GB1586724A - Monoazo acetoacetarylide pigments and process for their production - Google Patents

Monoazo acetoacetarylide pigments and process for their production Download PDF

Info

Publication number
GB1586724A
GB1586724A GB673/78A GB67378A GB1586724A GB 1586724 A GB1586724 A GB 1586724A GB 673/78 A GB673/78 A GB 673/78A GB 67378 A GB67378 A GB 67378A GB 1586724 A GB1586724 A GB 1586724A
Authority
GB
United Kingdom
Prior art keywords
group
carbon atoms
alkyl
amino
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB673/78A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of GB1586724A publication Critical patent/GB1586724A/en
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
    • C09B29/0011—Monoazo dyes prepared by diazotising and coupling from diazotized anilines from diazotized anilines directly substituted by a heterocyclic ring (not condensed)
    • 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
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/32—Monoazo dyes prepared by diazotising and coupling from coupling components containing a reactive methylene group
    • C09B29/33—Aceto- or benzoylacetylarylides
    • C09B29/335—Aceto- or benzoylacetylarylides free of acid groups

Abstract

New monoazo pigments of the formula I <IMAGE> where A, X1, X2, Z and R are each as defined in Claim 1, are prepared by coupling the diazo compound of corresponding anilines with an acetoacetarylamide of the formula III <IMAGE> in a molar ratio of 1:1. The compounds (I) are suitable for pigmenting macromolecular organic material, which can be natural or synthetic in origin. They are notable for ease of availability and good heat, light, overcoating, migration and weather fastness.

Description

(54) NOVEL MONOAZO ACETOACETARYLIDE PIGMENTS AND PROCESS FOR THEIR PRODUCTION (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 acetoacetarylide monoazo pigments.
The present invention provides useful novel monoazo pigments of the formula (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-amino groups -of 2 to 4 carbon atoms, trifluoromethyl groups, or by a group of the formula -COOR1 in which R, 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 or 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, 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, with the proviso that R2 represents a hydrogen atom when R represents an alkyl group of l to 4 carbon atoms, X, represents a hydrogen or chlorine atom, an alkyl or alkoxy group of l 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 Z, represents an oxygen or sulphur atom, the -NH- group or a group of the formula
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.
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)
with an acetoacetylarylide of the formula (III)
in the molar ratio 1:1.
The halogen substituents are in particular chlorine or bromine, preferably chlorine.
Alkyl group substituents are methyl, ethyl, n-propyl, isopropyl, n-butyl, secbutyl or tert-butyl groups, but are preferably methyl or ethy!.
Alkoxy group substituents are methoxy, ethoxy, n-propoxy, isopropoxy, nbutoxy, sec-butoxy or tert-butoxy groups, but are preferably the methoxy and ethoxy groups.
An alkanoylamino group substituent is for example an acetylamino, propionylamino, n-butyrylamino or isobutyrylamino group. Preferably it is the acetylamino group.
A cycloalkyl group R1 is a cyclopentyl group, especially however a cyclohexyl group.
A substituted phenyl group R1 is for example mono-, di- or trichlorophenyl, tolyl, xylyl or mesitilenyl, ethylphenyl, tert-butylphenyl, diethylphenyl, triethylphenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, propoxyphenyl, methoxycarbonylphenyl, ethoxycarbonylphenyl, dimethoxycarbonylphenyl, acetylaminophenyl, propionylaminophenyl, isobutyrylaminophenyl, the substituents being especially in the ortho- and paraposition and, in the case of mono-substituted phenyl, preferably in the paraposition. As a substituted phenyl group, R1 is preferably p-chlorophenyl or p-tolyl.
Substituted phenyl groups represented by R2 and R3 are tor example mono-, di- or trichlorophenyl, tolyl, xylyl or mesitilenyl, ethylphenyl, tert-butylphenyl, diethylphenyl, triethylphenyl, methoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, 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)
wherein R2, X1, X2 and Z are as defined in formula (I), Y1 represents a hydrogen or chlorine atom, an alkyl or alkoxy group òf 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 --COOR, in which R, has the given meaning, and Z2 represents the -NH- group or a group of the formula
in which R2 has the given meaning.
Preferred pigments are those of the formula (V)
wherein R2, X1, 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) wherein
6 and Z have the given meanings, RB 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.
Particularly interesting monoazo pigments are also those of the formula (VII)
wherein X, and X2 have the given meanings and R4 represents an alkyl or chloroalkyl group of I to 4 carbon atoms.
Particularly preferred monoazo pigments are those of the formula (VIII)
wherein X4 and X5, each independently of the other, represent a hydrogen or chlorine atom, a methyl, methoxy or ethoxy group, and R7 represents a methyl, ethyl or chloroethyl group.
Examples of diazo components are: l-amino-2 chlorobenzene-5-carboxylic acid 4'-methylphenyl ester l-amino-2-methoxybenzene-5-carboxylic acid 4'-methylphenyl ester 1-amino-2-methylbenzene-5-carboxylic acid phenyl ester 1-amino-2-methylbenzene-5-carboxylic acid 2'-chlorophenyl ester 1-amino-2-methylbenzene-5-carboxylic acid 4'-chlorophenyl ester 1-amino-2-methylbenzene-5-carboxylic acid 2',4'-dichlorophenyl ester 1-amino-2-methylbenzene-5-carboxylic acid 2',4',5'-trichlorophenyl ester 1-amino-2-chlorobenzene-5-carboxylic acid 2'-methylphenyl ester 1-amino-2-methylbenzene-5-carboxylic acid 4'-methylphenyl ester l-amino-2-methylbenzene-5-carboxylic acid 4'-methoxyphenyl ester l-amino-2-methylbenzene-5-carboxylic acid 4'-chloro-2'-methylphenyl ester l-amino-2-methylbenzene-5-carboxylic acid 4'-chloro-3'-methylphenyl ester l-amino-2-methylbenzene-5-carboxylic acid 4'-isobutylphenyl ester l-amino-2-methylbenzene-5-carboxylic acid 3'-trifluoromethylphenyl ester 2-aminoterephthalic acid diphenyl ester l-amino-2-chlorobenzene-5-carboxylic acid 4'-chlorophenyl ester l-amino-2-chlorobenzene-5-carboxylic acid h-naphthyl ester 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'-methylphenyl 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 acid phenyl ester 1-amino-2-methylbenzene-5-sulphonic acid phenyl ester 1-amino-2-methoxybenzene-5-sulphonic 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-phenoxy-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'-benzyloxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 4'-p-chloroethoxycarbonylphenyl ester 4-methyl-3-aminobenzoic acid 3'-p-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 by condensation of a nitrobenzoyl chloride or a nitrobenzenesulphonyl chloride of the formula
wherein X, and Z have the given meanings, with a hydroxybenzene 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 aminobena nesulphonates are diazotised and coupled with the acetoacetylarylides of the 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- 1 -benzimidezolone 5-amino- 1 -methyl-benzimidazolone 5-amino- 1 -n-butyl-benzimidazolone 5-amino- l-phenyl-benzimidazolone 5-amino-i -p-chlorophenyl-benzimidazolone 5-amino- l-p-methylphenyl-benzimidazolone 5-amino-l -p-methoxyphenyl-benzimidazolone S-amino-6-chloro-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'-am ino-3 '-methoxyphenyl)-quinazolone-4 2-(4'-amino-3'-chlorophenyl)-quinazolone 2-(3'-amino-4"-methylphenyl).quinazolone-4 6-amino-2,4-dihydroxyquinazoline 7-amino-phenmorpholone-3 6-amino-phenmorpholone-3 7-amino-6-chloro-phenmorpholone-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-4,6-dimethyl-quinolone-2 6-amino-7-chloro-4-methyl-quinolone-2 7-amino-4-methyl-6-methoxy-quinolone-2 6-amino-l ,3-dihydroxy-isoquinoline 6-amino-2,4-dihydroxy-quinoline 6-amino-2,3-dihydroxyquinoxaline The cited heterocyclic compounds are known compounds. The diazotisation is carried out by known methods.
The coupling preferably takes place in a weakly acid medium, advantageously in the presence of 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 l,l'-dinaphthyl methane-2,2'-disulphonic acid or polycondensation products of alkylene oxides.
The dispersion of the coupling component can also advantageously contain protective colloids, for example methylcellulose or minor amounts of inert organic 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 trichloroethylene, 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. Furthermore, 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 treating the coupling mixture with a diazotising agent, in particular an ester of nitrous acid, such as methyl, ethyl, butyl, amyl or octyl nitrate.
The pigments 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 solvents. After the grinding procedure, the assistants are removed in the conventional manner: soluble inorganic saits 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 100"C. 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 without pressure. The aftertreatment can also be carried out in water in the presence of organic solvents and/or with the addition of surface-active substances.
The aftertreatment is effected preferably by heating the pigment in the solvent to 1000 to 2000 C, 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, oilmodified alkyd resins or viscose or cellulose derivatives, such as acetyl cellulose and nitrocellulose, and in particular man-made organic polyplastics, 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); the polyesters used as varnish gums, namely both saturated polyesters, for example alkyd resins, and unsaturated polyesters, for example maleic resins, and also the polyaddition and polycondensation 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 invention, 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 ureaformaldehyde 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 these substrates using roll mills, mixing or grinding devices. The pigmented material is thereafter brought into the desired final form by known processes, such as calendering, pressing, extrud ing, coating, casting or by injection moulding.It is often desirable to add plasticisers to the compounds of high molecular 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 of the invention before or after the incorporation of the pigment 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 of 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 high colour strength.
Pigments similar to those of the invention are known from German Auslege schriften 1,808,015 and 1,808,017. 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.
Example 1.
31.3 parts of 4-methyl-3-aminobenzoic acid 4'-propoxycarbonylphenyl 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 OOC with ice, treated at 0"-5"C 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 I hour at 00-50C, excess nitrite is completely destroyed with sulphamic acid and the reaction mixture is then filtered clear. 23.3 parts of 5-acetoacetyl aminobenzimidazolone 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 (Hyflo is a Trade Mark) are then added to the solution, which is sub sequently 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 150-200C 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 200--250C, then heated to 800 C. The pigment is filtered off hot, washed with hot water and then with cold isopropanol. The filter cake is dried in vacuo at 700--800C, affording 52.9 parts (95% of theory) of a brown powder of the formula
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), giving 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 1500C 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.
TABLE
No. Diazo component Acetoacetyl compound of Shade Solvent 2 3-amino-4-methylbenzoic acid 4'- 5-aminobenzimidazolone yellow dichlorobenzene ethoxycarbonylphenyl ester 3 3-amino-4-chlorobenzoic acid 4'- " " " chlorophenyl ester 4 3-amino-4-methoxybenzoic acid 4'- " " " ethoxycarbonylphenyl ester 5 3-amino-4-methylbenzoic acid " " " phenyl ester 6 3-amino-4-chlorobenzoic acid 4'- " reddish " ethoxycarbonylphenyl ester yellow 7 " 5-aminobenzoxalone greenish " yellow 8 3-amino-4-methylbenzoic acid " greenish " phenyl ester yellow 9 3-amino-4-methylbenzoic acid 4'- 5-amino-1-methylbenz- yellow " propoxycarbonylphenyl ester imidazolone 10 3-amino-4-methylbenzoic acid 4'- " greenish " ethoxycarbonylphenyl ester yellow 11 3-amino-4-chlorobenzoic acid 4'- " reddish " chlorophenyl ester yellow 12 3-amino-4-methylbenzoic acid " yellow " phenyl ester TABLE (Continuation)
No. Diazo component Acetoacetyl compound of Shade Solvent 13 3-amino-4-methylbenzoic acid 4'- 6-aminoquinazolone-4 greenish dimethyl ethoxycarbonylphenyl ester yellow formamide 14 " 7-amino-4-methyl- yellow " quinolone-2 15 3-amino-4-chlorobenzoic acid 4'- 5-aminobenzimidazolone yellow " methoxycarbonylphenyl ester 16 " 7-amino-4-methyl- greenish " quinolone-2 yellow 17 3-amino-4-methylbenzoic acid 4'- " yellow N-methylmethylphenyl ester pyrrolidone 18 3-amino-4-methylbenzoic acid 3',5'- " reddish " dimethyl-4'-chlorophenyl ester yellow 19 3-amino-4-methylbenzoic acid 3',5'- " brown dimethyl dichlorophenyl ester formamide 20 3-amino-4-methylbenzoic acid ss- " reddish " naphthyl ester yellow 21 3-amino-4-chlorobenzoic acid 4'- 5-amino-6-chloro- greenish " methoxycarbonylphenyl ester benzimidazolone yellow 22 " 6-aminoquinazolone-4 " " 23 " 6-methoxy-5-amino- orange " benzimidazolone 24 3-amino-4-chlorobenzoic acid 4'- 4-methyl-6-amino-7- greenish " ethoxycarbonylphenyl ester chloroquinolone-2 yellow TABLE (Continuation)
No. Diazo component Acetoacetyl compound of Shade Solvent 25 3-amino-4-chlorobenzoic acid 4'- 4-methyl-6-amino-7- yellow dimethyl chlorophenyl ester chloroquinolone-2 formamide 26 3-amino-4-methyl-4'-ethoxy- 5-aminobenzimidazolone reddish N-methylcarbonylphenyl ester yellow pyrrolidone 27 3-amino-4-methylbenzenesulphonic " yellow N-methylacid phenyl ester pyrrolidone 28 3-amino-4-methylbenzenesulphonic " " dimethyl acid 4'-chlorophenyl ester formamide 29 " 5-amino-1-methyl- " " benzimidazolone 30 3-amino-4-chlorobenzoic acid 4'- 5-aminobenzimidazolone " " isopropoxycarbonylphenyl ester 31 3-amino-4-methylbenzoic acid 2'- " reddish " chloroethyl ester yellow 32 3-amino-4-methylbenzoic acid 4'- " greenish " chlorophenyl ester yellow 33 3-amino-4-chlorobenzoic acid 4'- 5-amino-1-methyl- " " isopropoxy-carbonylphenyl ester benzimidazolone 34 3-amino-4-methylbenzoic acid &alpha;- " yellow " naphthyl ester 35 3-amino-4-methylbenzoic acid 2'- " reddish " chloroethyl ester yellow TABLE (Continuation)
No. Diazo component Acetoacetyl compound of Shade Solvent 36 3-amino-4-methylbenzoic acid 4'- 5-amino-1-methyl- reddish dimethyl chlorophenyl ester benzimidazolone yellow formamide 37 3-amino-4-chlorobenzoic acid 5-aminobenzimidazolone " " methyl ester 38 3-amino-4-methylbenzoic acid " " " methyl ester 39 3-amino-4-methoxybenzoic acid " greenish " methyl ester yellow 40 3-amino-4-chlorobenzoic acid ethyl " " " ester 41 3-amino-4-methylbenzoic acid ethyl " " " ester 42 3-amino-4-methylbenzoic acid " yellow ethyl isopropyl ester cellosolve Example 43.
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 yellow colouration obtained is strong and fast to migration and light.
Example 44.
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 led octoate (24% Pb).
Using a stereotype block, this varnish is printed in an amount of I 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, such as intaglio printing, offset printing, flexographic printing, with equally good results.
Example 45.
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 soution 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 I and 2 g of titanium dioxide (rutile) and ground. The lacquer is sprayed onto cardboard and dried, giving a yellow coating of very good fastness to light and overstripe bleeding and very good resistance to atmospheric influences.
Example 46.
To 100 g of a stoving lacquer consisting of 58.5 g of a 60% solution of coconut alkyd resin in xylene, 23 g of a 65% solution of a melamine varnish m in butanol, 17 g of xylene and 1.5 go butanol, are added I g of the colourant of Example land 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 1200C, a brilliant yellow colouration of good fastness to light and overstripe bleeding and good resistance to atmospheric influences is obtained.
WHAT WE CLAIM IS: 1. Monoazo pigments of the formula (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-amino groups of 2 to 4 carbon atoms, trifluoromethyl groups, or by a group of the formula --COOR, in which R, represents an alkyl group of I 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 or 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, R2 represents a hydrogen atom, an alkyl group of I 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, with the proviso that R2 represents a hydrogen atom when R represents an alkyl group of I to 4 carbon atoms, X, represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, or a phenoxy group, X2 represents a hydrogen or chlorine atom, an alkyl or alkoxy group of I 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
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (9)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    Using a stereotype block, this varnish is printed in an amount of I 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, such as intaglio printing, offset printing, flexographic printing, with equally good results.
    Example 45.
    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 soution 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 I and 2 g of titanium dioxide (rutile) and ground. The lacquer is sprayed onto cardboard and dried, giving a yellow coating of very good fastness to light and overstripe bleeding and very good resistance to atmospheric influences.
    Example 46.
    To 100 g of a stoving lacquer consisting of 58.5 g of a 60% solution of coconut alkyd resin in xylene, 23 g of a 65% solution of a melamine varnish m in butanol, 17 g of xylene and 1.5 go butanol, are added I g of the colourant of Example land 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 1200C, a brilliant yellow colouration of good fastness to light and overstripe bleeding and good resistance to atmospheric influences is obtained.
    WHAT WE CLAIM IS: 1. Monoazo pigments of the formula (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-amino groups of 2 to 4 carbon atoms, trifluoromethyl groups, or by a group of the formula --COOR, in which R, represents an alkyl group of I 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 or 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, R2 represents a hydrogen atom, an alkyl group of I 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, with the proviso that R2 represents a hydrogen atom when R represents an alkyl group of I to 4 carbon atoms, X, represents a hydrogen or chlorine atom, an alkyl or alkoxy group of 1 to 4 carbon atoms, or a phenoxy group, X2 represents a hydrogen or chlorine atom, an alkyl or alkoxy group of I 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
    Zr represents an oxygen or sulphur atom, the NH- group or a group of the formula
    in which R3 represents a hydrogen atom, an alkyl group of I to 4 carbon atoms or a phenyl radical which is unsubstituted or substituted by halogen atoms, alkyl or alkoxy groups of I to4 carbon atoms.
  2. 2. Monoazo pigments according to claim 1 of the formula (IV)
    wherein R2, Xs, X2 and Z are as defined in claim 1, Y, represents a hydrogen or chlorine atom, an alkyl or alkoxy group of I 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 I to 4 carbon atoms, an alkanoylamino group of 2 to 4 carbon atoms or the group of the formula -COOR1 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. 3. Monoazo pigments according to claim 2 of the formula (V)
    wherein R2, X1, X2, Z and Z2 are as defined in claim 2 and R5 represents an alkyl group of I to 4 carbom atoms, a benzyl group or a phenyl group which is unsubstituted or substituted by chlorine atoms, alkyl or alkoxy groups of I to 4 carbon atoms.
  4. 4. Monoazo pigments according to claim 3 of the formula (VI)
    wherein RB and Z are as defined in claim 3, R6 represents a hydrogen atom or an alkyl group of I to 4 carbon atoms, X4 and X5, each independently of the other, represents a chlorine atom, a methyl, methoxy or ethoxy group.
  5. 5. Monoazo pigments according to claim I of the formula (VII)
    wherein X, and X2 are as defined in claim I and R4 represents an alkyl or chloroalkyl group of I to 4 carbon atoms.
  6. 6. Monoazo pigments according to claim 5 of the formula (VIII)
    wherein X4 and X5, each independently of the other, represent a hydrogen or chlorine atom, a methyl, methoxy or ethoxy group, and R7 represents a methyl, ethyl or chloroethyl group.
  7. 7. A process for pigmenting organic material of high molecular weight which comprises the use of the pigments according to claims I to 6.
  8. 8. The pigmented material obtained according to claim 7.
  9. 9. Monoazo pigments as claimed in claim 1, substantially as hereinbefore described with reference to any one of the foregoing Examples.
GB673/78A 1977-01-11 1978-01-09 Monoazo acetoacetarylide pigments and process for their production Expired GB1586724A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH26877A CH627200A5 (en) 1977-01-11 1977-01-11 Process for preparing new monoazo pigments and use thereof for pigmenting macromolecular organic material

Publications (1)

Publication Number Publication Date
GB1586724A true GB1586724A (en) 1981-03-25

Family

ID=4183129

Family Applications (1)

Application Number Title Priority Date Filing Date
GB673/78A Expired GB1586724A (en) 1977-01-11 1978-01-09 Monoazo acetoacetarylide pigments and process for their production

Country Status (8)

Country Link
JP (1) JPS5388036A (en)
BR (1) BR7800144A (en)
CA (1) CA1107274A (en)
CH (1) CH627200A5 (en)
DE (1) DE2800765C2 (en)
FR (1) FR2376886A1 (en)
GB (1) GB1586724A (en)
IT (1) IT1092719B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2845946A1 (en) * 1978-10-21 1980-04-30 Hoechst Ag AZO COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE
DE2845947A1 (en) * 1978-10-21 1980-04-30 Hoechst Ag AZO COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE
DE2847284A1 (en) * 1978-10-31 1980-05-14 Hoechst Ag MONOAZO CONNECTIONS, METHOD FOR THEIR PRODUCTION AND THEIR USE
JPS59232922A (en) * 1983-06-15 1984-12-27 Dainippon Ink & Chem Inc Manufacture of spindle-shaped goethite having high axial ratio
DE19733307A1 (en) * 1997-08-01 1999-02-04 Clariant Gmbh Quinoxaline monoazo acetarylide pigment

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE622476A (en) * 1961-09-14
BE646790A (en) * 1963-04-18
DE1644231A1 (en) * 1967-10-27 1970-12-10 Hoechst Ag Water-insoluble monoazo dye and process for its preparation
DE1808015C3 (en) * 1968-11-09 1973-11-15 Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt Water-insoluble monoazo dyes, process for their preparation and use
DE1955808A1 (en) * 1969-11-06 1971-06-09 Hoechst Ag New water-insoluble monoazo dyes and processes for their preparation
DE2013984C3 (en) * 1970-03-24 1974-03-07 Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt Water-insoluble yellow monoazo dyes, process for their preparation and use

Also Published As

Publication number Publication date
DE2800765A1 (en) 1978-07-13
CH627200A5 (en) 1981-12-31
DE2800765C2 (en) 1985-01-17
IT1092719B (en) 1985-07-12
BR7800144A (en) 1978-08-22
FR2376886A1 (en) 1978-08-04
CA1107274A (en) 1981-08-18
FR2376886B1 (en) 1980-12-05
IT7819134A0 (en) 1978-01-10
JPS5388036A (en) 1978-08-03

Similar Documents

Publication Publication Date Title
CA1040626A (en) Disazo pigments
US4392999A (en) Monoazo pigments containing hydroxynaphthoylamino benzimidazolone radical
US4220586A (en) Hetero-aryl azo acylamino substituted aceto-acetarylide pigments
GB1586724A (en) Monoazo acetoacetarylide pigments and process for their production
US3978038A (en) Disazo pigments containing at least one nitro group on the diazo component
USRE27575E (en) Water-insoluble benzimidazolone containing monoazo dyestuffs
US4080321A (en) Monoazo pigments from diazotized acylamino-anilines and acetoacetylamino benzimidazolones
CA1045120A (en) Disazo pigments and a process for their manufacture
US4024124A (en) Monoazo acetoacetylaminobenzimidazolone pigments containing carboxy group
US3555002A (en) Water-insoluble benzimidazolone containing monoazo dyestuffs
CA1091224A (en) Monoazo pigments and processes for producing them
US3923774A (en) Quinazolone containing phenyl-azo-pyridine compounds
US3985725A (en) Quinolino-azo-aceto-acetylaminobenzimidazolone pigments fast to heat
US4400319A (en) Monoazo pigments containing heterocycles, and high-molecular organic materials dyed therewith
US4065449A (en) Tetrachloro substituted disazo pigments
US4070353A (en) Dicarboxylic acid ester diazo pigments
US3923777A (en) Azo dye from an ortho-oxydiazolylaniline diazo component
US3963693A (en) Quinolone azo barbituric acid pigments
US5428136A (en) Water-insoluble azo colorants having two azo groups and a 1,4-bis (acetoacetylamino) benzene coupling component
US3781266A (en) Water-insoluble phenyl-azo-naphthyl-amido-benzimidazolone dyestuffs
GB1588579A (en) Azo pigments and process for their production
US4062838A (en) Disazo pigments containing acylamino groups
US4263205A (en) Monoazo pigments derived from substituted aminothiophenes
US4081439A (en) Aromatic disazo pigments
US4055559A (en) Disazo pigment containing at least 2 chlorine atoms and process for their manufacture

Legal Events

Date Code Title Description
PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee