCH2CH(CH2)3CH3
C2H5
calculated 70.1 % C 7.1 % H 12.9 % N
found 69.7 % C 7.1 % H 13.3 % N
1.52 g (0.007 mol) of the hydrazone obtained by reacting
3-acetyl-2,4-dihydroxy-quinoline and hydrazine hydrate
in alcohol, and 1 84 g (0.00735 mol) of nickel acetate
tetrahydrate are stirred in 60 ml of N-methylpyrrolidone
for 1/2 hour at 60. After the addition of 2.28 g
(0.007 mol) of the above methine-isoindolinone, the
.. .
~5S~Z2
- 16 ~
mixture is heated to 150 to 155 and stirred for 3 hours.
The orange-coloured suspension is cooled to 70, diluted
with 50 ml of methanol and left to cool, with stirring.
The product is filtered off, washed with methanol and
dried. Weight: 2.0 g. The product is the compound
of the following formula or of a tautomeric formula:
OH CH3
N~ CONHCH2CH(CH2)3cH3
2 5
C30H30N6Ni3
calculated 62.0 % C 5.2 % H 14.5 % N 10.1 ~ Ni
found 62.0 % C 5.4 % H 14.7 % N 9.9 % Ni
In PVC sheets and surface coatings, the product produces
strong orange final colourations with very good fastness
properties.
Example 69: 1.52 g (0.007 mol) of the hydrazone of
3-acetyl-2,4-dihydroxyquinoline and 1.84 g (0.00735 mol)
of nickel acetate tetrahydrate are stirred in 60 ml of
N-methylpyrrolidone for 1/2 hour at 60. After the
addition of 2.93 g (0.007 mol) of 1-(cyano-N-p-n-octyl-
oxyphenylcarbamoyl-methylene)-isoindolin-3-one, the
mixture is heated and stirred for 3 hours at 150 to 155.
The product of the following formula (only one of the
possible tautomeric forms has been considered) precipi-
tates out as red needles. It is filtered off at 100,
washed with dimethylformamide and methanol and dried at
80 in vacuo. Weight: 2.6 g.
l~S5 ,~X
- 17 ~
OH C~3
O ~.~/ ; 36 34N6Nio4
~-~ NC/ CONH--\ /- C8H17 (n)
calculated 64.2 ~ C 5.1 % H 12.5 % N 8.7 % Ni
found 64.6 % C 5.4 % H 12.7 % N 8.6 % Ni
When finely dispersed, the product colours plastics and
surface coatings in strong, pure bluish red shades with
excellent fastness to migration and light.
Ex~es70-92: Equally valuable pigments are obtained,
following an analogous procedure, by reacting a hydrazone
of the formula
OH CH3
R2 T '~ OH
R3
in which R1 to R3 are as defined in columns 2 to 4 of
Table 3, in the presence of a nickel salt, with an iso-
indolinone of the formula
.~ \./
! I!
NC/ CON~-Q
in which Q is as defined in column 5. The colour shade
of final colourations in polyvinyl chloride is indicated
in column 6.
~55~2Z
Table 3
Ex- _ _ 2 R ¦ Q Colour
ample 3 ! shade
H -COOCH3 H -CH2CHtCH2)3CH3 orange
C2H5
71 H H H -(CH2)30cH2 Cll(CH2) 3 orange
72 H -COOCH3 H ditto orange
73 H -COOCH3 H \ ~ C8Hl7(n) red
74 Cl H Cl \ / red
. 2 8 17 .
H -COOCH3 a ditto orange
76 H H H ~~ COCH(CH2)3CH~ red
C2H5
77 H -COOCX3 H dit~o red
78 -~ HCO--~ ~- H H H orange
I ~
79 -NHCO--~ ~- H H -CH2CH(CE12)3CH3 orange
. C2H5
ditto H H -(CH2)17CH3 orange
81 ditto H . H -(cH2)3ocH2-cH(cH2)3cH3 orarge
. . . _ _. . . __ _ C2H5 .. ___
11~5~ zz
- 19 _
(continuation)
_ _ . .. ~
~pi~ Rl R2 --R3-- Colour
No shade
. . __ ~_ .. .. ... ... _
82 H -COOCH3 H H range
83 -NHCOCH3~ H H H range .
84 -NHCOCH3 I H 2)17 3 range
85 -NHCOCH~ H H ~ .. red
86 -NHCOC13 H H ~~ CH - red
87 -S2NH2 H ~ H orange
88 -52N82 H H Cl range
89 -52NH2 H I ~ ~--C1 red
H :H ~-OC13 -(CH2~17C13 red
91 H I -OCH3: ~ \ /- C8H17(n) red
92 H H -OCH3 \ ./ o~ange
. 2 8 17( )
. .
~ , .
.
': '. : ~ , ~,
.
1~55
- 20 -
Example 9~: If the procedure described in Example 65 is
repeated, except that 2.85 g of 1-(cyano-benzimidazolyl-
methylene)-isoindolin-3-one are used in place of the
1-(cyano-N-benzylcarbamoyl-methylene)-isoindolin-3-one,
a very fast, orange pigment is likewise obtained.
Example 94: Following an analogous procedure to that of
Example 69, a pigment which colours plastics and surface
coatings in fast, bluish red shades is obtained from
1.92 g of 3-acetyl-6-acetylamino-2,4-dihydroxy-quinoline-
hydrazone, 1.84 g of nickel acetate tetrahydrate and 1.6 g
of 1-(cyano-thiocarbamoyl-methylene)-isoindolin-3-one.
Example_25: 65 parts of stabilised polyvinyl chloride,
35 parts of dio~tyl phthalate and 0.2 part of the pigment
obtained according to Example 67 are stirred with one
another and then worked on a twin-roll mill for 7 minutes
at 140. An orange-red _coloured sheet with very good
fastness to light and migration is obtained.
Example 96: 10 g of titanium dioxide ~nd 2 g of the pig-
ment prepared according to Example 1 are ground with ~8g
of a mixture of 26.4 g of coconut alkyd resin, 24.0 g of
melamine/formaldehyde resin (50% solids content), 8.8 g
of ethylene glycol monomethyl ether and 28.8 g of xylene,
for 48 hours in a ball mill.
If this surface coating is sprayed onto analumin-
ium foil, predried for 30 minutes at room temperature and
then stoved for 30 minutes at 120, a red coating is
obtained, which has good colour intensity and is distin-
guished by a very good fastness to overcoa~ing, light and
weather.
Example 97: 4 parts of the finely divided pigment accord-
ing to Example 67 are stirred into 20 parts of solvent
of the following composition: 50 parts of Solvesso 150
(mixture of aromatic hydrocarbons), 15 parts of butyl
acetate, 5 parts of Exkin II (ketoxime-based levelling
agent), 25 parts of methyl isobutyl ketone and 5 parts of
silicone oil (1% in Solvesso 150).
After complete fine dispersion has been reached
~L~l551~Z
_ 21 -
(in about 15-60 minu-tes, depending on the type of
stirring), the binders are added, i.e. 48.3 parts of
. Baycryl L 530 (acrylic resin) (51% in xylene/butanol 3:1)
and 27.7 parts of Maprenal TTX (melamine resin) (55% in
butanol).
After a short period of homogenisation, the sur-
face coating is applied by customary methods, such as
spraying and dipping or, especially for the continuous
coating of metal sheets, by the "coil-coating" process,
and stoved (stoving: 30 minutes, 130). The red
coatings obtained are distinguished by very good level-
ling, high gloss and excellent fine dispersion of the
pigment, and also by excellent fastness to weather.
Example 98: If the procedure described in Example 76
is repeated, except that 2.78 parts of Staybelite Resin
(HERCULES) are added to the kneading mixture, a pigment
containing 10% of resin is obtained, which is distin-
guished by being easier to incorporate and by better
dispersibility.
