Note: Descriptions are shown in the official language in which they were submitted.
It is known that pigments which are distinguished
by outstanding fastness properties are obtained by conden-
sation of azodyestuff carboxylic acid halides of the for-
mula
Y
~ COHal
wherein A represents an aromatic radical, Q, X, Y and Z
represent hydrogen atoms or non-solubilising substituents,
and Hal represent a halogen atom, with a diamin~ o the
formula
H2N-B-NH2
wherein B represents an arylene radical which optionally
contains non-solubilising substituents, in the molar ratio
2:1. Depending on the nature of the substituents, the pig-
ments obtained leave something to be desired as regards
colour strength and purity of shade.
It has now been found that pigments having increased
colour strength and purity are obtained by condensing a
mixture consisting of 70-98 % by weight of a carboxylic
acid halide of the formula I ~main component) and 30-2 %
by weight of an additional component of the formula
,r ~
~9~
Y '
N 1' (II)
~ COHa 1
wherein Hal represents a haloge:n atom, Q', X', Y' and Z'
represent non-water-solubilising substituents, whilst at
least one of the substituents X', Y' and Z' contains at
least two atoms more selected from the series consisting
of C, V, S, N or Si than X, Y or Z, or at least two of
the substitusnts X', Y' or Z' contains at least one atom
more selected from the series consisting of C, 0, S, N
or Si than X, Y or Z, and A has the given meaning, with
a diamine of the formula
H2N-B--NH2
wherein ~ represents an arylene radical which optionally
contains non-solubilising substituents, in the molar
ratio 2:1, or by coupling a mixture consisting of 70-98
of the diazo compound of an amine of the formula
H N-~-Y (III)
and 30-2 % by weight of an amine of the formula
~'
2 ~. .
wherein X, X', Y, Y', Z and Z' have the given meanings,
with a bis-naphthol of the formula
-- 3 --
~'
a~
~H ~O
CONH-B-~HO(,
wherein Q and B have the given meanings.
The main component and t:he addi-tional component thus
differ from each other in their bulkiness.
By non-solubilising substituents are meant those which
do not cause the pigment to dissolve in water or in organic
solvents, i.e. for example halogen atoms, alkyl or alkoxy
groups of 1 to 6 carbon atoms, nitro, trifluoromethyl,
carbamoyl, ureido, sulphamoyl or cyano groups, alkoxycarbonyl,
alkanoyl, alkylcarbamoyl, alkylureido or alkanoylamino groups
of 2 to 6 carbon atoms, alkylsulphonyl or alkylsulphamoyl
groups of 1 to 6 carbon atoms, aryloxycarbonyl, aroyl,
aroylamino, arylsulphonyl, arylcarbamoyl, arylsulphamoyl,
aryl, arylureido or arylazo groups.
Q preferably represents a hydrogen or a bromine atom,
a methoxy, nitro or cyano group.
For the substituents X', Y' and Z' of the additional
component, it suffices that they are not water-solubilising.
Since the amo~mt of additional component is usually small,
Xl, Y' and Z' can also represent those groups which cause
the dye to dissolve to some extent in organic solvents.
Accordingly, X', Y' and Z' can represent for example halogen
atoms, alkyl or alkoxy groups of 1 to 6 carbon atoms, nitro,
1095~?~92
trifluoromethyl, carbamoyl, sulphamoyl, ureido or cyano
groups, alkoxycarbonyl, alkylcarbamoyl, alkanoyl, alkylureido
or alkanoylamino groups of 2 to 6 carbon atoms, alkylsul-
phonyl or alkylsulphamoyl groups of 1 to 6 carbon atoms,
aryloxycarbonyl, aroyl, arylsulphonyl, arylsulphamoyl,
aroylamino, arylureido, arylcarbamoyl or arylazo groups.
The starting carboxylic acid halides are preferably
those of the indicated formulae wherein A represents a phenyl
radical and X, X', Y, Y', Z and Z' represent hydrogen or
halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms,
trifluoromethyl, nitro, carbamoyl or cyano groups; alkoxy-
carbonyl groups,the alkyl moieties of which can be substituted
by halogen atoms or alkoxy groups of 1 to 4 carbon atoms,
phenoxy-halogenphenoxy or methylphenoxy groupsi phenoxycarbonyl
groups which can be substituted in the phenyl moiety by
halogen atoms, methyl, phenyl, phenoxy or alkoxycarbonyl
groups of 1 to 4 carbon atoms; naphthoxycarbonyl groups,
alkanoyl groups or alkylcarbamoyl groups of 2 to 6 carbon
atoms,,or phenylcarbamoyl groups which can be substituted
in the phenyl moiety by halogen atoms, alkyl or alkoxy groups
of 1 to 6 carbon atoms or trifluoromethyl groups.
Particularly good results are obtained by using as
main component an azo dyestuff carboxylic acid chloride of
the formula
.. ., .. ... . . -- . . . . . .... . ~, ,
~ ~ 5~
;~Yl '
Zl (VI~
~ COCl
wherein Xl represents a chlorine atom, a methyl or nitro
group~ an alkoxy group of 1 to 4 carbon atoms or an alkoxy-
carbonyl group of 2 to 6 carbon atoms, Yl represents a
hydrogen or chlorine atom, a methyl or nitro group and Zl
represents a hydrogen or chlorine atom or an alkoxycarbonyl
or chloroalkoxycarbonyl group of 2 to 6 carbon atoms, and
Yl and Zl are in the meta- or para-position to the azo group,
and as additional component a chloride of the formula
N ~z 2 (VII)
~1 COCl
wherein Ql represents a hydrogen or halogen atom, an alkoxy
group of 1 to 4 carbon atoms, a nitro or cyano group, X2
represents a -COOR group, in which R represents alkyl of 3
to 6 carbon atoms, halogenalkyl of 2 to 6 carbon atoms, a
phenyl group which is unsubstituted or substituted by halogen,
-- 6 --
.
alkyl or alkoxy of 1 to 6 carbon atoms or alkoxycarbonyl
of 2 to 6 carbon atoms~ a carbamoyl group, an alkylcar-
bamoyl group of 2 to 6 carbon atoms, a phenyl group which
is unsubstituted or substituted by chlorine, nitro, tri-
fluoromethyl, alkyl or alkoxy of 2 to 6 carbon atoms; and
Y2 and Z2 represent hydrogen or chlorine atoms, methyl or
nitro groups or alkoxycarbonyl groups of 2 to 6 carbon
atoms.
Outstanding results are obtained by starting from
mixtures which contain as main component a carboxylic
acid chloride of the formula
x3
N ~ (vIII~
~ OCl
wherein X3 represents a chlorine atom or a methyl group,
and Y3 represents a chlorine atom or a methoxycarbonyl
group, and as additional component a chloride of the
formula
~4
COOR
0}l 1
f .
,...
. . ~ .
wherein Ql has the given meaning, X~ represents a hydro-
gen or ~hlorine atom, a methyl group, an alkoxycarbonyl
group of 2 to 5 carbon atoms, and Rl represents an alkyl
group of 3 to 6 carbon atoms, a chloroalkyl group of 2 to
4 carbon atoms or a group of the formula
~V
wherein V represents a hydrogen or chlorine atom or a
methyl group and W represents a hydrogen or chlorine atom,
a methyl, phenyl or alkoxycarbonyl group of 2 to 6 carbon
atoms.
It is also possible to use ternary or quaternary
mixtures; however, these have no advantage as a rule over
the binary mixtures.
The azo dyestuff carboxylic acids on which the
chlorides of the formulae I and II are based are advan-
tageously obtained by coupling the diazo compounds of the
amines of the formulae III and IV with a 2,3-hydroxynaph-
thoic acid of the formula
COOH
-- 8 --
f~
,
To prepare the azo dyestuff carboxylic acids on which
the chlorides of the formulae (VI) to (IX) are based, amines
of the formulae
~2N ~ H2 ~ H2 ~ or H2N ~
~1 Y3 COOR
Xl~ X2, X3, X4, Yl, Y2, Y3 and R have the given
meanings, are preferably used.
Examples of amines of the formulae (III) and (IV) are:
anilines, such as
2-, 3- or 4-chloroanilines
3,4-dichloroaniline
2,3-dichloroaniline
2,4-dichloroaniline
2,5-dichloroaniline
2,6-dichloroaniline
2,4,5-trichloroaniline
2,4,6-trichloroaniline
2-, 3- or 4-bromoaniline
2,4-dibromoaniline
2,5-dibromoaniline
2-methyl-5-chloroaniline
2-methyl-4-chloroaniline
2-methyl-3-chloroaniline
2-chloro-5-t:rifluoromethylaniline,
_ 9 _
J. ~ ~ ~
~959~Z
alkylated anilines, such as
2-, 3- or 4-methylaniline
4-tert-butylaniline
2,4-dimethylaniline, and
nitroanilines, for example
2~, 3- and 4-nitroanilines
4-chloro-2-nitroaniline
2-chloro-4 nitroaniline
4-methyl-3-nitroaniline
2,4-dimethyl-3-nitroaniline
2-methyl-5-nitroaniline
2-methyl-4-nitroaniline, as well as
alkoxyanilines and
phenoxyanilines, for example
2- and 4-methoxyaniline
2- and 4-ethoxyaniline
3-chloro-4-methoxyaniline
4-trimethxlsilylaniline
4-amino-4'-trimethylsilyldiphenyl
2-methoxy-5-nitroaniline
2-methoxy-5-chloroaniline
2-methoxy-5-trifluoromethylaniline
2-amino-4-tri~luoromethyl-4'-chloro-diphenyl ether
2-nitro-4-ethoxyaniline
2-methoxy-4-chloro-5-methyLaniline
2-amino-4-chlorodiphenyl ether
- 10 -
.
.
2-amino-2',4~dichlorodiphenyl ether
2-amino-4,4'-dichlorodiphenyl e~her
as well as aminobenzoic acid esters, such as
anthranilic acid methyl~ ethyl or isopropyl ester
phenyl anthranilate
p-chlorophenyl anthranilate
p-methoxycarbonylphenyl anthranilate
l-amino-4-chloro-2-benzoic acid methyl ester
l-amino-4-nitro-2-benzoic acid methyl ester
l-amino-3-benzoic acid methyl ester
l-amino-3-benzoic acid phenyl ester
l-amino-3-benzoic acid 2'-diphenyl ester
l-amino-2-chloro-benzoic acid methyl ester
l-amino-2-chloro-benzoic acid phenyl ester
l-amino-2-chloro-benzoic acid 4'-diphenyl ester
l-amino-2-chloro-5-benzoic acid 4'-propoxycarbonylphenyl ester
l-amino-2-methyl-5-benæoic acid phenyl ester
3-amino-2-methyl-5-benzoic acid ethyl ester
l-amino-2-methyl-5-benzoic acid propyl ester
l-amino-2-methyl-5-benzoic acid isopropyl ester
l-amino-2-methyl-5-benzoic acid ~-chloroethyl ester
l-amino-2-methyl-5-benzoic acid phenyl ester
l-amino-2-me~hyl-5-benzoic acid o,m-, or p-methylphenyl ester
l-amino-2-methyl-5-benzoic acid o-, m-, or p-tert-octylphenyl
ester
l-amino-2-methyl-5-benzoic acid 3',5'-dimethylphenyl ester
~ ~ 5~ ~ Z
l-amino-2-methyl-5-benzoic acid 4'-methoxycarbonylphenyl ester
l-amino-2-methyl-5-benzoic acid 4'-ethoxycarbonylphenyl ester
l-amino-2-methyl-5-benzoic acid 4'-propoxycarbonylphenyl ester
l-amino-2-methyl-5-benzoic acid ~-naphthyl ester
l-amino-2-methoxy-5-benzoic acid 4'-isopropoxycarbonylphenyl
ester
l-amino-2-methyl-5-benzoic acid stearyl ester
l-amino-2-chloro-5-benzoic acid stearyl ester
l-amino-2-methoxy-5-benzoic acid stearyl ester
dimethyl aminoterephthalate
diisopropyl aminoterephthalate
diphenyl aminoterephthalate
and also
aminobenzamides, such as
anthranilamide
anthranilic acid methyl amide
anthranilic acid phenyl amide
l-amino-3-benzoic acid methyl amide
l-amino-3-benzoic acid phenyl amide
l-amino-2-chloro-S-benzamide
l-amino-2-chloro-5-benzoic acid methylamide
l-amino-2-chloro-5-benzoic acid phenylamide
l-amino-2-methyl-5-benzamide
l-amino-2-methyl-5-benzoic acid methylamide
l-amino-2-methyl-5-benzoic acid phenylamide
a-naphthylamine
- 12 -
-- -- . . {
l-aminoanthraquinone
l-amino-3-chloroanthraquinone
l-amino-4-benzoylaminoanthraquinone
3-aminopyrene.
The resultant azo dyes-tuff carboxylic acids are treatecl
with agents which are capable-of converting carboxylic acids
into their halides, for example the chloride~ or bromides,
in particu1ar with phosphorus halides, such as phosphorus
pentachloride or phosphorus trichloride or pentabromide,
phosphoroxy halides and preferably with thionyl chloride.
The treatment with such acid halogenating agents is
preferably carried out in inert organic solvents, such as
dimethyl formamide, chlorobenzenes, for example mono- or
dichlorobenzene, toluene, xylene or nitrobenzene. In the case
of these five last mentioned solvents, dimethyl formamide is
optionally added.
In the preparation of the carboxylic acid halides, it
is usually advantageous to dry the azo compounds obtained
in aqueous medium beforehand or to free them from water
azeotropically by boiling them in an organic solvent. The
azeotropic drying can be carried ou-t, if desired, directly
before the treatment with the acid halogenating agents.
The mixtures of carboxylic acid halides of the formulae
I and II to 'be used according to the invention can be obtained
either by mixing the carbo~ylic acid halides of the formulae
,, . . . . . . . . . . . . . . . .... ~,
I and II or by treating a mixture of the corresponding
carboxylic acids with acid halogenating agents or by coupling
a mixture o~ the amines of the formulae III and IV with 2,3-
hydroxynaphthoic acld and subsequently effecting acid
halogenation.
Phenylenediamines are preferably used as arylenediamines,
in particular those of the for!mula
~5
~2N~ N1~2
wherein X5 and Y5 represent halogen atoms3 alkyl or alkoxy
groups of 1 to 4 carbon atoms.
Examples of arylenediamines are:
1,4-phenylenediamine
2-chloro-1,4-phenylenediamine
2-methyl-1,4-phenylenediamine
2-methoxy-1,4-phenylenediamine
2-ethoxy-1,4-phenylenediamine
2-propoxy-1,4-phenylenediamine
2-isopropoxy-1,4-phenylenediamine
2-butoxy-1,4-phenylenediamine
2-nitro-1,4-phenylenediamine
2-cyano-1,4-phenylenediamine
2-methoxycarbonyl-1,4-phenylenediamine
2-ethoxycarbonyl-1,4-phenylenediamine
2-trifluoromethyl-1,4-phenylenediamine
- 14 -
2-aminocarbonyl-1,4-phenylenediamine
2,5-dichloro-1,4-phenylenediamine
2,5-dibromo-1,4-phenylenediamine
2,5-dimethyl-1,4-phenylenediamine
2,5-dimetho~y-1,4-phenylenediamine
2,5-diethoxy-l,L~-phenylenediamine
2-methoxy-5-ethoxy-1,4-phenylenediamine
2-methoxy-5-propoxy-1,4-phenylenediamine
2,5-dipropoxy-1,4-phenylenediamine
2,5-bis-triflu~romethyl-1,4-phenylenediamine
2-chloro-5-methyl-1,4-phenylenediamine
2-chloro-5-methoxy~ -phenylenediamine
2-chloro-5-ethoxy-1,4-phenylenediamine
2-methyl-5-methoxy-1,4-phenylenediamine
2-methyl-5-ethoxy-1,4-phenylenediamine
2,6-dichloro-1,4-phenylenediamine
2,3,6-trichloro-1,4-phenylenediamine
2,3,5,6-~etrachloro-1,4-phenylen~diamine
4,4'-diaminodiphenyl
3,3'-dichloro-4,4'-diaminodiphenyl
3,3'-dimethyl-4,4'-diaminodiphenyl
3,3'-dimethoxy-4,4'-diaminodiphenyl
2,2'-dimetho~y-5,5'-dichloro-4,4'-diaminodiphenyl
3,3',5,5'-tet:rachloro-4,4'-diaminodiphenyl
2,2',5,5'-tet;rachloro-4,4'-diaminodiphenyl
.
3,3'-dichloro-5,5'-dimethyl-4,4'-diaminodiphenyl
- 15 -
.... . . - . . .. ., .. . .. .. . ,, ... ~,.
2,2'-dichloro-5,5'-dimethyl-4,~'-diaminodiphenyl
4,4'-diamino-diphenyl-3,3'-dicarboxylic acid methyl ester
4,4'-diamino-diphenyl ethèr
4,4'-diamino-diphenylketone
4,4'-diamino-diphenylsulphone
3,3'-diamino-4,4'-dimethyl-diphenylsulphone
4,4'-diamino-diphenylmethane
4,4'-diamino-3,3'-dimethyl-diphenylmethane ..
4,4'-diamino-diphenylsulphide
4,4'-diamino-diphenylurea
4,4'-diamino-diphenylstilbene
2,7-diamino-diphenyleneoxide
2,7-diamino-fluorene
2,7-diamino-fluorenone
2,7-diamino-carbazole
3,6-diamino-carbazole
1,4-diamino-2-carbomethoxybenzene
1,4-diamino-naphthalene
1,5-diamino-naphthalene.
Instead of using homogeneous diamines, it is also
possible to use mixtures of different diamines without a
surprising effect being thereby attained.
The condensation between the carboxylic acid halides of
the kind mentioned at the outset and the aromatic diamines is
expediently carried out in anhydrous medium. Under this
. - 16 -
.. . ... . . . .. ., . . ... , ... . . .. . .. .. .. .... , .. . . . .. ~ .. . .....
~18~
.
condition, the condensation takes place as a rule with
surprising ease at temperatures which lie in the boiling range
of the normal organic solvents, for example, toluene, mono-
chloroben~ene, dichlorobenzene, trichlorobenzene or nitro-
benzene. In order to hasten the reaction it is in general
advisable to use an acid acceptor, for example anhydrous
sodium acetate or pyridine. The resulting pigments are partly
crystalline and partly amorphous and are obtained in most
cases in very good yield and in a pure state. It is advisable
to first precipitate the acid chlorides obtained from the
carboxylic acids. In many cases, however, precipitation of
the acid chloride can without detriment be dispensed with
and the condensation carried out directly after the manufacture
of the carboxylic acid chlorides.
The new co-condensates constitute valuable pigments
which, in finely divided form, may ~e used for pigmenting
organic material of high molecular weight, for example
cellulose ethers and esters, polyamides, polyurethanes or
polyesters, acetyl cellulose, nitrocellulose, natural resins
or artificial resins, such as polymerisation or condensation
resins, for example aminoplasts, in particular urea and
melamine/formaldehyde resins, alkyd resins, phenolic plastics,
polycarbonates, polyolefins, such as polystyrene, polyvinyl
chloride, polyethylene, polypropylene, polyacrylonitrile,
polyacrylic esters, rubber, casein, silicones and silicone
~ 2
resins, individually or in mixtures.
It is immaterial whether the cited materials of high
molecular weight are in the form of plastics, melts or in the
form os spinnin~ solutions, lacquers o~ printing inks.
Depending on the use to which they are put, it is advantageous
to use the new pigments as toners or in the form of preparations.
In addition to the pure pigment, the preparations can
contain in addition for example natural resins, for example
abietic acid or esters thereof, ethyl cellulose, cellulose
acetobutyrate, alkaline earth metal salts of higher fatty
2cids, fatty amines, ~or example stearylamine or rosinamine,
copolymers of vinyl chloride/vinyl acetate, polyacrylonitrile
or polyterpene resins or water-soluble dyes, for example
dyestuff sulphonic acids or the alkaline earth metal salts
thereof.
The colourants of the present invention are distinguished
by their reasonable price, high colour streng~h, and good
fastness to light, overstripe bleeding, migration and good
resistance to atmospheric influences. They differ substantially
in their properties from the mixtures which are obtained by
mechanically mixing the individual pigments which are obtained
on the one hand by condensing the main component by itself
with a diamine, and on the other hand condensing the addi~ional
component by itself with the same diamine. They sometimes
show new or modified X-ray diagrams, which point to the
formation o new crystal modifications. Compared with the
- 18 -
......... . . . .. . .. .... , . , . . . . _ . .... ..... .. . . . . . ... . . , .. . .. .. _
5~2
mixtures of the individual pigrnents, the co-condensates of the
present invention are distinguished by brighter shades, even
ir the additional component by itself results in very dull
shades, by greater colour strength and in many cases by a
considerable bathochromic disp:Lacement of the shade. In
addition, they exhibit a lesser dichroism and increased
stability to recrystallisation in organic solvents.
A further substantial advantage of the pigments of the
present invention consists in the fact that they do not
absolutely require a conditioning, i.e. a crystal comminution,
for example by grinding or kneading, and can be processed
direct to give pigment preparations.
The invention is illustrated by the following Examples;
in which the parts and percentages are by weight.
- 19 -
~ ~ ;
~L~9~i9i~
Example 1
A. 72.2 parts of the azo dye obtained by coupling
diazotised l-amino-2,5-dichlorobenzene with 2,3-hydroxy-
naphthoic acid are dispersed in 520 parts of o-dichlorobenzene
and the dispersion is heated, ~ith stirring, to 85C. Then
3~.7 parts of thionyl chloride are added dropwise in the
course of 10 minutes. The reaction mixture is further heated
and kept for 60 minutes at 115-120C. After cooling to 20C,
the precipitated crystalline azo dyestuff carboxylic acid
chloride is isolated by filtration, washed with a small amount
of cold o-dichlorobenzene, then with petroleum ether and
dried in a vacuum cabinet at 70C.
B. 82.5 parts of the azo dye obtained by coupling
diazotised 4-methyl-3-aminobenzoic acid 2'-chloroethyl ester
with 2,3-hydroxynaphthoic acid are converted into the
carboxylic acid chloride as described in A).
Co-condensation
With stirring, 14.42 parts of chloride A (95% by weight of
the total amount of acid chloride) and 0.86 part of the
acid chloride B (5% by weight of the total amount of the
acid chloride) are heated, with stirring, in 260 parts of
o-dichlorobenzene to 110-120C. Then a warm solution of
- 20 -
'
1~0C containing 2.16 parts of l,~-phenylenediamlne in 65
parts of o-dichlorobenzene are added in the course of 2 to 3
minutes. The precipitated pigment mixture is stirred for 16
hours at 140-145C. The resulting disazo pigment mixture is
collected by filtration at 100C, washed firstly wi~h warm
o-dichlorobenzene of 100C, then with warm methanol of 20C,
and finally with warm water. The filter cake is dried in a
vacuum cabinet at lOO~C, affording 14.7 parts of a red disazo
pigment mixture which is virtually insoluble in the customary
solvents. The product colours polyvinyl chloride and lacquers
in bright red shades of excellent fastness to light~ migration
and overstripe bleeding.
Example 2
A. 68.2 parts of the azo dye obtained by coupling diazotised
l-amino-2-methyl-5-chlorobenzene with 2,3-hydroxynaphthoic
acid are converted into the carboxylic acid chloride as
described in Example 1 A.
B. 78.4 parts of the azo dye obtained by coupling diazotised
4-methyl-3-aminobenzoic acid isopropyl ester with 2,3-hydroxy-
naphthoic acid are converted into the carboxylic acid chloride
as described in Example 1 A.
- 21 -
.. , ............................. . : .. .. .. . .. , . . ~,.. ..
Co-condensation
12.92 ~arts of the acid chloride A ~90% by weight o~ the
total amount) and 1.6~ parts of the acid chloride B (lOr/o of
the total amount) are condensed with 3.13 parts of 2-methyl-5-
chloro-1,4-phenylenediamine and worked Up as in Example 1,
affording 14.8 parts of a carmine red disazo pigment mixture
having the same good fastness properties as the product of
Example 1.
Example 3 (Single step process)
17.2 parts of the azo dye obtained by coupling diazotised
l-amino-2,5-dichlorobenzene with 2,3-hydroxynaphthoic acid
(95% of the total amount) and 1.14 parts of the azo dye
obtained by coupling diazotised 4-methyl-3-aminobenzoic acid
3',5'-dimethylphenyl ester with 2,3-hydroxynaphthoic acid
are dispersed in 325 parts of o-dichlorobenzene and the
dispersion is heated, with stirring, to 85C. Then 8.2 parts
of thionyl chloride are added at 80-90C in the course of
10 minutes. The reaction mixture is further heated and kept
for 60 minutes at 115-120C. Then excess thionyl chloride
is distilled off together with 65 parts of o-dichlorobenzene
at 100C under a low vacuum. To the resulting solution, which
contains the mixture of the azo dyestuff carboxylic acid
chlorides, is added at 110-120C a warm solution of 120C
9~ '
containing 2.i parts of 1,4-phenylenediamine and 130 parts of
o-dichlorobenzene in the course o~ 2 to 3 minutes. The
condensàtion mixture is stirred for 16 hours at 140-145C
and worked up at 100C as iTl Example 1, affording 18.4 parts
of a scarlet red disazo pigment mixture having the same good
fastness properties as the mixture of Example 1.
Example 4 (Single step process)
18.15 parts of a mixture of the azo dyestuff carboxylic acids
obtained by coupling a mixture consisting 98% of diazotised
2,5-dichloroaniline and 2% of diazotised 1-amino-2-methyl-5-
benzoic acid (3',5'-dimethylphenyl) ester and 2,3-hydroxy-
naphthoic acid are condensed, after conversion into the azo
dyestuff carboxylic acid chloride, with 2.7 parts of 1,4-
phenylenediamine according to the particulars of Example 3,
affording 18.2 parts of a scarlet red disazo pigment mixture
which is substantially identical with the pigment mixture
obtained in Example 3.
Example 5
A. 72.8 parts of the azo dye obtained by coupling
diazotised 4-methyl-3-aminobenzoic acid methyl ester with
2,3-hydroxynaphthoic acid are converted into the carboxylic
acid chloride as described in Example 1 A.
- 23 -
, ~ .
B. 102.4 parts of the azo dye obtained by coupling
diazotised 4-methyl-3-aminobenzoic acid 4'-propoxycarbonyl-
phenyl ester with 2,3-hydroxynaphthoic acid are converted
into the carboxylic acid chloride as described in Example 1 A.
Co-condensation
14.52 parts of the acid chloride A (95% of the total amount
of acid chloride) and 1.06 parts of the acid chloride B
(5% of the total amount of acid chloride) are condensed with
2.72 parts of 2,5-dime~hyl-1,4-phenylenediamine and working
up is effected according to the particulars of Example 1,
affording 15.4 parts of a red disazo pigment mixture which
has the same good fastness properties as the product obtainéd
in ~.xample 1.
Example 6
A mixture consisting of 16.98 parts (80% of the total amount
of acid chloride) of the azo dyestuff acid chloride obtained
according to Example 5B and 3.04 parts (20% of the total amount
of acid chloride) of the azo dyestuff acid chloride obtained
according to Example lA is condensed with 2.16 parts of 1,4-
phenylenediamine according to the particulars of Exarnple 1,
affording 18.6 parts of a red disazo pigment mixture having
the same good fastness properties as the product obtained in
Example 1.
- 24 -
.
:
.
- - : ,
.,
~ 9~ 2
Examples 7-118
The following table lists further disazo pigments which are
obtained by diazotising the amines of columns III and V by
the procedure of Example 1, coupling the resultlng diazo
compounds with 2,3-hydroxynaphthoic acid, converting the
resulting azo dyestuff carboxylic acids into the acid chlorides,
mixing these latter and condensing the mixture with the diamine
of column VI in the molar ratio 2:1. Columns II and IV
indicate the percentages by weight of the azo dyestuff
carboxylic acid chlorides used.
' ,, :~
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_O ~ ~ C a~ Q ._ Il~
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e o e n~ I~ ~ e c e o~ e _ c c o u~
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e Q e Qe ~ e ~ e c è ~ _c ~e u~ e C~ e c ~ e _c
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- 26 -
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- 27 -
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- 28 -
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_C _c o ~ o O
E E ~ O O _ E E 5.> E _c _c 8 _ a c~ E Q
._ ._ o S_ ~_ ._ ._ o _ Lc ._ _ O ._ o ._ ~ E c
E E c~ ~ E ~ nJ ~c~ c I '--O I ~
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c
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- 29 -
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l c~
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- 30 -
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- 31 -
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- 32 -
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L~- ~ ~ Lr~ u~ In Ln L
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- 34 -
.
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- 35 -
.. . .
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CD C~ O.> CD
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.~ ~ la CD O O ._:~ ~ D> C~ CD e~ CD S_ CD
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- 36 -
. .,
` .. .
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'
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Exam~les 119-136
.
The following table lists further disazo pigment mixtures
which are obtained by diazotising on the one hand the amines
of column III according to the particulars of Example 1,
coupling the diazo compounds obtained with 2,3-hydroxynaphthoic
acid, and on the other hand coupling the amines o~ column V
with the respective hydroxynaphthoic acid of column VI,
converting the resulting azo dyestuff carboxylic acids into
the acid chlorides, mixing these latter and condensing the
mixture in the molar ratio 2:1 with the diamine of column VII.
Columns II and IV indicate the percentages by weight of the
azo dyestuff carboxylic acid chlorides used.
- 37 -
,
. .
... ..
` ' '
- : , , . :
5~
+. ~ ~ c +~ +~
_ ~ ~
~ ~ C ~ C ~ o> ~>
c C ~ ~ ~ ~ C ~~ ~ C ~ ~ ~ e
O ,_
_ _c c ~ C q, ~ C ~ C C ~0, ~ r o n~ ~ _C
o ~ o ~ o C
~ .
~,~ ,.' ~
C
~ L
= C C~ -C. o~ o~
. --L~l cn cO~ o C~ c
.
- 38 -
.. ,
:
~s~
c~
_ ~ o
c c~
~ _c c ~ e ~ c ~
'O I = ~ -O Q ~ C~
C _ Ll-~ O C Q 11-~ -O
_ O O ' _ O O C
C O C O _ C O C 0'--
_ '- _C E~ '-- C '- _C ~ C ~
_1 1-o I_C I 1-o l_C
~_o ~
I ~ I ~
I ~
X 'o = = - _C
_~ _C E~ ~
r~ ~ ~ ,
.~`,`
O 'O
I C ~
::' _C _ _C
C`J Q . C`J +'
CCo 1~
. . C O C
._ O ._ O
= 'O I ~ ` Z I
_ _~, _ ~ _~, _
r ~~ _C C ~ ~ C
=
~ -
_ # _
.
- 39 -
`
,
'
az
Example 137
0.6 g of the pigment obtained in Example 1 is mixed with 67 g
of polyvinyl chloride, 33 g of dioctyl phthalate~ 2 g of
dibutyl tin dilaurate and 2 g of titanium dioxide and the
mixture is processed to a thin sheet for 15 minutes at 160C
on a roll mill. The red colouration obtained is strong and
fast to migration and light.
Example 138
To 100 g of a stoving lacquer consisting of 58.5 g of a 60%
solution of a coconut alkyd resin in xylene, 23 g of a 65%
solution of a melamine varnish gum in butanol, 17 g of xylene
and 1.5 g of butanol, are added 1 g of the colourant of
Example 1 and 5 g of titanium dioxide. The mixture is ground
for 48 hours in a ball mill and the pigmented lacquer is
sprayed onto a clean metal surface. After stoving at 120~,
a brilliant red colouration of good fastness to light and
overstripe bleeding and good resistance to atmospheric
influences is obtained.
Example 139
1 g of the pigment obtained in Example 1 is finely ground in
an Engelsmann grinding machine with 4 g of a litho varnish of
- 40 -
,
:.... ; .:
.: . ; , .,
.,
59ai~
the composition:
29.4% of linseed oil-stand oil (300 poise)
67.2% of linseed oil-stand oil (20 poise)
2.1% of cobalt octoate (8% Co) and
1.3% of lead octoate (24~/o Pb).
Using a stereotype block, this varnish is printed in an
amount of 1 g/m2 on art paper by letterpress printing. A
strong, bright, red shade of good transparency and good gloss
is obtained.
The pigment is also suitable for other printing methods,
such as intaglio printing, offset printing, flexographic
printing, with equally good results.
Example 140
15 g of collodion cotton containing 35% of butanol, 15 g of
a phthalate resin modified with castor oil, 15 g of a 70%
butanolic solution of a urea varnish gum, 20 g of butyl
acetate, 10 g of glycol monoethyl ether, 20 g of toluene and
5 g of alcohol are processed to a lacquer. This lacquer is
then pigmented with 2 g of the colourant of Example 1 and 2 g
of titanium dioxide (rutile) and ground. The lacquer is
sprayed onto cardboard and dried, giving a red coating of very
good fastness to light and overstripe bleeding and very good
resistance to atmospheric influences.
. .
