PREPARATION OF AZO PIGMENTS

Abstract: Azo pigments of the formula where X and Y are the same or different and are selected from the group consisting of -H, -R¹, -OR¹,-Cl -CONH₂, NO₂ and -SO₂NH₂, where -R¹ is lower alkyl; and -R is where -R², - R³ and -R⁴ are the same or different and are selected from the group consisting of -H, -OR¹, -R¹ and -Cl; where - R⁵, -R⁶, and -R⁷ are the same or different and are selected from the group consisting of -H, -OR¹, -R¹ and -Cl; where -R⁸ is -H or -Cl and The pigments are prepared by an in situ diazotization-­ coupling reaction in which an optionally substituted anthra­ nilamide is reacted with a coupler in the presence of a diazotization agent and an acid in an aqueous medium at a pH range 1.0 to 7.0 at preferably 10°C to 50°C.

Description: TITLE AZO PIGMENTS AND THEIR PREPARATION Background of the Invention Field of the Invention The present invention relates to azo pigments derived from certain anthranilamides and an in situ diazotization-coupling process for their manufacture. Prior Art There are numerous patents which disclose azo pigments having a carboalkoxy group ortho to the azo group. A one-step process for the preparation of azo dyes is disclosed in U.S. 3,793,305. Anthranilamide has been diazotized and coupled with active methylene compounds previously. Very strong acid ( 10N hydrochloric acid) was used as the diazotizing medium. This is disclosed in "Triazines and Related Products, Part XIV, Decomposition of 1,2,3-Benzotriazin -4(3H)-cnes in the Presence of Reactive Methylene Systems", J. Chem. Soc., Perkin I, 1974 pp 2482-2486. Summary of the Invention The present invention relates to azo pigments cf the general structure EMI1.1 wherein R has the meaning defined below. These pigments cannot be prepared by the conventional technique of diazotization followed by coupling because when an o-aminobenzamide (anthranilamide) is treated with a nitrite the following reaction takes place. EMI2.1 The cyclic triazine, II, does not undergo azo coupling reactions. As a result, azo compounds having an ortho carboxamide group are rare in the art. In the process of the present invention the diazotiazation is done in situ with the coupling reaction so that the cyclic triazine, II, is not formed. Detailed Description The present invention relates to azo pigments of the formula EMI2.2 where X and Y are the same or different and are selected from the group consisting of -H, -R1, -OR1, -C1, -CONH2, -NO2 and -SO2NH2, where -R1 is lower alkyl, and where -R is selected from the group consisting of EMI2.3 where -R2, -R3 and -R4 are the same or different and are selected from the group consisting of -H, -OR1, -R1, and -Cl; EMI3.1 where -R5, -R6, and -R7 are the same or different and are selected from the group consisting of -H, -OR1,-C1, and -R1 EMI3.2 Azo pigments having a carboalkoxy group (IIIa) ortho to the azo group are known. The corresponding pigments of the present invention with an ortho carboxamide group (IIIb) invariably exhibit improved bleedfastness and usually improved lightfastness EMI3.3 Solubility in o-dichlorobenzene Fadeometer Z g/l at 1000C lightfastness IIIa -OCH3 52 < 200 hrs. IIIb -NH2 1.9 > 800 hrs. As a measure of the bleedfastness, the solubility of the pigments is shown. Pigment IIIb is less soluble than pigment IIIa by a factor of 25. The fadeometer lightfastness of pigment IIIb is greater than 800 hours without exhibiting a break while that of IIIa is less than 200 hours. As compared with similar pigments having the carboxamide group in the meta or para position, the ortho carboxamide pigments of the present invention generally exhibit superior lightfastness. The pigments of the present invention are prepared by an in situ diazotization-coupling reaction wherein an optionally substituted anthranilamide and coupler are reacted in a medium comprising a diazotization agent, acid, water, and, if necessary, an organic solvent. The acid may be an organic acid such as, but not limited to, formic acid, acetic acid, propionic acid, hydroxyacetic acid, tartaric acid or oxalic acid, or it may be a mineral acid such as, but not limited to, hydrochloric acid, hydrobromic acid, sulfuric acid, or phosphoric acid. The medium may be buffered at an optimum pH for the particular combination of anthranilamide and coupler by the additional use of a base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, pyridine, or picoline. If the reaction is carried out by slowly adding the diazotization agent to the reaction mass, it is preferred to buffer the reaction mass at pH 1.0 to 5.5. On the other hand, the reaction may be effected by slowly adding the acid to the mixture of optionally substituted anthranilamide, coupler, water, diazotization agent and optional organic solvent. In this latter case, the pH may range from 8.0 at the start, down to pH 1.0 at the completion of reaction. The preferred diazotization agent is sodium nitrite. However, a lower alkyl nitrite may also be used as the diazotization agent. Generally the reaction will be carried out at from 0 to 1000C with from 100 to 500C being the preferred range. The amount of water in the solvent-acid-buffer system generally will be from 10 to 90% by weight. The amount of acid present in the solvent-acid-buffer system generally will be from 5 to 90% by weight. If the anthranilamide or coupler are insoluble in the aqueous acid-buffer system a polar organic solvent should be added to the system. Suitable polar organic solvents include but are not limited to dimethylformamide, dimethylacetamide, N-methylpyrrolidone, methanol, ethanol and isopropanol. The crude pigments may be heat treated to develop their optimum properties. The pigments may be heated in an organic solvent such as dimethylformamide, dimethylacetamide, chlorobenzene, o-dichlorobenzene, or ethyleneglycol monoethylether to name a few. The pigment maybe heat treated in water at elevated temperature with or without additional solvents, and with or without auxiliary agents to control the particle size. The pigments of this invention are eminently suitable for the coloration of paints, lacquers, varnishes, natural and synthetic polymers, and inks. The good fastness properties of these pigments renders them suitable for the coloration of surface coatings such as thermosetting and thermoplastic acrylics, and alkyd resins, for example. The excellent thermal stability of these pigments makes them suitable for the mass coloration of plastics such as polyolefins, polystyrenes, polyvinyls, polyacrylic acid esters, polyamides, polyurethanes, and silicone resins. Description of the Preferred Embodiments Example 1 To a mixture of 3.4 g anthranilamide, 5.2 g acetoacet-o-anisidide, 40 ml glacial acetic acid, 30 ml of water and 10 g sodium acetate, is slowly added 5.5 ml 30% aqueous sodium nitrite over a two hour period at 200-250C. The mixture is stirred for an additional hour and then filtered. The solids are washed with water and dried. The resulting green shade yellow pigment is obtained in good yield. The pigment has the formula EMI6.1 The pigment is dispersed in a thermoplastic acrylic lacquer wherein it displays excellent lightfastness. The pigment also displays utility in the coloration of plastics due to its good heat stability. Example 2 To a mixture of 4.5 g of aminoterephthalamide, 5.2 g of acetoacet-o-aniside, 25 ml dimethylformamide, 15 ml glacial acetic acid, and 5.0 ml pyridine,is slowly added 5.5 ml pf 30% aqueous sodium nitrite over a period of two hours at 200-250C. After agitating for another 30 minutes, the solids which form are collected on a filter and washed with water. The solids are dried and crystallized further by heating in dimethylformamide at 1400-1500C. The resulting green shade yellow pigment has the formula EMI7.1 The pigment is dispersed in a thermoplastic acrylic paint where it displays excellent lightfastness and bleedfastness. The pigment is incorporated into high density polyethylene where it displays good heat stability and lightfastness. Example 3 Concentrated hydrochloric acid (5.0 ml) is added over 75 min. to a mixture of 11.7 g acetoacetamidobenzimidazolone 6.8 g anthranilamide, 50 ml of dimethylacetamide, 30 ml of water and 11 ml of 30% aqueous sodium nitrite. The pH is 7.4 initially and slowly falls to 4.9 at the end of the hydrochloric acid addition. The reaction mass is agitated for an additional one hour. Water, 100 ml, is added and the solids are collected on a filter, washed with water and dried. The dried solids are crystallized further by heating in dimethylformamide at 140-1500C. The resulting red shade yellow pigment has the formula EMI7.2 This a phase displays an X-ray diffraction pattern, 20 being 4-30, as shown below: Interplanar spacing A (Intensity)* 12.98 (w) 11.87 (w) 9.51 (m) 6.63 (s) 5.83 (m) 5.25 (m) 4.82 (m) 4.62 (m) 4.47 (w) 4.26 (m) 4.03 (m) 3.92 (w) 3.70 (m) 3.55 (s) 3.40 (m) 3.23 (s) 3.13 (m) 3.01 (m) *where (w) equals weak; (m) equals moderate; and (s) equals strong. If the crude pigment is heated in dimethylformamide at 75-1000C, a second red shade yellow phase (designated ss) is obtained. The ss phase displays an X-ray diffraction as follows: Interplanar spacing A (Intensity)* 9.96 (s) 8.54 (m) 7.98 (w) 7.48 (w) 6.76 (m) 5.86 (w) 5.11 (s) 4.95 (m) 4.59 (m) 4.31 (m) 4.11 (m) 3.97 (w) 3.84 (m) 3.68 (m) 3.47 (s) 3.40 (s) 3.35 (s) 3.05 (m) *where (w) equals weak; (m) equals moderate; and (s) equals strong. The pigment is dispersed in a thermoplastic acrylic paint where it displays excellent lightfastness. Example 4 To a mixture of 4.5 g aminoterephthalamide, 7.0 g 2-hydroxy-3-naphth-o-anisidide, 45 ml dimethylformamide, 10 ml pyridine, 30 ml glacial acetic acid and 30 ml water is slowly added 5.5 ml aqueous sodium nitrite over a period of two hours at 200-250C. After agitating for an additional hour, the solids which form are collected on a filter and washed with water. The solids are crystallized by heating in dimethylformamide at 1500C to yield a bright red pigment of the formula EMI9.1 lne pigment is dispersed in a thermoplastic acrylic lacquer wherein it exhibits excellent lightfastness and bleedfastness. Example 5 To a mixture of 6.0g 5-acetoacetamidobenzimidazolone, 4.5 g 2-amino-5-chlorobenzamide, 30 ml glacial acetic acid, 5 ml pyridine and 30 ml water is slowly added 5.5 ml 30% aqueous sodium nitrite over a period of two hours at 200-250C. After stirring an additional 30 minutes, the reaction mass is filtered and the solids which formed washed with water. The dry solids are crystallized by heating at 1450C in dimethylformamide to form a bright yellow pigment of the formula EMI10.1 The pigment is dispersed in a thermoplastic acrylic lacquer wherein it displays excellent lightfastness and bleedfastness Example 6 Pyridine is added to a mixture of 4.5 g aminoterephthalamide, 4.4 g 3-methyl-l-phenyl-2-pyrazoline-5one, 40 ml dimethylformamide, 30 ml water and 30 ml acetic acid to raise the pH to 3.5. Sodium nitrite (5.5 ml of a 30% aqueous solution) is slowly added over a two hour period at 200-250C. Additional water is added to maintain a fluid reaction mass. Additional acetic acid is added to maintain the pH at 3.5 to 4.0. The solids which form are collected on a filter and washed with water. The resulting pigment is crystallized further by heating in water at 1000C for one hour to provide a yellow pigment having the formula EMI10.2 The pigment is dispersed in a thermoplastic acrylic lacquer wherein it displays excellent lightfastness and bleedfastness. Example 7 Pyridine is added to a mixture of 5.23 g p-chlorophenylmethylpyrazolone, 3.40 g anthranilamide, 50 ml dimethylformamide, 30 ml glacial acetic acid and 30 ml water to adjust the pH to 3.7. Sodium nitrite (5.5 ml of 30% aqueous solution) is slowly added to the mixture over a period of two hours at 200-250C. Additional acetic acid is added to maintain the pH at 3.7 to 4.2. Additional water is added to fluidize the reaction mass. After agitating an additional 30 minutes the reaction mass is filtered to recover the solids which form. The solids are dried and crystallized further by heating in dimethylformamide at 1400-1450C to yield a pigment of the formula: EMI11.1 The pigment is dispersed in a thermoplastic acrylic lacquer wherein it displays outstanding lightfastness and good bleedfastness. Example 8 To a mixture of 4.5 g of 2-amino-5-chlorobenzamide, 5.2 g p-chlorophenylmethylpyrazolone, 30 ml dimethylformamide, 30 ml glacial acetic acid, 2 ml pyridine and 30 ml water is slowly added 5.5 ml 30% aqueous sodium nitrite over a period of two hours at 200-250C. The pigment which forms is filtered washed with water and dried. The pigment is recrystallized from dimethylformamide to yield a pigment of the formula: EMI12.1 Example 9 To a mixture of 4.5 g aminoisophthalamide, 4.4 g methylphenylpyrazolone, 30 ml glacial acetic acid, 5 ml pyridine, 30 ml water and 25 ml dimethylformamide is slowly added 5.5 ml 30% aqueous sodium nitrite over a period of two hours at 200-250C. The resulting pigment is isolated and recrystallized from dimethylformamide to yield a yellow pigment of the formula EMI12.2 The pigment is dispersed in a thermoplastic acrylic lacquer wherein it displays very good lightfastness. Example 10 To a mixture of 5.4 g of 5-nitroanthranilamide, 6.6 g of acetoaceto-o-anisidide, 25 ml of dimethylacetamide, 25 ml of acetic acid and 50 ml of water was added 6 ml of 5 N aqueous sodium nitrite over a 2.5 hour period at 20 to 250C. During the addition of the sodium nitrite solution the pH of the mixture was maintained at 2 to 2.5 by the addition of 10.8 g of 85% phosphoric acid. After the addition of the sodium nitrite solution was complete the mixture was stirred for an additional hour and filtered. The solids were washed with water and dried. The resulting green shade yellow pigment was obtained in good yield. The pigment has the following formula: EMI13.1 This phase, designated as the a phase, displays an X-ray diffraction pattern, 20 being 4-30, as shown below: Interplanar spacing o * A (Intensity) 14.75 (w) 13.19 (s) 11.15 (m) 8.96 (m) 7.43 (m) 6.57 (m) 5.94 (w) 5.58 (m) 4.96 (w) 4.94 (w) 4.42 (m) 4.18 (w) 4.03 (m) 3.87 (w) 3.79 (w) 3.78 (w) 3.60 (m) 3.49 (m) 3.27 (s) 3.05 (w) 3.03 (w) *where (w) equals weak; (m) equals moderate; and (s) equals strong. The pigment can be further crystallized by warming in dimethylformamide to give a red shade yellow pigment. This red shade yellow, designated as the ss phase, displays an X-ray diffraction pattern as follows: Interplanar spacing A (Intensity)* 15.79 (m) 7.80 (s) 6.68 (w) 6.05 (w) 5.90 (w) 5.54 (w) 4.47 (w) 4.44 (w) 4.34 (w) 3.94 (w) 3.88 (w) 3.52 (w) 3.44 (m) 3.38 (m) 3.32 (w) 3.29 (w) 3.18 (w) 3.17 (w) 3.10 (w) 3.03 (w) *where (w) equals weak; (m) equals moderate; and (s) equals strong. Examples 11-47 In a similar manner the following pigments are prepared and evaluated in Table I. Table I Bleed- Light Ex. Pigment Formula Color fastness fastness EMI16.1 <tb> 11 <SEP> CONH, <tb> <SEP> yellow <SEP> good <SEP> good <tb> <SEP> 9 <SEP> N=N <SEP> ss <SEP> 3 <tb> <SEP> C0NH <SEP> 0 <tb> <SEP> 2 <SEP> H <tb> 12 <SEP> ICOMI, <SEP> QH <SEP> yellow <SEP> good <SEP> good <tb> <SEP> )Y2 <tb> <SEP> CH3 <SEP> green <SEP> fair <SEP> Very <SEP> good <tb> 13 <SEP> C0NH <SEP> ' <SEP> shade <tb> <SEP> 2 <SEP> 0=0 <SEP> yellow <tb> <SEP> b <SEP> -N=N-CHCONH- <SEP> O <tb> <SEP> CH3 <tb> 14 <SEP> 2 <SEP> 0=0 <SEP> yellow <SEP> fair <SEP> Very <SEP> good <tb> <SEP> U <SEP> -N=N-CHCONH <SEP> e <SEP> -OCH3 <tb> <SEP> C3 <tb> 15 <SEP> CONH2 <SEP> 0=0 <SEP> green <SEP> fair <SEP> fair <tb> <SEP> ¯¯ <SEP> -N=N-CHCONH <SEP> e <SEP> C1 <SEP> shade <tb> <SEP> -- <SEP> yellow <tb> <SEP> CR <tb> 16 <SEP> C0NH2 <SEP> 2 <SEP> C=O <SEP> green <SEP> good <SEP> good <tb> <SEP> 0=0 <SEP> shade <tb> <SEP> t <SEP> -N=N-CHCONH- <SEP> O <SEP> yellow <tb> <SEP> 2 <tb> Table I (continued) Bleed- Light Ex. Pigment Formula Color fastness fastness EMI17.1 <tb> <SEP> CR <tb> <SEP> OCR <tb> 17 <SEP> C0NH2 <SEP> C <SEP> 3 <SEP> 3 <SEP> red <SEP> Very <SEP> good <SEP> Very <SEP> good <tb> <SEP> > <SEP> N=N-CHCONH <SEP> e <SEP> OCH3 <SEP> yellow <tb> <SEP> - <SEP> 00133 <SEP> yellow <tb> <SEP> CONH2 <tb> <SEP> OH <tb> 18 <SEP> CONH <SEP> 0=0 <SEP> yellow <SEP> good <SEP> good <tb> <SEP> U <SEP> -N=N-CHCONH- <SEP> O <SEP> -OCH3 <tb> <SEP> CONH2 <tb> <SEP> CH <tb> 19 <SEP> 2 <SEP> CR3 <SEP> OCH <SEP> yellow <SEP> good <SEP> Very <SEP> good <tb> <SEP> 0=0 <tb> <SEP> N=NC'RCONH)ffiJOOR3 <tb> <SEP> C1 <tb> <SEP> CR <tb> 20 <SEP> CONH2 <SEP> =O <SEP> ,OCH3 <SEP> yellow <SEP> fair <SEP> good <tb> <SEP> 4 <SEP> -N=N-CHCONH- <SEP> ss <tb> <SEP> 00133 <tb> <SEP> CH3 <tb> 21 <SEP> 2 <SEP> C=0 <SEP> NH <SEP> red <SEP> good <SEP> good <tb> <SEP> 4 <SEP> -N=N-CHCONH- <SEP> C) <SEP> =o <SEP> shade <tb> <SEP> yellow <tb> <SEP> ONH2 <tb> Table I (continued) Bleed- Light Ex. Pigment Formula Color fastness fastness EMI18.1 <tb> <SEP> CH3 <tb> <SEP> 22 <SEP> CONH2 <SEP> C-O <SEP> =CH <SEP> yellow <SEP> Very <SEP> good <SEP> Very <SEP> good <tb> <SEP> f <SEP> -N=N-CHCONH- <SEP> q <SEP> -OCH3 <tb> <SEP> CONH2 <SEP> 1 <tb> <SEP> CH3 <tb> <SEP> 23 <SEP> 0 <SEP> CONH2 <SEP> C=O <SEP> OCH3 <SEP> yellow <SEP> good <SEP> good <tb> <SEP> H2NC-t-N=N-CHCONH <SEP> /t <tb> <SEP> 24 <SEP> ,CH3 <SEP> H <SEP> red <SEP> good <SEP> good <tb> <SEP> O <SEP> CONH <SEP> C'=O <SEP> / <SEP> N <SEP> \ <SEP> ¯O <SEP> shade <tb> <SEP> ("\5=0 <SEP> yellow <tb> H2NC-/ <SEP> -N=N-CHCONH <SEP> yellow <tb> <SEP> H <tb> <SEP> 25 <SEP> 0 <SEP> CONH <SEP> OH <SEP> CONH <SEP> ? <SEP> red <SEP> good <SEP> fair <tb> <SEP> H2 <SEP> C <SEP> b <SEP> A <SEP> OCH3 <tb> <SEP> H2NC- <SEP> OCH3 <tb> <SEP> CH <tb> <SEP> 26 <SEP> CONH2 <SEP> OH <SEP> CONH <SEP> 3 <SEP> 1 <SEP> red <SEP> good <SEP> good <tb> <SEP> > <SEP> N=N- <SEP> U <tb> <SEP> CONH2 <SEP> U <tb> Table I (continued) Bleed- Light Ex. Pigment Formula Color fastness fastness EMI19.1 <tb> 27 <SEP> CONH <SEP> red <SEP> Very <SEP> good <SEP> Very <SEP> good <tb> <SEP> shade <tb> <SEP> t-N=N <SEP> T <SEP> 2 <SEP> I <SEP> CH3 <SEP> yellow <tb> <SEP> CONH, <tb> <SEP> 2 <SEP> N <tb> <SEP> C1 <tb> 28 <SEP> CONH <SEP> red <SEP> good <SEP> Very <SEP> good <tb> <SEP> shade <tb> <SEP> -N=N <SEP> f <SEP> it <SEP> 3 <SEP> yellow <tb> <SEP> - <SEP> yellow <tb> <SEP> FONH, <SEP> FOCH3 <tb> 29CH3-i- <SEP> N=N--CH <tb> <SEP> 3 <SEP> green <SEP> good <SEP> Very <SEP> good <tb> <SEP> shade <tb> <SEP> yellow <tb> <SEP> > <SEP> yellow <tb> <SEP> Cue130 <tb> <SEP> CONH <tb> 30 <SEP> 2 <SEP> H <SEP> red <SEP> good <SEP> Very <SEP> good <tb> <SEP> 013 <SEP> o <SEP> N=N3 <SEP> shade <tb> <SEP> Nl <tb> <SEP> C1 <tb> <SEP> Cl <tb> <SEP> CONR <tb> 31CH <SEP> 4 <SEP> / <SEP> 3 <SEP> NH <SEP> yellow <SEP> Very <SEP> good <SEP> Very <SEP> good <tb> <SEP> CONH <SEP> $/ <tb> Table I (continued) Bleed- Light Ex. Pigment Formula Color fastness fastness EMI20.1 <tb> 32 <SEP> /COCH3 <SEP> Brownish <SEP> Very <SEP> good <SEP> good <tb> <SEP> O2NN=N-C13 <SEP> J <SEP> H <SEP> \50 <SEP> yellow <tb> <SEP> CONH2 <SEP> CONH <SEP> 9 <SEP> NH <tb> 33 <SEP> C, <SEP> OCR3 <SEP> Orange <SEP> good <SEP> <tb> <SEP> 020 <SEP> N=N-CN <tb> <SEP> CONH2 <SEP> CONH0 <SEP> 0C2 <SEP> 135 <tb> 34 <SEP> FOCHs <SEP> Orange <SEP> Very <SEP> good <SEP> Very <SEP> good <tb> <SEP> 02N <SEP> )-N=N-CH <tb> <SEP> CONH2 <SEP> CONHCH3 <tb> <SEP> OCR3 <tb> 35 <SEP> COCH3 <SEP> Reddish <SEP> Very <SEP> good <SEP> Very <SEP> good <tb> <SEP> 7 <SEP> Cl <SEP> brown <tb> <SEP> Oii2 <SEP> C0NHCH3 <tb> <SEP> \CONH <SEP> F13 <tb> <SEP> OCH3 <tb> 36 <SEP> COCH3 <SEP> Red <SEP> Shade <SEP> Good <SEP> Good <tb> <SEP> 2X¯ <SEP> > <SEP> N=N-CH <SEP> yellow <tb> <SEP> CONH2 <SEP> CONH <SEP> t <SEP> H3 <tb> <SEP> CH3 <tb> 37 <SEP> COCH3 <SEP> Orange <SEP> Very <SEP> good <SEP> good <tb> <SEP> N <SEP> I <tb> <SEP> 0 <SEP> N=N-C13 <SEP> CH3 <tb> <SEP> CONH2 <SEP> CONH- <SEP> > <SEP> C1 <tb> <SEP> OCH3 <tb> 38 <SEP> COCH3 <SEP> Green <SEP> Fair <SEP> Fair <tb> <SEP> N <SEP> I <tb> <SEP> 0 <SEP> N=N-CH <SEP> shade <tb> <SEP> yellow <SEP> \ <SEP> yellow <SEP> yellow <tb> <SEP> CONH2 <SEP> CONH- <SEP> 9 <SEP> C1 <tb> Table I (continued) Bleed- Light Ex. Pigment Formula Color fastness fastness EMI21.1 <tb> 39 <SEP> COCH <SEP> Orange <SEP> Good <SEP> Very <SEP> good <tb> <SEP> /3 <tb> <SEP> O <SEP> 2N <SEP> c)N=N-CH <tb> <SEP> CONY2 <SEP> CONH <SEP> SOCH3 <tb> 40 <SEP> COCH3 <SEP> Green <SEP> Good <SEP> Fair <tb> <SEP> shade <tb> <SEP> 02NN=N-CH <SEP> yellow <tb> <SEP> CONH <SEP> Q <tb> <SEP> CONR <SEP> 9 <tb> <SEP> di <tb> 41 <SEP> COUCH, <SEP> Green <SEP> Good <SEP> Fair <tb> <SEP> O <SEP> 2N <SEP> =N-C1H <SEP> shade <tb> <SEP> yellow <tb> <SEP> CONH--(n, <tb> <SEP> CONH2 <SEP> \Y/ <tb> 42 <SEP> COCH <SEP> Orange <SEP> Good <SEP> Fair <tb> <SEP> 2 <SEP> < <SEP> N=N-CH <SEP> OCH3 <tb> <SEP> CONH2 <SEP> CONH- <SEP> ss <tb> <SEP> OCR3 <tb> 43 <SEP> COCH <SEP> Green <SEP> Very <SEP> good <SEP> Fair <tb> <SEP> I <SEP> / <SEP> 3 <SEP> shade <tb> <SEP> 02N <SEP> 7t <SEP> N=N-CH <SEP> C1 <SEP> yellow <tb> <SEP> CONH2CONRCQl <tb> <SEP> C1 <tb> 44 <SEP> ,C0CH3 <SEP> Green <SEP> Good <SEP> Good <tb> <SEP> 02N- <SEP> N=N-CH <SEP> shade <tb> <SEP> ON <SEP> yellow <tb> <SEP> CONH2 <SEP> CONH <SEP> t <SEP> 1 <tb> Table I (continued) Bleed- Light Ex. Pigment Formula Color fastness fastness EMI22.1 <tb> 45 <SEP> COCH <SEP> Green <SEP> Good <SEP> Good <tb> <SEP> 2 <SEP> 1 <SEP> 3 <SEP> I <SEP> -, <SEP> shade <tb> <SEP> N=N-CH <tb> <SEP> CONH2 <SEP> CONH- <SEP> tci <tb> <SEP> Cl <tb> 46 <SEP> COCK, <SEP> Green <SEP> Fair <SEP> Fair <tb> <SEP> I <SEP> 3 <SEP> shade <tb> <SEP> ON <SEP> ON=N-CH <SEP> CR3 <SEP> yellow <tb> <SEP> CONH2 <SEP> CONHe <tb> 47 <SEP> SOCH, <SEP> Yellow <SEP> Good <SEP> Very <SEP> good <tb> <SEP> 2 <SEP> 2 <SEP> 4 <SEP> N=N-CH <tb> <SEP> CONH <SEP> 9 <tb> <SEP> SOCH3 <tb>

Claims: CLAIMS 1. An azo pigment having the formula EMI23.1 wherein X and Y are the same or different and are selected from the group consisting of -H, -R , -OR -Cl -CONH2, -NO2 and -SO2NH2 where -R@ is lower alkyl; and -R is EMI23.2 where -R2, -R3 and -R4 are the same or different and are selected from the group consisting -H, -OR1, -R1, and -Cl; EMI23.3 where R5, R6, and R7 are the same or different and are selected from the group consisting of -H, -OR1, -R1, and -C1, EMI23.4 where -R8 is -H or -C1; EMI23.5 2. The azo pigment of Claim 1 wherein -X is -NO2 and -Y is -H. 3. The azo pigment of Claim 1 wherein -R is EMI24.1 4. The azo pigment of Claim 1 wherein -X and -Y are -H. 5. The azo pigment of Claims 1 or 4 wherein -R is EMI24.2 6. The azo pigment of Claim 1 wherein -Y is -CONH2 and -X is -H. 7. The azo pigment of Claims 1 or 6 wherein -R is EMI24.3 8. A process comprising an in situ diazotization and coupling reaction wherein an anthranilamide of the formula EMI24.4 where X and Y are the same or different and are selected from the group consisting of -H, -R1, -OR1, -Cl, -CONH2, -NO2 and -SO2NH2 where -R1 is lower alkyl; is reacted with a coupler, R, in the presence of a diazotization agent and an acid in a liquid medium comprising of water and, optionally, a polar organic solvent at a pH from 1.0 to 7.0 at a temperature from 0 C to 1000C to form a pigment of the formula EMI25.1 wherein -R is selected from the class consisting of EMI25.2 where -R2, -R3, -R4 are the same or different and are selected from the group consisting of -H, OR1, -R1 and -Cl; EMI25.3 where -R5, -R6, -R7 are the same or different and are selected from the group consisting of -H, -OR1, -R1, and -Cl; EMI26.1 where -R8 is -H, or-Cl; and EMI26.2 9 . The process of Claim 8 wherein said liquid medium contains a polar organic solvent. 10 . The process of Claim 9 wherein the reaction is carried out at from 100 to 500C. CLAIMS FOR AUSTRIA EMI27.1 1. A process for producing an azo pigment having the formula EMI27.2 wherein X and Y are the same or different and are selected from the group consisting of -H, -R1, -OR1, -Cl -CONH2, -NO2 and -SO2NH2 where -R1 is lower alkyl; and -R is EMI27.3 where -R2, -R3 and -R4 are the same or different and are selected from the group consisting-H, -OR1, -R1, and -Cl; EMI27.4 where R5, R6, and R7 are the same or different and are selected from the group consisting of -H,-OR1,-R1, and -Cl, EMI27.5 where -R8 is -H or -C1; EMI27.6 comprising an in situ diazotization and coupling reaction wherein an anthranilamide of the formula EMI28.1 wherein X and Y are defined as above; is reacted with a coupler, RH, wherein R is defined as above, in the presence of a diazotization agent and an acid in a liquid medium comprising of water and, optionally, a polar organic solvent at a pH from 1.0 to 7.0 at a temperature from OOC to 100 C. 2. The process of Claim 1 wherein -X is -NO2 and -Y is -H. 3. The process of Claim 1 wherein -R is EMI28.2 4. The process of Claim 1 wherein -X and -Y are -H. 5. The process of Claims 1 or 4 wherein -R is EMI28.3 6. The process of Claim 1 wherein -Y is -CONH2 and -X is -H. 7. The process of Claims 1 or 6 wherein -R is EMI28.4 EMI29.1 8. The process of Claims 1 to 7 wherein said liquid medium contains a polar organic solvent. 9. The process of Claims 1 to 8 wherein the reaction is carried out at from 100 to 5O0C.

Inventors: BRUNO, SALVATORE ANTHONY, TOJI, MASUO
Applicants: HEUBACH, INC.
Application year: 1982
Main classification: C09B29
IPC codes: C09B29, C09B41