Title of Invention	A METHOD OF PREPARING A GREEN SHADE YELLOW PIGMENT COMPOSITION
Abstract	A method of preparing a green shade yellow pigment composition which comprises making a disazo pigment by coupling (i) a diazonfum component made from of one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline with (ii) at least one coupling component characterized by the formula: wherein R1 and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl.

Title of Invention

A METHOD OF PREPARING A GREEN SHADE YELLOW PIGMENT COMPOSITION

Abstract

A method of preparing a green shade yellow pigment composition which comprises making a disazo pigment by coupling (i) a diazonfum component made from of one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline with (ii) at least one coupling component characterized by the formula: wherein R1 and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl.

Full Text	1 Title: STRONG GREEN-SHADE YELLOW DISAZO PIGMENT Technical Field This invention generally relates to novel green-shade yellow disazo pigments and to the use of such pigments in plastics, paints and inks. Background of the Invention Azo yellow pigments are a class of colorants that are tinctoriaily strong and relatively inexpensive. Monoazo yellow pigments exhibit good lightfastness and are useful as coloring agents for paints and some printing inks. In plastics, however, monoazo yellow pigments tend to undesirably bloom and discolor at high temperatures, so their use is disfavored. Diarylide disazo yellow pigments, made from 3,3'-dichlorobenzidine, are much stronger tinctoriaily and show a much lower tendency to bloom and discolor at high temperatures. C.I. Pigment Yellow 1 7 is a strong green-shade diarylide yellow and has often been used for plastics. W. Herbst and K. Hunger, Industrial Organic Pigments. VCH, New York, 1993, p. 252, state: "The plastics industry, however, uses P.Y. 17 extensively, . . . P.Y. 17 is also frequently used in polyolefins ... Its heat stability in these media was said to be about 220 to 240cC* However, R. Az et a! reported in Dyes and Pigments, _L5_, 1 (199V', that diarylide yellows are degraded to potentially carcinogenic by-products (e.g., 3,3'-dichlorobenzidine) in plastics processed above 200°C, a temperature lower than that used in processing most plastics (many plastics are processed at temperatures from 230°C to 330°C). In efforts to overcome these disadvantages, azo pigment manufacturers have actively pursued development of other types of azo yellows. One alternative type of azo yellows include disazo yellow pigments made by coupling bis(acetoacetamido)benzenes (BAAAB) into aniline derivatives. U.S. Patent 5,616,778 to Goldmann et al relates to coupling 2 1,4-BAAAB into 2,5-dicarbomethoxyaniline (to give C.I. Pigment Yellow 155) and heating the pigment in an organic solvent at 80-150°C for up to 6 hours. U.S. PatTCTTr 5/559,216-.to Jung et aJ gives. 4-7_£xarnpJes and describes coupling 1,4-bisacetoacetamidobenzene German Offenlegungsschrift 3501199 (1985, Sandoz GmbH) relates to coupling 1,4-BAAAB into mixtures of anilines substituted with one or two carboalkoxy groups to give pigments that disperse easily into polypropylene. Canadian Patent 1135688 (1982. Hoechst AGJ relates to the pigments resulting from coupling 1,4-BAAAB into anilines substituted with nitro and carboalkoxy groups. Czech Patents 188727 (1981) and 185798 (1978} relate to the pigments resulting from coupling 1,4-BAAAB into anilines substituted with urea groups. U.S. Patents 4,146,558 and 4,103,092 to Jefferies et al relate to coupling 1,4-BAAAB into anilines substituted with quaterni2ed aminoatkyl or aminoalkoxy groups to give water-soluble dyes. Swiss Patent 585247 (1977, Sandoz Ltd.) relates to coupling 1,4-BAAAB into an aminoquinoline derivative and heating with N,N-dimethylformamide at 14O3C to-obtain a greenish yellow pigment for coloring.polyvinylchioride ptestics. U.S. Patent. 3,978,038 to Cseh et al lists 327 Examples of pigments resulting from coupling 1,4-BAAAB or various substituted 1,4-BAAABs into anilines substituted with nitro groups. U.K. Patents 1400533 and 1396526 (1975, Ciba-Geigy AG> relate to the pigments resulting from coupling 1,4-BAAAB or various substituted 1,4-BAAABs into anilines substituted with a chlorine and methyl groups or two chlorine groups. German Offenlegungsschrift 2336915 (1973, Farbwerke Hoechst AG> relates to the pigments resulting from coupling 1,4-BAAAB or various substituted 1,4-BAAABs into anilines substituted with nitro groups and other groups. 3 Other alternative types of azo yellows include the metallized monoazo yellows, analogous to the metallized azo red pigments that exhibit high temperature .stabilrtv in plastics. CJfPigmeRt YeMow 62. is a. sirgfcrfy redder yellow, but much weaker tinctoriafly than C.I. Pigment Yellow 17. Another metallized monoazo yellow, described in U.S. Patent 5,669,967 to Hays, is stronger tinctorially than C.I. Pigment Yelfow 17, but is an even redder yellow (though not as red as metallized medium-shade yellows C.I.Pigment Yellows 183 and 191). Two alternative yellow pigments used by plastics processors include C.I. Pigment Yellow 109 (isoindolinone) and C.I. Pigment Yellow 138 (quinophthalone). These green-shade yellows are very close in hue to C.l. Pigment Yollow 17, but are much more expensive, much weaker and contain eight chlorine atoms per molecule, a potential environmental disadvantage. In this connection, generally speaking, the possibility of degradation into polychlorinated biphenyls (PCBs) and other dangerous compounds exists with aromatic compounds containing chlorine atoms. Plastics processors using diarylrde yellows are particularly conscious of the increased costs of using the higher concentrations of weaker yellows required for coloring plastics to the required tinctorial strengths. Although C.L Pigment Yellow T55, a dtsazo pigment made from coupling 1,4-BAAAB, is available, this pigment (Sandorin 4G) is much weaker and slightly redder than C.i. Pigment Yellow 17 endstiows poor heat stability (see below) at 288CC, a temperature commonly used to process polypropylene and other plastics. Thus, there is a need for new green-shade yellow azo pigments that exhibit strength comparable to C.I. Pigment Yellow 17, exhibit good heat stability and good lightfastness, and present little or no adverse environmental-impact. Summary of the Invention In one embodiment, the present invention relates to a green shade yellow pigment composition comprising a compound having the formula: WO 00/09614 PCT/USW/17384 4 wherein R, and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbonatoms, an aikoxycarbonyl group having 1 to abaul 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl. In another embodiment, the present invention relates to a method of preparing a green shade yellow pigment composition which comprises making a disazo pigment by coupling (i) a diazonium component made from one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline with (ii) at least one coupling component characterized by the formula: 5 wherein R, and R2 are independently hydrogen, halogen, an alkyl group having 1 to about-4-carboc atoms, an alkoxy group having 1 to about 4 carbon atoms, analkoxycartsonyl group having T to abo"r-6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl. In yet another embodiment, the present invention relates to plastics, paints or inks containing disazo pigments according to the invention. The disazo pigments according to the present invention are very surprising because one substituent, the 2-ethoxy group, is believed to impart high tinctorial and chromatic strength, good heat stability and good lightfastness. Detailed Description of the Invention The present invention relates to green-shade yellow disazo pigments suitable for use as a coloring, agent, methods of making and-usrng the disazo pigment, and plastics, paints and inks containing the disazo pigments. Disazo pigments according to the present invention, made with an ethoxy group in the 2-position relative to the diazo group, exhibit unexpectedly high tinctorial strengths, even higher than that of C.I. Pigment Yellow 17, while simultaneously exhibiting good heat stability. In addition, the disazo pigments according to the present invention exhibit a combination of unexpectedly good heat stability and good fightfastness, in comparison to different disazo pigments with substituents other thanthe 2-ethoxvgroup. In many embodiments, the disazo pigments according to. the present invention contain little (less than 2 or 11 or no halogen atoms per pigment molecule, so the disazo pigments are environmentally friendly. Since the ethoxy group is believed to impart instability through decomposion via E1 elimination of ethylene giving an easily oxidized phenolic derivative, the stability of the disazo pigments according to the present invention is unexpected. In one embodiment, the present invention relates to coupling 1,4-bis(acetoacetamido)benzene or substituted 1,4-bis 6 into about two equivalents of 2-ethoxyaniline (o-phenetidine) to give a disazo yellow pigment having the following chemical structure: wherein R, and R2 are independently hydrogen, tralogers, an-aWcyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl. In one embodiment, the disazo pigment is free of halogen atoms, and free of chlorine atomes in particular. In a preferred embodiment, the present invention relates to coupling 1,4-bis(acetoacetamido)benzene or substituted 1,4- bis(acetoacetamido)benzene into about two equivalents of 2-ethoxyaniline (o-phenetidine) to give a disazo yellow pigment having the foiiowing chemical structure:. 7 wherein R, and R? are independently hydrogen, halogen, an alkyl group having 1 to about 2 carbon atoms, an alkoxy group having 1 to about 2 carbon^atcms, or an-alkoxycatbanyregroup having 1 -to-abourAC In another preferred embodiment, the coupling of 1,4-bis(acetoacetamido}into about two equivalents of 2-ethoxyaniline (or phenetidine) provides the disazo yellow pigment having the formula: The pigments of the present invention may be prepared by initially diazotizing one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline; and thereafter coupling the diazonium component with a coupling component comprised of a bis(acetoacetamido)benzene coupler to form the desired pigment. 2-ethoxyaniline is aJso known as o-phenetidine. At least one of the aromatic amines is free of halogen atoms, such as chlorine atoms, and nrtro groups. Mixtures of two or more aromatic amines, such as 2-ethoxyantline and an aromatic amine that is not 2-ethoxyaniline are within the scope of this invention. Aromatic amines that are not 2-ethoxyaniline include various aniline compounds, aminobenzoate compounds, aminobenzamide compounds, anilide compounds, aminoanthraquinone compounds, benzimidazole compounds, benzimidazolone compounds, benzimidazolethione compounds, benzoxazole compounds, benzoxazolone compounds, benzothiazole compounds, benzothiazolone compounds, indazole compounds, phthalimide 8 compounds, naphthalimide compounds, benzotriazole compounds, quinoline compounds, quinazoline compounds, quinazolmone compounds, phthalazine compmtsss^pntfjalazJnGne compounds, toerEO^oxazirHanfiJCXimpourrds, dibenzo-phenazine compounds, quinoxalinone compounds, carbazole compounds, indofe compounds, aminonaphthalene compounds, and naphthylamino compounds. The aromatic amines from which the diazonium components are prepared are available commercially or can be prepared using methods known in the art: The diazotization of the amines useful for the purposes of this invention may be carried out in the manners known to those skilled in the art. For example, diazotization may be carried out through the use of alkali metal nitrites or lower alkyl nitrites together with an adequately strong acid such as a mineral acid. Examples of useful mmeraracids include hydrochloric acid and sulf uric acid. Nitrosy! sulfuric acid also can be utilized. The diazotization reaction can be conducted at a temperature in the range of from about -2O°C to about 30°C, preferably from about 0°C to about 20°C. In one embodiment, it is advantageous in the diazotization reaction mixtures (and in the subsequent coupling reaction mixtures) to include one or more surface active agent such as a non-ionic, an anionic or a cationic surface active agent before, during the reaction or^fter the reaction is complete. In another embodiment, it is advantageous in the diazotization reactions {and in the subsequenfcousftng reactions) not to jnciude-a surface active agent. In a preferred embodiment, one or more cationic surface active agents is included in the coupling reaction mixture before or during the reaction. In another preferred embodiment, one or more anionic surface-active agents is included in the coupling reaction mixture after the reaction is completed. In one embodiment, tfre-caazotization reaction mixture and/or the coupling reaction mixture contains from about 2 wt. % to about 10 wt. % of a surface active agent (for example, abouf"4 or about 8 wt %), and preferably, from about 2 wt. % to about 10 wt. % of a cationic surface active agent. In another embodiment, the diazotization reaction mixture and/or the coupling 9 reaction mixture contains from about 3 wt. % to about 9 wt. % of a surface active agent, and preferably from about 3 wt. % to about 9 wt. % of a -cetionic surface-acttve-aaeETT: .._ In one embodiment, the-fliazotrzattDn reaction mixture and/or the coupling reaction mixture, during or after the reaction, contains from about 2 wt. % to about 30 wt. % of a surface active agent (for example, about 20 wt %), and preferably from about 2 wt. % to about 30 wt. % of an anionic surface active agent. In another embodiment, the diazotization reaction mixture and/or the coupling reaction mixture, during or-after the: reaction, contains from about 5 wt. % to about 25 wt. % of a surface active agent, and preferably from about 5 wt. % to about 25 wt. % of an anionic surface active agent. In embodiments where one or more surface active agents are employed, anionic and/or cationic surfactants are preferred. Examples of surface active agents include amine oxide surfactants, and specifically cationic amine oxide surfactants, sulfosuccinate surfactants and derivatives thereof and specifically anionic sulfosuccinate surfactants and derivatives thereof. Amine oxide surfactants include N,N-bis(2-hydroxyethyl>cocoalkylamrne oxide, N,N-dimethylcocoalkylamine oxide, dimethyl (hydrogenated tallow) amine oxide, dimethylhexadecylamine oxide, bis(2-hydroxyethyl)tallowamine oxide, coco amidopropyl amine oxide, lauryl (12,14,16 biend) dimethyl amine oxide, mynstyl dimethyl-amine oxide, ctjeamictopnjpyiaTrjne oxide,.and stearyl dimethylamine oxide. Examples include those-under the trade-designation Aromox available from Akzo Nobel Chemicals and specifically product designations C/12, C/12W, DMC, DMC-W, DMHT, DM16, and T/12; those under the trade designation Barlox® available from Lonza and specifically product designations C. 12 and 14; those under the trade designation DeMox available from DeForest Enterprises and specifically product designations CAPO and LAO; and those under the trade designation Schercamox available from Scher Chemicals and specifically product designation DMS. 10 Sulfosuccinate surfactants include disodium ethoxylatedalcohol half ester of sulfosuccinic acid, disodium ethoxylated nonylphenol half ester of sutfosuccinic acid, dicy-ciobexyi ester of sodium sutfosooctmc acid, disodium isodecyl sulfosuccinate, diamyt ester of sodium sulfosuccinic acid, dihexy! ester of sodium sulfosuccinic acid, sodium salt of sulfated nonylphenoxy-polyethoxy ethanol, dioctyl ester of sodium sulfosuccinic acid, bis(tridecyl) ester of sodium sulfosuccinic acid, and disodium alkyl sulfosuccinate. Examples include those under the trade designation Aerosol available from Cytec Industries and specifically product designations A-102, A-103, A-196, A-268, AY, MA-801, NPES, OT, TR-70 and 501; those under the trade designation Geropon available from Rhone-Poulenc and specifically product designations SDS, SS-0 and 99; and those under the trade designation Mackanate available from The Mclntyre Group and specifically product designations DOS-70M5 and DOS-75. In another embodiment, the sulfosuccinate surfactant is a sodium dialkylsulfosuccinate surfactant having the molecular formula: in which R is an alkyl group having from about 3 to about 20 carbon atoms and preferably from about 4 to about 13 carbon atoms. In one embodiment, it is advantageous in the diazotization reactions (and in the subsequent coupling reactions) to include one or more appropriate organic solvents. For example, suitable organic solvents include one or more of glacial acetic acid, lower alkanols, dioxane, formamide, dimethyl formamide, dimethyl sulfoxide, pyridine or N-methyl pyrrolidone. In another embodiment, 11 it is advantageous in the diazotization reactions (and in the subsequent coupling reactions) not to include one or more organic solvents. EsiaeetsacetarTHdolbmuene co^£ersqmclud& T,4-bis(acetoacetamido)benzene and substituted 1,4- bis(acetoacetamido)benzenes. The bis(acetoacetamido)benzene couplers useful for the purposes of this invention are represented by the formula: wherein R, and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl. Halogens include fluorine, chlorine, t^omine-and iodine. These compounds are knowrror can be synthesized using-techniques known in the art. In a preferred embodiment, the bis(acetoacetamido)benzene couplers useful for the purposes of this invention are characterized by the formula: 12 20 where'n R, and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 2 carbon atoms, an alkoxy group having 1 to about 2 carbon atoms, or an alkoxycarbony! group having 1 to about 4 carbon atoms. Specific examples of bis(acetoacetamido)benzene couplers include 1,4-bis(acetoacetamido)benzene; 2-chloro-1,4-bis(acetoacetamido)benzene; 2-bromo-1,4-bis{acetoacetamido)benzene; 2-trifluoromethyl-1,4-bis(acetoacetamido)benzene; 2,6-bis-trifluoromethyl-l ,4-bis(acetoacetamido)benzene; 2-methoxycarbonyl-1,4-bis(acetoacetamido}benzene; 2-ethoxycarbonyl-1,4-bis(acetoacetamido)benzene; 2,5-diethoxycarbonyl-1,4-btstacctoacetamiiloiJ3enzfirte; 2.-cyano-1,4-bis\|acetoacetamido)benzene; 2-meihyi-1,4-bis(3cetoacetamido}bjenzene; 2-methoxy-1,4-bis(acetoacetamido>benzene; 2-ethyl-1,4-bis(acetoacetamido>benzene; 2-ethoxy-l,4-bts(acetoacetamido)benzene; 2-propoxy-l,4-bis(acetoacetamido)benzene; 2-isopropoxy-1,4-bis(acetoacetamido)benzene; 2-ijoto3cy-1,4-1)is(acetoacetam"do\|benzene7 2-phenoxy-1,4-bislacetoacetarnidolbenzene; 2nitro-1,4-bis{acetoacetamido)benzene; 2,5-dimethoxy-1,4-bis(acetoacetamido)benzene; 2,5-diethoxy-1,4-bis(acetoacetamido)benzene; 2-ethoxy-5-methoxy-1,4-bis(acetoacetamido)benzene; 2,5-dichloro-1,4-bis(acetoacetamido)benzene; 13 2,3-dichloro-1,4-bis(acetoacetamido)benzene; 2,6-dichloro-1,4-bis{acetoacetamido)benzene; 2,5-dibromo-1,4-bts(acetoacetamido)benzene; 2-,6-dibTC!TnQ--l-;4-bis(acetoacetamido)benzene; ^-chioro^S-naetnoxy-i ,4-btstacetoacetamidojbenzene; 2-chloro-5-ethoxy-1,4-bislacetoacetamido)benzene; 2-chloro-5-methyl-l ,4- bis(acetoacetamido)benzene; 2,5-dimethyl-l ,4-bis{acetoacetamido)benzene; 2-methyl-5-methoxy-1,4-bis(acetoacetamido)benzene; 2-methyl-5-ethoxy-1,4-bis{acetoacetamido)benzene; 2-methyl-5-propoxy-1,4-bis(acetoacetamido)benzene; 2-mettiyl-5-isopropoxy-1,4-bis(acetoacetamido)benzene; and 2-methyl-5-butoxy-1,4-bis{acetoacetamido)benzene. Mixtures of two or more of any of the bis(acetoacetamido)benze~ie coupler components are within the scope of this invention. The coupling reaction useful for the-purposes of the present invention may be effected preferably by adding the coupling components to diazonium components, but the diazonium components can be added to the coupling components. Coupling is generally effected at a temperature of from about 20°C to about 80°C, preferably from about 0°C to about 40°C. As in the diazotization reaction, coupling may be carried out in the presence or absence of an suitable surface active agent and/or organic solvent, such as all of those identified above for the diazotization reaction. In one ^moodiment, the coupling-tromponem is dissolved in a basic solution such as a hydroxide solution including 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 slight stoichiometric excess of trie coupling component. That is, two equivalents of the diazoruarn -component are coupled with slightly more than two equivalents of the coupling component. In one embodiment, the ratio of equivalents of the diazonium component to the coupling component is from about 1.7:2 to about 2.1:2. In another embodiment, the ratio of equivalents 14 of the diazonium component to the coupling component is from about 1.8:2 to about JJLL and preferably from about 1.9:2 to about 2:2. tn another emtaorfinjgr/saf the present invention, the dispersibJity cf the pigments of the present invention can be improved by adding alkali-soluble resin-tike products before, during, or after the coupling is completed. Various resin-like materials can be added for this purpose, and these include for example, rosin resins, polymeric rosins, resin soap, chemically modified rosin resins, such as rosin-maleinate resins, alkyd resins, and other synthetic hydrocarbon resins with a higher acid number, or combination of these resins. The resins may be present in a product with free carboxyl groups that are capable of forming a salt, or may be partially or completely in the form of salts, for example, with alkali metat ions. It n ay also be advantageous to perform the coupling reaction in the presence of a finely divided insoluble material, for example, alkaline earth metal sulphates and carbonates, titanium dioxide or clay materials or very finely divided organic plastic materials. In most applications, it is desirable, in order to achieve the full brightness and tinctorial strength, to heat the disazo pigment. For example, the disazo pigment may be heated to reflux temperature for about 1 to 3 hours or at temperatures above about 100°C under pressure in the presence or absence of the above-described resirt soaps or other soluble resins. After completion of the reactions and oplional heating.the disazopigments are recovered from the wjter-based fraction sJurry by filieoog xa iomua presscake of pigment which is washed with hot water (e. 15 flushed bases or dispersed into aqueous vehicles to prepare aqueous dispersions. The pigment compositions of this invention provide strong green-shade yellow pigments having improved color strength, fcant fastness and/or heat stability and are useful as coloring agents in plastics, paints and inks. This invention, therefore, also relates to plastic, paint and ink compositions comprising major ampunts of a plastic, paint vehicle or ink vehicle and minor amounts of the disazo pigment compositions of this invention. The paint, ink and plastic compositions in which the compositions of this invention are useful are well known to thos^ of ordinary skill in the art. Examples of inks include printing inks and lacquers, and examples of plastics include thermoplastic and thermosetting materials, natural resins and synthetic resins, polystyrene and its mixed polymers, polyolefins, in articular polyethylene and polypropylene, polyacrylic compounds, polyvinyl compounds, for example polyvinyl chloride and polyvinyl acetate, polyesters and rubber, and also filaments made of viscose and cellulose ethers, cellulose esters, polyamides, polycarbonates, polyurethanes, polyesters, for example polyglycol terephthalates, and polyacrylonitrile. It is also useful for pigment printing and for the pigmenting of paper in the mass. Due to its excellent heat resistance, the disazo pigment is particularly suitable for the pigmenting of plastics in the mass, such as, for example, of polystyrene and its mixed polymers, polyolefins, in particular polyethylene and polypropylene and the corresponding mixed polymers and copoJymers, polyvinyl chloride and polyesters in particular polyethylene lerephthaiate and polybutylene terephthalate and the corresponding mixed condensation products based on polyesters, and mixtures and copolymers thereof. See, for example, with regard 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 regard to paints: CM. Hare, Protective Coatings, Technology Publishing Co., Pittsburgh (1994), particularly pages 63-288; and with regard to plastics: T. G. Webber, Coloring of Plastics. John Wiley & Sons, New York (1979), particularly pages 16 79-204. The foregoing references are hereby incorporated by reference herein for their teachings of ink, paint and plastic compositions, formulations and-vehicles in which the compositions of this invention may .tie used including amounts of colorants. The following examples illustrate the pigments of the present invention. Unless otherwise indicated in the following examples, in the specification and in the appended claims, all parts and percentages are by weight, temperatures are in degrees centigrade and pressures are at or near atmospheric pressure. Example 1 A diazo solution is prepared by dissolving 13.7 parts 2-ethoxyaniline (o_-phenetidine> in 25.8 parts 20°C Baume hydrochloric acid and 200 parts hot water, icing to 0°C, adding 7.0 parts sodium nitrite dissolved in 21 parts water, stirring the solution at 0-5°C for 60 minutes, adding sufficient sulfamic acid to eliminate excess nitrous acid and diluting the solution to 600 parts. To the diazo solution is added a solution of 1.18 part N,N-bis{2-hydroxyethyO-cocoalkylamine oxide and then, immediately prior to starting coupling, a solution of 7.2 parts sodium acetate dissolved in 16.8 parts water, which brings the pH to about 5.1 at 8-10°C. A coupler solution is prepared by dissolving 14.8 parts 1,4-bisacetoacetamidobenzene (1,4-BAAAB) in 550 parts warm water containing 4i2.parts sodium hydroxide and diluting to~600 parts. The coupler sorution ^s pumpea into the diazo solution over 18 minutes, at the end of which time the pH is 5.9 and the slurry temperature is 19°C. The pH of the slurry is raised to about 6.4 with 10% sodium hydrogen carbonate solution, at which point the slurry still shows excess diazo when tested with K-salt solution; after being stirred 30 minutes, the slurry shows no excess diazo and pH 6.6. The slurry is stirred for an hour, followed by adjusting the pH to 5.5, heating to 100°C, boiling for 30 minutes, icing to lower than 60°C and filtering; the filtercake is washed, dried overnight at 82°C and pulverized in an Osterizer to give 29.8 parts greenish-yellow powder. 17 Example 2 The procedure of Example 1 is repeated, except that dimethyl-cocoaHtylamtne oxide-is substituted for the bisH2-hYJc!roxYetf?yt>-cocoalkylamine oxide, giving 29.6 parts greenish-yellow powder. Example 3 The procedure of Example 1 is repeated, except that 2.37 parts bis-(2-hydroxyethylj-cocoalkylamine oxide are used, giving 30.4 parts greenish-yellow powder. Example 4 The procedure of Example 1 is repeated, except that 2.37 parts dimethyl-cocoalkylamine oxide is substituted for the bis-(2-hydroxyethyl)-rocoalkylamine oxide, and, after coupling, a solution of 8.4 parts of a 70% solution of sodium bistridecyl sulfosuccinate dissolved in 400 parts water is added, giving.36.4 parts greentsh-yettow powder. Example 5 The procedure of Example 1 is repeated, except that a nonionic surfactant made from C ,,.1S linear alcohol and 20 moles ethylene oxide (cloud point 100°C) is substituted for the bis-(2-hydroxyethyl)-cocoalkylamine oxide, giving 28.4 parts greenish-yellow powder. Example 6 The procedure of Example 1 is repeated, except that 2.37 parts of a nonionic surfactant .made-from C17 ,s alcohol/7moles ethylene oxide/4moles propytene oxide (cloud point 40°) is substituted for the bis-(2-hydroxyethyl)-cocoalkylamine oxide, giving 31.2 parts greenish-yellow powder. Comparative Example 1 The procedure of Example 6 is used, except that 9.3 parts aniline are used-tn-place of 2-ethoxyanUine, giving 25_2 parts greenish-yellow powder. Comparative Example 2 The procedure of Example 6 is used, except that 12.3 parts 2-methoxyaniline are used in place of 2-ethoxyaniline, giving 29.6 parts greenish-yellow powder. 18 Comparative Example 3 The procedure of Example 6 is used, except that 12.1 parts 2-eUwtsnftine are-used in place of 2-ethoxyaniUrTe, giving. 25.2 parts greeatsft-yeilow powder. Comparative Example 4 The procedure of Example 6 is used, except that 10.7 parts 2-methylaniline are used in place of 2-ethoxyaniline, giving 22.8 parts greenish-yellow powder. Comparative Example 5 The procedure of Example 6 is used, except that 12.8 parts 2-chloroaniline are used in place of 2-ethoxyaniline, giving 30.4 parts greenish-yellow powder. Comparative Example 6 The procedure of Example 6 is used, except that 17.2 parts 2-bromoaniline are used in place of 2-ethoxyaniline, giving 34.0 parts greenish-yellow powder. Comparative Example 7 The procedure of Example 6 is used, except that 18.5 parts 2-phenoxyaniline are used in place of 2-ethoxyaniline, giving 35.6 parts greenish-yellow powder. CornDarative Example 8 The procedure of-Example 6 is used, except that 16.1 parts 2-trifluoromethylannine are used in place of 2-ethoxyaniline, giving 33.6 parts greenish-yellow powder. Comparative Example 9 The procedure of Example 6 is used, except that 11.8 parts 2-cyanoaniline are used in piace_of 2-elhoxyaniline, giving 30.0 parts reddish-yellow powder Comparative Example 10 19 The procedure of Example 6 is used, except that 15.1 parts 2-carbomethoxyaniline are used in place of 2-ethoxyaniline, giving 32.4 parts greeni sh-yello w-po wder. Comparative Example 11 The procedure of Example 6 is used, except that 13.5 parts 2-acetoaniline are used in"place of 2-ethoxyaniline, giving 30.4 parts yellow powder. Comparative Example 12 The procedure of Example 6 is used, exceprthat 12.3 parts 4-methoxyaniline are used in place of 2-ethoxyaniline, giving 30.4 parts greenish-yellow powder. Comparative Fxample 13 The procedure of Example 6 is used, except that 13.7 parts 4-ethoxyaniline are used in place of 2-ethoxyaniline, giving 31.6 parts gieenrsh-yellow powder. Comparative Example 14 The procedure of Example 6 is used, except that 10.7 parts 4-methylaniline are used in place of 2-ethoxyaniline, giving 29.2 parts greenish-yellow powder. Comparative Example 15 The procedure of Example 6 is used, except that 12.8 parts 4-chloroaniiine are used in place~crf 2-ettioxyaniWne, giving 3Q.& parts greenish-yellow powder. During the testing of pigments, the standard pigment, to which the experimental pigments are compared, is a green-shade diarylide yellow (C.I. Pigment Yellow 17) used in plastics under product designation RX1276 available from Engelhard. Several commercial green-shade yellow pigments are included for comparison: Sandorin Yellow 4G {C.I. Pigment Yellow 155), which is a commercial example of this type of disazo pigment made with 1,4-bisacetoacetamidobenzene (1,4-BAAAB) available from Sandoz; Permanent 20 Yellow NCG-71 (C.I. Pigment Yellow 16), which is another kind (different) of disazb pigment (made with bisacetoacetylated~3,3'-dimethyibenzidine) -available from Hoecfest; YeHow 2GLTE (C.l.-Pigmesr-Y^llow 1O9). an isoindolinone pigment available from Ciba; and^aUotol Yetiow K 0S61 HD (C.I. Pigment Yellow 138), a quinophthalone pigment available from BASF For comparing tinctorial strength and other coloristic values, the pigments are tested initially as 1:1 (0.1 phr pigment: 0.1 phr titanium dioxide) tints in high density polyethylene injection molded chip.s, as follows: A mixture of 0.59©-part pigment, 0.500 part titanium dioxide and 500 parts high density polyethylene (Solvay T50-2000-G) is shaken on a paint shaker for 15 seconds, then injection molded at 232°C for 1.5 minutes in a 30 ton Battenfeld machine. Spectrophotometric values of the molded chips are measured with a Macbeth Color-Eye (specular component included, large area) to givteK/S apparent strength versus the standard pigment and CIE LCh chroma, hue angle and lightness under Illuminant D, 10 degrees, as shown in Table I. To obtain a better measure of the tinctorial strengths, the strongest of the Experimental pigments is then tested in a reduced tint as 0.50:1 (50% reduction in pigment content) by repeating this procedure, except that 0.250 part pigment is used in place of the 0.500 part pigment; the K/S apparent strength and CIE LCh chroma, hue angle and lightness under Illuminant D, 10 degrees, of this reduced tint are measured against a 1:1 tint of RX1276 and are shown in Table M. To obtain a better measure of the tinctorial strengths, the strongest of the Experimental pigments is then tested in a reduced tint as 0.30:1 (70% reduction in pigment content) by repeating this procedure, except that 0.150 part pigment is used in place of the 0.500 part pigment; the K/S apparent strength and CIE LCh chroma, hue angle and lightness under Illuminant D, 10 degrees, of this reduced tint are measured against a 1:1 tint of Paliotol Yellow K 0961 HD (C.I. Pigment Yellow 138) and are shown in Table III. To obtain another comparison of tinctorial strengths, the strongest of the Experimental pigments is then tested in a reduced tint as a 0.20:1 tint (80% reduction in pigment content) by 21 repeating this procedure, except that 0.100 part pigment is used in place of the 0.5OG part pigment; the K/S apparent strength and CIE LCrr-chJoma, true angte arad-aghtness under Hkim"naot-O 10 degrees, T>f this reducscfeirit are measured against a 1:1 tint of Yellow 2GLTE (C.i. Pigment Yellow 109] and are shown in Table IV. For comparing heat stabilities, the pigments are tested as above for coloristic values of 1:1 tints, except that the chips are molded and held at 288° for 3 mjnutes. Spectrophotometric values of the molded chips are measured with a Macbeth Color-Eye (specular component included, large area) versus the chips molded at 232° to give CIElab delta E values, as shown in Table V. For comparing fade resistance, the high density polyethylene injection molded 1:1 tint chips used for coloristic values are exposed for 100 hours in an Atlas Xenon Hade-Ometer. Spectrophotometric values of the exposed chips are measured with a Macbeth Color-Eye (specular component included, large area) versus unexposed chips to give CIElab delta E values, as shown in Table V. For comparing apparent strength and hue angles in a paint vehicle, the standard pigment and the pigments of Examples 1 and 4 are tested as 1:1 .tints as follows: A mixture of 0.50 part pigment, 0.50 parts titanium dioxide (DuPont Ti-Pure R-960), 23.2 parts air-dry alkyd enamel vehicle (containing 36% mediam oil alkyd, 13% mineral spirits and 1 % driers/antrskinrving agent) and 75" parts media (Zircoa Zirbeads Y1304) is stirred with a spatula to a uniform mixture, sealed with a lid and shaken on a paint shaker for 30 minutes. The dispersion is separated from the media, drawn down with a 0.15 mm. gap coating bar on coated cardboard (Leneta Form 2-C) and allowed to dry for 1-2 days. Spectrophotometric values are measured with a Macbeth Color-Eye (specular component included, large area) to give the apparent strength and hue angles under Illuminant D, 10 degrees, shown in Table VI. 22 Table Coloristic Values of 1:1 Tints in HI3PF Pigment Apparent Strenath Chroma (Q ) Hue Arraie to) LiohtnessfL* P.Y 17 Standard 89.9 90.3° .88.4 (K/S = 23.655) Example 1 (2-ethoxy) +23% 91.6 91.2° 87.6 (K/S = 29.164) Example 2 (2-ethoxy) +21% 92.2 91.4= 88.1 Example 3 (2-ethoxy) +16% 91.1 91.9° 88.1 Example 4 (2-ethoxy) +20% 92.4 92.3" 89.0 Example 5 (2-ethoxy) +23% 90.9 90.7° 87.3 Example 6 (2-ethoxy) + 19% 89.7 90.1° 86.6 Com. Ex. 1 (no substttuents) -19% 78.4 95.5* 89.3 Com. Ex. 2 (2-methoxy) +20% 89.3 91.4° 87.2 Com. Ex. 3 (2-ethyl) -6% 81.5 88.9° 85.5 Com. Ex. 4 (2-methyl) + 1 % 84.2 89.3° 85.8 Com. Ex. 5 (2-chloro) -4% 84.0 87.1° 85.8 Com. Ex. 6 (2-bromo) -4% 84.9 89.0° 87.0 Com. Ex. 7 (2-phenoxy) Equal 83.6 92.4° 88.3 Com. Ex. 8 (2-trifluoromethyi) -27% 78.4 89.6° 87.3 Com. Ex. 9 (2-cyano) + 1-0% 70.1 72.3° 74.1 Com. Ex. 10 (2-carbomethoxy) -10% 82.6 aa-jo* 67.1 Com. Ex. 11 (2-aceto) +9% 80.6 78.7° 80.8 Com. Ex. 12 (4-methoxy) +20% 83.9 86.3° 82.3 Com. Ex. 13 (4-ethoxy) +16% 84.8 87.9° 83.8 Com. Ex. 14 (4-methyl) -4% 81.8 91.2° 86.6 Com. Ex. 15 (4-chloro) -1% 86.0 90,0c 87.2 C.I. P.Y. 155 (2,5-dicarbomethoxy) -13% 82. 1 88.3° 86.0 C.I. Pigment Yellow 16 +2% 87.5 90.9° 88.4 C.I. Pigment Yellow 138 -18% 84.3 93.5° 89.4 C.I. Pigment Yellow 109 -39% 77.9 93.6° 89.7 23 In Table I, the apparent strengths of the Examples, all containing the 2-ethoxy substituent and made with different surfactants, are estimated to be T6:23% stronger than P.Y. 1 7 in 1:1-twits: even-though the pigment of Example 4 is diluted about 20% with surfactant, it maintains its apparent strength and chroma. The hue angles of the Example tints are generally slightly higher (slightly greener) than the P.Y. 17 tint. The apparent strengths of several Comparative Examples (C.E.), containing no substituent or substituents other than 2-ethoxy, are equal to 20% stronger than P.Y. 1 7; however, the chroma and lightness values indicate that, excepttor C.E. 2, these Comparative Examples obtain their apparent strengths not from strong chromas, but from lower lightness (dirtiness). Pigment Yellow 155 (Sandorin Yellow 4G), which is like the Comparative Examples ard contains carbomethoxy groups at the 2- and 5- position, is 13% weaker and slightly redder than P.Y. 17. Pigment Yellow 16 (Permanent Yeliow NCG-71). which is another kind of drsazo yellow (made with bisacetoacetvlated 3,3'-dimethylbenzidine), is about equal in strength and hue, but shows lower chroma. Also, for comparison, P.Y. 138 (Patiotol Yellow K 0961 HD), is 18% weaker and somewhat greener than P.Y. 17; P. Y. 109 (Irgazin Yellow 2GLTE) is 39% weaker and somewhat greener than P.Y. 17. When the apparent strengths or weaknesses in Table I are greater than about 10%. they tend to be underestimated, as demonstrated in the following Tables. Table II Coloristic Values Of a 0, 5:1 Tint in HDPE Pigment Apparent Strenath CJnojpalC o) H\\e, Anale(h) Liohtnessd. o1 P.Y 17 (1 :1) Standard 89. 8 9O.4o 8& .7 (K/S = 23.080) Example 1 (0.5:1) +5% 89! '.3 93.8° 89 .4 (K/S = 24.144) 24 In Table II, the apparent strength of Example 1, coupled in the presence of 5% N,N-bis(2-hydroxyethyl)-cocoalkylamine oxide, is estimated to be +5% in a 0.5:1 tim; this means that Example 1 is_more"than 100% stronger than P.Y. 17. Although the apparent strength, chroma and lightness values for the 0.5:1 tint of Example 1 are close to those of 1:1 P.Y. 17, the hue angle for the 0.5:1 tint of Example 1 is significantly higher (greener), which distinguishes it from 1:1 P.Y. 17. Table III Coloristic Values of a 0.3:1 Tint in HDPE Pigment Apparent Strength Chroma (C) Hue Angle fh) Lightnessd) ^.Y 138 (1:1) Standard 84.3 93.5° 89.3 (K/S = 18.959) Example 1 {0.3:1) +4% 33.8 94.1 o 89.3 (K/S = 19.664) In Table III, the apparent strength of Example 1, coupled in the presence of 5% N,N-bis(2-hydroxyethyl)-cocoalkylamine oxide, is estimated to be +4% in 0.3:1 tint; this means that Example 1 is more than 3.3 times stronger than P.Y. 138. The chroma, hue angle and lightness values for the 0.3:1 tint of Example 1 indicate that it is a good match for 1:1 P.Y. 138. Table (V Coloristic Values of a 0.2:1 Tint in HDPE Pigment ApDarent Strenath ChromafC) Hue Anqle(h) LiqhtnessIL") P.Y 109 (1 .1) Standard 77 .9 93. 8° 89.7 Example 1 (0.2:1) +10% 79. 2 96 .3° 90.4 (K/S = 15.519) 25 In Table IV, the apparent strength of Example 1, coupled in the presence of 5% N,N-bis(2-hydroxyethyl)-cucoatt Table V Change (Delta E) in Coloristic Values of 1:1 Tints in HOPE After; Heat Stability Testing Fade Resistance Testing Piament P.Y. 17 1.5 1, .4 Example 1 .{2-ethoxy) 2.0 1 .2 Example 2 (2-ethoxy} 0.9 1 .9 Example 3 (2-ethoxy) 1.5 0 .7 Example 4 (2-ethoxy) 1.7 0 .8 Example 5 (2-ethoxy) 1.3 2 .1 Example 6 (2-ethoxy) 2.0 1 .3 Comparative Example 1 (no subst.) 24.0 5.8 Comparative Example 2 (2-methoxyH2.1 3.1 Comparative Example 3 (2-ethyl) 3.5 6.4 Comparative: Example Ar {2-methyO 1.0 7.5 Comparative Example 5;(2-chioroJ 2.2 2.4 Comparative Example 6 (2-bromo) 4.3 2.3 Comparative Example 7 (2-phenoxy)6.4 1.9 Comparative Example 8 (2-trifluoromethyl)12.9 3.2 Comparative ExaropieiJ (2-cyano) 23.2 2.9 Comparative Example 10 (2-carbomethoxy)11.0 2.0 Comparative Example 11 (2-aceto) 16.7 4.7 Comparative Example 12 (4-methoxy)6.8 9.0 Comparative Example 13 (4-ethoxy) 4.1 12.8 26 Comparative Example 14 (4-methyD 2.8 2.7 Comparative Example 1-5 * (4-chloro) 3.7 2,5 C".!. Figment Yeffow T55 C^^drcarbomethoxv) 19.5 3.5 C.I. Pigment Yellow V6" 7.0 0.8- C.I. Pigment Yellow 138 3.6 1.1 C.I. Pigment Yellow 109 0.4 0.5 in Table V, the delta Es (a measure of change) for the heat stabilities of the Examples are about the same as for P.Y. 17 ar.d are at or lower than the delta E = 2.0, typically considered to be the upper limit for concern by plastics processors. The delta Es for the fade resistances of the Examples range from 0.7 to 2.1, with four of them being lower than the 1.4 of P.Y. 17, which is considered to have fairly good fade resistance (W. Herbst and K. Hunger, ibid, p. 252, state:. "P.Y.17 is aimost as lightfast as the somewhat redder P.Y.13 (step 6-7 at 1/3 SD)."). In Table V, the delta Es for the heat stabilities of the Comparative Examples (except for the acceptable 1.0 of Comparative Example 4, with the 2-methyl substituent) range from marginal (Comparative Example 5. with the 2-chloro substituent) to extremely poor {Comparative Examples 1 and 9, with no substituent and the 2-cyano substituent)- The delta Es for the fade resistances of the Comparative Examples range from a marginal 1.9 (Comparative Example 7, with-a -2-ptwnoxy substituenti to a very .poor 12.8 (Comparative Example 13, with the 4-etiioxy substituent}. The delta €s for the heat stabilities of the commercial green-shade yellow pigments range, with the exception of P.Y. 109, from poor for P.Y. 138 to very poor for P.Y. 155. The delta Es for the fade resistances of the commercial green-shade yellow pigments are good (1.1; 1.5) to very good t0.5; 0:8). 27 Table VI Coloristic Values of 1 o1 Tints in Ajr-Dry Enamel Piqment ADDarent Str"n P.Y. 17 Standard 90.4 86.6° 84.8 (K/S = 30.261 > Example 1 -7% 88.5 87.9° 85.0 Example 4 -6% 90.6 89.7° 86.5 In Table VI, Example 1 is about 7% weaker and shows lower chroma than P.Y. 17 in 1:1 tints in air-dry enamel. This weakness is surprising in light of the strength of Example 1 in HDPE and may arise from poorer dispersibility of Example 1 in air-dry enamel. Example 4, which h post-treated with 20% sodium bistridecyl sulfosuccinate, is also slightly weak; however, its chroma is as high as that of P.Y. 17, indicating better dispersibility in air-dry enamel, so its lower apparent strength probably derives from its higher lightness. The hue angles of the Examples tint are higher (greener) than that of the P.Y. 17 tint. When incorporated in polyolefins, the pigments obtained according to the present invention display strong, bright greenish shade yellows in contrast to the generally weaker shades displayed by conventional pigments. The relatively high chromaticity values are consistent with the brightness of the color displayed while the high strength is reflected by a relatively-high K/S values. While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, rt is to be understood that the invention disclosed beretf* is intended to cover such modifications as fall within the scope of the appended claims. 28 We Claim 1. A method of preparing a green shade yellow pigment composition which comprises making a dlsazo pigment by coupling (i) a diazonium component made from of one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline with wherein Ri and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trffluoromethyl. 2. The method as claimed in claim 1 wherein (0 and (li) are coupled in the presence of at least one surfactant selected from N,N-bls(2- hydroxyethyi)cocoalkylamine oxide and N.N-dimethylcocoalkylamine oxide. 3. The method as claimed in claim 1 further comprising adding bis(tridecyl) ester of sodium sulfosuccinic acid. 4. The method as claimed in claim 1 wherein the ratio of equivalents of (i) to (li) Is from about 1.7:2 to about 2.1:2. 29 5. The method as claimed in claim 1 wherein Rt and Ffcare hydrogen. A method of preparing a green shade yellow pigment composition which comprises making a disazo pigment by coupling (i) a diazonfum component made from of one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline with (ii) at least one coupling component characterized by the formula: wherein R1 and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl.

Full Text

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Title: STRONG GREEN-SHADE YELLOW DISAZO PIGMENT
Technical Field
This invention generally relates to novel green-shade yellow disazo pigments and to the use of such pigments in plastics, paints and inks.
Background of the Invention
Azo yellow pigments are a class of colorants that are tinctoriaily strong and relatively inexpensive. Monoazo yellow pigments exhibit good lightfastness and are useful as coloring agents for paints and some printing inks. In plastics, however, monoazo yellow pigments tend to undesirably bloom and discolor at high temperatures, so their use is disfavored. Diarylide disazo yellow pigments, made from 3,3'-dichlorobenzidine, are much stronger tinctoriaily and show a much lower tendency to bloom and discolor at high temperatures. C.I. Pigment Yellow 1 7 is a strong green-shade diarylide yellow and has often been used for plastics. W. Herbst and K. Hunger, Industrial Organic Pigments. VCH, New York, 1993, p. 252, state: "The plastics industry, however, uses P.Y. 17 extensively, . . . P.Y. 17 is also frequently used in polyolefins ... Its heat stability in these media was said to be about 220 to 240cC* However, R. Az et a! reported in Dyes and Pigments, _L5_, 1 (199V', that diarylide yellows are degraded to potentially carcinogenic by-products (e.g., 3,3'-dichlorobenzidine) in plastics processed above 200°C, a temperature lower than that used in processing most plastics (many plastics are processed at temperatures from 230°C to 330°C). In efforts to overcome these disadvantages, azo pigment manufacturers have actively pursued development of other types of azo yellows.
One alternative type of azo yellows include disazo yellow pigments made by coupling bis(acetoacetamido)benzenes (BAAAB) into aniline derivatives. U.S. Patent 5,616,778 to Goldmann et al relates to coupling

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1,4-BAAAB into 2,5-dicarbomethoxyaniline (to give C.I. Pigment Yellow 155) and heating the pigment in an organic solvent at 80-150°C for up to 6 hours. U.S. PatTCTTr 5/559,216-.to Jung et aJ gives. 4-7_£xarnpJes and describes coupling 1,4-bisacetoacetamidobenzene German Offenlegungsschrift 3501199 (1985, Sandoz GmbH) relates to coupling 1,4-BAAAB into mixtures of anilines substituted with one or two carboalkoxy groups to give pigments that disperse easily into polypropylene. Canadian Patent 1135688 (1982. Hoechst AGJ relates to the pigments resulting from coupling 1,4-BAAAB into anilines substituted with nitro and carboalkoxy groups. Czech Patents 188727 (1981) and 185798 (1978} relate to the pigments resulting from coupling 1,4-BAAAB into anilines substituted with urea groups. U.S. Patents 4,146,558 and 4,103,092 to Jefferies et al relate to coupling 1,4-BAAAB into anilines substituted with quaterni2ed aminoatkyl or aminoalkoxy groups to give water-soluble dyes. Swiss Patent 585247 (1977, Sandoz Ltd.) relates to coupling 1,4-BAAAB into an aminoquinoline derivative and heating with N,N-dimethylformamide at 14O3C to-obtain a greenish yellow pigment for coloring.polyvinylchioride ptestics. U.S. Patent. 3,978,038 to Cseh et al lists 327 Examples of pigments resulting from coupling 1,4-BAAAB or various substituted 1,4-BAAABs into anilines substituted with nitro groups. U.K. Patents 1400533 and 1396526 (1975, Ciba-Geigy AG> relate to the pigments resulting from coupling 1,4-BAAAB or various substituted 1,4-BAAABs into anilines substituted with a chlorine and methyl groups or two chlorine groups. German Offenlegungsschrift 2336915 (1973, Farbwerke Hoechst AG> relates to the pigments resulting from coupling 1,4-BAAAB or various substituted 1,4-BAAABs into anilines substituted with nitro groups and other groups.

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Other alternative types of azo yellows include the metallized monoazo yellows, analogous to the metallized azo red pigments that exhibit high temperature .stabilrtv in plastics. CJfPigmeRt YeMow 62. is a. sirgfcrfy redder yellow, but much weaker tinctoriafly than C.I. Pigment Yellow 17. Another metallized monoazo yellow, described in U.S. Patent 5,669,967 to Hays, is stronger tinctorially than C.I. Pigment Yelfow 17, but is an even redder yellow (though not as red as metallized medium-shade yellows C.I.Pigment Yellows 183 and 191).
Two alternative yellow pigments used by plastics processors include C.I. Pigment Yellow 109 (isoindolinone) and C.I. Pigment Yellow 138 (quinophthalone). These green-shade yellows are very close in hue to C.l. Pigment Yollow 17, but are much more expensive, much weaker and contain eight chlorine atoms per molecule, a potential environmental disadvantage. In this connection, generally speaking, the possibility of degradation into polychlorinated biphenyls (PCBs) and other dangerous compounds exists with aromatic compounds containing chlorine atoms.
Plastics processors using diarylrde yellows are particularly conscious of the increased costs of using the higher concentrations of weaker yellows required for coloring plastics to the required tinctorial strengths. Although C.L Pigment Yellow T55, a dtsazo pigment made from coupling 1,4-BAAAB, is available, this pigment (Sandorin 4G) is much weaker and slightly redder than C.i. Pigment Yellow 17 endstiows poor heat stability (see below) at 288CC, a temperature commonly used to process polypropylene and other plastics. Thus, there is a need for new green-shade yellow azo pigments that exhibit strength comparable to C.I. Pigment Yellow 17, exhibit good heat stability and good lightfastness, and present little or no adverse environmental-impact.
Summary of the Invention
In one embodiment, the present invention relates to a green shade yellow pigment composition comprising a compound having the formula:

WO 00/09614

PCT/USW/17384

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wherein R, and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon*atoms, an aikoxycarbonyl group having 1 to abaul 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl.
In another embodiment, the present invention relates to a method of preparing a green shade yellow pigment composition which comprises making a disazo pigment by coupling (i) a diazonium component made from one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline with (ii) at least one coupling component characterized by the formula:

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wherein R, and R2 are independently hydrogen, halogen, an alkyl group having 1 to about-4-carboc atoms, an alkoxy group having 1 to about 4 carbon atoms, analkoxycartsonyl group having T to abo"r-6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl.
In yet another embodiment, the present invention relates to plastics, paints or inks containing disazo pigments according to the invention.
The disazo pigments according to the present invention are very surprising because one substituent, the 2-ethoxy group, is believed to impart high tinctorial and chromatic strength, good heat stability and good lightfastness.
Detailed Description of the Invention
The present invention relates to green-shade yellow disazo pigments suitable for use as a coloring, agent, methods of making and-usrng the disazo pigment, and plastics, paints and inks containing the disazo pigments. Disazo pigments according to the present invention, made with an ethoxy group in the 2-position relative to the diazo group, exhibit unexpectedly high tinctorial strengths, even higher than that of C.I. Pigment Yellow 17, while simultaneously exhibiting good heat stability. In addition, the disazo pigments according to the present invention exhibit a combination of unexpectedly good heat stability and good fightfastness, in comparison to different disazo pigments with substituents other thanthe 2-ethoxvgroup. In many embodiments, the disazo pigments according to. the present invention contain little (less than 2 or 11 or no halogen atoms per pigment molecule, so the disazo pigments are environmentally friendly. Since the ethoxy group is believed to impart instability through decomposion via E1 elimination of ethylene giving an easily oxidized phenolic derivative, the stability of the disazo pigments according to the present invention is unexpected.
In one embodiment, the present invention relates to coupling 1,4-bis(acetoacetamido)benzene or substituted 1,4-bis
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into about two equivalents of 2-ethoxyaniline (o-phenetidine) to give a disazo yellow pigment having the following chemical structure:

wherein R, and R2 are independently hydrogen, tralogers, an-aWcyl group
*
having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl. In one embodiment, the disazo pigment is free of halogen atoms, and free of chlorine atomes in particular. In a preferred embodiment, the present invention relates to coupling 1,4-bis(acetoacetamido)benzene or substituted 1,4-
bis(acetoacetamido)benzene into about two equivalents of 2-ethoxyaniline (o-phenetidine) to give a disazo yellow pigment having the foiiowing chemical structure:.

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wherein R, and R? are independently hydrogen, halogen, an alkyl group having 1 to about 2 carbon atoms, an alkoxy group having 1 to about 2 carbon^atcms, or an-alkoxycatbanyregroup having 1 -to-abourAC In another preferred embodiment, the coupling of 1,4-bis(acetoacetamido}into about two equivalents of 2-ethoxyaniline (or phenetidine) provides the disazo yellow pigment having the formula:

The pigments of the present invention may be prepared by initially diazotizing one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline; and thereafter coupling the diazonium component with a coupling component comprised of a bis(acetoacetamido)benzene coupler to form the desired pigment.
2-ethoxyaniline is aJso known as o-phenetidine. At least one of the aromatic amines is free of halogen atoms, such as chlorine atoms, and nrtro groups. Mixtures of two or more aromatic amines, such as 2-ethoxyantline and an aromatic amine that is not 2-ethoxyaniline are within the scope of this invention. Aromatic amines that are not 2-ethoxyaniline include various aniline compounds, aminobenzoate compounds, aminobenzamide compounds, anilide compounds, aminoanthraquinone compounds, benzimidazole compounds, benzimidazolone compounds, benzimidazolethione compounds, benzoxazole compounds, benzoxazolone compounds, benzothiazole compounds, benzothiazolone compounds, indazole compounds, phthalimide

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compounds, naphthalimide compounds, benzotriazole compounds, quinoline compounds, quinazoline compounds, quinazolmone compounds, phthalazine compmtsss^pntfjalazJnGne compounds, toerEO^oxazirHanfiJCXimpourrds, dibenzo-phenazine compounds, quinoxalinone compounds, carbazole compounds, indofe compounds, aminonaphthalene compounds, and naphthylamino compounds. The aromatic amines from which the diazonium components are prepared are available commercially or can be prepared using methods known in the art:
The diazotization of the amines useful for the purposes of this invention may be carried out in the manners known to those skilled in the art. For example, diazotization may be carried out through the use of alkali metal nitrites or lower alkyl nitrites together with an adequately strong acid such as a mineral acid. Examples of useful mmeraracids include hydrochloric acid and sulf uric acid. Nitrosy! sulfuric acid also can be utilized. The diazotization reaction can be conducted at a temperature in the range of from about -2O°C to about 30°C, preferably from about 0°C to about 20°C.
In one embodiment, it is advantageous in the diazotization reaction mixtures (and in the subsequent coupling reaction mixtures) to include one or more surface active agent such as a non-ionic, an anionic or a cationic surface active agent before, during the reaction or^fter the reaction is complete. In another embodiment, it is advantageous in the diazotization reactions {and in the subsequenfcousftng reactions) not to jnciude-a surface active agent.
In a preferred embodiment, one or more cationic surface active agents is included in the coupling reaction mixture before or during the reaction. In another preferred embodiment, one or more anionic surface-active agents is included in the coupling reaction mixture after the reaction is completed.
In one embodiment, tfre-caazotization reaction mixture and/or the coupling reaction mixture contains from about 2 wt. % to about 10 wt. % of a surface active agent (for example, abouf"4 or about 8 wt %), and preferably, from about 2 wt. % to about 10 wt. % of a cationic surface active agent. In another embodiment, the diazotization reaction mixture and/or the coupling

9
reaction mixture contains from about 3 wt. % to about 9 wt. % of a surface active agent, and preferably from about 3 wt. % to about 9 wt. % of a -cetionic surface-acttve-aaeETT: .._
In one embodiment, the-fliazotrzattDn reaction mixture and/or the coupling reaction mixture, during or after the reaction, contains from about 2 wt. % to about 30 wt. % of a surface active agent (for example, about 20 wt %), and preferably from about 2 wt. % to about 30 wt. % of an anionic surface active agent. In another embodiment, the diazotization reaction mixture and/or the coupling reaction mixture, during or-after the: reaction, contains from about 5 wt. % to about 25 wt. % of a surface active agent, and preferably from about 5 wt. % to about 25 wt. % of an anionic surface active agent.
In embodiments where one or more surface active agents are employed, anionic and/or cationic surfactants are preferred. Examples of surface active agents include amine oxide surfactants, and specifically cationic amine oxide surfactants, sulfosuccinate surfactants and derivatives thereof and specifically anionic sulfosuccinate surfactants and derivatives thereof.
Amine oxide surfactants include N,N-bis(2-hydroxyethyl>cocoalkylamrne oxide, N,N-dimethylcocoalkylamine oxide, dimethyl (hydrogenated tallow) amine oxide, dimethylhexadecylamine oxide, bis(2-hydroxyethyl)tallowamine oxide, coco amidopropyl amine oxide, lauryl (12,14,16 biend) dimethyl amine oxide, mynstyl dimethyl-amine oxide, ctjeamictopnjpyiaTrjne oxide,.and stearyl dimethylamine oxide. Examples include those-under the trade-designation Aromox available from Akzo Nobel Chemicals and specifically product designations C/12, C/12W, DMC, DMC-W, DMHT, DM16, and T/12; those under the trade designation Barlox® available from Lonza and specifically product designations C. 12 and 14; those under the trade designation DeMox available from DeForest Enterprises and specifically product designations CAPO and LAO; and those under the trade designation Schercamox available from Scher Chemicals and specifically product designation DMS.

10
Sulfosuccinate surfactants include disodium ethoxylatedalcohol half ester of sulfosuccinic acid, disodium ethoxylated nonylphenol half ester of sutfosuccinic acid, dicy-ciobexyi ester of sodium sutfosooctmc acid, disodium isodecyl sulfosuccinate, diamyt ester of sodium sulfosuccinic acid, dihexy! ester of sodium sulfosuccinic acid, sodium salt of sulfated nonylphenoxy-polyethoxy ethanol, dioctyl ester of sodium sulfosuccinic acid, bis(tridecyl) ester of sodium sulfosuccinic acid, and disodium alkyl sulfosuccinate. Examples include those under the trade designation Aerosol available from Cytec Industries and specifically product designations A-102, A-103, A-196, A-268, AY, MA-801, NPES, OT, TR-70 and 501; those under the trade designation Geropon available from Rhone-Poulenc and specifically product designations SDS, SS-0 and 99; and those under the trade designation Mackanate available from The Mclntyre Group and specifically product designations DOS-70M5 and DOS-75.
In another embodiment, the sulfosuccinate surfactant is a sodium dialkylsulfosuccinate surfactant having the molecular formula:

in which R is an alkyl group having from about 3 to about 20 carbon atoms and preferably from about 4 to about 13 carbon atoms.
In one embodiment, it is advantageous in the diazotization reactions (and in the subsequent coupling reactions) to include one or more appropriate organic solvents. For example, suitable organic solvents include one or more of glacial acetic acid, lower alkanols, dioxane, formamide, dimethyl formamide, dimethyl sulfoxide, pyridine or N-methyl pyrrolidone. In another embodiment,

11
it is advantageous in the diazotization reactions (and in the subsequent coupling reactions) not to include one or more organic solvents.
EsiaeetsacetarTHdolbmuene co^£ersqmclud& T,4-bis(acetoacetamido)benzene and substituted 1,4-
bis(acetoacetamido)benzenes. The bis(acetoacetamido)benzene couplers useful for the purposes of this invention are represented by the formula:

wherein R, and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl. Halogens include fluorine, chlorine, t^omine-and iodine. These compounds are knowrror can be synthesized using-techniques known in the art.
In a preferred embodiment, the bis(acetoacetamido)benzene couplers useful for the purposes of this invention are characterized by the formula:

12

20

where'n R, and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 2 carbon atoms, an alkoxy group having 1 to about 2 carbon atoms, or an alkoxycarbony! group having 1 to about 4 carbon atoms.
Specific examples of bis(acetoacetamido)benzene couplers include 1,4-bis(acetoacetamido)benzene; 2-chloro-1,4-bis(acetoacetamido)benzene; 2-bromo-1,4-bis{acetoacetamido)benzene; 2-trifluoromethyl-1,4-bis(acetoacetamido)benzene; 2,6-bis-trifluoromethyl-l ,4-bis(acetoacetamido)benzene; 2-methoxycarbonyl-1,4-bis(acetoacetamido}benzene; 2-ethoxycarbonyl-1,4-bis(acetoacetamido)benzene; 2,5-diethoxycarbonyl-1,4-btstacctoacetamiiloiJ3enzfirte; 2.-cyano-1,4-bis|acetoacetamido)benzene; 2-meihyi-1,4-bis(3cetoacetamido}bjenzene; 2-methoxy-1,4-bis(acetoacetamido>benzene; 2-ethyl-1,4-bis(acetoacetamido>benzene; 2-ethoxy-l,4-bts(acetoacetamido)benzene; 2-propoxy-l,4-bis(acetoacetamido)benzene; 2-isopropoxy-1,4-bis(acetoacetamido)benzene; 2-ijoto3cy-1,4-1)is(acetoacetam"do|benzene7 2-phenoxy-1,4-bislacetoacetarnidolbenzene; 2*nitro-1,4-bis{acetoacetamido)benzene; 2,5-dimethoxy-1,4-bis(acetoacetamido)benzene; 2,5-diethoxy-1,4-bis(acetoacetamido)benzene; 2-ethoxy-5-methoxy-1,4-bis(acetoacetamido)benzene; 2,5-dichloro-1,4-bis(acetoacetamido)benzene;

13
2,3-dichloro-1,4-bis(acetoacetamido)benzene; 2,6-dichloro-1,4-bis{acetoacetamido)benzene; 2,5-dibromo-1,4-bts(acetoacetamido)benzene; 2-,6-dibTC!TnQ--l-;4-bis(acetoacetamido)benzene; ^-chioro^S-naetnoxy-i ,4-btstacetoacetamidojbenzene; 2-chloro-5-ethoxy-1,4-bislacetoacetamido)benzene; 2-chloro-5-methyl-l ,4-
bis(acetoacetamido)benzene; 2,5-dimethyl-l ,4-bis{acetoacetamido)benzene; 2-methyl-5-methoxy-1,4-bis(acetoacetamido)benzene; 2-methyl-5-ethoxy-1,4-bis{acetoacetamido)benzene; 2-methyl-5-propoxy-1,4-bis(acetoacetamido)benzene; 2-mettiyl-5-isopropoxy-1,4-bis(acetoacetamido)benzene; and 2-methyl-5-butoxy-1,4-bis{acetoacetamido)benzene. Mixtures of two or more of any of the bis(acetoacetamido)benze~ie coupler components are within the scope of this invention.
The coupling reaction useful for the-purposes of the present invention may be effected preferably by adding the coupling components to diazonium components, but the diazonium components can be added to the coupling components. Coupling is generally effected at a temperature of from about 20°C to about 80°C, preferably from about 0°C to about 40°C. As in the diazotization reaction, coupling may be carried out in the presence or absence of an suitable surface active agent and/or organic solvent, such as all of those identified above for the diazotization reaction.
In one ^moodiment, the coupling-tromponem is dissolved in a basic solution such as a hydroxide solution including 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 slight stoichiometric excess of trie coupling component. That is, two equivalents of the diazoruarn -component are coupled with slightly more than two equivalents of the coupling component. In one embodiment, the ratio of equivalents of the diazonium component to the coupling component is from about 1.7:2 to about 2.1:2. In another embodiment, the ratio of equivalents

14
of the diazonium component to the coupling component is from about 1.8:2 to about JJLL and preferably from about 1.9:2 to about 2:2.
tn another emtaorfinjgr/saf the present invention, the dispersibJity cf the pigments of the present invention can be improved by adding alkali-soluble resin-tike products before, during, or after the coupling is completed. Various resin-like materials can be added for this purpose, and these include for example, rosin resins, polymeric rosins, resin soap, chemically modified rosin resins, such as rosin-maleinate resins, alkyd resins, and other synthetic hydrocarbon resins with a higher acid number, or combination of these resins. The resins may be present in a product with free carboxyl groups that are capable of forming a salt, or may be partially or completely in the form of salts, for example, with alkali metat ions. It n ay also be advantageous to perform the coupling reaction in the presence of a finely divided insoluble material, for example, alkaline earth metal sulphates and carbonates, titanium dioxide or clay materials or very finely divided organic plastic materials.
In most applications, it is desirable, in order to achieve the full brightness and tinctorial strength, to heat the disazo pigment. For example, the disazo pigment may be heated to reflux temperature for about 1 to 3 hours or at temperatures above about 100°C under pressure in the presence or absence of the above-described resirt soaps or other soluble resins.
After completion of the reactions and oplional heating.the disazopigments are recovered from the wjter-based fraction sJurry by filieoog xa iomua presscake of pigment which is washed with hot water (e.
15
flushed bases or dispersed into aqueous vehicles to prepare aqueous dispersions.
The pigment compositions of this invention provide strong green-shade yellow pigments having improved color strength, fcant fastness and/or heat stability and are useful as coloring agents in plastics, paints and inks. This invention, therefore, also relates to plastic, paint and ink compositions comprising major ampunts of a plastic, paint vehicle or ink vehicle and minor amounts of the disazo pigment compositions of this invention.
The paint, ink and plastic compositions in which the compositions of this invention are useful are well known to thos^ of ordinary skill in the art. Examples of inks include printing inks and lacquers, and examples of plastics include thermoplastic and thermosetting materials, natural resins and synthetic resins, polystyrene and its mixed polymers, polyolefins, in articular polyethylene and polypropylene, polyacrylic compounds, polyvinyl compounds, for example polyvinyl chloride and polyvinyl acetate, polyesters and rubber, and also filaments made of viscose and cellulose ethers, cellulose esters, polyamides, polycarbonates, polyurethanes, polyesters, for example polyglycol terephthalates, and polyacrylonitrile. It is also useful for pigment printing and for the pigmenting of paper in the mass.
Due to its excellent heat resistance, the disazo pigment is particularly suitable for the pigmenting of plastics in the mass, such as, for example, of polystyrene and its mixed polymers, polyolefins, in particular polyethylene and polypropylene and the corresponding mixed polymers and copoJymers, polyvinyl chloride and polyesters in particular polyethylene lerephthaiate and polybutylene terephthalate and the corresponding mixed condensation products based on polyesters, and mixtures and copolymers thereof.
See, for example, with regard 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 regard to paints: CM. Hare, Protective Coatings, Technology Publishing Co., Pittsburgh (1994), particularly pages 63-288; and with regard to plastics: T. G. Webber, Coloring of Plastics. John Wiley & Sons, New York (1979), particularly pages

16
79-204. The foregoing references are hereby incorporated by reference herein for their teachings of ink, paint and plastic compositions, formulations and-vehicles in which the compositions of this invention may .tie used including amounts of colorants.
The following examples illustrate the pigments of the present invention. Unless otherwise indicated in the following examples, in the specification and in the appended claims, all parts and percentages are by weight, temperatures are in degrees centigrade and pressures are at or near atmospheric pressure.
Example 1
A diazo solution is prepared by dissolving 13.7 parts 2-ethoxyaniline (o_-phenetidine> in 25.8 parts 20°C Baume hydrochloric acid and 200 parts hot water, icing to 0°C, adding 7.0 parts sodium nitrite dissolved in 21 parts water, stirring the solution at 0-5°C for 60 minutes, adding sufficient sulfamic acid to eliminate excess nitrous acid and diluting the solution to 600 parts. To the diazo solution is added a solution of 1.18 part N,N-bis{2-hydroxyethyO-cocoalkylamine oxide and then, immediately prior to starting coupling, a solution of 7.2 parts sodium acetate dissolved in 16.8 parts water, which brings the pH to about 5.1 at 8-10°C.
A coupler solution is prepared by dissolving 14.8 parts 1,4-bisacetoacetamidobenzene (1,4-BAAAB) in 550 parts warm water containing 4i2.parts sodium hydroxide and diluting to~600 parts. The coupler sorution ^s pumpea into the diazo solution over 18 minutes, at the end of which time the pH is 5.9 and the slurry temperature is 19°C. The pH of the slurry is raised to about 6.4 with 10% sodium hydrogen carbonate solution, at which point the slurry still shows excess diazo when tested with K-salt solution; after being stirred 30 minutes, the slurry shows no excess diazo and pH 6.6. The slurry is stirred for an hour, followed by adjusting the pH to 5.5, heating to 100°C, boiling for 30 minutes, icing to lower than 60°C and filtering; the filtercake is washed, dried overnight at 82°C and pulverized in an Osterizer to give 29.8 parts greenish-yellow powder.

17
Example 2
The procedure of Example 1 is repeated, except that dimethyl-cocoaHtylamtne oxide-is substituted for the bisH2-hYJc!roxYetf?yt>-cocoalkylamine oxide, giving 29.6 parts greenish-yellow powder.
Example 3
The procedure of Example 1 is repeated, except that 2.37 parts bis-(2-hydroxyethylj-cocoalkylamine oxide are used, giving 30.4 parts greenish-yellow powder.
Example 4
The procedure of Example 1 is repeated, except that 2.37 parts dimethyl-cocoalkylamine oxide is substituted for the bis-(2-hydroxyethyl)-rocoalkylamine oxide, and, after coupling, a solution of 8.4 parts of a 70% solution of sodium bistridecyl sulfosuccinate dissolved in 400 parts water is added, giving.36.4 parts greentsh-yettow powder.
Example 5
The procedure of Example 1 is repeated, except that a nonionic surfactant made from C ,,.1S linear alcohol and 20 moles ethylene oxide (cloud point 100°C) is substituted for the bis-(2-hydroxyethyl)-cocoalkylamine oxide, giving 28.4 parts greenish-yellow powder.
Example 6
The procedure of Example 1 is repeated, except that 2.37 parts of a nonionic surfactant .made-from C17 ,s alcohol/7moles ethylene oxide/4moles propytene oxide (cloud point 40°) is substituted for the bis-(2-hydroxyethyl)-cocoalkylamine oxide, giving 31.2 parts greenish-yellow powder.
Comparative Example 1
The procedure of Example 6 is used, except that 9.3 parts aniline are used-tn-place of 2-ethoxyanUine, giving 25_2 parts greenish-yellow powder.
Comparative Example 2
The procedure of Example 6 is used, except that 12.3 parts 2-methoxyaniline are used in place of 2-ethoxyaniline, giving 29.6 parts greenish-yellow powder.

18
Comparative Example 3
The procedure of Example 6 is used, except that 12.1 parts 2-eUwtsnftine are-used in place of 2-ethoxyaniUrTe, giving. 25.2 parts greeatsft-yeilow powder.
Comparative Example 4
The procedure of Example 6 is used, except that 10.7 parts 2-methylaniline are used in place of 2-ethoxyaniline, giving 22.8 parts greenish-yellow powder.
Comparative Example 5
The procedure of Example 6 is used, except that 12.8 parts 2-chloroaniline are used in place of 2-ethoxyaniline, giving 30.4 parts greenish-yellow powder.
Comparative Example 6
The procedure of Example 6 is used, except that 17.2 parts 2-bromoaniline are used in place of 2-ethoxyaniline, giving 34.0 parts greenish-yellow powder.
Comparative Example 7
The procedure of Example 6 is used, except that 18.5 parts 2-phenoxyaniline are used in place of 2-ethoxyaniline, giving 35.6 parts greenish-yellow powder.
CornDarative Example 8
The procedure of-Example 6 is used, except that 16.1 parts 2-trifluoromethylannine are used in place of 2-ethoxyaniline, giving 33.6 parts greenish-yellow powder.
Comparative Example 9
The procedure of Example 6 is used, except that 11.8 parts 2-cyanoaniline are used in piace_of 2-elhoxyaniline, giving 30.0 parts reddish-yellow powder
Comparative Example 10

19
The procedure of Example 6 is used, except that 15.1 parts 2-carbomethoxyaniline are used in place of 2-ethoxyaniline, giving 32.4 parts greeni sh-yello w-po wder.
Comparative Example 11
The procedure of Example 6 is used, except that 13.5 parts 2-acetoaniline are used in"place of 2-ethoxyaniline, giving 30.4 parts yellow powder.
Comparative Example 12
The procedure of Example 6 is used, exceprthat 12.3 parts 4-methoxyaniline are used in place of 2-ethoxyaniline, giving 30.4 parts greenish-yellow powder.
Comparative Fxample 13
The procedure of Example 6 is used, except that 13.7 parts 4-ethoxyaniline are used in place of 2-ethoxyaniline, giving 31.6 parts gieenrsh-yellow powder.
Comparative Example 14
The procedure of Example 6 is used, except that 10.7 parts 4-methylaniline are used in place of 2-ethoxyaniline, giving 29.2 parts greenish-yellow powder.
Comparative Example 15
The procedure of Example 6 is used, except that 12.8 parts 4-chloroaniiine are used in place~crf 2-ettioxyaniWne, giving 3Q.& parts greenish-yellow powder.
During the testing of pigments, the standard pigment, to which the experimental pigments are compared, is a green-shade diarylide yellow (C.I. Pigment Yellow 17) used in plastics under product designation RX1276 available from Engelhard.
Several commercial green-shade yellow pigments are included for comparison: Sandorin Yellow 4G {C.I. Pigment Yellow 155), which is a commercial example of this type of disazo pigment made with 1,4-bisacetoacetamidobenzene (1,4-BAAAB) available from Sandoz; Permanent

20
Yellow NCG-71 (C.I. Pigment Yellow 16), which is another kind (different) of disazb pigment (made with bisacetoacetylated~3,3'-dimethyibenzidine) -available from Hoecfest; YeHow 2GLTE (C.l.-Pigmesr-Y^llow 1O9). an isoindolinone pigment available from Ciba; and^aUotol Yetiow K 0S61 HD (C.I. Pigment Yellow 138), a quinophthalone pigment available from BASF
For comparing tinctorial strength and other coloristic values, the pigments are tested initially as 1:1 (0.1 phr pigment: 0.1 phr titanium dioxide) tints in high density polyethylene injection molded chip.s, as follows: A mixture of 0.59©-part pigment, 0.500 part titanium dioxide and 500 parts high density polyethylene (Solvay T50-2000-G) is shaken on a paint shaker for 15 seconds, then injection molded at 232°C for 1.5 minutes in a 30 ton Battenfeld machine. Spectrophotometric values of the molded chips are measured with a Macbeth Color-Eye (specular component included, large area) to givteK/S apparent strength versus the standard pigment and CIE L*C*h chroma, hue angle and lightness under Illuminant D, 10 degrees, as shown in Table I. To obtain a better measure of the tinctorial strengths, the strongest of the Experimental pigments is then tested in a reduced tint as 0.50:1 (50% reduction in pigment content) by repeating this procedure, except that 0.250 part pigment is used in place of the 0.500 part pigment; the K/S apparent strength and CIE L*C*h chroma, hue angle and lightness under Illuminant D, 10 degrees, of this reduced tint are measured against a 1:1 tint of RX1276 and are shown in Table M. To obtain a better measure of the tinctorial strengths, the strongest of the Experimental pigments is then tested in a reduced tint as 0.30:1 (70% reduction in pigment content) by repeating this procedure, except that 0.150 part pigment is used in place of the 0.500 part pigment; the K/S apparent strength and CIE L*C*h chroma, hue angle and lightness under Illuminant D, 10 degrees, of this reduced tint are measured against a 1:1 tint of Paliotol Yellow K 0961 HD (C.I. Pigment Yellow 138) and are shown in Table III. To obtain another comparison of tinctorial strengths, the strongest of the Experimental pigments is then tested in a reduced tint as a 0.20:1 tint (80% reduction in pigment content) by

21
repeating this procedure, except that 0.100 part pigment is used in place of the 0.5OG part pigment; the K/S apparent strength and CIE L*C*rr-chJoma, true angte arad-aghtness under Hkim"naot-O 10 degrees, T>f this reducscfeirit are measured against a 1:1 tint of Yellow 2GLTE (C.i. Pigment Yellow 109] and are shown in Table IV.
For comparing heat stabilities, the pigments are tested as above for coloristic values of 1:1 tints, except that the chips are molded and held at 288° for 3 mjnutes. Spectrophotometric values of the molded chips are measured with a Macbeth Color-Eye (specular component included, large area) versus the chips molded at 232° to give CIElab delta E values, as shown in Table V.
For comparing fade resistance, the high density polyethylene injection molded 1:1 tint chips used for coloristic values are exposed for 100 hours in an Atlas Xenon Hade-Ometer. Spectrophotometric values of the exposed chips are measured with a Macbeth Color-Eye (specular component included, large area) versus unexposed chips to give CIElab delta E values, as shown in Table V.
For comparing apparent strength and hue angles in a paint vehicle, the standard pigment and the pigments of Examples 1 and 4 are tested as 1:1 .tints as follows: A mixture of 0.50 part pigment, 0.50 parts titanium dioxide (DuPont Ti-Pure R-960), 23.2 parts air-dry alkyd enamel vehicle (containing 36% mediam oil alkyd, 13% mineral spirits and 1 % driers/antrskinrving agent) and 75" parts media (Zircoa Zirbeads Y1304) is stirred with a spatula to a uniform mixture, sealed with a lid and shaken on a paint shaker for 30 minutes. The dispersion is separated from the media, drawn down with a 0.15 mm. gap coating bar on coated cardboard (Leneta Form 2-C) and allowed to dry for 1-2 days. Spectrophotometric values are measured with a Macbeth Color-Eye (specular component included, large area) to give the apparent strength and hue angles under Illuminant D, 10 degrees, shown in Table VI.

22
Table

Coloristic Values of 1:1 Tints in HI3PF
Pigment Apparent Strenath Chroma (Q* ) Hue Arraie to) LiohtnessfL*
P.Y 17 Standard 89.9 90.3° .88.4
(K/S = 23.655)
Example 1 (2-ethoxy) +23% 91.6 91.2° 87.6
(K/S = 29.164)
Example 2 (2-ethoxy) +21% 92.2 91.4= 88.1
Example 3 (2-ethoxy) +16% 91.1 91.9° 88.1
Example 4 (2-ethoxy) +20% 92.4 92.3" 89.0
Example 5 (2-ethoxy) +23% 90.9 90.7° 87.3
Example 6 (2-ethoxy) + 19% 89.7 90.1° 86.6
Com. Ex. 1 (no substttuents) -19% 78.4 95.5* 89.3
Com. Ex. 2 (2-methoxy) +20% 89.3 91.4° 87.2
Com. Ex. 3 (2-ethyl) -6% 81.5 88.9° 85.5
Com. Ex. 4 (2-methyl) + 1 % 84.2 89.3° 85.8
Com. Ex. 5 (2-chloro) -4% 84.0 87.1° 85.8
Com. Ex. 6 (2-bromo) -4% 84.9 89.0° 87.0
Com. Ex. 7 (2-phenoxy) Equal 83.6 92.4° 88.3
Com. Ex. 8 (2-trifluoromethyi) -27% 78.4 89.6° 87.3
Com. Ex. 9 (2-cyano) + 1-0% 70.1 72.3° 74.1
Com. Ex. 10 (2-carbomethoxy) -10% 82.6 aa-jo* 67.1
Com. Ex. 11 (2-aceto) +9% 80.6 78.7° 80.8
Com. Ex. 12 (4-methoxy) +20% 83.9 86.3° 82.3
Com. Ex. 13 (4-ethoxy) +16% 84.8 87.9° 83.8
Com. Ex. 14 (4-methyl) -4% 81.8 91.2° 86.6
Com. Ex. 15 (4-chloro) -1% 86.0 90,0c 87.2
C.I. P.Y. 155 (2,5-dicarbomethoxy) -13% 82. 1 88.3° 86.0
C.I. Pigment Yellow 16 +2% 87.5 90.9° 88.4
C.I. Pigment Yellow 138 -18% 84.3 93.5° 89.4
C.I. Pigment Yellow 109 -39% 77.9 93.6° 89.7

23
In Table I, the apparent strengths of the Examples, all containing the 2-ethoxy substituent and made with different surfactants, are estimated to be T6:23% stronger than P.Y. 1 7 in 1:1-twits: even-though the pigment of Example 4 is diluted about 20% with surfactant, it maintains its apparent strength and chroma. The hue angles of the Example tints are generally slightly higher (slightly greener) than the P.Y. 17 tint. The apparent strengths of several Comparative Examples (C.E.), containing no substituent or substituents other than 2-ethoxy, are equal to 20% stronger than P.Y. 1 7; however, the chroma and lightness values indicate that, excepttor C.E. 2, these Comparative Examples obtain their apparent strengths not from strong chromas, but from lower lightness (dirtiness). Pigment Yellow 155 (Sandorin Yellow 4G), which is like the Comparative Examples ard contains carbomethoxy groups at the 2- and 5- position, is 13% weaker and slightly redder than P.Y. 17. Pigment Yellow 16 (Permanent Yeliow NCG-71). which is another kind of drsazo yellow (made with bisacetoacetvlated 3,3'-dimethylbenzidine), is about equal in strength and hue, but shows lower chroma. Also, for comparison, P.Y. 138 (Patiotol Yellow K 0961 HD), is 18% weaker and somewhat greener than P.Y. 17; P. Y. 109 (Irgazin Yellow 2GLTE) is 39% weaker and somewhat greener than P.Y. 17.
When the apparent strengths or weaknesses in Table I are greater than about 10%. they tend to be underestimated, as demonstrated in the following Tables.
Table II

Coloristic Values Of a 0, 5:1 Tint in HDPE
Pigment Apparent Strenath CJnojpalC o) H\\e, Anale(h) Liohtnessd. o1
P.Y 17 (1 :1) Standard 89. 8 9O.4o 8& .7
(K/S = 23.080)
Example 1 (0.5:1) +5% 89! '.3 93.8° 89 .4
(K/S = 24.144)

24
In Table II, the apparent strength of Example 1, coupled in the presence of 5% N,N-bis(2-hydroxyethyl)-cocoalkylamine oxide, is estimated to be +5% in a 0.5:1 tim; this means that Example 1 is_more"than 100% stronger than P.Y. 17. Although the apparent strength, chroma and lightness values for the 0.5:1 tint of Example 1 are close to those of 1:1 P.Y. 17, the hue angle for the 0.5:1 tint of Example 1 is significantly higher (greener), which distinguishes it from 1:1 P.Y. 17.
Table III
Coloristic Values of a 0.3:1 Tint in HDPE
Pigment Apparent Strength Chroma (C) Hue Angle fh) Lightnessd*)
^.Y 138 (1:1) Standard 84.3 93.5° 89.3
(K/S = 18.959)
Example 1 {0.3:1) +4% 33.8 94.1 o 89.3
(K/S = 19.664)
In Table III, the apparent strength of Example 1, coupled in the presence of 5% N,N-bis(2-hydroxyethyl)-cocoalkylamine oxide, is estimated to be +4% in 0.3:1 tint; this means that Example 1 is more than 3.3 times stronger than P.Y. 138. The chroma, hue angle and lightness values for the 0.3:1 tint of Example 1 indicate that it is a good match for 1:1 P.Y. 138.
Table (V Coloristic Values of a 0.2:1 Tint in HDPE

Pigment ApDarent Strenath ChromafC*) Hue Anqle(h) LiqhtnessIL")
P.Y 109 (1 .1) Standard 77 .9 93. 8° 89.7
Example 1 (0.2:1) +10% 79. 2 96 .3° 90.4
(K/S = 15.519)

25
In Table IV, the apparent strength of Example 1, coupled in the presence of 5% N,N-bis(2-hydroxyethyl)-cucoatt Table V
Change (Delta E) in Coloristic Values of 1:1 Tints in HOPE After;
Heat Stability Testing Fade Resistance Testing

Piament
P.Y. 17 1.5 1, .4
Example 1 .{2-ethoxy) 2.0 1 .2
Example 2 (2-ethoxy} 0.9 1 .9
Example 3 (2-ethoxy) 1.5 0 .7
Example 4 (2-ethoxy) 1.7 0 .8
Example 5 (2-ethoxy) 1.3 2 .1
Example 6 (2-ethoxy) 2.0 1 .3
Comparative Example 1 (no subst.) 24.0 5.8
Comparative Example 2 (2-methoxyH2.1 3.1
Comparative Example 3 (2-ethyl) 3.5 6.4
Comparative: Example Ar {2-methyO 1.0 7.5
Comparative Example 5;(2-chioroJ 2.2 2.4
Comparative Example 6 (2-bromo) 4.3 2.3
Comparative Example 7 (2-phenoxy)6.4 1.9
Comparative Example 8 (2-trifluoromethyl)12.9 3.2
Comparative ExaropieiJ (2-cyano) 23.2 2.9
Comparative Example 10 (2-carbomethoxy)11.0 2.0
Comparative Example 11 (2-aceto) 16.7 4.7
Comparative Example 12 (4-methoxy)6.8 9.0
Comparative Example 13 (4-ethoxy) 4.1 12.8

26

Comparative Example 14 (4-methyD 2.8 2.7
Comparative Example 1-5 *
(4-chloro) 3.7 2,5
C".!. Figment Yeffow T55 C^^drcarbomethoxv) 19.5 3.5
C.I. Pigment Yellow V6" 7.0 0.8-
C.I. Pigment Yellow 138 3.6 1.1
C.I. Pigment Yellow 109 0.4 0.5
in Table V, the delta Es (a measure of change) for the heat stabilities of the Examples are about the same as for P.Y. 17 ar.d are at or lower than the delta E = 2.0, typically considered to be the upper limit for concern by plastics processors. The delta Es for the fade resistances of the Examples range from 0.7 to 2.1, with four of them being lower than the 1.4 of P.Y. 17, which is considered to have fairly good fade resistance (W. Herbst and K. Hunger, ibid, p. 252, state:. "P.Y.17 is aimost as lightfast as the somewhat redder P.Y.13 (step 6-7 at 1/3 SD).").
In Table V, the delta Es for the heat stabilities of the Comparative Examples (except for the acceptable 1.0 of Comparative Example 4, with the 2-methyl substituent) range from marginal (Comparative Example 5. with the 2-chloro substituent) to extremely poor {Comparative Examples 1 and 9, with no substituent and the 2-cyano substituent)- The delta Es for the fade resistances of the Comparative Examples range from a marginal 1.9 (Comparative Example 7, with-a -2-ptwnoxy substituenti to a very .poor 12.8 (Comparative Example 13, with the 4-etiioxy substituent}. The delta €s for the heat stabilities of the commercial green-shade yellow pigments range, with the exception of P.Y. 109, from poor for P.Y. 138 to very poor for P.Y. 155. The delta Es for the fade resistances of the commercial green-shade yellow pigments are good (1.1; 1.5) to very good t0.5; 0:8).

27

Table VI
Coloristic Values of 1 o1 Tints in Ajr-Dry Enamel
Piqment ADDarent Str"n P.Y. 17 Standard 90.4 86.6° 84.8
(K/S = 30.261 >
Example 1 -7% 88.5 87.9° 85.0
Example 4 -6% 90.6 89.7° 86.5
In Table VI, Example 1 is about 7% weaker and shows lower chroma than P.Y. 17 in 1:1 tints in air-dry enamel. This weakness is surprising in light of the strength of Example 1 in HDPE and may arise from poorer dispersibility of Example 1 in air-dry enamel. Example 4, which h post-treated with 20% sodium bistridecyl sulfosuccinate, is also slightly weak; however, its chroma is as high as that of P.Y. 17, indicating better dispersibility in air-dry enamel, so its lower apparent strength probably derives from its higher lightness. The hue angles of the Examples tint are higher (greener) than that of the P.Y. 17 tint.
When incorporated in polyolefins, the pigments obtained according to the present invention display strong, bright greenish shade yellows in contrast to the generally weaker shades displayed by conventional pigments. The relatively high chromaticity values are consistent with the brightness of the color displayed while the high strength is reflected by a relatively-high K/S values.
While the invention has been explained in relation to its preferred embodiments, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, rt is to be understood that the invention disclosed beretf* is intended to cover such modifications as fall within the scope of the appended claims.

28 We Claim
1. A method of preparing a green shade yellow pigment composition which comprises making a dlsazo pigment by coupling (i) a diazonium component made from of one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline with
wherein Ri and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trffluoromethyl.
2. The method as claimed in claim 1 wherein (0 and (li) are coupled in the
presence of at least one surfactant selected from N,N-bls(2-
hydroxyethyi)cocoalkylamine oxide and N.N-dimethylcocoalkylamine oxide.
3. The method as claimed in claim 1 further comprising adding bis(tridecyl)
ester of sodium sulfosuccinic acid.
4. The method as claimed in claim 1 wherein the ratio of equivalents of (i) to
(li) Is from about 1.7:2 to about 2.1:2.

29
5. The method as claimed in claim 1 wherein Rt and Ffcare hydrogen.
A method of preparing a green shade yellow pigment composition which comprises making a disazo pigment by coupling (i) a diazonfum component made from of one or more aromatic amines wherein at least one of said amines is 2-ethoxyaniline with (ii) at least one coupling component characterized by the formula:
wherein R1 and R2 are independently hydrogen, halogen, an alkyl group having 1 to about 4 carbon atoms, an alkoxy group having 1 to about 4 carbon atoms, an alkoxycarbonyl group having 1 to about 6 carbon atoms, nitro, cyano, phenoxy or trifluoromethyl.

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Patent Number

207217

Indian Patent Application Number

IN/PCT/2001/00129/KOL

PG Journal Number

22/2007

Publication Date

01-Jun-2007

Grant Date

31-May-2007

Date of Filing

01-Feb-2001

Name of Patentee

ENGELHARD CORPORATION

Applicant Address

101 WOOD AVENUE ,P.O.BOX 770, ISELIN , NEW JERSEY 08830-0770 ,

Inventors:

#	Inventor's Name	Inventor's Address
1	HAYS BYRON G	16871 CATS DEN ROAD CHAGRIN FALIS ,OHIO 44023

PCT International Classification Number

C09B33/153

PCT International Application Number

PCT/US99/17384

PCT International Filing date

1999-08-02

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	09/131,719	1998-08-10	U.S.A.