CA1095902A

CA1095902A - Process for the production of azo pigments

Info

Publication number: CA1095902A
Application number: CA294,023A
Authority: CA
Inventors: Karl Ronco; Andre Pugin; Paul Muller
Original assignee: Ciba Geigy Investments Ltd
Current assignee: BASF Schweiz AG
Priority date: 1976-12-31
Filing date: 1977-12-29
Publication date: 1981-02-17
Also published as: GB1595489A; CH624977A5; DE2758407C2; FR2376190B1; JPS6126591B2; BR7708740A; JPS5385826A; FR2376190A1; DE2758407A1; DK588677A

Abstract

Abstract of the Disclosure A process for the production of azo pigments having increased colour strength and purity by condensation of an azo dyestuff carboxylic acid halide of the formula (I) wherein A represents an aromatic radical, Q, X, Y and Z
represent hydrogen atoms or non-solubilising substituents, and Hal represents a halogen atom, with a diamine of the formula wherein B represents an arylene radical which optionally contains non-solubilising substituents, in the molar ratio 2:1, which process comprises the use, in addition to the carboxylic acid chloride of the formula I (main component).
of an additional component of the formula wherein A has the meaning given in formula I, Q', Y, X', Y' and Z' represent non-watersolubilising 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, O, S, N or Si than Z, Y or Z, or at least two of the substituents X', Y' or Z' contain at least one atom more selected from the series consisting of C, O, S, N or Si than X, Y or Z, or coupling a mixture of the diazo compound of the amines of the formulae and wherein X, X', Y, Y', Z and Z' have the given meanings, with a bis-naphthol of the formula

Description

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 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 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 ~' 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, .

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

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 .

.

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 -- -- . . {

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

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 ......... . . . .. . .. .... , . , . . . . _ . .... ..... .. . . . . . ... . . , .. . .. .. _

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.

~ ~ ;

~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 ' 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.

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

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.

, ~ .

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.

.

:

.
- - : , ., ~ 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.

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

~s~

-- c ~n -.' - ~
~ -c~ = = = = = == = = = =
~ --~ -~ Q ~
~ ~~ ~ ~ D O
o C~ ,_ ._ _l._ ,~> o .~
1`10 0 ~ O ~ :_ ~ ~ O _ ~ O
_O ~ ~ C a~ Q ._ Il~
~ x c _ _ ~ ._ _ ~n _ ~o __C = = _ C~ ._ O
_C ~ _C O~ C _C ' > _C _ _C O >. ~ ~ ~
_C _~, _ +. ~ ~ C ~, o ~ +~ _C +' e o e n~ I~ ~ e c e o~ e _ c c o u~
C~ ~ aO~
O Q O QO ~ O O C o C o ~ O -O O a> O ~, e Q e Qe ~ e ~ e c è ~ _c ~e u~ e C~ e c ~ e _c ~ O ~ OI clI c I I I _ac~ +C' ~ ~ U e c~
_ ._ : ._ _ a~ _ Q _ C~ _ C~, ~ 2~ _ ~ _ _ ~ ~ a~ _ _ _ .

~ u~ > ~ o ~ u o ~ _ L

_ _ _ _ _ Lr~ o ~n ~ o ~ ~u-> Ir~ u ~
_ _ _ -- x ~ ¢- a~ o = C~ r~
... .

,.
` ,, .
j . .

S~

- -c ~ = = ~ ~ = = = -~ = ' t = =
~ ~ -o - ~ - -~ ~-o `C
- c = = : = = = = l ~> = =
c C~ -o a~ -l r~ c a~ ~ c, ~ _ I
-o -- ~ ~~ ~ ~ ~ ~ x -o -o -o _C -C ~ Q ",~, 1~ 1 ~ o~-o O 0~ ~ ~ O O I

o C> O ~ C CC oC -~ ~ C o C -I C C C o C -c~ C o - E3 -[~ n - ~ C ~ I ~ o - ., ~
~, ~ ~ ~ :r> o ~ o o u~ L~ Ln ~ o ~ ~
_ l .~c~ = = = = = = = = = = = = = =
c~C
_ Ln ~ æ 0, o _ x a- o ~ ~ ~ ~ u~ o _ ~ ~
.

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

59(~;2 _ .

_ ~

~ .
^

_ Q ~ = ~ = , e = = = _ =

_ O e ~
_ _ +' V ~ ' >~ O O Q
O Q~ > IQ ~

_ ._ ~ ~ ~ ~ ~ I .~ ~ ~ ~ I ~ _ If~ L~ ~> ~ Ln C~J _ ~ ~ U~
~ ~ -~o ol _ _ ~ = = = ~ = = = ~ = = = = = .
c~
- -= cn cn cn cn cn cn cn cn cn cn cn cn cn _ .
_ ~ C_ co cn O _~ ~ ~ ~

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

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_ o -o ._ = = C E
_ _o o D

_ ._ _ C
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_c _ ._ _ '; I _c ~ c .

C ~
+' ' :.~ C>
~ ~ OQ
=~ C ~ O ~

D ~ 'D ~ D D a~ D ~, D O ~ _O ~_ ~ ~
~ ~ _C I I ~ C I ~
_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 ~

. _ c _ _ _ E

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-o - -c = c~

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~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ o a~ o ~- ~o c~ o - o ~

C ~` ~` C

- . _ 8 ~ ~ c~ e Es E3 E3 ~ -o ~ _c ~ r~

~ ~0~ = = e _ _ cn L~ ~ U~ LO ~0 U~ 0 ~0 ~0 ~

., :

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~ c c ~ c - - -= Lo ~s 7 cn 0> 0~ C cJ~ cn ~ C7~

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I a~ o _C ~ O_C ~_C ~ - O
~ O> O~D O ~D +. ~ _ _C X
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_ ~ 3 3 _ ~ E E E E
_ CD C~ O.> CD
~ C ~ 1 ~1 C e I I I

.~ ~ la CD O O ._:~ ~ D> C~ CD e~ CD S_ CD
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=~ ~" c I ~ ~, c _~ E 1 8 1 e~ _C C
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tD
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7 ~
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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.

, . .

... ..

` ' ' - : , , . :

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 .

.. , :

~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

=
~ -_ # _ .

`

, ' 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 , :.... ; .:
.: . ; , ., ., 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.

. .

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the production of azo pigments having increased colour strength and purity by condensation of 70-98% by weight of an azo dyestuff carboxylic acid halide of the formula wherein A represents an aromatic radical, Q, X, Y and Z
represent hydrogen atoms or non-sulubilising substituents, and Hal represents a halogen atom, with a diamine of the formula wherein B represents an arylene radical which optionally contains non-solubilising substituents, in the molar ratio 2:1, which process comprises the use, in addition to the carboxylic acid chloride of the formula I (main component), of 30-2% of an additional component of the formula wherein A has the meaning given in formula I, Q', Y, X', Y' and Z' represent non-watersolubilising 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, O, S, N or Si than X, Y or Z, or at least two of the substituents X', Y' or Z' contain at least one atom more selected from the series consisting of C, O, S, N or Si than X, Y or Z, or coupling a mixture of 70-98% by weight of the diazo compound of an amine of the formula and 30-2% by weight of the diazo compound of an amine of the formula wherein X, X', Y, Y', Z and Z' have the given meanings, with a bis-naphthol of the formula wherein Q and B have the given meanings.

2. A process according to claim 1 wherein the main component is a carboxylic acid chloride of the formula wherein X1 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, Y1 represents a hydrogen or chlorine atom, a methyl or nitro group and Z1 represents a hydrogen or chlorine atom or an alkoxycarbonyl or chloro-alkoxycarbonyl group of 2 to 6 carbon atoms, and Y1 and Z
are in the meta- or para-position to the azo group.

3. A process according to claim 1 wherein the additional component is a carboxylic acid chloride of the formula wherein Q1 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, alkyl or alkoxy of 1 to 6 carbon atoms or alkoxycarbonyl of 2 to 6 carbon atoms; a carbamoyl group, an alkylcarbamoyl group of 2 to 6 carbon atoms, a phenyl group which is unsubstituted or substituted by chlorine, nitro, trifluoromethyl, alkyl or alkoxy of 2 to 6 carbon atoms; Y2 and Z2 represent hydrogen or chlorine atoms, methyl or nitro groups or alkoxycarbonyl groups of 2 to 6 carbon atoms.

4. A process according to claim 1 wherein the main component is a carboxylic acid chloride of the formula wherein X3 represents chlorine or methyl, Y3 represents chlorine or alkoxycarbonyl of 1 to 4 carbon atoms.

5. A process according to claim 1 wherein the additio-nal component is a carboxylic acid chloride of the formula wherein Y1 and Q1 are as defined in claim 3, X4 represents hydrogen, chlorine, methyl or alkoxycarbonyl of 2 to 6 carbon atoms, and R1 represents alkyl of 3 to 6 carbon atoms, chloroalkyl of 2 to 4 carbon atoms or the radical of the formula wherein V represents hydrogen, chlorine or methyl, and W
represents hydrogen, chlorine, methyl, phenyl or alkoxy-carbonyl of 2 to 6 carbon atoms.

6. A process according to claim 1 wherein the amount of main component is 95 to 98% and the amount of additional component is 5 to 2 %.

7. A process according to claim 1 wherein a phenylene-diamine or naphthylenediamine is used as diamine.

8. A process according to claim 7 which comprises the use of a phenylenediamine of the formula wherein X5 and Y5 are hydrogen or halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms.