MXPA00012016A - Heat stable laked monoazo pigment compositions - Google Patents

Abstract

Red shade yellow pigment compositions characterized by formula (1) wherein X is a lower alkyl or a -COOR1 group;wherein R1 is hydrogen or lower alkyl group;each Y is independently a lower alkyl, lower alkyloxy or halogen group;a is 0,1, or 2;and M is a divalent metal. Also disclosed is a process for preparing red shade pigment compositions prepared by initially a diazonium component comprised of one or more aromatic amines wherein at least one of said amines is a 1-sulfo-2-naphthylamine;and thereafter coupling the diazonium component with a coupling component comprised of a pyrazolone coupler to form a dye, and metallizing said dye with at least one divalent metal.

Description

COMPOSITIONS OF PIGMENT MONOAZO LAQUEADO STABLE TO HEAT DESCRIPTION OF THE INVENTION This invention relates to novel lacquered azo pigments, processes for their preparation and compositions for paint, plastic and ink containing such pigments. Metal salts of individual azo compounds containing a portion of pyrazolone containing two sulfo groups are known in the art as pigments. For example, German Patent 2,616,981 discloses metal salts of azo pyrazolone dyes which are obtained by coupling diazotised acid 2-amino-4,5-dichlorobenzene-1-sulfonic acid with compounds 1- (sulfoaryl) -3-methyl-5-pyrazolone. and subsequent lagging with metallic salts. Japanese Patent 62,166,359 describes electrophotographic toners containing monoazo pigments of the formula X = C1 or S03: m = l or 2; M = Mg, Ca or Ba; n = 1 or 2 When X is Cl, then m is 1 and n is 2, and when X is S? 3 ~, then m is 2 and n is 1. U.S. Patent 4,595,411 describes where R is CH3 or COO ", X is Cl, CH3, CH30, C2H50 C2H5CONH, NH2CONH, C6H5CONH, CH3S02NH, CH3CONH or hydrogen, Y is hydrogen, Cl or CH3, Z is hydrogen or Cl, n is 0, 1 or 2; e + is an equivalent of a cation selected from the group consisting of NH4 +, Li +, K +, Na + Sr2 +, * á Mn2 +, Ni2 +, Ba2 +, * í Mg2 + and Ca2 +, with the proviso that R is COO-, the additional equivalent charge is compensated for by an additional equivalent of the same or another cation. European Patent 0,126,405 (German Patent 33,180,373) also describes labile azo pyrazolone pigments of the formula wherein D is a tri or tetrasubstituted phenyl ring; R is CH3 or COO "; X is Cl, Br, CH3, CH30, C2H50 CH3CONH, S02NH2, S03"; Y is Cl, Br, CH3 or S03"Z is Cl, Br or CH3 US Patent 5,047,517 refers to a yellow monoazo pigment which is obtained by the diazotization of 2-amino-4-chloro-5-methylbenzene acid -l-sulphonic acid, coupling the diazonium compound with l- (3'-sulfophenyl) -3-methyl-5-pyrazolone and subsequent lacquering of the coupling product with the calcium salt International Application WO 96/22334 describes a compound azo pyrazolone of formula in the form of a salt and its use as a pigment. There is a desire, however, to obtain pigments that have red shades of yellow with high heat stability and ease of preparation, as well as reduced cost. There is a need for these yellow pigments to show improved performance in one or more of the following properties: color strength, polar solvent resistance and light resistance. This invention relates to azo pigments suitable for use as coloring agents and processes for their preparation. In one embodiment, this invention relates to red yellow compositions comprising one or more compounds characterized by the formula: wherein X is a lower alkoyl or a -COOR group; wherein R is hydrogen or a lower alkyl group; each Y is independently a lower alkyl, lower alkyloxy or halogen group; to 0, 1 or 2; and M is a divalent metal. In another embodiment, this invention relates to a process for preparing an azo pigment which comprises forming a colorant by coupling (i) a diazonium component comprised of one or more aromatic amines wherein at least one of the amines is 1-sulfo -2-naphthylamine characterized by the formula: and you come out of it; with (ii) at least one coupling component characterized by the formula: and salts thereof; wherein X is a lower alkoyl or a -COOR3 group; wherein Ri is hydrogen or a lower alkyl group; each Y is independently a lower alkyl, lower alkyloxy or halogen group; a is 0, 1 or 2; and metallizing the dye with at least one divalent metal. In another embodiment, this invention relates to compositions for paint, plastic and ink which contain the azo pigment compositions of this invention.

As previously stated, this invention provides azo pigments and processes for their preparation. The pigments of the present invention can be prepared by initially diazotizing one or more aromatic amines wherein at least one of the amines is 1-sulfo-2-naphthylamine; and subsequently coupling the diazonium component with a coupling component comprising a pyrazolone coupler to form the desired dye. The l-sulfo-2-naphthylamines are characterized by the formula: and you come out of them. Mixtures of two or more of any of the 1-sulfo-2-naphthylamines are within the scope of this invention. Also within the scope of this invention are mixtures of one or more 1-sulfo-2-naphthylamine and one or more secondary amines, other than 1-sulfo-2-naphthylamines, selected from aromatic amines containing at least one acid group and salts of them. Such secondary amines can be used for pigment tone adjustments of this invention. Examples of preferred salts include ammonium and alkali metal salts such as the sodium and potassium salts. A variety of suitable aromatic amines can be mixed with the 1-sulfo-2-naphthylamines for the purposes of the present invention. Almost any aromatic primary amine can be used wherein the aromatic portion of such amine contains at least one substituent acid group or salts thereof, preferably alkali metal and ammonium salts (Ar). The aromatic amines can be monoamines or polyamines containing up to four or more amine groups per molecule. Thus, the diazonium components derived from such amines may contain a diazonium group (mono-diazonium), two diazonium groups (bis-diazonium), three diazonium groups (tris-diazonium), etc. The aromatic amines may be monocyclic amines such as aniline and its derivatives, or bicyclic amines such as naphthylamine. The aromatic amines can also be diphenylamines or polyamines such as aminobiphenyl, benzidine and 3,3 ',,' -biphenyltetramine. In one embodiment, the aromatic amine is a primary aromatic amine characterized by the formula (Formula I) wherein each R is independently a halogen, hydrocarbyl, hydrocarbyloxy, carboxylic acid ester, sulfonic acid ester, carboxylic acid amide, imidazolone, sulfonic acid amide or nitro group; n is 0, 1 or 2; each Z is independently a -COOH or -S03H group, or salts of such groups; m is 1 or 2; wherein it is understood that the imidazolone group is represented by the formula -NH-C-NH- which, when taken together with the aromatic ring, the nitrogen atoms are bonded to the adjacent carbons to form a five-membered ring. The term "hydrocarbyl" as used in this specification and the claims is intended to include hydrocarbons which may contain substituent groups such as ether, ester, nitro or halogen, which do not materially affect the hydrocarbon character of the group. The aromatic amines characterized by Formula I may contain 0, 1 or 2 R groups which are each independently a halogen, hydrocarbyl, hydrocarbyloxy, carboxylic acid ester, sulfonic acid ester, carboxylic acid amide, imidazolone, acid amide sulfonic, or nitro group. The halogen group can be any of the halogens, although the • Chlorine and bromine, with chlorine being the most preferred example of a halogen substituent. The hydrocarbyl groups can independently be alkyl, cycloalguyl, aryl, aralkyl or alkaryl groups. For example, if R is an unsubstituted aryl group, the aromatic amine is a biphenyl amine. When R is an alkyl group, the alkyl group will generally contain from one to four carbon atoms. As used in • The present, "lower alkyl" will mean those alkyl groups containing from 1 to 4 carbon atoms. When R is a hydrocarbyloxy group, the hydrocarbyl portion can be any of the hydrocarbyl groups discussed above although the hydrocarbyloxy group is generally an alkoxy group containing from 1 to about 4 or more carbon atoms. Preferred R groups are the methyl, ethyl and chloro groups. The aromatic amines characterized by Formula I also contain one or two acid groups of -COOH and -S03H, or salts thereof. In one embodiment, the aromatic amine of Formula I contains a -S03H group. Examples of aromatic amines characterized by Formula I wherein Z is a sulfonic acid group and m is 1 include 2-aminobenzene-1-sulfonic acid, 4-25 aminobenzene-1-sulfonic acid, 2-amino-5-methylbenzene-1-sulfonic acid, 2-amino-5-methoxybenzene-1-sulphonic acid, 3-amino-6-methylbenzene-1-sulphonic acid, 2-amino-4-chloro-5-methylbenzene-1-sulfonic acid, 2-amino-5-chloro-4-ethylbenzene-1-sulphonic acid, 2-amino-5-chloro-4-methylbenzene-1-sulfonic acid, etc. Examples of aromatic amines characterized by Formula I wherein Z is a carboxylic acid group and m is 1 include 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-amino-5-methylbenzoic acid, 2-amino acid, 6-methylbenzoic acid, 3-amino-2-methylbenzoic acid, 2-amino-3-methoxybenzoic acid, 4-amino-3-methoxybenzoic acid, 4-amino-5-chloro-2-methoxybenzoic acid, 2-amino-4 acid -chlorobenzoic acid, 3-amino-4-chlorobenzoic acid, etc. Benzenesulfonic acid and benzoic acid compounds can be used per se or as their salts. Examples of preferred salts include the alkali metal salts such as the sodium and potassium salts. The aromatic amines from which the diazonium components are prepared may be fused cyclic aromatic amine compounds such as compounds derived from various naphthalenes other than l-sulfo-2-naphthylamines including 4-aminonaphthalene-1-sulfonic acid, etc. Examples of aromatic amines which are biphenyl amines and polyamines include 4-aminobiphenyl-3'-sulphonic acid and 4,4'-diaminobiphenyl-2,2'-disulfonic acid.

The diazotization of the amines useful for the purposes of this invention can be carried out in the forms known to those skilled in the art through the use of alkali metal nitrites or lower alkyl nitrites together with a suitably strong acid such as a mineral acid Examples of useful mineral acids include hydrochloric acid and sulfuric acid. Nitrosyl sulfuric acid can also be used. The diazotization reaction can be conducted at a temperature in the range of about -20 to + 30 ° C, preferably 0 to 20 ° C. Although not required, it may be advantageous in some of the diazotization reactions (and in the subsequent coupling reactions) to include a surfactant such as a nonionic, anionic or cationic surfactant, and optionally appropriate organic solvents such as, for example, example, glacial acetic acid, lower alkanols, dioxane, formamide, dimethylformamide, dimethylsulfoxide, pyridine or N-methylpyrrolidone. The pyrazolone traps useful for purposes of this invention are represented by the formula: and salts thereof where X is a lower alkyl or a -COORi group; wherein Ri is hydrogen or a lower alkenyl group; each Y is independently a lower alkyl, lower alkyloxy or a halogen group; a is 0, 1 or 2. Preferably, the pyrazolone couplers useful for the purposes of this invention are characterized by the formula: wherein X is methyl, ethyl, -COOH, -COOCH3, -COOCH2CH3, more preferably, Mixtures of two or more of any of the pyrazolone components are within the scope of this invention.

The coupling reaction useful for the purposes of the present invention can preferably be effected by adding the diazonium components to the coupling components, but the coupling components can be added to the diazonium components. The coupling is generally carried out at a temperature from about -20 ° to about 80 ° C, preferably from about 20 to about 65 ° C. As in a diazotization reaction, the coupling can be carried out in the presence of an appropriate surfactant or organic solvent, such as all those identified above for the diazotization reaction. In one embodiment, the coupling component is dissolved in a basic solution such as an aqueous alkali metal hydroxide solution and reprecipitated with a dilute acid such as acetic acid. In another embodiment, generally, the diazonium component is coupled with a stegeometrically light excess of the coupling component. That is, an equivalent of the diazonium component is coupled with slightly more than one equivalent of the coupling component. In another embodiment of the present invention, the dispersibility of the pigments of the present invention can be improved by adding alkali-soluble resin-like products, before, during or after the coupling is complete or after the metallization discussed below. Various resin-like materials can be added for this purpose, and these include, for example, turpentine resins, polymeric turpentines, resin soap, guimically modified turpentine resins, such as turpentine malonate, resins, and other hydrocarbon resins. synthetics with a higher number of acid, or combination of these resins. The resins can be present in a product with free carboxyl groups that are capable of forming a salt, or can be partially or completely in the form of salts, for example, with alkali metal ions. It may also be advantageous to carry out the coupling reaction in the presence of a finely divided insoluble material, for example, alkaline earth metal sulfates and carbonates, titanium dioxide or mud materials or finely divided organic plastic materials. The composition prepared by the coupling reaction described above can be metallized by a divalent metal salt which forms the sulfonate salt. This is also known as lagueado and forms the azo pigment. The metal salt may be an alkaline earth metal salt, manganese, niguel or zinc or mixtures of two or more of these metals. The alkaline earth metal salts are preferred. Alkaline earth metal salts such as SrCl 2 and CaCl 2 are particularly useful for this purpose. The metallization can preferably be achieved by adding the metal salt to the dye after all the coupling of the diazonium component present is completed, or, by including the metal salt in the diazonium component whereby metallization occurs as the dye is formed. In most applications, it is desirable to achieve full brilliance and dye strength, heat the azo pigment. For example, the metallization product may be heated at reflux temperature for about 1 to 3 hours or at temperatures above 100 ° C under pressure in the presence of the resin soaps described above or other soluble resins. After completing the metallization, the azo pigments are recovered from the water-based reaction suspension by filtering to form a pigment press cake which is washed with hot water (eg, 40-60 ° C) to remove the pigment. excess of acids, bases and salts formed in the coupling reaction. The press cake is typically washed with 10 to 20 times its volume of hot water. The filtered cake is generally washed until the filtrate gives only a slightly positive test for chloride ion. The washed press cakes can be dried, ground and used in the form of a coarse or finely divided powder. Alternatively, the azo pigments of this invention can be dispersed within oleoresin vehicles to prepare bases washed with water or dispersed in aqueous vehicles to prepare aqueous dispersions. The pigment compositions of this invention provide red-hued yellow pigments which have improved color strength, polar solvent resistance, light resistance, and / or heat stability and are useful as coloring agents in plastics, paints and inks. This invention, therefore, also relates to paint, ink and plastic compositions, which comprise major amounts of a paint vehicle, ink vehicle or plastic in minor amounts of the compositions of this invention. The paint, ink and plastic compositions in which the compositions of this invention are useful are well known to those of ordinary skill in the art. Examples of inks include printing inks and lacquers, and plastics include thermoplastic and thermoset materials, natural resins and synthetic resins, polystyrene and its mixed polymers, polyolefins, in particular, polyethylene and polypropylene, polyacrylic compounds, polyvinyl compounds, for example, polyvinyl chloride and polyvinyl acetate, polyester and rubber, and also filaments made of viscous ethers and cellulose, cellulose esters, polyamides, polyurethanes, polyesters, for example, polyglycol terephthalates and polyacrylonitrile. It is also useful for the printing of pigments and for the pigmentation of paper in the dough. Due to its excellent resistance to heat, the pigment is in particular suitable for the pigmentation of plastics in the mass, such as, for example, polystyrene and its mixed polymers, polyolefins, in particular polyethylene and polypropylene and the corresponding mixed polymers, polyvinyl and polyesters, in particular polyethylene glycol terephthalate and polybutylene terephthalate and the corresponding mixed condensation products based on polyesters. See, for example, with respect to ink: R. H. Leach, editor, The Printing Ink Manual, Fourth Edition, Van Nostrand Reinhold (International) Co. Ltd., London (1988), particularly pages 282-591; with respect to paints: C. H. Hare, Protective Coatings, Technology Publishing Co., Pittsburgh (1994), particularly pages 63-288; and with respect to plastics: T. G. Webber, Coloring of Plastics, John Wiley & Sons, New York (1979), particularly pages 79-204. The above references are hereby incorporated by reference herein, by their teachings of ink, paint and plastic compositions, formulations and vehicles in which the compositions of this invention can be used including amounts of colorants.

The following examples illustrate the compositions of the present invention and their methods of preparation. Unless stated otherwise in the following examples and elsewhere in the specification and claims, all parts and percents are by weight, temperatures are in degrees centigrade and pressures are at or near atmospheric. Example 1 2-Aminonaphthalene-1-sulfonic acid (13.1 parts) is dissolved in 300 parts of water and 2.5 parts of sodium hydroxide by stirring at 40-45 ° C. The solution is cooled to 0 ° C by the addition of ice and diazotized by the addition of 4 parts of sodium nitrite in 12 parts of water followed by the addition of 17.5 parts of Baume hydrochloric acid and stirring the solution to 0-10. ° C for 30 minutes. The excess of nitrous acid is then extinguished by the addition of sulfamic acid. The suspension is frozen at 0 ° C by the addition of ice. A solution of 6 parts of calcium chloride dihydrate in 14 of water is then added to the suspension. Sixteen parts of 1- (3? -sulfophenyl) -3-methyl-5-pyrazolone are dissolved in 500 parts of water 2.5 parts of sodium hydroxide and the temperature is adjusted to 20 ° C, the pH is adjusted to 6.5 and the The diazonium suspension is then slowly added thereto while maintaining the pH at 6-7 through the addition of sodium hydroxide. The mixture is then stirred for approximately twenty minutes to couple the coupling. Calcium chloride dihydrate (30 parts) is added in 70 parts of water. The volume is then adjusted to 1,800 ml and the pH is adjusted to 4.5. The suspension is then heated to boiling. After boiling for 60-90 minutes, the suspension is cooled with ice to less than 40 ° C and filtered; the filter cake is washed with water, dried overnight at 70 ° C and pulverized to give a reddish yellow pigment powder. Comparative Example 1 The sodium salt of 1-naphthylamine-4-sulfonic acid (8.9 parts) and 100 parts of water are stirred together with the addition of sufficient 50% sodium hydroxide solution to form an alkaline solution for Bright Yellow paper. The solution is placed in an ice bath and cooled to 0-5 ° C and 15 parts of Baume hydrochloric acid are added. A solution of 3.13 parts of sodium nitrite in 9.4 parts of water is added and the mixture is stirred at 0-5 ° C for 30 minutes. The excess of nitrous acid is then extinguished by the addition of sulfamic acid. The suspension is frozen at 0 ° C by the addition of ice. They are dissolved in 200 parts of water, 13.2 parts of 1- (3'-sulfophenyl) -3-methyl-5-pyrazolone and 2.5 parts of sodium hydroxide. The temperature of this solution is adjusted to 5 ° C. The pH is adjusted to 6.5 and the diazonium suspension is then added slowly while maintaining the pH at 6-7 through the addition of sodium hydroxide. The pH of the suspension is adjusted to 6.5 and the mixture is stirred overnight at room temperature. The reaction mixture is then heated to 90 ° C and a solution of 48 parts of calcium chloride dihydrate in 112 parts of water is added. The mixture is then further stirred for about 3 hours at 90 ° C, cooled to 55 ° C and filtered. The filter cake is washed with water, dried overnight at 70 ° C and pulverized to give an orange pigment powder. Comparative Example IA The procedure of Comparative Example 1 is repeated except that in place of the sodium salt of 1-naphthylamine-4-sulfonic acid, 8.9 parts of 1-naphthylamine-6-sulphonic acid. An orange pigment powder is obtained. EXAMPLE 2 The procedure of Example 1 is repeated except that in place of the addition of calcium chloride, 5.7 parts of strontium nitrate in 17.5 parts of water are added to the diazonium suspension and 21 parts of strontium nitrate are added to the suspension. 49 parts of water after coupling instead of the addition of calcium chloride. A yellowish orange pigment powder is obtained.

Comparative Example 2 The procedure of Comparative Example 1 is repeated, except that in place of the addition of calcium chloride, 48 parts of strontium nitrate are added in 112 parts of water. An orange powder pigment is obtained. Example 2A The procedure of Comparative Example IA is repeated, except that in place of the addition of calcium chloride, 48 parts of strontium nitrate and 112 parts of water are added. An orange powder pigment is obtained. EXAMPLE 3 The procedure of Example 1 is repeated, except that in place of the addition of "calcium chloride, 8 parts of hydrous manganese sulfate are added to the diazonium suspension and 18 parts of hydrated manganese sulfate are added after coupling. Instead of the addition of calcium chloride, a yellowish orange pigment powder is obtained Test Method A mixture of 0.5 parts of pigment, 0.5 parts of titanium dioxide (DuPont Ti-Pure R-960) and 500 parts of polyethylene High density (Solvay T50-2000-G) are agitated on a paint shaker until uniform, then injection molded at 232 ° C on a 30 ton Battenfield machine, spectrophotometric values are measured with a Macbeth Color-Eye ( specular component included, large area) to give the apparent strength of the dye angle under Illuminant D, 10 °, shown in Table I. TABLE 1 Results of the Pigment Test Method Angle Strength Value Apparent Dye Chromaticity (K / S) Example 1 73.0 66.3 ° 23.1 (Standard) Example 1 32.4 45.4 ° 4.9 (79% Weak) Comparative Example IA 59. 7 52. 6 ° 17.5 (24% Weak) Example 2 78. 2 70. 3 ° 26.8 (Standard) Example 2 37. 6 43 7th 6.3 (77% Weak) Comparative Example 2A 60.4 49.9 ° 20.3 (24% Weak) Comparative When incorporated into polyolefins, the pigments obtained according to the present invention exhibit strong bright reddish yellows in contrast to the orange-reddish-orange shades presented by the pigments derived from 1-naphthylamine-4-sulfonic acid and acid. -naphthylamine-6-sulfonic acid. The calcium salt of the dye obtained by the coupling of diazotized 2-amino naphthalene-1-sulfonic acid with 1- (3'-sulfophenyl) -3-methyl-5-pyrazolone (Example 1) exhibits a strong bright reddish yellow color ( dye angle 66.3). The high chromaticity value (73.0) is consistent with the brightness of the presented color while the high force is reflected by a high K / S value of 23.1. In contrast, the corresponding pigment obtained by using 1-naphthylamine-4-sulfonic acid instead of 2-aminonaphthalene-1-sulfonic acid (Comparative Example 1) shows a very weak and opaque reddish orange color (dye angle 45.4) of low color. chromaticity (32.4) and very low force (K / S value of only 4.9). The corresponding pigment obtained by using 1-naphthylamine-6-sulfonic acid (Comparative Example IA) also exhibits a weak orange color (dye angle 59.7) of low chromaticity (52.6) and low strength (K / S value of 17.8). Similarly, the strontium salt of the dye obtained by coupling diazotized 2-amino-naphthalene-1-sulfonic acid with 1- (3 '-sulfophenyl) -3-methyl-5-pyrazolone (Example 2) exhibits a strong bright reddish yellow color. (dye angle 70.3). The high chromaticity value (78.2) is consistent with the brightness of the presented color and the high strength is reflected by a high K / S value of 26.8. In contrast, the corresponding pigment obtained by using 1-naphthylamine-4-sulfonic acid instead of 2-aminonaphthalene-1-sulfonic acid (Comparative Example 2) shows a very weak and opaque reddish orange color (dye angle 43.7) of low color. chromaticity (37.6) and very low strength (K / S value of only 6.3). The pigment obtained by using 1-naphthylamine-6-sulfonic acid (Comparative Example 2A) has a faint orange color (dye angle 49.9) of low chromaticity (60.4) and relatively low strength (K / S value of 20.3).

Claims (24)

1. CLAIMS 1. A red pigment yellow pigment composition comprising one or more compounds, characterized by the formula: wherein X is a lower alkyl or a group
2. -COORi .; wherein Ri is hydrogen or a lower alkyl group; each Y is independently a lower alkyl, a lower alkyloxy group or halogen; a is 0, 1 or 2; and M is a divalent metal. 2. The composition according to claim 1, characterized in that X is a methyl or ethyl group.
3. 3. The composition according to claim 1, characterized by each Y is independently a methyl or chloro group; and a is 0 or 1.
4. 4. The composition according to claim 3, characterized by X is a methyl group and a is 0.
5. 5. The composition according to claim 1, characterized in that M is an alkaline earth metal, manganese, nitrile or zinc.
6. 6. The composition according to claim 4, characterized by M is calcium, strontium, barium or mixtures thereof.
7. 7. A red-colored yellow pigment composition comprising one or more compounds characterized by the formula: wherein X is a lower alkyl group; and M is a divalent metal.
8. 8. The composition according to claim 7, characterized in that M is a divalent metal selected from the group consisting of alkaline earth metals, manganese, nitrile and zinc.
9. 9. The composition according to claim 7, characterized in that X is a methyl or ethyl group.
10. 10. The composition according to claim 7, characterized by M, is calcium, strontium, barium or mixtures thereof.
11. 11. A process for preparing a reddish yellow pigment composition which comprises making an azo dye by coupling (i) a diazonium component comprised of one or more aromatic amines wherein at least one of the amines is l-sulfo 2-Naphthylamine characterized by the formula: and salts thereof; with (ii) at least one coupling component characterized by the formula: and salts thereof; wherein X is a lower alkyl or a -COORi group; wherein Ri is hydrogen or a lower alkyl group; each Y is independently a lower alkyl group, a lower alkyloxy group or halogen; a is 0, 1 or 2; and metallizing the dye with at least one divalent metal.
12. 12. The process in accordance with the claim 11, characterized in that X is a methyl or ethyl group.
13. 13. The process according to claim 11, characterized in that each Y is independently a methyl or chloro group; and a is 0 or 1.
14. 14. The process in accordance with the claim 13, characterized in that X is a methyl group and a is 0.
15. 15. The process according to claim 11, characterized in that M is an alkaline earth metal, manganese, nickel or zinc.
16. 16. The process in accordance with the claim 15, characterized in that M is calcium, strontium, barium or mixtures thereof.
17. 17. The composition prepared according to the process of claim 11.
18. 18. The composition prepared according to the process of claim 16.
19. 19. The paint composition characterized in that it comprises a paint vehicle and the composition according to claim 1. .
20. 20. The paint composition characterized in that it comprises a paint vehicle and the composition according to claim 17.
21. 21. The ink composition characterized in that it comprises an ink vehicle and the composition according to claim 1.
22. 22. The ink composition characterized in that it comprises an ink vehicle and the composition according to claim 17.
23. 23. The plastic composition characterized in that it comprises a plastic material and the composition according to claim 1.
24. 24. The plastic composition characterized in that it comprises a material plastic and the composition according to claim 17.