78 Organic Pigments 78.1. Introduction 78-1 78.2. The Colour Index System. 78-1 78.3. Pigment Selection, 78-2 Peter A. Lewis Organic Blues + Organi Green » Organic Oranges Rede = Sun Chemical Corporation ‘Organic Yellows 78.1 Introduction A definition of a pigment, as distinct from a dyestufl, has been prepared by the Dry Color Manufac- turers’ Association (DCMA) in response to a request from the Toxic Substances Interagency Testing, Committee. This definition should clarify the term “pigment” and “dyestuff” which are often errone- ously used interchangeably: Pigments are colored, black, white, or fuorescent particulate organic and inorganic solids which usually are insoluble in, and essentially physically and chemically unaffected by, the vehicle or substrate in which they are incorporated. They alter appearance by selective absorption and/or by scattering of light. Pigments are usually dispersed in vehicles or substrates for application, as for instance in inks, paints, plastics, or other polymeric materials, Pigments retain a crystal or particulate structure throughout the coloration process. ‘Asa result of the physical and chemical characteristics of pigments, pigments and dyes differ in their application; when a dye is applied, it penetrates the substrate in a soluble form after which it may or ‘may not become insoluble. When a pigment is used to color or opacify a substrate, the finely divided, insoluble solid remains throughout the coloration process. 78.2 The Colour Index System ‘The Colour Index System is a coding system as developed under the joint sponsorship of the Society of Dyers and Colourists (SDC) inthe United Kingdom and the Association of Textile Chemists and Colorists (AATCC) in the United States. The system is referred to as the “Colour Index. (This system is registered. as a trade name and the use of the “u” in “Colour” must be retained.) By giving a compound a “Colour Index Name” and a "Colour Index Number,” a colored compound can be readily placed into a classifi cation according to its chemical constitution and color. This description is recognized by many govern ‘ment bodies as adequate information for inclusion in hazard data sheets or material safety data sheets to fully identify the pigment in question and to provide accurate reference when including a pigment in any inventory listing. Thus, for example, phthalocyanine blue has a Colour Index name Pigment Blue 15 and the Colour Index number 74160. 78-178.2 Coatings Technology Handbook, Third Edition TABLE 78.1 Range of Colour Index Constitution Numbers Chemical Clase Colour Index Constitution Number Insoluble Azo 1, Acetoucety 14640-11790 2 Heteroylic hydroxy 3 iso 4. 2-Naphthot 20900-29999 5. 3-Hydroyy-2-naphthanilde 12300-12520 Precipitated Azo 1. 2-Naplaho (sulfone) acd 15500-16815 Precipitated Nona 1, Xanthene 45000-45999 2. Tiphenyimethane 2000-44999 Insoluble Nonszo 1. Phihalogyanine 2 Amthraguinine 3. Quinaeridone ‘The Colour Index 1s for pigments are abbreviated as follows: PB = Pigment Blue PBr = Pigment Brown PM = Pigment Metal PY = Pigment Violet PW = Pigment White Pigment Black sment Green igment Orange Pigment Red PY = Pigment Yellow Additionally, the Colour Index constitution number conveys information regarding the structure of the compound as shown in Table 78.1 78.3 Pigment Selection Once a formulator has decided upon the hue that is required for a particular coating, the next most important criteria of any pigment are its fastness properties. It is useless to formulate any coating with, ‘ pigment that will not withstand the exposure specifications of the coating’s end use. Such specifications. can extend 0 requiring as much as 5 years’ outdoor exposure in states such as Florida and Arizona. Due attention must be paid to the respective manufacturers literature to ensure that a pigment has been chosen that will stisly the end-use criteria for stability to locculation and crystallization, as well. as fastness to light, solvents, heat, and chemicals. Once a pigment class has been selected that will perform adequately in the end-use application, the formulator can consider such other factors as economy. The formulator should be aware, however, that the fastness properties of a pigment will be affected by the medium into which itis incorporated. Thus, even though intrinsically the pigment may feature the required properties, itis still necessary for the final pigmented coating to be tested in the end-use applicationOrganic Pigments 78:3 FIGURE 78.1. Structure of copper phthalocyanine blue (pigment blue 15). 78.3.1 Organic Blues 78.3.1.1 Copper Phthalocyanine Blue ‘The major blue used within the coatings industry is copper phthalocyanine blue (PB 15), with its usage far outweighing other blues such as Indathrone blue (PB 60), Phthalocyanines are planar molecules with a tetrabenzotetraazoporphin structure as shown in Figure 78.1. Manufacture is comparatively easy despite the superficial complexity of the phthalocyanine mole- cule. Reaction ofa phthalic acid derivative at temperatures approximating 190°C with a source of nitrogen such as urea and a metal or metal salt is usually all that is required to produce the appropriate metal phthalocyanine. Molybdate, vanadate, and certain compounds of titanium have been found to be useful catalysts for this condensation reaction, Figure 782 illustrates the chemistry behind the production of copper phthalocyanine blue. This condensation reaction results in the formation of copper phthalocyanine in a crude, nonpigmentary form. The product has thus tobe finished or conditioned to give the pigment grade of choice. Typically crude phthalocyanine blue is characterized by a crystal size of the order of 50 pm, a purity in excess of 929%, and a poor pigmentary strength “Metal-free phthalocyanine blue (PB 16) is normally manufactured via the sodium salt of phthalonitril. ‘Acid pasting is used to condition the crude and give the pigment. ‘Copper phthalocyanine is commercially available in two crystal forms known as the crand [3 The or form is described by the designations Pigment Blue 15, 15:1, and 15:2 and isa bright red-shade blue pigment. The (form is described as Pigment Blue 15:3 and 15:4 and isa bright green or peacock shade. ‘The cr form is meta-stable and requires special treatment to stabilize the crystal against its tendency to Copper Sat copper OG Gauge? Cone, —— eat FIGURE 782 Chemistry of copper phthalocyanine, "Molybdate or vanadate.784 Coatings Technology Handbook, Third Edition revert to the more stable, green-shade (crystal. Ifeither of the unstable cy crystal forms (PB 15 oF 15:1) js used with strong solvents, conversion to the } form will occur upon storage of the system. Conversion from the cto the f form is usually accompanied by an increase in crystal size with subsequent loss of strength and shift to a greener hue. ‘As stated earlier, copper phthalocyanine gives excellent service in most coatings applications, but there is considerable variation between both the chemical and crystal types available. Pigment Blue 15 is an cy crystal with the reddest shade of the types commonly available, It isthe least stable of the family and as such is often referred to as crystallizing red-shade (CRS) blue. This erystal form cannot be used in any solvent containing systems. Pigment Blue 15:1 is also an ¢, crystal, but chemical modifications have been made to stabilize the structure against crystallization. Most commonly the molecule is chlorinated to the extent of introducing tone chlorine molecule to give “monochlor” blue. Another technique involves the use of a substituted. phthalocyanine, added to the pigment at levels approaching 10 to 1596, that confers crystal stability 10 the system. The monochlorinated grade is, as a consequence of the introduced chlorine atom, greener than the additive-stabilized crystal Pigment Blue 15:2, described as “noncrystallizing nonflocculating” red-shade blue, is widely used Within the coatings industry. The product is an (crystal that is stabilized against both crystallization and flocculation using additive technology. Pigment Blue 15:3 represents the green-shade, } crystal phthalocyanine blue and, as it exists in the stable crystal form, itis less susceptible to crystallization. Most commercial grades of Pigment Blue 15:3, however, contain from 4 to 896 of the cecrysta, which will be adversely affected by strong solvent systems A-100% 3 blue is too dull, opaque, and weak to be commercially attractive; hence, a proportion of the Lerystal is left in the system, contributing considerably to the attractiveness of the system. Pigment Blue 15:4 represents 2 [j blue that has been modified with phthalocyanine-based additives to give a green-shade blue that is resistant to flocculation and can be used in strong solvent systems. ‘Copper phthalocyanine approximates the ideal pigment. It offers strength, brightness, economy, and all-around excellent fastness properties. Perhaps the pigment’s only disadvantages are its tendencies to change toa coarse, crystalline, nonpigmentary form in strong solvents and to flocculate or separate from, White pigments when used in paints and lacquers. 783.1.2 Miscellaneous Blues Although the organi blues used in the coatings industry are primaeily copper phthalocyanines, brief mention must be made of other blue pigments that find use in the coatings marketplace. Indanthrone blue, Pigment Blue 60, belongs tothe class of pigments described as vat pigments? This pigment is expensive relative to copper phthalocyanine, and thus economic considerations are a limitation to its widespread use, Idanthrone blue is a very red-shade pigment with outstanding fastness properties Carabazole violet, Pigment Violet 23, is a complex polynuclear pigment that is a very valuable red: shade blue of high tinctorial strength. The pigment possesses excellent fastness properties, and only its relatively high cost and its hard nature limit its more widespread use. From an economic standpoint it costs approximately three times as much as phthalocyanine blue ‘The pigment is used as a shading component in high performance coatings that call for particularly red-shade blue. 78.3.2. Organic Greens 78.3.2.1 Copper Phthalocyanine Green ‘The major green pigment used as a self shade in the coatings industry is based on halogenated copper phthalocyanine and, as such, is termed phthalocyanine green. The Colour Index names are Pigment Green 7 and Pigment Green 36 ©2009 Tyr Ar Gap.Organic Pigments 785 ae Pigment Green 7 er cr Pigment Groen 36 1 (Gluest shade alsoknown Br 83y) Br er Pigment Green 38 Br (yatlowest shade also known as 6) ct ct er be FIGURE 78.3 Structure of copper phthalocyanine greens. Pigment Green 7, the blue-shade green, is based on chlorinated copper phthalocyanine with a chlorine content that varies from between 13 to 15 atoms per molecule, Pigment Green 36, the yellower shade, is based on a structure that involves the progressive replacement of chlorine on the phthalocyanine structure with bromine. The composition of Pigment Green 36 varies with respect to the total halogen content, chlorine plus bromine, and in the ratio of bromine to chlorine. Figure 78.3 illustrates the proposed structures ofthe phthalocyanine greens. In practice, no single pigment consists of a specifie-molecular species; rather, each pigment is a complex mixture of closely related. isomeric compounds, ‘These pigments are ideal, since their tinctorial and fastness properties allow their use in the most severe application situations. They possess outstanding fastness to solvents, heat, light, and outdoor exposure. They can be used in masstone shades and tints down to the very palest of depths. Phthalocyanine greens are manufactured by a three-step process: crude phthalocyanine blue is first, ‘manufactured, then halogenated to give a crude copper phthalocyanine green, and finally conditioned. to give the pigmentary product. 783.22 Miscellaneous Greens ‘Table 78.2 gives a summary of the properties of some other commercially available organic greens that ‘may find some minor application in the coatings industry,78.6 Coatings Technology Handbook, Third Edition TABLE 782 Summary of Miscellaneous Green Properties (Colour Index Name (Chemical Name ‘Comments Pat Briliant Green lian, blue shade; poor alkali and soap resistance, solvent bled, (Triphenylmethane PIMA) and lightasiness may be sed in interior finishes. PG2 Permanent Green Blend of Pigaiene Green 1 and Piginent Yellow 18; right yellow (Triphenylmethane PIMA) shade; poor fatness overall Poa Malachite Green| Bright, blu shade; poor astnes properties overall (Tripheaylmethane PIMA) Pas Pigment Green 8 (Niteoso) Yellow shade dll hue: poor fstess properties: may be used in interior ermusions PG 10 Gueen Gold ‘elow shade loses meta in strong cid or lal: good ightfastnes moderate solvent fstess; used in omotive and exterior pants ‘TABLE 78.3 Organic Orange Pigments Colour Index Name Colour Index Number* Chemical Type Po? "060 hao Pos 7s Ao Pos Bistzo POIs Biswo post Bisizo condensation Pom iso Po36 Benzimidaalone(a20) PO 38 Azo Pou Perinone POA Azo Pous Quimeridone Pow Quinacridone post Pyranthvone pos Pyranthvone Po so ia Benzimidazolone (420) Post a “Tetrachlooisoindolinone pow ia Benzimidazolone (420) Post ia Hezocylic hydroxy Pos? a Pyrazologuinazolone ot asgned 78.3.3 Organic Oranges ‘Table 78,3 lists the orange pigments that are available in today’s marketplace. A broad subdivision can be made based on such chemical features of the molecule as azo based, benzimidazolone based, and miscellaneous oranges. 78.3.3.1 Azo-Based Oranges “The structure of the seven orange pigments that can be placed into the “azo” category are shown in 784 and are listed below: igure Pigment Orange 2, Orthonitroaniline Orange, is prepared by the classical diazotization and coupling technique in which diazotized orthonitroaniline is coupled to [-napthol. The pigment’s major ‘market isin the field of printing inks, ls use in coatings is not recommended because the pigment’s solvent fastness is poor and its lightfastness inadequate. Pigment Orange 5, Diniteoaniline Orange, is manufactured by a diazotization and coupling sequence in which diazotized dinitroaniline is coupled onto f-napthol. This pigment offers good lightfast- ness in full tone and moderate solvent fastness, As such, the pigment finds widespread use inOrganic Pigments 78.7 Poe Cnhontraanilin Orange Nos HQ moma Dintroaniline Orange Po1s OL nO by Pyrazlone Orange oly Orange ct HO gO} mrcoon P38 i Han ©) 8 Napiol Orange Hite row | oC Qf S05- Cation Red FIGURE 784. Structure of azo-based oranges.78-8 Coatings Technology Handbook, Third Edition NO, Hicxoe0 4 4 Pose Oy Ou a é Ne , 4 Benzimidazolone Orange nee i 4 PO60 SNe C-0 Oe foe FIGURE 785. Structure ofthe benzimidazolone oranges latex-based paints and, with the exception of high bake enamels, in both architectural and industrial coatings. Pigment Orange 13, Pyrazolone Orange, is synthesized by coupling tetazotized 33-dichlorobenzidine conto 3-methyl-1-phenyl-pyrazol-5-one. The pigment isa bright, clean yellow-shade product that is tinctorially stronger than Pigment Orange 5. It may be recommended for interior coatings, particulary asa replacement for lead-based oranges. Pigment Orange 16, Dianisidine Orange, isa diaryide orange tha is prepared by coupling etrazotized 3 ,3-dimethoxyhenzidine onto acetoacetanilde. The pigment finds use in baking enamels, since its heatfastness is superior to that of other orange pigments with similar economics. Usage in interior coatings at full tone levels is also recommended. Pigment Orange 34, Tolyl Orange, is produced by coupling ttrazoized3,3-dichlorobenzidine onto 3- ‘methyl-1-(4-methyl-pheny)-pyrazo-5-one. The pigment isa bright, reddish orange that offers moderate lightfstness and good alkali resistance, but poor Solvent fastness. As such, the material is used in interior coatings applications, particularly where a lead-free formula is specified. Pigment Orange 38, Naphthol Orange, is manufactured by coupling diazotized 3-amino-4-chloroben- amide onto 4-acetamido-3-bydroxy-2-napthanilide. The pigment is a bright reddish orange that exhibits excellent alkali and acd fasness, moderate solvent fastness, and acceptable light fastness when used at full tint. As such, the pigment finds use in baking enamels, latex, and rmasoney paints. Pigment Orange 45, Clarion Red, isa metalized azo pigment manufactured by coupling diazotized 2- amino-5-chloro-4ethylbenzene-sulfonic acid onto [/-napthol and metalizng the product with barium to yield the pigment. The pigment has poor lightfastness, inferior alkali resistance, and inadequate solvent fistness, hence is not recommended for use in coatings. 78.3.3.2 Benzamidazolone-Derived Oranges ‘The three benzimidazolone-derived oranges contain the azo chromophore and are all based on the 5: acetoacetylaminobenzimidazolone as the coupling component. Pigment Orange 36 is the product of coupling diazotized 4-chloro-2-nitroaniline to the benzimida- zolone, Pigment Orange 60 is the product of the coupling of 4-nitroaniline to the benzimidazolone. Because ofthe proprietary nature ofthis product, the structure of Pigment Orange 62 has not been fully declared (Figure 78.5 illustrates two typical structures) Pigment Orange 36 is a bright red-shade orange of very high tint strength. The opacified form of this pigment offers excellent fastness properties to both heat and solvents and a hue similar tothe lead containing pigment, Molybdate Orange (PO 104). As such, Pigment Orange 36 finds major use in lead-free automotive and industrial high performance coatings. ©2009 Tyr Ar Gap.Organic Pigments 78.9) TABLE 784 Summary ofthe Properties ofthe Miscellaneous Oranges (Colour Index Name Common NameiDesription Properties Poa Petinone ed shade, steong, clean, vat pigment with excellent stess properties; used in metallized finishes and high grade pants ‘hots light solvent Bleed Poa8 Quinscrdone Gold Yellow shade; exellent ightstnss; lacks brightness a masstone; ‘sed in metal finishes row Quinacrdone Deep Gold Red shade; dll massone; excellent durability, used in metals PosI Pyranthvone Orange “Medium shade excelent fstness to slvent, ight, and hes: dll in tin: eahiis slight solvent bleed; used ina dey and bake enamels pos Pyrantheone Orange, ed Vat pigment with excellent fasines to solvent light, and heat; dull shade in nts: slight solvent bled: used in aie dry and bake enamels Pos Teachlorosoindoliaone Medium shade; eahbits some solvent bleed: used in metalic orange ‘suomotive finishes Poe Bright shade eed client solvent and lghtasines used in industial coatings pos Yellow shade Excellent briliance in fll shade; good gloss retention; very good ‘weather- and ightisnes infill shade; used in industrial and utomative coatings Pigment 60 is a transparent, yellow-shade orange that also exhibits excellent heat and solvent fastness With an exterior durability that allows the pigment to be used in high quality industrial and automotive finishes Pigment Orange 62 is also a yellow-shade orange that shares the lghtfastness properties ofthe other two oranges. Currently itis used in oil-based inks and artists’ colors. Its use in the coatings industry has yet tobe fully explored, 783.33 Miscellaneous Oranges “The structures of Pigment Orange 53, a pyranthrone, Pigment Orange 64, a heterocyclic hydroxy, and Pigment Orange 67, a pyrazologuinazolone, have not been fully declared. Table 78 summarizes the properties of this class of pigments, which represents a series of oranges that are finding increased application inthe coating industy. 78.3.4 Reds 783.41 Metallized Azo Reds Many of the reds used in the coatings industry fll into the chemical category of azo pigments because the azo chromophore —N=N— is a feature of the molecule. ‘A further subdivision may be made into acid, monazo metallized pigments such as Manganese Red 2B (PR 48:4) and Calcium Lithol (PR 49:2) and nonmetallized azo reds such as the Naphthols (e.g. PR 17 PR 23) and Toluidine Red (PR 3). Typically, each of the acid, monoazometallized pigments contains ionic grouping such as a carboxylic (COOH) or sulfonic acid (—SO,H) group, which will ionize react with a metal cation such as calcium oF manganese to form an insoluble, metallized pigment. Nonmetallized pigments do not contain an anionic group in their structure and, as such, will not complex with a metal cation All azo reds contain one or more azo groups and are produced by similar reaction sequences. The initial reaction sequence, described as diazotization, involves reacting an aromatic primary amine with, nitrous acid, formed in situ by reacting sodium nitrite with hydrochloric acid at low temperatures to, yield a diazonium salt. Invariably the diazonium salt that is formed by this process is unstable and should be kept cold to avoid any decomposition, ‘The diazonium satis reacted quickly with the second half ofthe pigment, which is called the couplet. ‘The coupling reaction takes place rapidly in the cold to yield the sodium sat ofthe pigment. This sodium, salt is all but useless asa pigment for the coatings industry because of its marked tendency to bleed even.78-10 Coatings Technology Handbook, Third Edition p00 paer aod oe 500 pass Eran AB, one "9 g00 vores PRED 3 ‘CHs—=CHs Methylene (—CH,—) Addition "coo" Cty rao IO C00 ‘sutact-COOH oe, "9 om NH Caron Ret P04 CH CH, Subtrat CH, oe Ho cy pasa xe RedLake C iS, FIGURE 786 Metallized azo reds in the weakest of solvent systems. The pigment is, therefore, metallized to confer improved properties fon the product. The pigment suspension is then filtered and washed to remove any residual inorganies derived from the reaction Figure 78.6 illustrates the structures of the different metallized azo reds that are readily available. ‘The Lithol Reds are primarily Barium Lithol (PR 49:1) and Calcium Lithol (PR 49:2). Although limited in their application in the coating industry, these pigments do find some use at masstone levels — that is, the pigment is not tinted with a white tint base — where their fastness properties are acceptable. ‘The pigments are bright reds with high tint strength and good dispersion characteristics. The barium salt is lighter and yellower in hue compared to the calcium salt, Permanent Red 2B isthe generic name that encompasses Barium Red 2B (PR 48:1), Calcium Red 2B (PR 48:2), and Manganese Red 2B (PR 48:4). The major use ofthe calcium and barium salts i in baked industrial enamels, which are not required to be fast to outdoor exposute. Use in alkaline systems is severely restricted because of the poor alkaline fastness of these saltsOrganic Pigments 78-11 leew vo CO - ‘The barium salt is characterized by a clean, yellow hue and, although slightly poorer than the bluer calcium salt in lightfastness and tinting strength, it does possess a sight advantage in bake stability “Manganese Red 2B has a sufliciently improved lightfastness to be used in implement finishes. The manganese salt is slightly blue, dirtier, and less intense when compared to the calcium sal Rubine Red also known as Calcium Lithol Rubine (PR 57:1) is a clean, blue-shade red. pigment exhibiting the high tinting ability typical of the azo reds of this class. Its major use in coatings isin interior systems that call for an inexpensive red with good solvent and heat resistance. Again, to maintain, ‘maximum fastness properties, use of the pigment at near to masstone levels is recommended. BON red, used as calcium BON Red (PR 52:1) or Manganese BON Red (PR 52:2), is characterized by outstanding cleanliness, brightness, and purity of color, The manganese salt offers a very blue-shade red with improved lightfastness compared to the calcium salt. As such, this sal is suitable for exterior coatings applications. BON Maroon, (PR 63:1) is illustrated in Figure 78.7; the manganese salt of BON Maroon is of considerably more importance than either the calcium or barium sats, Is lightfastness is such that the pigment can be used at masstone levels for implement finishes, 7834.2 Nonmetallized Azo Reds ‘As implied by ther classification, the nonmetallized azo reds do not contain a precipitating metal cation s such, offer increased stability against hydrolysis in strongly acidic or alkaline environments Synthesis of this cass of pigment follows the previously described classical method of diazotization of a primary aromatic amine followed by coupling of the resultant diazonium salt. No anionic groups capable of accepting a metal cation are present in the molecule; thus metallization is nota factor in theie synthesis. Typical nonmetalized reds are Toluidine Red (PR 3) and the wide range of Napthol Reds as represented by Pigment Reds 17, 22, and 23. “Toluidine Red is used in full shade in such coatings applications as farm implements, lawn and garden equipment, and bulletin paints, where a bright, economical red of adequate lightfasiness is required, Because ofthe pigments poor durability in tint shades, itis rarely used at any level other than a fall shade. ‘The individual properties of the Napthol Reds depend on the specific composition of the product as wel asthe conditioning steps used during pigment manufacture. Asa class, they ae a group of pigments that exhibit good tinctorial properties combined with moderate fastness to heat, light, and solvents. Unlike the metalized azo reds, the Napthol Red are extremely resistant to acd, alkali, and soap. These properties lead to their use in latex emulsion systems and masonry paint. In terms of performance and economic characteristics, the Napthols form a link between the toluidine reds at the lower end of the scale and the perylene and quinacridone reds atthe higher end 783.43 High Performance Reds Pigments for the exacting standards of today’s automotive coatings are required to show satisfactory durability to outdoor exposure in such states as Arizona and Florida for 2 and possibly 5 years before being approved for use in automotive finishes. Similar requirements are placed on pigments chosen for use in automotive repair systems and marine coatings FIGURE 787 BON maroon, ©2009 Tyr Ar Gap.78-12 Coatings Technology Handbook, Third Edition COO FIGURE 788. Structure of trnslinear quinac High performance reds fall into four basic clases: quinacridone reds and violets, reds based on vat dyestuffs known to include the perylene reds, eds derived from the benzimidazolone diazonium salts, and the disazo condensation reds. 78.3431 Quinacridone Reds Quinacridones may be described as heterocyclic pigments in that their structure comprises a fused ring structure in which the ring atoms are dissimilar. Inthe case of quinacridones, the ring atoms are carbon. and nitrogen (Figure 78.8). Addition of differing auxochromiec groups such as methyl (—CH,) and. chlorine (—Cl) gives Pigment Red 122 and Pigment Red 202, respectively. ‘The two most commercialized routes in the synthesis of quinacridone (PV 19) involve either the oxidation of dihydroquinacridone or the cyclization of 2,5-diarylaminoter-ephthalic acid as outlined in Figure 78.9, Subsequent conditioning leads to the desired ceystal modification, Use of 2,5-diarylamino- ‘A. cyclization of 2, 5-diarylaminotorephthalic Acid CH,COOC;Hs (i) cyclization a | Ts ante CH,CO0C;H, fi) oxidation “oe 8,050 n can in Polyphospore Acid * é. N sovaietanysonimetim CLIO 4 é 4,000, cH.—Cooc.H, o 000M, cH.—Cooc.H, Hoog, n€ ° NSH c, OCT sm 8 " ‘quinacridone FIGURE 789 Routes to quinacridone.Organic Pigments 78-13 ‘TABLE 78.5 Types of Quinacridone (Colour tndex Name Hue Comments Pow Gold {Quimacridone quinone Pow Deep Gold Quinterdone quinone PR 122 Magent-yellow — 29-Dimethy quinaridone PRI Red-yllow UUnsymmesizal monomethyl quinscridone PR 202 Magenta-biue —29-Dichloroquinscridone PR 206 Maroon ‘Mined solid solution PR 207 Seale 4A1-Dichloraguinacridone PR 209 Yllow-shade ed 3,10-Dichloraquinacridone pv Violt-blue B-Quinaridone Redeyllow ——_“+-Quinaerdone pve Maroon Mined solid solution terephthalic acid at the cyclization stage yields the unsubstituted trans linear quinacridone. Use of 2,5 ditoluidinoterephthalic acid yields the 2,9-dimethyl quinacridone, Pigment Red 122. ‘As a group of high performance pigments, quinacridones find their primary uses in automotive finishes, both metallic and solid shades, industrial finishes, and exterior finishes. ‘The pigments combine excellent tinctorial properties with outstanding durability, solvent fastness, lightfastness, heatfastness, and chemical resistance. Table 78.5 lists the shades currently available. 783432 Vat Reds ‘The red pigments, based on anthraquinine, include such structures as Anthraquinone Red (PR 177), Perinone Red (PR 194), Brominated Pyranthone Red (PR 216), and Pyranthone Red (PR 226), as ilustrated in Figure 78.10, ‘These anthraquinone-derived pigments are manufactured via a series of complex reactions to include such processing as sulfonation, nitration, halogenation, condensation, and substitution 783433 Perylene Reds Perylene reds provide pure, transparent shades and novel styling effects when used in metallic finishes. ‘These pigments offer improved flow characteristics when used in highly pigmented coatings formulations such as those required for high solids base coatclear cost systems, as well as high transparency and good. bleed resistance ‘The perylenes possess high color strength, good thermal stability, excellent light- and weatherfastness , with the exception of Pigment Red 224, excelent chemical resistance. Perylenes may also he described as vat pigments and in fact are the only class of vat pigments to be specifically developed as pigments rather than as dyestuls. Almost all the perylene pigments have a structure as shown by the generic formula illustrated in Figure 78.115 that is they are based on NN: substituted perylene-34,9,10-tetracarboxylic diimide. A notable exception is Pigment Red 224 (Figure 78.12), which is actually derived from the perylene tetracarboxylic dianhydride. "Acenaphthene is oxidized to 1,8-naphthalic anhydride followed by ammonation to yield the naphthal- imide, The napthalimide is condensed in a fused caustic medium to yield the perylene-3,4,9,10-tetracar- boxylic acid diimide. The diimide can then be conditioned to convert the etude into pigment and achieve Pigment Violet 26, or methylated to give Pigment Red 179, “The diimide may be hydrolyzed to produce the dianhydride, Pigment Red 224, or condensed with various aromatic of aliphatic amines to give such pigments as those featured in Figure 78.13. As with, ‘many of the pigments already described, the perylenes have to be conditioned to obtain the compounds in a pigmentary form. 783434 Thioindigo Reds ‘The thioindiogoid chromophore serves as a nucleus for a wide range of red to violet pigments. The thioindigo reds include Pigment Reds 36, 87, 88, 181, and 198. These pigments are noted for their ©2009 Tyr Ar Gap.78-14 Coatings Technology Handbook, Third Edition Pyranthrone Red (PR 226) FIGURE 7810 Structure of translinearquinacridone brightness of shade and all-around good fastness properties. These properties have resulted in the use of the thioindigoes in quality coatings; Pigment Red 88 isthe prime pigment, followed by Pigment Red 198. 783433 Bensimidazolone-Based ‘The benzimidazolone pigments feature Pigment Reds 171, 175, 176, 185, and 208, These pigments are azo-based compounds that contain the benzimidazolone structure as part of their coupling component. ‘Although used primarily forthe coloring of plastics because oftheir outstanding thermal stability, this class of pigments does find application in the coatings industry. Benzimidazolones show excellent fastness to light, good weatherability, and excellent fastness to overspraying at elevated temperatures, The benz: imidazolone pigments are prepared using the diazotization and coupling techniques described earlier Generally, after the coupling process, the pigment is treated to obtain a uniform, controlled crystal growth and particle size distribution,Organic Pigments 78-15 a Q5Q é OOS, R=-C,H0C.H, A123. Vermition R=-CiHy(CHs)2 PR 149, Scarlet R=-CHy R179. Maroon R=-C4H,0CH, PR190 Red Ro-H PBr26 Bordeaux R=-C4H,Cl PA 189. Yellow Shade Red =n PRI78 Red FIGURE 7811 Perylene structures FIGURE 7812. Pigment Red 4 OLN LO 9 Pe > Naphthatimige ‘Typical Perylene Structure NaOH fusion faci 8 ° HN NH NH, é > Parylene -3, 4,9, 10-Tetracarboxylic N80 ‘Acid diimige Pigment Red 224 FIGURE 7813 Perylene synthesis,78-16 Coatings Technology Handbook, Third Edition HQ CO-NH-R-NH-CQ OH one) Ree A A cr or Red MW. 6285 a or Red wt, 263 a cH, FIGURE 7814 Structures of the disazo condensation reds. 78.3436 Disazo Condensation Reds ‘These pigments feature such properties as high tinctorial strength and fastness to solvents and heat. Disazo condensation reds have found considerable use as replacement pigments for lead containing pigments, ‘Their outstanding fastness properties have resulted in their use in high quality industrial finishes. sure 78.14 illustrates three typical structures of the disazo condensation reds. Colour Index names for these three pigments have not been assigned, The synthesis sequence generally is similar for each of the disazo condensation pigments. The azo components are initially coupled to yield monoazo dyestutl carboxylic acids, which are converted to acid chlorides before final conversion to the disazo by conden- sation with the arylide component to yield the pigment in question, 78.3437 Miscellaneous High Performance Reds In recent years a number of novel high performance reds have been commercialized by such companies as Sandoz and BASF. New from Sandoz are Pigment Reds 242, 214, and 257. Pigment Red 242 is shown in Figure 78.15. The product i a yellow-shade red with a clean bright shade and very good all-around fastness properties. I is recommended for lead-free coatings formulations for the production of high quality finishes and bright red shades. y N } d . 2 FIGURE 7815. Structure of Pigment Red 242.Organic Pigments 78.17 7 ci of of O N ; \ ft N Hi Ho. NH. Ne ¢ FIGURE 7816 Structure of Pigment Red 214 o a. 7 or Sor FIGURE 78.17 Structure of Pigment Red 257. Pigment Red 214 (Figure 78.16) is a bluish red with properties similar to those of Pigment Red 242. Pigment Red 257 (Figure 78.17) isa nickel complex pigment witha red violet masstone anda magenta undertone; is fastness properties are similar to those of the quinacridone pigments 78.3.5 Organic Yellows Yellow pigments can be subdivided into four broad classifications based on their chemical constitution, ‘These classifications are comprised of monoarylide yellows, diarylde yellows, benzimidazolone yellows, and heterocyclic yellows. 78.3.5.1 Monoarylide Yellows Monoarylide yellows are all azo pigments; their manufacture is based on the diazotization procedure, followed by coupling. The structures ofthe major monoarylide yellows are represented in Figuse 78.18, ‘Pigment Yellow 1 is often referred to as Hansa Yellow G for historical reasons. This pigment is a bright yellow that finds outlets in trade sales, emulsion, and masonry paints. The pigment’s major drawbacks ae its poor bleed resistance, poor lightfastness in tint shades, and markedly inferior bake. ‘Pigment Yllow 3, referred to as Hansa Yellow 10G, isa pigment that is considerably greener and cleaner than Pigment Yellow 1. The pigment finds a market in trade sales, water-based emulsions, and masonry paints. The pigment suffers from the same deficiencies of poor bleed resistance and poor tint lightfastness exhibited by Pigment Yellow 1. Pigment Yellow 3 s, however, suitable for exterior use at high tint strength, ‘Pigment Yellow 65 is a monarylde yellow that finds use in trade sales, latex, and masoney paints. The pigment offersa lightfastness in fll shade of 7 and 6-7 in tint, a considerable improvement over Pigment Yellow 1 ‘Pigment Yellow 73s pigment close in shade to Pigment Yellow 1 which again finds use in trade sales, latex, and masonry paints. Its not, however, considered to be durable enough for exterior applications.78-18 Coatings Technology Handbook, Third Edition foo goo CH go, M0 say He oO pre ony endanger) 3 Noe q fe ogo, 80 Frea0e niga mr Opes enbicC)-o ‘obH 8 OCH: #5 coc 80 gos goo pres wor Greening) pve oCprnendinen mC Nr cocty "a6 Cott, wr oOpnm eng) erie Grice Op meen coh FIGURE 7818 Monoarylide yellow structures Pigment Yellow 73 plays an important role in interior, intermix systems because of its stability against recrystallization in the presence of glycols and wetting agents as used in aqueous systems, ‘Pigment Yellow 74 offers the user a pigment that is suitable for outdoor applications and considerably stronger and somewhat greener than Pigment Yellow 1. Again usage in trade sales, latex, and masonry paints is widespread. ‘Pigment Yellow 97 isa newer pigment that shows the advantages associated with a smaller particle size, less agglomeration, and an improved particle size distsibution when compated to the other monoarylide yellows. Pigment Yellow 97 gained significant use in trade sales applications primarily because it was available when demands for lead-free formulations were increasing, Additionally, the pigment finds use in high quality decorative paint ‘Pigment Yellow 98 isa pigment that has met with only limited commercial success to date. The pigment is similar in shade to Pigment Yellow 3 but is considerably stronger and mote heat stable; it finds use in trade sales, masonry, and latex-based paints ‘Pigment Yellow 116 is a pigment similar in shade to light chrome yellow (PY34). Pigment Yellow 116 exhibits improved chemical resistance compared to the other monoarylide yellows, showing improved fastness to solvent, heat, and light. Its major area of use is currently in the formulation of lead-free coatings In summary, the monoarylide yellows constitute the most important dass of organic yellows as consumed by the coatings industry. Because of the absence of any lake forming groups (e.g, COOH 'SO,H) in thei structure, they possess excellent alkali fastness, which enables them to be used in all ‘major aqueous paint formulations. Additionally, when compared to their inorganic lead containing counterparts, the chrome yellows, the monoarylides offer considerably higher tinting strength, bright yellow hue of high chrome, and less tendency to darken on exposure to atmospheric pollutants. 78.3.5.2 Diarylide Yellows Figure 78.19 illustrates the structure of the diarylide yellows, and Table 78.6 presents a summary of the properties ofthis class of yellows. ly, an inspection of the structures indicates that this class of yellows has a backbone structure that hinges on 3,3-dichlorobenzidine with properties that differ depending on the nature ofthe coupling component. Properties that are common features of this group of yellows are low cost, reasonable heat stability, and moderate chemical resistance ©2009 Tyr Ar Gap.Organic Pigments 78.19 FIGURE 78.19 Diarylie yellow structures, ‘The major market for the diarylde yellows is the printing ink industry. The diarylide yellows are approximately twice as strong as the monoarylide yellows; additionally they offer improved bleed resis- tance and fastness to heat. However, none of the diarylide yellows has durability adequate for the pigment to be considered in exterior coatings applications; thus the diarylide yellows should not be used in any outdoor situations 7835.3 Benzimidazolone Yellows Figure 78.20 illustrates the structure of the organic yellows that fall nto the classification of benzimida zolone yellows because each is an azo pigment derived from 5-acetoacetyl-aminobensimidazolone ‘The exceptional fastness to heat and the excellent weatherfastness of this cass of pigments are atributed to the structural presence of the benzimidazolone group. Used initially fr coloring plastics, these pigments are finding increased use in coatings systems, where their excellent weatherfastness, heat stability, and fastness to overstripping are required (e.g, when formulating high quality industrial finishes). Table 78.7 gives a summary of the properties of the benz: imidazolone yellows. 783.54 Heterocyclic Yellows ‘This class of pigments contains an assortment of yellows that all contain a heterocyclic molecule in their structure as presented in Figure 78.21. In spite of the apparent degree of complexity in the synthesis of such structures, these new high performance pigments continue to be introduced into the marketplace78-20 ratings Technology Handbook, Third Edition TABLE 786 Summary of Diaryide Yellow Properties Colour tndex Name ‘Common Name ‘Comments Pre Py py Pv pyr py ss pyar py as PY 106 py pris ard py? py is? AAA Yallow MX Yellow OF Yellow (iT) Yellow NOG 0A yellow (275-0562), Pr Yalow Yellow #106 Yellow HR (295-0570), (295-0050), alow GER. alow HOG Yalow GAR Yellow DER alow GR, Yalow YR ‘oor lights: poor bled resistance; major use in piating inks [Redider shade than PY 12; improved heat stability and solvent fatness; jor se in printing inks {Green shade some us in interior finishes; poor tnt Iighfastnes ‘right green shade: improved heat and solvent iste: used in fll shade or coatings {Green shade some use in interior finishes; poor lightastness Red shade some use in interior Finishes poor lighthstnes omer of PY 14 Bright, econ shade same shade but much stonger than PY 3 ‘Very re shade: improved transparency eat stability andlightfstness over PY 12; some use in interior finishes, Green shade: poor tint lighfastness: major use in packaging inks Very green shade: move transparent than PY 12 and offering better heat and solvent fstnes; some interioe finish use Red shade improved solvent and lightastness over PY 12: major use in ol- based inks Similar shade to PY 12 but offering improved hest and solvent fasness major se in printing inks Bright, ed shade; poor lightfastnss; major use in oe inks Very re, opaque product poor lightfastness some use in atrior fnshes asa ead chrome replacement "Numbers in parentheses are codes used by Sun Chemical Corporation, to full the exact ng demands of the consuming industries. Compounds such as Isoindoline Yellow (PY 139) and Quinophthalone Yellow (PY 138) are particular examples of such complex, novel pigments. All these yellows offer the user additional high performance pigments that find applications in high quality coatings, where the end use can justify the economies of purchasing, Table 78.8 summarizes the properties of these heterocyélic pigments. ©2009 Tyr Ar Gap.Organic Pigments Py. 120 Py.151 Py. 154 Py. 156 PY.A75 78.21 o ct Not NH FIGURE 7820. Benzimidazolone yellow structures. ‘TABLE 78.7 Summary of Benzimidazole Yellow Properties (Colour Index Name ‘Common Name PY 20 prist pr ist PY 156 pris Yalow FBG Yllow HAG Yllow HIG Yellow HLR allow HOG ‘Medium shade; good solvent fase excellent ightastnes used in industeial finishes Greener shade; good solvent fastnss excellent lightness industrial and "sinish applications GGreen shade but redder than PY 151; god solvent fstness; excellent lighfatnes industrial and automotive refinish applications Reader shade; tansparent; good exterior durabliy in fl shade an tn; all ‘eeror coatings and reins applications Very gieenshude; good solvent fstness excellent lightfastness all eerin coatings and reinsh applications78-22 Coatings Technology Handbook, Third Edition o Ps — N—cots Py.60 andy oN I dy ott ay yo a. MOVE ci Py.109 pied cr of No cl a § boa ay a a i 1 pvt Se or of cl ab 7 a ° S a Ae ao A” § 1 evi on Neo BT a 1 ra e 9 Mice oN py.1s0 O= Noonan ‘0 Nnioe Soonn~ So o Ni complex FIGURE 7821. Structure of heterocyclic yellowsOrganic Pigments 78.23 TABLE 784 Summary of the Properties ofthe Heterocyclic Yellows (Colour index Name Common Name/Desciption Comments Pye ‘Asyide Yellow Very ved shade: moderatelightand solvent istnes trade sales latex and masonry pants: good aid and alll astness py 101 Methine Yellow Bright yellow; highly transparent and exceptionally brillant industri finishes and pecaycoatngs only moderate eed and alkali fastness Py 109 “Tetrachloroisoindotine Green shade; exelent brightness strength and durability ‘automotive finishes pur ‘Greenish yellow complex Excellent chemical, ight and heat fatness specialty finishes of an azomethine py i Azomethine Yellow Very green shade; excellent eral fists industrial and specialty coatings Pye Green shade quinophthalone Clean he and exllent overall fatness properties high quality industrial and automotive finishes py Red-shade soindoline Similar in masstoneto medium chrome (PY 34)exallent light and solvent istnes: industrial and automotive coatings Py 50 Pyrimidine Yellow Very green shade good heat and ightfastnes: industrial coatings Pyiss Red-shade Nickel Dione Edllentfasnes propertisspecialty coatings andbaking enamels, poor acid resitunce py iss ‘Azo Condensation Yellow Green shade; exllent overall fasts properties in full shade; industrial and specialty coatings pyar luoindolone Yellow Very green shade; excellent fastnes properties industial and special finishes py ue "TViazny! Yellow Medium shade excellent fasnes properties at masstone evel: industrial fees ©2009 Tyr Ar Gap.