CA1107274A

CA1107274A - Monoazo pigments and process for their production

Info

Publication number: CA1107274A
Application number: CA294,623A
Authority: CA
Inventors: Rolf Muller; Armand Roueche
Original assignee: Ciba Geigy Investments Ltd
Current assignee: BASF Schweiz AG
Priority date: 1977-01-11
Filing date: 1978-01-09
Publication date: 1981-08-18
Also published as: DE2800765A1; CH627200A5; DE2800765C2; IT1092719B; BR7800144A; FR2376886A1; FR2376886B1; GB1586724A; IT7819134A0; JPS5388036A

Abstract

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Abstract of the Disclosure Monoazo pigments of the formula wherein R represents a naphthyl group or a phenyl group which is unsubstituted or substituted by halogen, alkyl, alkoxy, alkanoyl, trifluoromethyl or by a group of the formula in which R1 represents alkyl which is unsubstituted or substituted by halogen or alkoxy, or represents cyclo-alkyl, benzyl or phenyl which is unsubstituted or substituted by halogen, alkyl, alkoxy, alkoxycarbonyl or alkanoylamino and, with the proviso that R2 represents hydrogen, R can also be alkyl which is unsubstituted or substituted by halogen.

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R2 represents hydrogen. alkyl or phenyl which is unsubstituted or substituted by halogen. alkyl or alkoxy, X1 represents hydrogen or chlorine, alkyl or alkoxy.
alkoxycarbonyl or phenoxy, X2 represents hydrogen or chlorine, alkyl, alkoxy or phenoxy, X3 represents a direct bond or phenylene, n is 1 or 2, Z represents a -CO- or -?? group. and Z1 represents oxygen or sulphur. the -NH- group or a group of the formula -OCH2-, -NHCO, or .

in which R3 represents hydrogen, alkyl or phenyl which is unsubstituted or substituted by halogen, alkyl or alkoxy, are valuable pigments coloring plastics.
lacquers and printing inks in yellow to red shades of excellent fastness properties.

Description

~ 1~ 7 2 7 4 The present invention relates to useful novel monoazo pigments of the formula (I) _ _ C~

2 (X2)n CO
~; 1 3-NHCOCH ~ (I) ZOR

wherein R represents a naphthyl group or a phenyl group which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms, alkanoyl groups of 2 to 4 carbon atoms, trifluoromethyl groups, or by a group of the formula ~ COORl in which Rl represents an alkyl group of 1 to 4 carbon atoms which is unsubstituted or substituted by halogen atoms or alkoxy groups of 1 to 4 carbon atoms, or represents a cycloalkyl group of 5 to 6 carbon atoms, a benzyl group or a phenyl group which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms, alkoxycarbonyl groups of 2 to 4 carbon atoms or by alkanoylamino groups of 2 to 4 carbon atoms, and, with the proviso that R2 represents t hydrogen, R can also be an alkyl group of 1 to 4 carbon ... .. . .

1~)7Z74 atoms which is unsubsti.tuted or substltuted by halogen, R2 represents a hydrogen atom, an alkyl group of 1 ~o 4 carbon atoms or a phenyl radical which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms, Xl represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, an alkoxycarbonyl group of 2 to 4 carbon atoms or a phenoxy group, X2 represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms or a phenoxy group, X3 represents a direct bond or a phenylene group, n is 1 or 2, Z represents a -CO- or -SO2- group, and Zl represents an oxygen or sulphur atom, the-NH- group or a group of the formula -Cl=C-, -OCH2-, -NHCO-, I OH
-Cl=C or -N=IC-, in which R3 represents a hydrogen atom, R3 R3 .
an alkyl group of 1 to 4 carbon atoms or a phenyl radical which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms.
The monoazo pigments of the formula (I) can in general be unconditioned and are obtained by coupling the diazo compound of an amine of the formula (II~

.. . . ..

.

-H2~ ~ (II) Z~ .
with an acetoacetylarylide of the formula (III) ~ ~ - X3-NHCOC112COCH3 (III) in the molar ratio 1:1.
The halogen substituents are in particular chlorine or bromine, preferably chlorine.
Alkyl group substituents are for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl or tert-butyl groups, but are preferably methyl or ethyl.
Alkoxy group substituents are for example methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy or tert-butoxy groups, but are preferably the methoxy and ethoxy groups.
An alkoxycarbonyl group substituent is for example a methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl or iso-propoxycarbonyl group. Preferably it is a methoxycarbonyl group.
An alkanoylamino group substituent is for example an , .
" - - " ' 7~74 acetylamino, propionylamino, n-butyrylamino or isobutyrylamino group. Preferably it is the acetylamino group.
A cycloalkyl group Rl is a cyclopentyl group, especially however a cyclohexyl group.
A substituted phenyl group Rl is for example mono-, di-or trichlorophenyl, tolyl, xylyl or mesitilenyl, ethylphenyl, tert-butylphenyl, diethylphenyl, triethylphenyl, methoxy-phenyl, dirnethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, propoxyphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, dimethoxycarbonylphenyl, acetylaminophenyl, propionylamino-phenyl, isobutyrylaminophenyl, the substituents being especially in the ortho- and para-position and, in the case of mono-substituted phenyl, preferably in the para-position. As a substituted phenyl group, Rl is preferably p-chlorophenyl or p-tolyl.
Substituted phenyl groupsrepresented by R2 and R3 are for example mono-, di- or trichlorophenyl, tolyl, xylyl or mesitilenyl, ethylphenyl, tert-butylphenyl, diethylphenyl, triethylphenyl, methoxyphenyl, dimethoxyphsnyl, trimethoxy-phenyl, ethoxyphenyl, propoxyphenyl, the substituents being especially in the ortho- and para-position and, in the case of mono-substituted phenyl, preferably in the para-position.
As substituted phenyl groups, R2 and R3 are preferably p-chlorophenyl or p-tolyl.
Particularly interesting monoazo pigments are those of the formula (IV) ' '' ', '-, ::
- . . . .
, -- , - . .
- . ~ .
-~ i~ 7 ~ 4 O C / 2 ~ ~ NnICOCI~ ll (IV) 2 N-N ~ Yl ~ Y3 wherein R2, Xl, X2 and Z are as defined in formula (I), Yl represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, Y2 and Y3, each independently of the other, represent a hydrogen or chlorine atom, a trifluoromethyl group, an alkyl or alkoxy group of 1 to 4 carbon atoms, an alkanoylamino group of 2 to 4 carbon atoms or the group of the formula -COORl - in which Rl has the given meaning, and ~2 represents the -NH- group or a group of the formula -IC-CH-, in which R2 has the given meaning.

Preferred pigments are those of the formula (V) ' . , . .

" 11~7;~4 fH3 \ N ~ NHCOCH 1l (V) ` 12 N~-N - ~ `

wherein R2, Xl, X2, Z and Z2 have the given meanings and R5 represents an alkyl group of 1 to 4 carbon atoms, a benzyl group or a phenyl group which is unsubstituted or substituted by chlorine atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms .
Particularly preferred monoazo pigments are those of the formula (VI) . . CH3 H CO

O C/ ~ N~N ~ (VI) .: R6 ZO ~ COOR5 .
wherein ~-R5 and Z have the given meanings, R6 represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, -' 7~74 X4 and X5, each independently of the other, represents a chlorine atom, a methyl, methoxy or ethoxy group.
Particularly interes~ing monoazo pigments are also those of the formula (VII) qH3 H CO
O C / ~ NUCOCU ~ (VII) wherein Xl and X2 have the given meanings and R~ represents an alkyl or chloroalkyl group of 1 to 4 carbon atoms.
Particularly preferred monoazo pigments are those of the formula (VIII) - .
CH
H C~O
NHCOCH ~ ~VIII) . . COOR7 wherein X4 and X5, each independently of the other, represent a hydrogen or chlorine atom, a methyl, methoxy or alkoxy group, and R7 represents a methyl, ethyl or chloroethyl group.
Examples of diazo components are:

. , 8 -~, . ~ .. ' - .

:, . .

anthraniiic acid phenyl ester anthranilic acid 4'-chlorophenyl ester anthranilic acid 4'-methylphenyl ester l-amino-2-chlorobenzene-5-carboxylic acid 4'~methylphenyl ester l-amino-2-methoxybenzene-5-carboxylic acid 4'-methylphenyl ester l-amino-2-methylbenzene-5-carboxylic acid phenyl ester l-amino-2-methylbenzene-5-carboxylic acid 2'-chlorophenyl ester l-amino 2-methylbenzene-5-carboxylic acid 4'-chlorophenyl ester l-amino-2-methylbenzene-5-carboxylic acid 2',4'-dichlorophenyl ester l-amino-2-methylbenzene-5-carboxylic acid 2',4',5'-trichloro-phenyl ester l-amino-2-chlorobenzene-5-carboxylic acid 2'-methylphenyl ester l-amino-2-methylbenzene-5-carboxylic acid 4'-methylphenyl ester l-amino-2-chlorobenzene-5-carboxylic acid 4'-phenylphenyl ester l-amino-2-methylbenzene-5-carboxylic acid 4'-methoxyphenyl ester l-amino-2-methylbenzene-5-carboxylic acid 4'-chloro-2'-methyl-phenyl ester l-amino-2-methylbenzene-5-carboxylic acid 4'-chloro-3'-methyl-phenyl ester l-amino-2-methylbenzene-5-carboxylic acid 4'-isobutylphenyl ester :
l-amino-2-methylbenzene-5-carboxylic acid 3'-trifluoromethyl-phenyl ester ~jJ _ 9 l-amino-2-methylbenæene-4-carboxylic acid 4'-chloro-2'-methyl-phenyl ester l-amino-2-methylbenzene-4-carboxylic acid 4'-phenylphenyl ester l-amino-2-methylbenzene-4-carboxylic acid phenyl ester l-amino-2-methylbenzene-4-carboxylic acid 4'-chlorophenyl ester l-amino-2-methylbenzene-4-carboxylic acid 4'-methylphenyl ester 2-aminoterephthalic acid diphenyl ester

3-aminoisophthalic acid diphenyl ester l-amino-2-chlorobenzene-5-carboxylic acid 4'-chlorophenyl ester l-amino-2-chlorobenzene-5-carboxylic acid ~-naphthyl es~er l-amino-2-methoxybenzene-5-carboxylic acid 4'-chlorophenyl ester l-amino-2-methoxybenzene-5-carboxylic acid 4'-methoxyphenyl ester l-amino-2-phenoxybenzene-5-carboxylic acid 4'-rnethylphenyl ester l-amino-2-chlorobenzene-5-sulphonic acid 4'-methoxyphenyl ester l-amino-2-methylbenzene-5-sulphonic acid 4'-chlorophenyl ester l-amino-2-methoxybenzene--5-sulphonic acid 4'-methylphenyl ester l-amino-2-chlorobenzene-5-sulphonic aci.d phenyl ester l-amino-2-methylbenzene-5-sulphonic acid phenyl ester l-amino-2-methoxybenzene-5-sulphonic acid phenyl ester 1~ 7 ~ ~

l-amino-2-nitro-5-carboxylic acid phenyl ester

4-methyl-3-aminobenzoic acid 4'-methoxycarbonylphenyl ester 4-chloro-3-aminobenzoic acid 4'-methoxycarbonylphenyl ester 4-methoxy-3-aminobenzoic acid 4'-methoxycarbonylphenyl ester 4-pheno.xy-3-aminobenzoic acid 4'-methoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 3' methoxycarbonylphenyl ester 4-chloro-3-aminobenzoic acid 3'-methoxycarbonylphenyl ester 4-phenoxy-3-aminobenzoic acid 3'-methoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 4'-ethoxycarbonylphenyl ester 4-methoxy-3-aminobenzoic acid 3'-ethoxycarbonylphenyl ester 4-methyl-3~aminobenzoic acid 3'-ethoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 4'-n-propoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 3'-n-propoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 4'-isopropoxycarbonylphenyl ester : 4-methyl-3-aminobenzoic acid 3'-isopropoxycarbonylphenyl ester 4-chloro-3-aminobenzoic acid 4'-isopropoxycarbonylphenyl ester 4-methoxy-3-aminobenzoic acid 4'-isopropoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 4'-benzylo~ycarbonyLphenyl ester 4-methyl-3-aminobenzoic acid 4'-~-chloroethoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 3'-~-chloroethoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 4'-n-butoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 4;-isobutoxycarbonylphenyl ester.
The amines of the formula II are advantageously obtained , 7 ~

by condensation of a nitrobenzoyl chloride or a nitrobenzene-sulphonyl chloride of the formula X

~Cl wherein Xl and Z have the given meanings, with a hydroxy-benzene derivative of the formula HOR
wherein R has the given meaning, and reduction of the resulting nitro ester to give the aminocarboxylate or aminobenzenesulphonate. A catalytic reduction is preferably carried out.
The aminobenzenecarboxylates or aminobenzenesulphonates are diazotised and coupled with the acetoacetylarylides of the formula III.
The coupling components are obtained in simple manner by treating the corresponding amines with diketene. Examples of such amines are:

5 amino-benzimidazolone 5-amino-1-methyl-benzimidazolone 5-amino-1-n-butyl-benzimidazolone 5-amino-1-phenyl-benzimidazolone 5-amino-1-p-chlorophenyl-benzimidazolone . . .... . . ... ... .

` li~ 7~74 5-amino-1-p-methylphenyl-benzimidazolone 5-amino-1-p-methoxyphenyl-benæimidazolone 5-amino-6-chloro-benzimidazolone 5-amino-6-bromo-benzimidazolone 5-amino-6-methyl-benzimidazolone 5-amino-6-methoxy-benzimidazolone

6-amino-benzoxazolone 5-amino-benzoxazolone :' 5-amino-7-chloro-benzoxazolone 6-amino-5-chloro-benzoxazolone 6-amino-5-methyl-benzoxazolone 6-amino-5-chloro-benzthiazolone 6-amino-5-methyl-benzthiazolone 6-amino-quinazolone-4 -6-amino-2-methyl-quinazolone-4 6-amino-2-methoxy-quinazolone-4 6-amino-7-chloro-2-methyl-quinazolone-4

7-amino-quinazolone-4 2-(4'-aminophenyl)-quinazolone-4 2-(3'-aminophenyl)-quinazolone-4 2-(4'-amino-3'-methoxyphenyl)-quinazolone-4 2-(4'-amino-3'-chlorophenyl)-quinazolone-4 2-(3'-amino-4'-methylphenyl)-quinazo].one-4 6-amino-2,4-dihydroxyquinazoline 7-amino-phenmorpholone-3 ~ 27 6-amino-phenmorpholone-3 7-amino-6-chloro-pllenmorpholone-3 7-amino-6-methyl-phenmorpholone-3 7-amino-6-methoxy-phenmorpholone-3 6-amino-quinolone-2 6-amino-4-methyl-quinolone-2 7-amino-4-methyl-quinolone-2 7-amino-4,~-dimethyl-quinolone-2 6-amino-7-chloro-4-methyl-quinolone-2 7-amino 4-methyl-6-methoxy-quinolone-2 6-amino-1,3-dihydroxy-isoquinoline 6-amino-2,4-dihydroxy-quinoline 6-amino-2,3-dihydroxyquinoxaline 4-amino-phthalamide The cited heterocyclic compounds are known compounds.
The diazotisation is carried out by kno~n methods.
The coupling preferably takes place in a weakly acid medium, advantageously in the presence of conventional agents that promote the coupling. As such coupling promoters there may be mentioned in particular dispersants, for example aralkylsulphonates, such as dodecylbenzenesulphonate, or 1,1'-dinaphthylmethane-2,2'-disulphonic acid or polyconden-sation products of alkylene oxides. The dispersion of the coupling component can also advantageously contain protective colloids, for example methylcellulose or minor amounts of : ; 5 1 ~ 72~74 inert orgar.ic solvents which are sparingly soluble or insoluble in water, for example optionally halogenated or nitrated aromatic hydrocarbons, for example, benzene, toluene, xylene, chlorobenzene, dichlorobenzene or nitrobenzene, and also aliphatic halogenated hydrocarbons, for example, carbon tetrachloride or ~richloroethylene, and furthermore water-miscible organic solvents,for example acetone, methyl ethyl ketone, methanol, ethanol or isopropanol, or preferably dimethyl formamide.
The coupling can also advantageously be carried out by continuously combining an acid solution of the diazonium salt with an alkaline solution of the coupling component in a mixing nozzle, whereupon an immediate coupling of the component occurs. Care must be taken that the diazo component and the coupling component are present in equimolecular amounts in the mixing nozzle, and a slight excess of coupling component proves to be advantageous. This is most simply achieved by controlling the pH of the liquid in the mixing nozzle. Further-more, intense turbulent mixing of the two solutions in the mixing nozzle must be ensured. The resultant colourant dispersion is continuously drawn off from the mixing nozzle and the colourant separated by filtration.
Finally, the coupling can also be carried out by suspending the amine to be diazotised with the coupling component in the molar ratio 1:1 in an organic solvent and , . . .

~ ~ 7Z~4 treating the coupling mixture with a diazotising agent, in particular an ester of nitrous acid, such as methyl. ethyl, butyl, amyl or octyl nitrite.
The pigmen~s of the present invention have in general a good texture and can be generally used with entirely satisfactory results as crude products. If desired, however, the crude products can be converted into a finely dispersed form by grinding or kneading, advantageously using grinding assistants, such as inorganic and/or organic salts in the presence or absence of organic so].vents. After the grinding procedure, the assistants are removed in the conventional manner: soluble inorganic salts for example with water, and water-insoluble assistants for example by steam distillation.
The properties of the crude pigments can often be improved by treating them with organic solvents, preferably those having a boiling point above 100C. Particularly suitable organic solvents are: benzenes which are substituted by halogen atoms, alkyl or nitro groups, for example xylenes, chlorobenzene, o-dichlorobenzene or nitrobenzene, as well as pyridine bases, such as pyridine, picoline or quinoline, and also ketones, for example, cyclohexanone; ethers, for example ethylene glycol monomethyl or monoethyl ether; amides, such as dimethyl formamide or N-methylpyrrolidone, as well as dimethyl sulphoxide, sulpholane or water alone, with or with-out pressure. The aftertreatment can also be carried out in water in the presence of organic solvents and/or with the , .. .. ,~ .. , . . ... - ... . --.
.
. . :

.

~1~7Z7~

addition of surface active substances.
The aftertreatment is effected preferably by heating the pigment in the solvent to 100 to 200C, whereupon in certain cases an increase in the granular size and, in appropriate circumstances, a change in the crystal modification, occurs. The fastness to light and migration of the resultant pigments are thereby favourably influenced.
The pigments obtained according to the invention are suitable for colouring organic material of high molecular weight of natural or synthetic origin. Such material can comprise for example natural resins, drying oils or rubber.
However, it can also comprise modified natural materials, for example chlorinated rubber, oil-modified alkyd resins or viscose or cellulose derivatives, such as acetyl cellulose and nitrocellulose, and in particular man-made organic poly-plastics, that is to say, plastics which are obtained by polymerisation, polycondensation and polyaddition. The following products may be mentioned in particular as belonging to this class of plastics: polyethylene, polypropylene, polyisobutylene, polystyrene, polyvinyl chloride, polyvinyl acetate, polyacrylonitrile, polyacrylates~ polymethacrylates;
polyesters, in particular esters of high molecular weight of aromatic polycarboxylic acids and polyfunctional alcohols;
polyamides, the condensation products of formaldehyde and phenols (phenolic plastics), and the condensation products of formaldehyde and urea, thiourea and melamine (aminoplasts);

.

~ 72~

the polyesters used as varnish gums, namely both saturated polyesters, for example alkyd resins, and unsaturated poly-esters, for example maleic resins, and also the polyaddition and polycon~ensation products of epichlorohydrin and polyols or polyphenols known as epoxide resins; in addition thermoplasts, i.e. the non-curable polyplastics. It must be emphasised that not only the homogeneous compounds can be pigmented according to the i~vention, but also mixtures of polyplastics, as well as co-condensates and copolymers, for example those based on butadiene.
The pigments of the present invention are particularly suitable for colouring polyplastics, such~as the film formers or binders known as vehicles, especially'for colouring boiled linseed oil, nitrocellulose, alkyd resins, melamine resins and ure-formaldehyde resins. The pigmenting of the organic substances of high molecular weight with the pigments of the formula (I) is effected for example by mixing such a pigment, optionally in the form of masterbatches, with th0se substrates using roll mills, mixing or grinding devices. The pigmented material is thereafter brought into the desired final form by knowm processes, such as calendering, pressing, extruding, coating, casting, or by injection moulding. It is often desirable to add plasticisers to the compounds of high mole--cular weight before forming them in order to obtain non-rigid moulded articles or to diminish their brittleness. Examples of such plasticisers are esters of phosphoric acid, phthalic acid or sebacic acid. The plasticisers can be added in the process 1~'7Z~7'~

of the invention before or after the incorporation of thepigment dye in the polyplastics. In order to obtain different shades it is also possible to add, in addition to the compounds of the formula (I), fillers or other colouring constituents, such as,white, coloured or black pigments, in any amounts to the organic substances.
For pigmenting lacquers and printing inks, the organic materials of high molecular weight and the compounds of the formula (I), optionally together with additives, such as fillers, other pigments, siccatives or plasticisers, are finely dispersed or dissolved in a joint organic solvent or solvent mixture. The procedure can consist for example in dispersing or dissolving each of the components individually or also several jointly, and only thereafter combining all the components.
The pigmented organic materials of high molecular weight contain normally amounts from 0.001 to 30% by weight of a compound of the formula (I), based on the organic substance o high molecular weight to be pigmented. Polyplastics and lacquers contain preferably 0.1 to 5% by weight, and printing inks contain preferably 10 to 30% by weight. The amount of pigment to be chosen depends primarily on the desired colour strength, on the layer thickness of the moulded article, and finally also on the content of white pigment, if any, in the polyplastic.

', ~, .

The colourants of the present invention are distinguished by their easy accessibility, and by their good fastness to heat, light, overstripe bleeding, migration and good resistance to atmospheric influences. Compared with disazo pigments, they have the advantage that the aftertreatment in organic solvents is not absolutely necessary in order to obtain a good texture and fastness to migration. In spite of the high molecular weight of the diazo bases, and in comparison to diazo bases of lower molecular weight, the pigments of the present invention have a h'gh colour strength.
Pigments similar to those of the invention are known from German Auslegeschriften 1,808,0L5 and 1,808,017. The comparable pigments of the former patent specification differ from those of the invention in that the carboxylic acid alkyl ester group is in the ortho- and not in the meta-position to the azo group; and the pigments of the latter patent specifica-tion differ in that they contain a N-alky]-substituted benz-imidazolone radical. Surprisingly, the pigments of the present invention, compared to the comparable, structurally very similar pigments of the two patent specifications referred to above, have improved pigment properties, especially an improved fastness to migration.
In the following Examples which illustrate the invention the parts and percentages are by weight unless otherwise stated.

7~7 Examp~e 1 31.3 parts of 4-methyl-3-aminobenzoic acid 4'-propoxycarbonyl-phenyl ester are stirred at room temperature in 200 parts by volume of glacial acetic acid. After about 5 minutes, 25 parts by volume of concentrated hydrochloric acid are added to the completely clear solution. The solution is cooled to 0C with ice, treated at 0 5C with 25.5 parts by volume of 4N sodium nitrite solution over the course of 15 minutes, and then diluted with 150 parts by volume of ice-water. After stirring for about 1 hour at 0-5C, excess nitrite is completely destroyed with sulphamic acid and the reaction mixture is then filtered clear. 23.3 parts of 5-acetoacetylaminobenzimidaz-olone are dissolved at room temperature in 20 parts by volume of 30% sodium hydroxide solution and 350 parts by volume of water. Two parts of Hyflo are then added to the solution, which is subsequently filtered clear. To the coupling solution are then added 7.5 parts by volume of 30% hydrochloric acid and then, in addition, 20 parts of calcined sodium carbonate.
The diazo solution is added to the coupling component at 15-20C in the course of about 30 minutes. When the addition of diazo solution is complete, the pH falls from 12.2 to 4.3.
The batch is stirred for 6 to 8 hours at 20-25C, then heated to 80C. The pigment is filtered off hot, washed with hot water and then with cold isopropanol. The filter cake is dried ~ 21 -in vacuo at 70-80C, affording 52.9 parts t95% of theory~
of a brown powder of the formula C~13 ~0-C1~3 N~ C0-NH ~ C0 C00 ~ C00-C1~2-C~12 CH3 which colours PVC in fast, yellowish brown shades.
A change in crystal modification occurs after an aftertreatment in dimethyl formamide (30 minutes at boiling temperature), giVi1lg a pigment which colours PVC in a bright, yellow shade of very good fastness to migration and light and very good resistance to atmospheric influences. The same crystal modification is also obtained by heating the crude pigment for 6 hours in water, with the addition of 1% oleyl alcohol, at 150C under pressure.
The following table lists further pigments which are obtained by coupling the diazo compound of the amine of column I with the acetoacetyl compound of the amine of column II and subsequently subjecting them to an aftertreatment in the solvent indicated in column IV. Column III indicates the shade in which PVC is coloured with 0.2% of these pigments.

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Example 46 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 dikutyl tin dilaurate and 2 g of titanium dioxide and the mixture is processed to a thin sheet for 15 minutes at 160~
on a roll mill. The yellow colouration obtained is strong and fast to migration and light.

Example 47 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, yellow shade of good transparence and good gloss is obtained. In three- or four-colour printing, very brilliant green shades can be obtained by superimposing on blue.
The pigment is also suitable for other printing methods, ~ .

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such as intaglio printing, offset printing, flexographicprinting, ~ith equally good results.

Example 48 ... .

15 g of collodion cotton containing 35% of butanol, 15 g of a phthalate resin rnodified 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 etl~er, 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, giv~ng a yellow coating of very good fastness to light and overstripe bleeding and very good resistance to atmospheric influences.

Example 49 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 120C, - . .
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a brilliant ~ellow colouration of good fastness to light and o~7erstripe bleeding and good resistance to atmofipheric influences is obtained.

Claims

WHAT IS CLAIMED IS:

1. Monoazo pigments of the formula (I) (I) wherein R represents a naphthyl group or a phenyl group which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms, alkanoyl groups of 2 to 4 carbon atoms, trifluoromethyl groups, or by a group of the formula in which R1 represents an alkyl group of 1 to 4 carbon atoms which is unsubstituted or substituted by halogen atoms or alkoxy groups of 1 to 4 carbon atoms, or represents a cycloalkyl group of 5 to 6 carbon atoms, a benzyl group or a phenyl group which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms, alkoxycarbonyl groups of 2 to 4 carbon atoms or by alkanoylamino groups of 2 to 4 carbon atoms, and, with the proviso that R2 represents hydrogen, R can also be an alkyl group of 1 to 4 carbon atoms which is unsubstituted or substituted by halogen, R2 represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms or a phenyl radical which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms, Xl represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, an alkoxycarbonyl group of 2 to 4 carbon atoms or a phenoxy group, X2 represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms or a phenoxy group, X3 represents a direct bond or a phenylene group, n is 1 or 2, Z represents a -CO- or -SO2- group, and Z1 represents an oxygen or sulphur atom, the NH- group or a group of the formula , -OCH2-, -NHCO-, or , in which R3 represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms or a phenyl radical which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms.

2. Monoazo pigments according to claim 1 of the formula (IV) (IV) wherein R2, Xl, X2 and Z are as defined in claim 1, Y1 represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, Y2 and Y3, each independently of the other, represent a hydrogen or chlorine atom, a trifluoromethyl group, an alkyl or alkoxy group of 1 to 4 carbon atoms, an alkanoylamino group of 2 to 4 carbon atoms or the group of the formula -COORl in which R1 is as defined in claim 1, and Z2 represents the -NH- group or a group of the formula , in which R2 has the given meaning.

3. Monoazo pigments according to claim 2 of the formula (V) (V) wherein R2, X1, X2, Z and Z2 are as defined in claim 2 and R5 represents an alkyl group of 1 to 4 carbon atoms, a benzyl group or a phenyl group which is unsubstituted or substituted by chlorine atoms, alkyl or alkoxy groups of 1 to 4 carbon atoms.

4. Monoazo pigments according to claim 3 of the formula (VI) (VI) wherein R5 and Z are as defined in claim 3, R6 represents a hydrogen atom or an alkyl group of 1 to 4 carbon atoms, X4 and X5, each independently of the other, represents a chlorine atom, a methyl, methoxy or ethoxy group.

5. Monoazo pigments according to claim 1 of the formula (VII) (VII) wherein X1 and X2 are as defined in claim 1 and R4 represents an alkyl or chloroalkyl group of 1 to 4 carbon atoms.

6. Monoazo pigments according to claim 5 of the formula (VIII) (VIII) wherein X4 and X5, each independently of the other, represent a hydrogen or chlorine atom, a methyl, methoxy or alkoxy group.
and R7 represents a methyl, ethyl or chloroethyl group.

7. The monoazo pigment according to claim 1 of the formula

8. A process for pigmenting organic material of high molecular weight which comprises the use of the pigments according to claim 1.

9. The pigmented material obtained according to claim 8.