GB2185491A - New azo pigments and their production - Google Patents
New azo pigments and their production Download PDFInfo
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- GB2185491A GB2185491A GB08601394A GB8601394A GB2185491A GB 2185491 A GB2185491 A GB 2185491A GB 08601394 A GB08601394 A GB 08601394A GB 8601394 A GB8601394 A GB 8601394A GB 2185491 A GB2185491 A GB 2185491A
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- azo pigments
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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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
- C09B29/3652—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles
- C09B29/366—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles containing hydroxy-1,2-diazoles, e.g. pyrazolone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
- C08K5/3447—Five-membered rings condensed with carbocyclic rings
-
- 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
- C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
- C09B35/02—Disazo dyes
- C09B35/021—Disazo dyes characterised by two coupling components of the same type
- C09B35/03—Disazo dyes characterised by two coupling components of the same type in which the coupling component is a heterocyclic compound
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Abstract
Azo pigments of the formula: <IMAGE> wherein each of X1, X2 and X3, independently, represents a hydrogen atom, a halogen atom, or an alkyl or alkoxy group containing from 1 to 6 carbon atoms; n is 1 or 2 and when n is 1, A represents the radical of a diazotisable carbocyclic or heterocyclic aromatic mono-amine, and when n is 2, A represents the radical of a tetrazotisable carbocyclic aromatic di-amine, and their production are described.
Description
SPECIFICATION
New azo pigments and their production
The present invention relates to water-insoluble monoazo and bisazo pigments and to processes for their preparation.
The present invention provides azo pigments of the general formula:
wherein each of X1, X2 and X3, independently, represents a hydrogen atom, a halogen atom, or an alkyl or alkoxy group containing from 1 to 6 carbon atoms; n is 1 or 2, and when n is 1, A represents the radical of a diazotisable carbocyclic or heterocyclic aromatic mono-amine, and when n is 2, A represents the radical of a tetrazotisable carbocylic aromatic di-amine.
The present invention also provides a process for the preparation of azo pigments of formula I comprising coupling a diazotised or tetrazotised amine of general formula (2) A[NH2]n (2) wherein n and A are as defined above, with a coupling component of the general formula (3)
wherein X1, X2 and Xs have the meanings given above.
As mono-amines of said general formula (2) wherein n is 1, compounds of the benzene, naphthalene, anthraqinone or heterocyclic series, for example, quinoline and benzimidazole, may be mentioned. The radical A when n is 1 may contain further substituents, for example, halogen atoms, alkyl, aralkyl, alkoxy, phenoxy, trifluoromethyl, cyano, nitro, alkylsulphonyl, arylsulphonyl, acyloxy, acylamino, aroylamino, carboxylic acid amide, sulphonic acid amide, carboxylic acid ester, sulphonic acid ester, carboxylic acid and/or sulphonic acid groups.
As di-amines of said general formula (2) wherein n is 2, compounds of the benzene, naphthal ene, anthraquinone, diphenyl, diphenylether, diphenylsulphone and diphenylmethane series may be mentioned. The radical A when n is 2 may contain further substitutents for example halogen atoms, alkyl, alkoxy, nitro, carboxylic acid and/or sulphonic acid groups.
As suitable amines of said formula (2) wherein n is 1, there may be mentioned for example:
Aniline; mono, di or tri-alkylanilines such as 2- or 3- or 4-methyl aniline; 2- or 3- or 4ethylaniline; 2,3- or 2,4- or 2,5-dimethylaniline; 2,4,6-trimethylaniline;
Mono-, di-or tri-haloanilines such as 2- or 3- or 4-chloro-aniline; 2,3- or 2,4- or 2,5- or 2,6- or 3,4- or 3,5- dichloroaniline; 2,4,5- or 2,4,6-trichloroanilines; 2- or 3- or 4-bromoaniline; 2- or 3or 4-fluoroaniline;C-alkyl-mono, di-or trichloroanilines such as 2-methyl-4-chloroaniline, 2-methyl5-chloroaniline, 2,4-dichloro-5-ethylaniline, 2,5-dichloro-4-methyl-aniline, 2,4,6-trichloro-3-methylaniline;
Alkoxyanilines such as 2- or 3- or 4- methoxyaniline; 2- or 3- or 4-ethoxyaniline; 2,5dimethoxyaniline, 2,5-diethoxyaniline, 2-methoxy-4-chloroaniline, 2-methoxy-5-chloroaniline, 2ethoxy-5-chloroaniline, 3-chloro-4-benzyloxyaniline, 2-ethoxy-5-methoxyaniline, 2,4-dichloro-5-methoxyaniline;
Nitroanilines such as 2- or 3- or 4-nitroaniline, 2-nitro-4-methylaniline, 4-nitro-2-methylaniline, 2-methoxy-4-nitro-aniline, 4-methoxy-2-nitroaniline, 2 -chloro-4-nitroaniline, 4-chloro-2-nitroaniline, 2-chloro-5-nitroaniline, 2,4-di-nitroaniline, 2-methoxy-4-nitro-5-methylaniline;
Cyanoanilines such as 2- or 3- or 4-cyanoaniline, 2-cyano-5-nitroaniline;;
Acyl- and aroyl-aminoanilines such as 4-acetylaminoaniline, 2-nitro-4-acetylaminoaniline, 2chloro-4-methyl-5-acetylaminoaniline, 2,4-dichloro-5-acetylaminoaniline, 2-chloro-5-benzoylaminoaniline, 2-methoxy-4-benzoylamino-5-methylaniline;
Trifluoromethylanilines such as 2- or 3- or 4-trifluoromethylaniline, 2-chloro-5-trifluoromethylaniline, 3,5-bis(trifluoromethyl)aniline, 2-nitro-4-trifluoromethylaniline;
C-acylated anilines such as 3-acetylaniline;
Carboxyanilines such as 2- or 3- or 4-carboxyaniline, 2-nitro-4-carboxyaniline, 2-carboxy-4methylaniline, 2-carboxy-4-chloroaniline, 2-carboxy-4-nitroaniline, 2,3-or 1,4- or 1,5- or 3,5-dicarboxyaniline; or the esters e.g. the methyl or ethyl esters of these carboxyanilines;
Amides of carboxy anilines such as 4-carboxamidoaniline;
Sulfo-anilines such as 2- or 3- or 4-aniline sulphonic acid;
4-methyl-2-aniline sulphonic acid, 4-methyl-5-chloro-2-aniline sulphonic acid, 4-chloro-5-methyl2-aniline sulphonic acid, 4-chloro-3-aniline sulphonic acid;
Amides of sulfo-anilines such as 2-methoxy-5-methylaminosulphonylaniline,2-methoxy-4-diethyl- aminosulphonylaniline;
Isocyclic aromatic amines such as 1-amino-2-methoxynaphthalene, 2-amino-5-nitronaphthalene, 2-aminonaphthalene-2-sulphonic acid, 1- and 2- aminoanthraquinone;
Heterocyclic amines such as 4-methyl-7-amino-2-quinolone, 2-aminobenzothiazole, 5-aminobenzimidazolone, 5-amino-6-methylbenzimidazolone, 5-amino-6-methoxybenzimidazolone;;
As suitable amines of said formula (2) wherein n is 2, there may be mentioned, for example:
Benzene diamines such as 1,3- or 1,4-diaminobenzene, 1 ,4-diamino-2-chlorobenzene, 1,4-diamino-2-methylbenzene
Naphthalene diamines such as 1,5-diaminonaphthalene;
Anthraquinone diamines such as 1,5-diaminoanthraquinone;
Diphenyl diamines such as 3,3'-dichloro-4,4'-diaminodiphenyl, 2,2',55'-tetrachloro-4,4'-diaminodiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenyl, 3,3'-dimethoxy-4,4'-diaminodiphenyl, 4,4'-diaminodiphenyl-2,2'disulphonic acid;
Bridged diphenyl diamines such as 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylsulphone, 4,4'-diaminodiphenylmethane and 2,2-bis(4-aminophenyl)propane.
When groups X1, X2 and X3 represent a halogen atom, this is preferably chlorine. When groups X1, X2 and X3 represent an alkyl group containing 1 to 6 carbon atoms, this is preferably a methyl group. When groups X1, X2 and X3 represent an alkoxy group containing from 1 to 6 carbon atoms, this is preferably a methoxy or an ethoxy group.
The starting materials of formula (3) for use in the process of the present invention are known compounds having been described in German Offenlegungsschrift 2533958.
The coupling components used in the process of the present invention for the preparation of the monoazo and bisazo dyestuffs can be prepared by known methods for example, by diazotising the 5-aminobenzimidazolone; reducing the diazonium salt to the hydrazinium salt with stannous chloride in hydrochloric acid; and reacting the hydrazinium salt with acetoacetamide to give the pyrazolone.
When preparing pigment dyestuffs it is sometimes expedient to precipitate the coupling component from dilute aqueous alkaline solution using acetic acid, prior to coupling. Often a softer textured pigment dyestuff is obtained in this manner. The coupling process may be performed in the "normal" manner, that is, the addition of the diazonium salt solution to the coupling component; in the "invert" manner, that is, the addition of the coupling component to the diazonium salt solution; or in the "simultaneous" manner, that it, the simultaneous addition of the diazonium salt solution and the coupling component to an aqueous, buffered medium. Use of surfactants may be advantageous during the coupling reaction to assist in the dispersion of coupling component and pigment dyestuff.
The pigment dyestuffs obtained by the process of this invention sometimes possess a hard grain and, in order to convert these into products of soft grain and full tinctorial strength, they can be heated in the form of an aqueous paste, if desired with the addition of an organic solvent, under elevated pressure at a temperature exceeding 100 C. Alternatively, the dyestuff in the form of an aqueous paste or the dry dyestuff may be subjected to an after-treatment with an organic solvent. Examples of such solvents are ethanol, pyridine, dimethylformamide, Nmethylpyrrolidone, 1 ,2-dichlorobenzene, toluene and xylene. Temperatures of such treatments are in the range from ambient to the boiling point of the solvent.It is often advantageous to remove the water by azeotropic distillation in the case of those solvents forming azeotropes with water, or by simple distillation in the case of those solvents not forming azeotropes with water.
The present invention also provides a method for the colouration of organic material comprising incorporating into the organic material a pigmenting proportion, preferably 0.1 to 5% by weight, of a pigment of formula I.
The new pigment dyestuffs are suitable e.g. for the preparation of coloured lacquers and lacquer forming agents, solutions and products made from acetyl cellulose as well as cellulose ethers, natural or synthetic resins, for example polymerisation or condensation resins, such as aminoplasts or phenolplasts, as well as products made from polystyrene or polyolefins, for example polyethylene or polypropylene, polyacryl or polyvinyl compounds, for example polyvinylchloride or polyvinyl acetate, polyesters, rubber, casein or silicone resins. They may also be used in other applicational fields, for example in finely dispersed form for dyeing rayon from viscose or cellulose ethers or esters, polyamides, polyurethanes, polyglycol terephthalates or polyacrylonitrile in the spinning solution, or for dyeing paper.
The pigments of the present invention are yellow to red powders which are insoluble in conventional solvents. They excel by their high tinctorial strength, excellent resistance to overpainting and to migration and by their outstandingly good fastness to light and weathering.
When compared with known mono- and bis-azo pigment dyestuffs based on 1-aryl-3-methyl-5pyrazolone, the new pigments are distinguished by an improved fastness to solvents in addition to superior fastness to light.
The following Examples further illustrate the present invention.
Example 1
15.2 g (0.1 mol.) of 2-nitro-4-methyl-aniline were stirred into 60 ml. of 5M. hydrochloric acid until a smooth paste was obtained. The paste was cooled with ice to a temperature of -5"C.
and diazotised by addition of 20 ml. of 5M. sodium nitrite over a period of 5 minutes, stirring at 0-5"C, was continued for 1 hour nd the diazo then treated with 1 .0g of activated carbon, stirred for a further five minutes and filtered.
23.09. (0.1 mol.) of 1-(benzimidazolon-5-yl)-3-methyl-5-pyrazolone were dissolved in 200 ml.
of water containing 42 ml. of 20% aqueous sodium hydroxide, the solution was filtered and the pyrazolone precipitated by slow addition of glacial acetic acid until a pH of 5.5 was attained.
The diazo solution was added over a period of 30 minutes to the stirred precipitated pyrazolone maintaining the temperature at 20"C and the pH at 5.0-5.5 by addition of 20% aqueous sodium hydroxide as required. On completion of coupling, the product was stirred for 30 minutes at room temperature, filtered, washed salt free and dried in an air circulating oven at 90"C. The yield was 36.99 (94% theory).
Analysis: Calculated: C 54.9% H 3.8% N 24.9%
Found: C 54.3% H 3.8% N 24.6%
Example 2
Solutions of the diazo and coupling component were prepared as in Example 1. The coupling component was precipitated by slow addition of 5M hydrochloric acid giving a pH of 5.5. The product was coupled and isolated by the method outlined in Example 1. The yield was 37.39 (95% theory).
Example 3
The diazo solution and coupling component were prepared as in Example 1. The coupling component was added to the stirred diazo at room temperature over a period of one hour and the product slurry stirred until excess diazo could not be detected. The product was isolated by filtration, washed salt-free and dried in an air circulating oven at 90"C. The yield was 35.7 g (91 ,ó theory) Example 4 1-(Benzimidazolon-5-yl)-3-methyl-5-pyrazolone 23.09 (0.1 mol) was dissolved in 400 ml. of water containing 42 ml. of 20% aqueous sodium hydroxide. The filtered solution was run into the stirred diazo solution (prepared as in Example 1) over a period of 1 hour.On completion of coupling the pH was adjusted to 5.5 by addition of 20% aqueous sodium hydroxide, stirred for 1 hour and isolated by the method outlined in Example 3. The yield was 37.3 g (95% theory).
Example 5
The diazo and coupling component were prepared as in Example 1 and added simultaneously over a period of 30 minutes to a stirred solution containing 16.4 g of anhydrous sodium acetate in 100 ml. of water, the temperature was maintained at approximately 20"C. and the pH kept at 4.5-5.0 by addition of 20% aqueous sodium hydroxide as required. The product was isolated by filtration, washed salt free and dried in an air circulating oven at 90"C. The yield was 36.59 (93% theory).
Example 6
50 g. of aqueous presscake(approx. 20% pigment)from Examples 1-5 were each dispersed in 500 ml. of water and the stirred slurries heated at 100"C. for 1 hour, filtered hot and dried in an air circulating oven at 90"C.
Example 7
509. of aqueous presscake(approx. 20% pigment) from Examples 1-5 were each dispersed in 500 ml. of toluene containing 1 ml of Solumin F.10.S (the sodium salt of sulphated nonylphenoxy polyethoxyethane) and the slurry stirred and refluxed until all water had been removed in the toluene water azeotrope. The products were isolated by filtration and dried in an aircirculating oven at 90"C.
Example 8
50 9. of aqueous presscake (approx. 20% pigment) from Examples 1-5 were each stirred into 50 ml. of N-methyl-pyrrolidone and the agitated slurry heated at reflux for 1 hour, diluted with 50 ml. of water, filtered, water washed and dried in an aircirculating oven at 900C.
N-Methylpyrrolidone may be substituted by other dipolar aprotic solvents, for example, dimethylacetamide or dimethylformamide to give products with similar colouristic and pigmentary properties.
By similar methods as described in Examples 1-8, the following pigments (Examples 9 to 52) were prepared using the monoamine and coupling component depicted in the following Table TABLE I
Example Mono amine Coupling component Colour of pigment in
No. lacquer
Red-shade yellow
Red-shade yellow
Red-shade yellow
Red-shade yellow
Red-shade yellow
Red-shade yellow TABLE I(continued)
Example Mono amine Coupling Component Colour of Pigment in
No. lacquer
yellow " yellow " brown " red-shade yellow " red-shade yellow " yellow " Table I (continued)
Example
No Mono amine Coupling Component Colour of Pigment ing lacquer
brown " red shade-yellow " red - shade yellow " red-shade yellow " orange " red-shade yellow " TABLE I (continued)
Example Mono amine Coupling Component Colour of Pigment in
No. lacquer
brown " red-shade yellow " red-shade yellow " red-shade yellow " red-shade yellow " yellow " TABLE I (continued)
Example Mono Amine Coupling Component Colour of Pigment in
No. lacquer
red-shade yellow " red-shade yellow " yellow " orange " brown " orange " TABLE I (continued)
Example Mono Amine Coupling Component Colour of Pigment in
No. lacquer
orange orange red red-shade yellow red-shade yellow TABLE I (continued)
Example No. Mono Amine Coupling Component Colour of Pigment in Lacquer
red-shade yellow red-shade yellow red-shade yellow red-shade yellow red-shade yellow yellow TABLE I(continued)
Example No.Mono Amine Coupling Component Colour of Pigment
Lacquer
red-shade yellow red-shade yellow red-shade yellow Example 53
25.3 g(0. 1 mol) of 3,3'-dichlorobenzidine were stirred with 104 ml. of 5M hydrochloric acid until a smooth paste was obtained. The paste was cooled with ice to a temperature of -5"C.
and 40 ml of 5 M sodium nitrite added quickly to the stirred suspension. On completion of the tetra-azotization (30 mins), the solution was treated with 1.0 g of activated carbon, stirred for 5 minutes and filtered.
46.09 (0.2 mol.) of 1-(benzimidazolon-5-yl)-3-methyl-5-pyrazolone were dissolved in 400 ml of water containing 83 ml. of 20% aqueous sodium hydroxide, the solution was filtered and the pyrazolone precipitated by slow addition of glacial acetic acid till a pH of 5.5 was attained.
The tetra-azo solution was added over 30 minutes to the stirred precipitated pyrazolone maintaining the temperature at 20"C and the pH at 5.5 by addition of 20% aqueous sodium hydroxide as required. On completion of coupling the thick red product slurry was stirred for 30 minutes at 20"C. then filtered, washed salt free and dried in an air circulating oven at 90"C. The yield was 67.89 (92% theory).
Analysis: Calculated: C 55.5% H 3.3% N 22.8% Cl 9.7%
Found: C 54.2% H 3.4% N 22.3% Cl 9.9%
Example 54
Solutions of tetra-azo and coupling component were prepared as in Example 53. The coupling component was precipitated by slow addition of 5M hydrochloric acid giving a pH of 5.5. The product was coupled and isolated by the procedure outlined in Example 53. The yield was 68.4 9. (93% theory).
Example 55
The tetra-azo solution and coupling component were prepared as in Example 53. The coupling component was added to the stirred tetra-azo solution at a temperature of 20"C over a period of 1 hour and the product slurry stirred until no excess of tetra-azo was detected. The product was isolated by filtration, washed salt free and dried in an air circulating oven at 90"C. The yield was 65.4 g. (89% theory).
Example 56
1-(Benzimidazolon-5-yl)-3-methyl-5-pyrazolone (46.0g; 0.1 mol.) was dissolved in 400 ml. of water containing 83 ml. of 20% aqueous sodium hydroxide. The filtered solution was run into the tetra-azo solution (prepared as in Example 53) over a period of 1 hour. On completion of coupling the pH was adjusted to 5.5 with 20% aqueous sodium hydroxide and the product isolated by the procedure described in Example 53 The yield was 66.1 g (90% theory).
Example 57
The tetra-azo and coupling component were prepared as in Example 53 and added simultaneously over a period of 30 minutes to a stirred solution containing 16.4 g of anhydrous sodium acetate in 100 ml. of water, the temperature was maintained at 20"C. The pH was kept at 4.5-5.0 by addition of 204/0 aqueous sodium hydroxide as required. The product was isolated by filtration, washed salt free and dried in an air circulating oven at 90"C. The yield was 69.lg (94% theory).
Example 58
The tetra-azo and coupling component were prepared as in Example 53 and coupled as in
Example 57. The product was isolated by filtration, water-washed and dried at 90"C. in an air circulating oven. The yield was 69.49. (94% theory).
Example 59
Each of the aqueous presscakes, (50 g.: approx 20% pigment) from Examples 53 to 58 were dispersed in 500 ml. of water and the stirred slurries heated at 100"C for 1 hour, filtered hot and dried in an air circulating oven at 90 C, giving a series of dull red pigments.
Example 60
50 g. of aqueous presscake (approx. 20% pigment) from Examples 53 to 58 were each slurred in 500 ml. of toluene containing 1 ml. of Solumin F.10.S and the mixtures stirred and refluxed until all the water had been removed in the toluene/water azeotrope. The products were isolated by filtration and dried in an air circulating oven at 90"C.
Example 61
50 g. of aqueous presscake (approx. 20% pigment) from Examples 53 to 58 were each slurried in 100 ml. of N-methyl-pyrrolidone and the stirred mixtures refluxed for 1 hour during which time the colour changed from dull red to orange. The products were isolated by filtration, water-washed and dried at 90"C in an air-circulating oven.
N-methylpyrrolidone may be substituted by other dipolar aprotic solvents, for example, dimethylacetamide or dimethylformamide, to give products with similar colouristic and pigmentary properties.
Further pigments of the invention (Examples 62 to 76) were prepared using the procedures set forth in Examples 53 to 58 and employing the diamines and coupling components depicted in the following Table II: TABLE II
Example Diamine Coupling component Colour of pigment in
No. lacquer
Red
Bordeaux
Orange
Red-shade yellow yellow TABLE II (continued)
Example
No. Diamine Coupling component Colour of pigment in pigment
Yellow "
Yellow "
Red-shade yellow " red " red " Table II (continued)
Example No.Diamine Coupling Component Colour of pigment in lacquer
red-shade yellow red red-shade yellow red-shade yellow orange Example 77
The pigment from Example 53 (0.59) was treated as in Example 61 and was passed through a 200 mesh sieve and incorporated into dioctyl phthalate (1 g) using a muller. This dispersion was then mixed with polyvinyl chloride plastisol so that the final pigment concentration was 0.2%.
After spreading to a depth of 1mm the pigmented plastic was cured at 165"C for 5 minutes in an air-circulating oven. The orange product showed excellent heat stability, lightfastness and was totally resistant to migration.
Example 78
The pigment from Example 53 was treated as in Example 61 and was incorporated into an industrial alkyd-melamine formaldehyde paint system by ballmilling the solvent system being toluene-butanol. Panels were sprayed with this paint at 6% pigmentation and stoved at 120"C for 30 minutes. The orange paint film showed excellent heat stability, lightfastness, overpaint fastness and durability.
Claims (22)
1. Azo pigments having the formula:
wherein each of X1, X2 and X3, independently, represents a hydrogen atom, a halogen atom, or an alkyl or alkoxy group containing from 1 to 6 carbon atoms; n is 1 or 2 and when n is 1, A represents the radical of a diazotisable carbocyclic or heterocyclic aromatic mono-amine, and when n is 2, A represents the radical of a tetrazotisable carbocylic aromatic di-amine.
2. Azo pigments according to claim 1 wherein each of X1, X2 and X3, independently, is hydrogen, chlorine, methyl, methoxy or ethoxy.
3. Azo pigments according to claim 1 or 2 wherein n is 1 and A is the radical of a diazotisable mono-amine of the benzene, naphthalene, anthraquinone or heterocyclic series.
4. Azo pigments according to claim 3 wherein the heterocyclic mono-amine is quinoline or a benzimidazole derivative.
5. Azo pigments according to any of the preceding claims wherein the radical A is substituted by one or more substituents selected from halogen, alkyl, aralkyl, alkoxy, phenoxy, trifluormethyl, cyano, nitro, alkylsulphonyl, acyloxy, acylamino, aroylamino, carboxylic acid amide, sulphonic acid amide, carboxylic acid ester, sulphonic acid ester, carboxylic acid and sulphonic acid groups.
6. Azo pigments according to claim 1 or 2 wherein n is 2 and A is the radical of an optionally substituted tetrazotisable di-amine of the benzene, naphthalene, anthraquinone, diphenyl, diphenylether, diphenylsulphone or diphenylmethane series.
7. Azo pigments according to any of the preceding claims wherein n is 2 and A is the radical of a substituted di-amine of the diphenyl series.
8. Azo pigments according to claim 6 or 7 wherein radical A contains one or more substituents selected from halogen, alkyl, alkoxy, nitro, carboxylic acid and sulphonic acid groups.
9. Azo pigments according to claim 1 substantially as described with reference to any of the
Examples.
10. A process for the production of azo pigments of formula I as defined in claim 1, comprising coupling a diazotised or tetrazotised amine of formula:
A [NH2n (2) wherein A and n are as defined in claim 1, with a coupling component of the formula:
wherein X, X2 and X3 are as defined in claim 1.
11. A process according to claim 10 wherein the coupling component of formula (3) is prepared by diazotising the corresponding 5-aminobenzimidazolone; reducing, using stannous chloride in hydrochloric acid, the resulting diazonium salt to produce the corresponding hydrazinium salt; and reacting the latter with acetoacetamide to produce the desired coupling component of formula (3).
12. A process according to claim 10 or 11 wherein the coupling component is precipitated from dilute aqueous solution, using acetic acid, prior to coupling.
13. A process according to any of claims 10 to 12 wherein the product of the process is (a) heated in the form of an aqueous paste, optionally with the addition of an organic solvent, under elevated pressure at a temperature exceeding 100"C. or (b) subjected, in the form of an aqueous paste or a dry powder, to an after-treatment with an organic solvent.
14. A process according to claim 13 wherein the organic solvent is ethanol, pyridine, dimethylformamide, N-methylpyrrolidone, 1 ,2-dichlorobenzene, toluene or xylene.
15. A process according to claim 13 or 14 wherein the after-treatment is effected at a temperature in the range of from ambient to the boiling point of any solvent used.
16. A process according to any of claims 13 to 15 wherein, when solvents are used which form azeotropes with water, water is removed by azeotropic distillation; or, when solvents are used which do not form azeotropes with water, water is removed by simple distillation.
17. A process of producing azo pigments of formula I substantially as described with reference to any of the Examples.
18. Azo pigments of formula I when produced by a process claimed in any of claims 10 to 17.
19. A method for the colouration of organic material comprising incorporating into the organic material a pigmenting proportion of an azo pigment of formula I.
20. A method according to claim 19 wherein the proportion used of the azo pigment of formula I is from 0.1 to 5% by weight, based on the weight of the organic material.
21. A method according to claim 19 or 20 wherein the organic material is a lacquer or lacquer-forming agent; or solution of, or an end product made from acetyl cellulose or cellulose ethers; a natural or synthetic resin;
a product made from polystyrene, a polyolefin, polyacryl or polyvinyl compounds, polyester, rubber, casein or silicone resins.
22. Coloured organic material when produced by a method claimed in any of claims 19 to 21.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08601394A GB2185491A (en) | 1986-01-21 | 1986-01-21 | New azo pigments and their production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08601394A GB2185491A (en) | 1986-01-21 | 1986-01-21 | New azo pigments and their production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8601394D0 GB8601394D0 (en) | 1986-02-26 |
| GB2185491A true GB2185491A (en) | 1987-07-22 |
Family
ID=10591697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08601394A Withdrawn GB2185491A (en) | 1986-01-21 | 1986-01-21 | New azo pigments and their production |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2185491A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5179207A (en) * | 1991-08-19 | 1993-01-12 | Eastman Kodak Company | Substituted 2-amino-5-maleimido thiophenes and substituted 2-amino-maleimido thiazoles |
| US5235047A (en) * | 1991-08-19 | 1993-08-10 | Eastman Kodak Company | Bathochromic azo dyes derived from 2-aminothiophenes and 2-aminothiazoles |
| WO1996025464A1 (en) * | 1995-02-13 | 1996-08-22 | Engelhard Corporation | Pigment compositions |
| US5669967A (en) * | 1996-05-30 | 1997-09-23 | Engelhard Corporation | Pigment compositions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2533958A1 (en) * | 1975-07-30 | 1977-02-17 | Hoechst Ag | Azo-azomethine pigments and metal complexes - and aminoarylene azo intermediates for their prepn. |
| EP0055218A2 (en) * | 1980-12-23 | 1982-06-30 | Ciba-Geigy Ag | Manufacture of azoic compounds |
-
1986
- 1986-01-21 GB GB08601394A patent/GB2185491A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2533958A1 (en) * | 1975-07-30 | 1977-02-17 | Hoechst Ag | Azo-azomethine pigments and metal complexes - and aminoarylene azo intermediates for their prepn. |
| EP0055218A2 (en) * | 1980-12-23 | 1982-06-30 | Ciba-Geigy Ag | Manufacture of azoic compounds |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5179207A (en) * | 1991-08-19 | 1993-01-12 | Eastman Kodak Company | Substituted 2-amino-5-maleimido thiophenes and substituted 2-amino-maleimido thiazoles |
| US5235047A (en) * | 1991-08-19 | 1993-08-10 | Eastman Kodak Company | Bathochromic azo dyes derived from 2-aminothiophenes and 2-aminothiazoles |
| WO1996025464A1 (en) * | 1995-02-13 | 1996-08-22 | Engelhard Corporation | Pigment compositions |
| US5746821A (en) * | 1995-02-13 | 1998-05-05 | Engelhard Corporation | Pigment compositions |
| US5669967A (en) * | 1996-05-30 | 1997-09-23 | Engelhard Corporation | Pigment compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8601394D0 (en) | 1986-02-26 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |