GB1595489A - Process for the production of azo pigments - Google Patents

Process for the production of azo pigments Download PDF

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GB1595489A
GB1595489A GB5156977A GB5156977A GB1595489A GB 1595489 A GB1595489 A GB 1595489A GB 5156977 A GB5156977 A GB 5156977A GB 5156977 A GB5156977 A GB 5156977A GB 1595489 A GB1595489 A GB 1595489A
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methyl
carbon atoms
amino
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ester
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Novartis AG
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C09B67/0046—Mixtures of two or more azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B43/00—Preparation of azo dyes from other azo compounds
    • C09B43/32—Preparation of azo dyes from other azo compounds by reacting carboxylic or sulfonic groups, or derivatives thereof, with amines; by reacting keto-groups with amines
    • C09B43/38—Preparation of azo dyes from other azo compounds by reacting carboxylic or sulfonic groups, or derivatives thereof, with amines; by reacting keto-groups with amines by reacting two or more ortho-hydroxy naphthoic acid dyes with polyamines

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Azo pigments of increased colour strength and purity are prepared by condensing an azo dye-carboxylic acid halide of the formula <IMAGE> wherein A denotes a carbocyclic or heterocyclic aromatic radical, Q, X, Y and Z denote H atoms or substituents which do not confer solubility and Hal denotes a halogen atom, with a diamine of the formula H2N-B-NH2 wherein B is an arylene radical which optionally contains substituents which do not confer solubility, in the molar ratio of 2:1, using, in addition to the carboxylic acid chloride of the formula I (main component), an additional (auxiliary) component of the formula <IMAGE> where A has the meaning given and Q, X', Y' and Z' are substituents which do not confer solubility in water, with at least one of the substituents X', Y' and Z' containing at least 2 more atoms from the series C, O, S, N or Si than X,Y or Z contains, or at least 2 of the substituents X', Y' or Z' contain at least one more atom from the series C, O, S, N or Si than X, Y or Z contains.

Description

(54) PROCESS FOR THE PRODUCTION OF AZO PIGMENTS (71) We, CIBA-GEIGY AG, a Swiss Body Corporate, of Basle, Switzerland, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to the production of azo pigments.
It is known that pigments which are distinguisbed by outstanding fastness properties are obtained by condensation of azo dyestuff carboxylic acid halides of the formula
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 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 pigments 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 of a carboxylic acid halide of the formula I (main component) with an additional component of the formula
wherein Hal represents a halogen atom, Q, X', Y' and Z' represent non-water solu bilising substituents, whilst at least one of the substituents X', Y' and Z' contains at least two atoms more selected from C, O, S, N and Si than X, Y or Z, or at least two of the substituents X', Y' or Z' contains at least one atom more selected from C, O, S, N and Si than X, Y or Z, and A has the given meaning, with a diamine of the formula H2N-B-NH2 wherein B represents an arylene radical which optionally contains non-solubilising substituents, in the molar ratio 2::1, or by coupling a mixture of the diazo compound of the amines of the formulae
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.
The main component and the additional 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, arylsulphony!, 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 amount of additional component is usually small, X', 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, trifluoromethyl, carbamoyl, sulphamoyl, ureido or cyano groups, alkoxycarbonyl, alkyl carbamoyl, alkanoyl, alkylureido or alkanoylamino groups of 2 to 6 carbon atoms, alkylsulphonyl or alkylsulphamoyl groups of 1 to 6 carbon atoms, aryloxycarbonyl, aroyl, arylsulphonyl, arylsulphamoyl, aroylamino, atylureido, 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; alkoxycarbonyl 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 groups; 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
wherein X1 represents a chlorine atom, a methyl or nitro group, an alkoxy group of 1 to 4 carbon atoms or an alkoxycarbonyl group of 2 to 6 carbon atoms, Yl represents a hydrogen or chlorine atom, a methyl or nitro group and Z1 represents a hydrogen or chlorine atom or an alkoxycarbonyl or chloroalkoxycarbonyl group of 2 to 6 carbon atoms, and Yl and Z1 are in the meta- or para-position to the azo group, and as additional component a 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; and Y and Z2 represent 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
wherein X, represents a chlorine atom or a methyl group, and Y, represents a chlorine atom or alkoxycarbamoyl of 1 to 4 carbon atoms, and as additional component a chloride of the formula
wherein Q1 has the given meaning, X4 represents a hydrogen or chlorine atom, a methyl group, an alkoxycarbonyl group of 2 to 6 carbon atoms, and R1 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
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.
The amount of main component is preferably 70 to 99% or 90 to 99%, most preferably 95 to 98%, by weight, and the amount of additional component is 30 to 1% or 10 to 1%, most preferably 5 to 1%, by weight, based on the total amount.
For reasons of economy, the more easily obtainable component is usually used as main component.
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 advantageously obtained by coupling the diazo compounds of the amines of the formulae III and IV with a 2,3-hydroxynaphthoic acid of the formula
To prepare the azo dyestuff carboxylic acids on which the chlorides of thg formulae (VI) to (IX) are based, amines of the formulae
wherein X1, X2, X3, X4, Yl, Y2, Ys 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 2,3-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-S-chloroaniline 2-methyl-4-chloroaniline 2-methyl-3 chloroaniline 2-chloro-S-trifluoromethylaniline, 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-eth.oxyaniline 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-trifluoromethyl-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 ether as well as aminobenzoic acid esters, such as anthranilic acid methyl, ethyl or isopropyl ester phenyl anthranilate p-chlorophenyl anthranilate p-methoxycarbonylphenyl anthranilate 1-amino-4-chloro-2-benzoic acid methyl ester 1-amino-4-nitro-2-benzoic acid methyl ester 1-amino-3-benzoic acid methyl ester 1-amino-3-benzoic acid phenyl ester 1-amino-3-benzoic acid 2'-diphenyl ester 1-amino-2-chloro-benzoic acid methyl ester 1-amino-2-chloro-benzoic acid phenyl ester 1-amino-2-chloro-benzeic acid 4'-diphenyl ester 1-amino-2-chloro-5-benzoic acid 4'-propoxycarbonylphenyl ester 1 amino-2-methyl-5-benzoic acid phenyl ester 3.amino-2-methyl-5-benzoic acid ethyl ester 1-amino-2-methyl-5-benzoic acid propyl ester 1-amino-2-methyl-5-benzoic acid isopropyl ester 1-amino-2-methyl-5-benzoic acid ,$-chloroethyl ester 1-amino-2-methyl-5-benzoic acid phenyl ester 1-amino-2-methyl-5-benzoic acid, o,m-, or p-methylphenyl ester l-amino-2-methyl-5-benzoic acid o-, m-, or p-tert-octylphenyl ester 1-amino-2-methyl-5-benzoic acid 3',5'-dimethylphenyl ester 1-amino-2-methyl-5-benzoic acid 4'-methoxycarbonylphenyl ester 1-amino-2-methyl-5-benzoic acid 4'-ethoxycarbonylphenyl ester 1-amino-2-methyl-5-benzoic acid 4'-propoxycarbonylphenyl ester 1-amino-2-methyl-5-benzoic acid ss-naphthyl ester 1 -amino-2-methoxy-5-benzoic acid 4'-isopropoxycarbonylphenyl ester 1-amino-2-methyl-5-benzoic acid stearyl ester 1-amino-2-chloro-5-benzoic acid stearyl ester 1-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 1-amino-3-benzoic acid methyl amide 1-amino-3-benzoic acid phenyl amide 1 -amino-2-chloro-5 -benzamide 1-amino-2-chloro-5-benzoic acid methylamide 1-amino-2-chloro-5-benzoic acid phenylamide 1 -amino-2-methyl-5 -benzamide 1-amino-2-methyl-5-benzoic acid methylamide 1-amino-2-methyl-5-benzoic acid phenylamide a-naphthylamine 1-aminoanthraquinone 3 -amino-3 -chloroanthraquinone 1-amino-4-benzoylaminoanthraquinone 3 -aminopyrene.
The resultant azo dyestuff carboxylic acids are treated with agents which are capable of converting carboxylic acids into tbeir halides, for example the chlorides or bromides, in particular 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 tive 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 out, 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 carboxylic 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 of the amines of the formulae III and IV with 2,3-hydroxynaphthoic acid and subsequently effecting acid halogenation.
Phenylenediamines are preferably used as arylenediamines, in particular those of the formula
wherein X5 and Yc represent hydrogen or halogen atoms, 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 -dimethoxy- 1,4-phenylenediamine 2,5-diethoxy-1,4-phenylenediamine 2-methoxy-5-ethoxy-1,4-phenylenediamine 2-methoxy-S -propoxy-l 1 ,4-phenylenediamine 2,5-dipropoxy- 1,4-phenylenediamine 2,5-bis-trifluoromethyl- 1,4-phenylenediamine 2-chloro-5 -methyl- 1,4-phenylenediamine 2-chloro-5-methoxy- 1 ,4-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-trichl oro-1 4-nhenvlenediamine 2,3,5,6-tetrachloro- 1 ,4-phenylenediamine 4,4'-diaminodiphenyl 3,3'-dichloro-4,4'-diaminodiphenyl 3,3'-dimethyl-4,4'-diaminodiphenyl 3,3'-dimethoxy-4,4'-diaminodiphenyl 2,2'-dimethoxy-5,5'-dichloro-4,4'-diaminodiphenyl 3,3',5,5'-tetrachloro-4,4'-diaminodiphenyl 2,2',5,5'-tetrachloro-4,4'-diaminodiphenyl 3,3'-dichloro-5,5'-dimethyl-4,4'-diaminodiphenyl 2,2'-dichloro-5,5'-dimethyl-4,4'-diaminodiphenyl 4,4'-diamino-diphenyl-3,3'-dicarboxylic acid methyl ester 4,4'-diamino-diphenyl ether 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 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, monochlorobenzene, dichlorobenzene, tricblorobenzene or nitrobenzene. 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 be 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 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 of spinning solutions, lacquers or 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 acids, fatty amines, for example stearylamine or rosinamine, copolymers of vinyl chloride/vinyl acetate.
polyacrylonitrile of 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 strength, and good fastness to light, overstrip 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 additional component by itself with the same diamine. They sometimes show new or modified X-ray diagrams, which point to the formation of new crystal modifications.Compared with the mixtures of the individual pigments, the co-condensates of the present invention are distinguished by brighter shades, even if the additional component by itself results in very dull shades, by greater colour strength and in many cases by a considerable bathochromic displacement 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.
We are aware of the Carcinogenic Substances Regulations, 1967 ,and make no claim to the use of this invention in contravention of those Regulations.
The in vention is illustrated by the following Examples; in which the parts and percentages are by weight.
Example 1.
A. 72.2 parts of the azo dye obtained by coupling diazotised 1-amino-2,5dichlorobenzene with 2,3-hydroxy-naphthoic acid are dispersed in 520 parts of odichlorobenzene and the dispersion is heated, with stirring, to 85"C. Then 32.7 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 115 120 C. After cooling to 20"C, 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 70"C.
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 1100--1200C. Then a warm solution of 1200C containing 2.16 parts of 1,4-phenylenediamine 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"--145"C. The resulting disazo pigment mixture is collected by filtration at 1000C, washed firstly with warm o-dichlorobenzene of 100"C, then with warm methanol of 20"C, and finally with warm water.The filter cake is dried in a vacuum cabinet at 1000C, 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 1-amino-2-methyl S-cblorobenzene 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-hydroxynaphthoic acid are converted into the carboxylic acid chloride as described in Example 1 A.
Co-condensstion.
12.92 parts of the acid chloride A (90% by weight of the total amount) and 1.64 parts of the acid chloride B (10% of the total amount) are condensed with 3.13 parts of 2-methyl-3-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 1-amino-2,3-dichloro benzene 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 85"C. Then 8.2 parts of thionyl chloride are added at 800--90"C in the course of 10 minutes. The reaction mixture is further heated and kept for 60 minutes at 115 -120 C. Then excess thionyl chloride is distilled off together with 65 parts of o-dichlorobenzene at 100 C under a low vacuum.To the resulting solution, which contains the mixture of the azo dyestuff carboxylic acid chlorides, is added at 110"--120"C a warm solution of 1200C containing 2.7 parts of 1,4-phenylenediamine and 130 parts of o-dichlorobenzene in the course of 2 to 3 minutes. The condensation mixture is stirred for 16 hours at 140-145 C and worked up at 100 C as in 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',3'-dimethylphenyl) ester and 2,3-hydroxy-naphthoic acid are condensed, after ccnversion 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'-propoxycarbonylphenyl etser with 2,3-hydroxynaphthoic acid are converted into the carboxylic acid cholride 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-dimethyl-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 obtained in Example 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.W parts (20% of the total amount of acid chloride) of the azo dyestuff acid chloride obtained according to Example 1A is condensed with 2.16 parts of 1,4-phenylenediamine according to the particulars of Example 1, affording 18.6 parts of a red disazo pigment mixture having the same good fastness properties as the product obtained in Example 1.
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 resulting 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.
I II III IV V VI VII Ex. 7 95 2,5-dichloroaniline 5 1-amino-2-methoxy-5-benzoic acid p-phenylenediamine scarlet isopropoxycarbonylphenyl ester 8 95 " 5 1-amino-2-methyl-5-benzoic acid " " isopropyl ester 9 95 " 5 1-amino-2-methyl-5-benzoic acid " " ss-naphthyl ester 10 95 " 5 1-amino-5-benzoic acid 2'-diphenyl " " ester 11 90 " 10 1-amino-2-methyl-5-benzoic acid " " ss-chloroethyl ester 12 95 " 5 1-amino-2-methyl-3-benzoic acid " " phenyl ester 13 95 " 5 anthranilic acid p-chlorophenyl ester " " 14 80 " 20 1-amino-2-methyl-5-benzoic acid " " 3',5'-dimethylphenyl ester 14a 98 " 2 " " " 14b 99 " 1 " " " 15 95 " 5 1-amino-2-methyl-5-benzoic acid " red 1',3'-dichloroisopropyl ester 16 95 " 5 4-aminodiphenyl " " 17 95 " 5 aminoterephthalic acid diisopropyl " " ester 18 95 " 5 1-amino-2-chloro-5-benzoic acid 4@ " " diphenyl ester
I II III IV V VI VII Ex. 19 95 2,5-dichloroaniline 5 1-amino-2,5-dimethoxy-4-chlorobenzene p-phenylenediamine bluish red 20 95 " 5 aminoterephthalic acid diphenyl ester " red 21 95 " 5 1-amino-2-methyl-5-benzoic acid " " m-trifluoromethylanilide 22 95 " 5 1-amino-2-methyl-5-benzoic acid anilide " " 23 90 " 10 1-amino-4-benzoic acid phenyl ester " yellowish red 24 95 " 5 1-amino-2-methyl-5-benzoic acid " red (p-isopropoxycarbonyl)-phenyl ester 25 90 " 10 1-amino-2-methyl-3-benzoic acid butyl " " ester 26 90 " 10 aminoterephthalic acid dimethyl ester " " 27 95 " 5 1-amino-2-methyl-5-benzoic acid 1',3'@ 2-chloro-1,4-phenylene- " dichloroisporopyl ester diamine 28 95 " 5 1-amino-2-methyl-5-benzoic acid " bluish red p-propoxycarbonylphenyl ester 29 95 " 5 1-amino-2-methyl-5-benzoic acid " " (3',5'-dimethylphenyl) ester 30 95 " 5 1-amino-2-methoxy-5-p-isopropoxy- " " carbonylphenyl ester 31 90 " 10 1-amino-2-methyl-5-benzoic acid " red ss-chloroethyl ester 32 95 " 5 1-amino-2-chloro-5-benzoic acid " " 4'-diphenyl ester 33 97 " 3 1-amino-2-methyl-5-benzoic acid " " isopropyl ester
I II III IV V VI VII Ex. 34 95 2,5-dichloroaniline 5 anthranilic acid p-chlorophenyl ester 2-chloro-1,4-phenylene- red diamine 35 95 " 5 anthranilic acid 2'-diphenylyl ester " " 36 95 " 5 aminoterephthalic acid diisopropyl " " ester 37 95 " 5 1-amino-2,5-dimethoxy-4-chlorobenzene " bluish red 38 95 " 5 2-aminoterephthalic acid diphenyl ester " red 39 95 " 5 1-amino-2-methyl-5-benzoic acid methyl " " ester 40 95 " 5 1-amino-2-methyl-5-benzoic acid " " ss-naphthyl ester 41 95 2-methyl-5-chloroaniline 5 1-amino-2-methyl-5-benzoic acid 2-methyl-5-chloro-1,4- carmine red (3',5'-dimethylphenyl) ester phenylenediamine 42 98 " 2 1-amino-2-methyl-5-benzoic acid " " isopropyl ester 42a 99 " 1 " " " 43 95 " 5 1-amino-2-methyl-5-benzoic acid " " ss-chloroethyl ester 44 95 " 5 1-amino-2-methyl-5-benzoic acid " bluish red 1',3'-dichloroisopropyl ester 45 95 " 5 1-amino-2-methyl-5-benzoic acid " " ss-naphthyl ester
I II III IV V VI VII Ex. 46 95 2,5-dichloroaniline 5 1-amino-2-methyl-3-benzoic acid phenyl 2-methyl-5-chloro-1,4- bluish red ester phenylenediamine 47 95 " 5 1-amino-2-methyl-5-benzoic acid " " p-propoxycarbonylphenyl ester 48 95 " 5 anthranilic acid p-chlorophenyl ester " " 49 95 " 5 1-amino-2-chloro-5-benzoic acid " " 4'-diphenyl ester 50 95 " 5 1-amino-2-methyl-5-benzoic acid 2,5-dimethyl-1,4- carmine red p-propoxycarbonylphenyl ester phenylenediamine 51 95 " 5 1-amino-2-methyl-5-benzoic acid " " (3',5-dimethylphenyl) ester 52 95 " 5 1-amino-2-methyl-5-benzoic acid " " ss-chloroethyl ester 53 95 " 5 aminoterephthalic acid diisopropyl ester " " 54 95 " 5 1-amino-2-methyl-5-benzoic acid " " diisopropyl ester 55 95 1-amino-2-methyl-5- 5 1-amino-2-methyl-5-benzoic acid " bluish red benzoic acid methyl (3',5'-dimethylphenyl) ester ester 56 95 " 5 1-amino-2-methyl-5-benzoic acid " " isopropyl ester 57 95 " 5 amino-terephthalic acid diisopropyl ester " " 58 96 methyl 3-amino-4- 4 1-amino-2-methyl-5-benzoic acid 2,5-dimethyl-1,4- " methylbenzoate ss-chloroethyl ester phenylenediamine
I II III IV V VI VII Ex. 59 30 2-methyl-5-chloroaniline 70 1-amino-2-methyl-5-benzoic acid p-phenylenediamine bluish red p-propoxycarbonylphonyl ester 60 95 2-methyl-4,5- 5 1-amino-2-methyl-5-benzoic acid " claret dichloroaniline 3',5'-dimethylphenyl ester 61 95 " 5 1-amino-2-methyl-5-benzoic acid " " ss-chloroethyl ester 62 95 " 5 1-amino-2-methyl-5-benzoic acid " " p-propoxycarbonylphenyl ester 63 95 " 5 1-amino-2-methyl-5-benzoic acid " " isopropyl ester 64 95 2-methyl-3-chloroaniline 5 1-amino-2-methyl-5-benzoic acid 1,5-diaminonaphthaline bluish red isopropyl ester 65 95 " 5 1-amino-2-chloro-5-benzoic acid " " 4'-diphenyl ester 66 95 " 5 1-amino-2-methoxy-5-p-isopropoxy- " " carbonylphenyl ester 67 95 " 5 anthranilic acid p-chlorophenyl ester " " 68 95 " 5 aminoterephthalic acid diisopropyl ester " " 69 95 2,5-dichloroaniline 5 &alpha;-naphthylamine 2,5-dimethyl-1,4- red phenylenediamine 70 95 " 5 1-aminoanthraquinine " " 71 99 " 1 1-amino-2-methyl-5-benzoic acid p-phenylenediamine " n-hexyl ester 72 95 2-methyl-5-chloroaniline 5 " 2-methyl-5-chloro-1,4- bluish red phenylenediamine
I II III IV V VI VII Ex. 73 95 2-methyl-5-chloroaniline 5 5-amino-benzimidazolone 2-methyl-5-chloro-1,4- bluish red phenylenediamine 74 98 " 2 1-amino-2-methyl-5-benzoic acid 2-chloro-5-methyl-1,4- carmine red p-n-propoxycarbonylphenyl ester phenylenediamine 75 99 " 1 " " " 76 95 2,5-dichloroaniline 5 2-aminoacridone " " 77 95 2-methyl-5-chloroaniline 5 1-amino-3-chloroanthraquinone p-phenylenediamine bluish red 78 95 2,5-dichloroaniline 5 5-amino-1-phenylbenzimidazolone " red 79 95 " 2,5 1-amino-2-methyl-5-benzoic acid " scarlet isopropyl ester 2,5 1-amino-2-methyl-5-benzoic acid 2',5'-dichlorophenyl ester 80 90 " 10 1-amino-2-methyl-5-benzoic acid 2-chloro-1,4-phenylene- red n-propyl ester diamine 81 95 " 5 1-amino-2-methyl-5-benzoic acid p-phenylenediamine scarlet (3',5'-dichloro-4'-n-propoxycarbonyl ester) 82 95 2-methyl-5-chloroaniline 5 " 2,5-dimethyl-1,4- carmine red phenylenediamine 83 95 2,5-dichloroamiline 5 1-amino-2-chloro-5-benzoic acid 2-chloro-1,4-phenylene- red 4'-isopropoxycarbonylphenyl ester diamine 84 95 " 5 1-amino-2-methyl-5-benzoic acid p-phenylenediamine scarlet 4'-isopropoxycarbonylphenyl ester 85 95 2-methyl-5-chloroaniline 5 " 2-chloro-5-methyl-1,4- carmine red phenylenediamine
I II III IV V VI VII Ex. 86 70 2-methyl-5-chloroaniline 30 1-amino-2-methyl-5-benzoic acid 2-chloro-5-methyl-1,4- carmine red 4'-n-propoxycarbonylphenyl ester phenylenediamine 87 95 " 5 1-amino-2-methyl-5-benzoic acid 2-methyl-5-methyl-1,4- " ss-chloroethyl ester phenylenediamine 88 95 2,5-dichloro-aniline 5 " " claret 89 95 2-methyl-5-chloroaniline 5 " 2,5-di-n-propoxy-1,4- violet phenylenediamine 90 95 2,5-dichloroaniline 5 1-amino-2-methyl-benzoic acid ss-chloro- " brown ethyl ester 91 95 2-chloro-5-trifluoro- 5 " m-phenylenediamine orange methylaniline 92 95 2,5-dichloroaniline 5 1-amino-2-methyl benzoic acid hexadecyl 3,3'-dichlorobenzidine red ester 93 95 " 5 1-aminoanthraquinone p-phenylenediamine scarlet 94 95 " 5 " 3,3'-dichlorobenzidine brown 95 95 2-methyl-5-chloroaniline 5 " 2-chloro-1,4-phenylene- red diamine 96 95 " 5 " 3,3'-dichlorobenzidine scarlet 97 95 " 5 1-amino-3-chloroanthraquinone " scarlet 98 95 2,5-dichloroaniline 5 1-aminonaphthalene p-phenylenediamine bluish red 99 95 " 5 1-aminonaphthalene 3,3'-dichlorobenzidine brown 100 95 2-methoxy-5-chloro- 5 1-amino-2-methyl-5-benzoic acid iso- 2,5-dimethoxy-1,4- claret aniline propyl ester phenylenediamine
I II III IV V VI VII Ex. 101 95 2-methoxy-5- 5 1-amino-2-methyl-5-benzoic acid iso- 2,5-diethoxy-1,4- claret chloroaniline propyl ester phenylenediamine 102 95 " 5 " 2,5-dichloro-1,4- violet phenylenediamine 103 95 " 5 " 2-chloro-5-methoxy-1,4- claret phenylenediamine 104 95 " 5 " 3,3'-dichlorobenzidine claret 105 95 " 5 " 3,3'-dimethylbenzidine claret 106 95 " 5 " 3,3'-dimethoxybenzidine violet 107 95 2-methoxyaniline 5 " 3,3'-dichlorobenzidine red 108 95 " 5 1-amino-2-methyl-5-benzoic acid 3,3'-dimethylbenzidine bluish red isopropyl ester 109 95 2-methoxy-4-nitroaniline 5 " p-phenylenediamine claret 110 95 " 5 " 2,5-dimethyl-1,4- brown phenylenediamine 111 95 " 5 " 2,5-dichloro-1,4- brown phenylenediamine 112 95 " 5 " 3,3'-dichlorobenzidine violet 113 95 2,5-dichloroaniline 5 1-amino-2-methyl-5-benzoic acid ethyl p-phenylenediamine scarlet ester 114 95 2,5-dichloroaniline 5 " 2-chloro-1,4-phenylene- red diamine 115 95 2-methyl-5-chloroaniline 5 " " carmine
I II III IV V VI VII Ex. 116 95 2-methyl-5-chloroaniline 5 1-amino-2-methyl-5-benzoic acid ethyl 2,5-dichloro-1,4-phenylene carmine ester diamine 117 95 " 5 " 2,5-dimethyl-1,4- carmine phenylenediamine 118 95 " 5 " 2-chloro-5-methyl-1,4- carmine phenylenediamine
Examples 119-136.
The following table lists further disazo pigment mixtures wihch 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 of 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.
I II III IV V VI VII VIII Ex. 119 98 2,5-dichloroaniline 2 1-amino-2-methyl-5-benzoic acid 6-methoxy-2-hydroxy-3- p-phenylenediamine scarlet ss-chloroethyl ester naphthoic acid 120 98 " 2 " " 2-chloro-1,4-phenylene- red diamine 121 98 2-methyl-5-chloroaniline 2 " " 2-chloro-5-methyl-1,4- carmine phenylenediamine 122 95 2,5-dichloroaniline 5 1-amino-2-methyl-5-benzoic acid 6-bromo-2-hydroxy-3 p-phenylenediamine scarlet ss-chloroethyl ester naphthoic acid 123 95 " 5 " " 2-chloro-1,4-phenylene- red diamine 124 95 2-methyl-5-chloroaniline 5 " " 2-chloro-5-methyl-1,4- carmine phenylenediamine 125 95 2,5-dichloroaniline 5 1-amino-2-methyl-5-benzoic acid 6-nitro-2-hydroxy-3- p-phenylenediamine scarlet isopropyl ester naphthoic acid 126 95 " 5 " " 2-chloro-1,4-phenylene- red diamine 127 95 2-methyl-5-chloroaniline 5 " " 2-chloro-5-methyl-1,4- carmine phenylenediamine 128 95 2,5-dichloroaniline 5 1-amino-2-methyl-5-benzoic acid 6-cyano-2-hydroxy-3- 1,4-phenylenediamine scarlet 3',5'-dimethylphenyl ester naphthoic acid 129 95 " 5 " " 2-chloro-1,4-phenylene- red diamine 130 95 2-methyl-5-chloroaniline 5 " " 2-chloro-5-methyl-1,4- scarlet phenylenediamine 131 95 2,5-dichloroaniline 5 1-amino-2-methyl-5-benzoic acid 8-methoxy-2-hydroxy-3- p-phenylenediamine scarlet p-propoxycarbonylphenyl ester naphthoic acid
I II III IV V VI VII VIII Ex. 132 95 2,5-dichloroaniline 5 1-amino-2-methyl-5-benzoic acid 8-methoxy-2-hydroxy-3- 2-chloro-1,4-phenylene- red p-propoxycarbonylphenyl ester naphthoic acid diamine 133 95 2-methyl-5-chloroaniline 5 " " 2-chloro-5-methyl-1,4- carmine phenylenediamine 134 95 2,5-dichloroaniline 5 1-amino-2-methyl-5-benzoic acid 6-methoxy-2-hydroxy-3- p-phenylenediamine scarlet ss-chloroethyl ester naphthoic acid 135 95 " " " 2-chloro-p-phenylene- red diamine 136 95 2-methyl-5-chloroaniline 5 " " 2-chloro-5-methyl-1,4- carmine phenylenediamine
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 160 C 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 C, 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 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% 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 alcchol 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.
WHAT WE CLAIM IS: 1. 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
wherein A represents an aromatic radical, Q, X, Y and Z represent hydrogen atoms or non-solubiiising substituents, and Hal represents a halogen atom, with a diamine of the formula H,N--B-NH, 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 nonwatersolubilising substituents, whilst at least one of the substituents X', Y' and Z' contains at least two atoms more selected from C, O, S, N and Si than X, Y or or at least two of the substituents X', Y' or Z' contain at least one atom more selected from C, O, S, N and Si than X, Y or Z, or coupling a mixture of the diazo compound of the amines of the formulae
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (14)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    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 alcchol 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.
    WHAT WE CLAIM IS: 1. 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
    wherein A represents an aromatic radical, Q, X, Y and Z represent hydrogen atoms or non-solubiiising substituents, and Hal represents a halogen atom, with a diamine of the formula H,N--B-NH, 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 nonwatersolubilising substituents, whilst at least one of the substituents X', Y' and Z' contains at least two atoms more selected from C, O, S, N and Si than X, Y or or at least two of the substituents X', Y' or Z' contain at least one atom more selected from C, O, S, N and Si than X, Y or Z, or coupling a mixture of the diazo compound of the amines of the formulae
    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. 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 alkoxycarbonyl group of 2 to 6 carbon atoms, Y1 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 V1 and Zl are in the meta- or para-position to the azo group.
  3. 3. A process according to claim 1 or 2 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 cr 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 alkcxycarbonyl 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; V and Z. represent chlorine atoms, methyl or nitro groups of alkoxycarbonyl groups of 2 to 6 carbon atoms.
  4. 4. A process according to any of claims 1 to 3 wherein the main component is a carboxylic acid chloride or the formula
    wherein X3 represents chlorine or methyl, Y, represents chlorine or alkoxycarbonyl of 1 to 4 carbon atoms.
  5. 5. A process according to any of claims 1 to 4 wherein the additional 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 Rl 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. methvl phenvl or alkoxycarbonyl of 2 to 6 carbon atoms.
  6. 6. A process according to any of claims 1 to 5 wherein the amount of main component is 70 to 99%, and the amount of additional component is 30 to 1%, based on the given amount of the components.
  7. 7. A process according to claim 6 wherein the amount of main component if 95 to 98% and the amount of additional component is 5 to 2%.
  8. 8. A process according to claim 1 wherein a phenylenediamine or naphthylenediamine is used as diamine.
  9. 9. A process according to claim 8 wherein the phenylenediamine has the formula
    wherein X and Ys are hydrogen or halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms.
  10. 10. A process according to claim 1, substantially as hereinbefore described with reference to any one of Examples 1 to 136.
  11. 11. The azo pigments obtained by the process according to any one of claims 1 to 10.
  12. 12. A process for pigmenting organic material of high molecular weight which comprises incorporating therein an azo pigment according to claim 10 or 11.
  13. 13. Organic material of high molecular weight which contain an azo pigment according to claim 10 or 11.
  14. 14. Organic material according to claim 13, substantially as hereinbefore described with reference to any one of Examples 137 to 140.
GB5156977A 1976-12-31 1977-12-12 Process for the production of azo pigments Expired GB1595489A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0822235A3 (en) * 1996-07-31 1998-08-26 Ciba SC Holding AG Process for the manufacture of disazo pigment mixtures with a high tinctorial power
CN102666734A (en) * 2009-12-22 2012-09-12 大日精化工业株式会社 Asymmetrical polyazo dye, manufacturing method for same, colouring agent and colouring method
CN102816457A (en) * 2012-08-23 2012-12-12 鞍山七彩化学股份有限公司 Red azo condensation mixed pigment with high tinting strength and its preparation method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0594789U (en) * 1992-05-26 1993-12-24 リズム時計工業株式会社 Mechanism of Karakuri Doll

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0822235A3 (en) * 1996-07-31 1998-08-26 Ciba SC Holding AG Process for the manufacture of disazo pigment mixtures with a high tinctorial power
US5883167A (en) * 1996-07-31 1999-03-16 Ciba Specialty Chemicals Corporation Process for the preparation of highly coloured diazo pigment mixtures
CN102666734A (en) * 2009-12-22 2012-09-12 大日精化工业株式会社 Asymmetrical polyazo dye, manufacturing method for same, colouring agent and colouring method
CN102666734B (en) * 2009-12-22 2014-11-19 大日精化工业株式会社 Asymmetrical polyazo dye, manufacturing method for same, colouring agent and colouring method
CN102816457A (en) * 2012-08-23 2012-12-12 鞍山七彩化学股份有限公司 Red azo condensation mixed pigment with high tinting strength and its preparation method
CN102816457B (en) * 2012-08-23 2013-12-11 鞍山七彩化学股份有限公司 Red azo condensation mixed pigment with high tinting strength and its preparation method

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JPS5385826A (en) 1978-07-28
BR7708740A (en) 1978-08-22
DE2758407C2 (en) 1987-07-23
CH624977A5 (en) 1981-08-31
DE2758407A1 (en) 1978-07-13
FR2376190A1 (en) 1978-07-28

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