A REVIEW OF THE CLASSES, STRUCTURES, AND

METHODS OF ANALYSIS OF SYNTHETIC ORGANIC

PIGMENTS

SUZANNE QUILLEN LOMAX AND TOM LEARNER

ABSTRACT-Synthetic organic pigments have been TITULO-Revision de las clases, estructuras y

manufactured since the latter part of the 19th century. metodos de analisis de pigmentos organicos sinteticos
Thousands of these pigments have been introduced for RESUMEN-Desde la ultima parte del siglo XIX se
a variety of applications,including paints,printing inks, han fabricado pigmentos organicos sinteticos. Miles
and the coloration of plastics and textiles. Many de estos pigmentos han sido introducidos .en una
synthetic organic pigments are azos,containing the azo variedad de aplicaciones, incluyendo pinturas, tintas
linkage (-N =N -). Newer classes of synthetic organic de imprenta y la coloracion de plasticos y textiles.
pigments have been introduced to overcome limitations Muchos pigmentos organicos sinteticos son azos,
of poor lightfastnessor solventfastness(bleedresistance) contienen el nexo azi (-N=N-). Para superar limita-
exhibited by some of the earlier pigments. This paper ciones de decoloracion por la accion de la luz 0 de los
reviews the major classesof synthetic organic pigments solventes (resistencia al veteado) presentado por
in terms of their structures, physical properties, and algunos de los pigmentos introducidos al principio, se
specific applications. These classes include arylide han introducido nuevas clasesde pigmentos organicos
yellows,diarylideyellows,B-naphthols,naphthols,benz- sinteticos. La monografia revisa las principales clases
imidazolones, disazo condensation pigments, pyra- de pigmentos organicos sinteticos en terminos de sus
zolones, nickel azo yellow, phthalocyanines, estructuras, propiedades fisicasy aplicaciones espedfi-
quinacridones, perylenes and perinones, isoindolinone cas. Estas clases incluyen amarillos arylide, amarillos
and isoindoline pigments, triarylcarbonium pigments, diarylide, naphthols 12-, naphthols, benzimidazolones,
diketopyrrolo-pyrrole pigments, thioindigoids, and pigmentos de condensaci6n disazo, pyrazolones,
several miscellaneous pigments. Current methods of amarillo niquel azo, phthalocyanines, quinacridones,
analysisof these pigments are discussed. perylenes y perinones, pigmentos isoindolinone e
isonindoline, pigmentos triarylcarbonium, pigmentos
TITRE-Une revue des classes,des structures et des DP'p' thioindigoids y varios pigmentos miscelaneos.
methodes d' analyse des pigments organiques de Se discuten los metodos corrientes de analisisde estos
synthese RESUME-La fabrication de pigments pigmentos.
organiques de synthese a debute au cours de la
seconde moitie du dix-neuvieme siecle. Depuis, des TITULO-Uma reVlsao das classes, estruturas e
milliers de ces pigments ont ete crees pour une metodos de analise dos pigmentos organicos sinteti-
variete d' applications. Ils sont utilises dans les encres cos RESUMO-Pigmentos organicos sinteticos tern
d'imprimerie, la peinture et les colorants pour textiles sido produzidos desde finais do seculo XIX. Milhares
et plastiques. Plusieurs de ces pigments organiques de destes pigmentos tern sido utilizados em uma
synthese sont azolques, c' est a dire qu'ils contiennent variedade de aplicas:oes, incluindo pinturas, tintas
une double liaison formee par deux atomes d' azote graficas, e coloras:ao de plasticos e tecidos. Muitos
(-N=N-). De nouveaux pigments organiques de pigmentos organicos sinteticos sao az6icos, contendo
synthese ont ete crees afin de pallier a la faible soli- ligas:oes az6icas (-N = N -). Classes mais novas de
dite a la lumiere et aux solvants des premiers pigmentos organicos sinteticos foram introduzidas a
pigments. Cet article examine non seulement les fim desuperar limitas:oescausadaspela escassezde luz
principales classes de pigments organiques de ou pela perda de solvente (resistencia ao sangra-
synthese selon leurs structures, leurs proprietes men to), exibido por alguns pigmentos introduzidos
physiques et leurs applications specifiques, mais anteriormente. Este trabalho faz uma revisao das
discute aussi des methodes d' analyse les plus principais classes de pigmentos organicos sinteticos
courantes. Les classes de pigments suivantes sont quanto as suas estruturas, propriedades fisicas e apli-
abordees: les jaunes arylide et diarylide,les pigments cas:oes especificas. Essas classes incluem amarelos de
u-naphtol, naphtol, benzimidazolone, pyrazolone, arilida, amarelos de diarilida, beta-naftois, naftois,
jaune de nickel azolque, phtalocyanine, quinacridone, benzimidazolonas, pigmentos da condensas:ao de
perylene et perinone, triarylcarbonium, DPP, thio- disazo, pirazolonas, azo niquel amarelo, fitalocianinas,
indigos, les pigments de condensation diazolque et les quinacridonas, perilenos e perinonas, isoindolinonas e
pigments isoindolinone et isoindoline, ainsi que pigmentos de isoindolinas, pigmentos de triarilcar-
divers autres pigments. bonion, pigmentos do DPP (diceto-pirrolo-pirrol),

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SUZANNE QUILLEN LOMAX AND TOM LEARNER

tioindigoides e vanos pigmentos misturados. Sao Synthetic organic pigments exhibit a wide range
discutidos metodos atuais de analise dessespigmentos. of physical and chemical properties such as lightfast-
ness, heat stability, solubility in water or organic
solvents, reactivity, and stability to recrystallization.
1. INTRODUCTION Usually, synthetic organic pigments within a chemi-
cal class will have similar properties, although this is
The term "synthetic organic pigment" refers to not always the case. Even with a particular pigment,
manufactured colorants that have carbocylic ring different grades can be manufactured to give
skeletons as part of their structure. Many of these ring improved lightfastness or opacity. Many of the early
systems are aromatic in structure, and it is these synthetic organic pigments are not particularly light-
mobile electron clouds that are the chromophores of fast, and their identification on a work of art may
the pigments. A chromophore refers to a characteris- provide information about the work's original
tic group of atoms that serve to impart color. There appearance or raise concerns about its display. In
also may be functional groups present in synthetic addition, since these synthetic organic pigments are
organic pigments that act as auxochromes, functional found in many media, such as inks, textiles, and plas-
groups or atoms that alter the appearance of the tics, in addition to paints, there is concern about their
primary hue. These functionalities include keto, thio, longevity in these media as well. Identification and
nitro, and nitroso groups. Some synthetic organic knowledge of synthetic organic pigments may also
pigments contain a metal ion, but due to the carbon- serve to provide a historical context for a work of art.
based ring system, they are considered organic Throughout this paper, the Colour Index system
pigments. of nomenclature is used (Society of Dyers and
All synthetic organic pigments are true pigments Colourists 1971). Each pigment is given a Colour
and not dyes,and as such are insoluble in the medium Index name (such as Pigment Yellow 1 or PY1), and
in which they are bound. As summarized by the Dry a Colour Index number. The Colour Index number
Color Manufacturers' Association, "Pigments are does convey some information about the chemical
colored, black, white, or fluorescent particulate constitution of the pigment, as certain classes of
organic and inorganic solids which usually are insol- pigments have specified ranges of numbers.
uble in, and, essentially physically and chemically
unaffected by, the vehicle or substrate in which they
are incorporated ... Pigments retain a crystal or partic- 2. HISTORY
ulate structure throughout the coloration process"
(Lewis 2001, 643). The first synthesis of an organic colorant of commer-
Synthetic organic pigments must also be distin- cial note occurred in 1856 when William Henry
guished from natural organic pigments that are Perkin combined aniline, toluidine, potassium dichro-
obtained from plant or animal sources. Some of these mate, and sulfuric acid. Instead of synthesizing the
materials, such as alizarin and indigo, are now synthe- expected quinine, a black solid was produced, which
sized in the laboratory. However, for the purposes of after washing with mineral spirits, dissolved to
this paper, these dyestuffs and pigments will not be produce a purple dye. Perkin obtained a British
considered. The term synthetic organic pigment patent and opened a factory, naming the new dye
refers specifically to those pigments that have no "mauve" in 1859 (Garfield 2000).
counterparts in nature, but are manufactured in a A rush to develop other aniline dyes followed,
laboratory to achieve a specific color or application. and blues, violets, and reds were available beginning
Synthetic organic pigments now dominate the in the 1860s (Ball 2001). These azo dyes were some-
colorant market. These pigments are used in a variety times called coal-tar colors, since compounds from
of applications, including printing and pen inks, coal tar, such as aniline, were used in their manufac-
architectural, industrial, automotive, and artists'paints, ture. Organic pigments began to be manufactured as
and for the coloration of plastics,rubber, and textiles. by-products from the manufacture of dyestuffs,
Synthetic organic pigments span the entire color usually by precipitation of the dyestuff with metallic
range from violet to blue, green, yellow, orange, and salts.These early synthetic organic pigments were of
red.The majority of these pigments are azo pigments, notoriously poor lightfastness,and rapidly achieved a
which are usually yellow;orange, or red. bad reputation. According to Doerner (1984, 90),

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A REVIEW OF THE CLASSES, STRUCTURES, AND METHODS OF ANALYSIS

OF SYNTHETIC ORGANIC PIGMENTS

"their [coal-tar colors'] preCIpItous and ill-advised 3.1 AZO PIGMENTS

introduction into painting was the cause of a great
deal of damage." Azo synthetic organic pigments contain one or
Germany took the lead in the manufacture of more azo linkages (-N = N -).Although represented by
synthetic organic pigments in the late 19th and early -N=N-, studies have shown that most (X-keto azo
20th centuries (Saltzman and Kessler 1991). Many of pigments exist in a ketohydrazone form (fig. 1). Azo
these early pigments were azo pigments, synthesized pigments are among the oldest of synthetic organic
by the diazotization reaction of a diazonium salt and pigments, and span the color range of yellow, orange,
a coupling component. Diazonium salts were discov- and red.
ered by Griess in 1858, and the coupling reaction by
Kekule and Hidegh in 1870 (Boyd 1955). By altering
the coupling component, different classes of synthetic 3.1.1 Arylide Yellows
organic pigments could be created, and by varying
substituents within a class, pigments of different hue The arylide yellows are monoazo pigments that have
and physical properties could be synthesized. The acetoacetarylamide coupling components. Representative
classes of Naphthol AS, B-naphthol pigments and structures of two arylide yellow pigments are shown in
lakes, and the arylide (formerly known as Hansa) figure 2. These pigments were formally known as Hansa
yellows were introduced between 1890 and 1910. yellows, and reflect the name under which PY 1 was
Diarylide yellows and oranges were introduced introduced by Meister, Lucius and Bruning (now
shortly after the arylide yellows. Hoechst) (Lambourne 1987). They are now more
N on-azo synthetic organic pigments were intro- correctly referred to as arylide or monoarylide yellows.
duced beginning in the 1930s with the introduction These synthetic organic pigments have been and
of phthalocyanine blue and green. Quinacridones, continue to be used in paints, colored pencils, drawing
another important synthetic organic pigment class, inks, and crayons. They have historically been used in
were introduced in the 1950s. High performance azo printing inks, although they have mostly been replaced in
pigments, with improved lightfastness and solvent this application by diarylide yellows.Arylide yellows span
fastness compared to traditional azo pigments, were the color range of greenish yellow to reddish yellow;and
also introduced beginning in the 1960s. These the most common members of this classare PY1 (11680),
include the benzimidazolones, azo condensation PY2 (11730), PY3 (11710), PY4 (11665), PY5 (11660),
pigments, and azomethines. PY65 (11740), PY73 (11738), PY74 (11741), PY75
(11770), PY97 (11767), PY98 (11727), and POl
(11725). Arylide yellows that also contain a pyrazolone
3. CLASSES OF SYNTHETIC functionality (fig. 2) include PYI0 (12710), PY60
ORGANIC PIGMENTS (12705), and P06 (12730). Historically; the two most
important members of this classin artists' paints are PY 1
A number of researchers have published general and PY3. PY1, commonly called HansaYellow G,became
information either devoted to or containing informa- commercially available in 1910, while PY3, commonly
tion on classes of synthetic organic pigments. These called HansaYellow lOG, was commercially introduced in
include Herbst and Hunger (2004), Christie (1993), 1928 (Lewis 1988a).
Lewis (1988a, 1988b), and de Keijzer (2002). Herbst Arylide yellows have good, but not exceptional
and Hunger's Industrial Organic Pigments (2004) is an lightfastness, especially in masstone (Keay 1977;
extremely comprehensive text containing specific Louisville Society 1975). Masstone refers to a color
information on more than 350 individual synthetic that is dispersed full-strength in a binder. PY3, PY65,
organic pigments. The three volumes of The Pigment PY73, PY74LF, and PY97 are listed as suitable
Handbook (Patton 1973a, 1973b; Lewis 1988b) pigments for use in oil, oill resin, and alkyd media by
contain sections on numerous classes of synthetic ASTM (1995). Arylide yellows characteristically have
organic pigments. Rolinson (1987) has also summa- high solubility in most solvents except aliphatic
rized different organic and inorganic pigments by hydrocarbons, a function of their low polarity and
class. A summary of the different classes of pigments relatively low molecular weight. PYl and PY3 are
presented in this paper is shown in table 1. very soluble synthetic organic pigments, resulting in
bleeding and blooming.

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SUZANNE QUILLEN LOMAX AND TOM LEARNER

Table 1. Classes of Synthetic Organic Pigments

Pigment Class Structure Characteristics Dates of Use Major Uses Important members

Arylide Yellows monoazo pigments with good lightfastness. poor ftrst commercialized artists' paints PY1, PY3, PY73, PY74
acetacetarylamide coupling solvent fastness 1910 PY75.PY98
components

Diarylide Yellows disazo pigments, products of not as lightfast as arylide fIrst patented 1911 printing inks P016. PY12, PY14,
and Oranges 3-3'-dichlorobenzidine yellows. more solvent fast not widely used PY55. PY126, PY127
until 1930s

~-Naphthol monoazo pigments with may be neutral or salts. PRl introduced in 1895, printing inks, artists' PR3, PR4. PR48, PR 49,
~-naphthol coupling not good fastness most others introduced materials PR52, PR53, PR57,
component properties in early 1900s PR63

Naphthol Reds monoazo pigments, derivatives good lightfastness ftrst synthesized in automotive. architectural PR2, PR7. PR9, PR112.
of2-hydroxy-3 naphthoic acid 1911 and artists' paints PR146, PR170, PR253.
PR256

Benzimidazolones monoazo pigments with good lightfastness. ftrst patented 1960s automotive, artists' paints, P036, P060, P062,
the 5-aminocarbonyl good solvent fastness printing inks PR175, PY154. PY175
benzimidazolone grouping

Disazo Condensation disazo pigments with aromatic excellent lightfastness, flrst patented 1950s automotive, artists' paints, PBr23. P031. PR214,
diamino carbonarnide linkage excellent solvent fastness plastics PR242. PY128. PY166

Pyrazolone mono or disazo pigments, good lightfastness, first pigment introduced artists' paints, printing POB, P034, PR37.
contain the pyrazolone ring reasonable solvent fastness in 1884 inks, plastics PR38,PR41

Nickel Azo Yellow metallized azo pigment excellent lightfastness developed 1945 automotive and artists' PG10
paints

Phthalocyanines metal porphyrins excellent lightfastness, blues introduced 1935 automotive and artists' PB15. PB16,PG7,
excellent solvent fastness greens 1938 and 1959 paints, plastics, textiles PG36

Quinacridones based on linear trans excellent lightfastness. introduced in 1955 automotive and artists' P048, P049, PR206.
quinacridone excellent solvent fastness paints. plastics, textiles PR207, PR209, PV19

Pery lene/Perinone Diimides of perylene tetra- excellent lightfastness, introduced 1950 automotive, industrial and P043, PR149. PR178,
carboxylic acid (perylenes). excellent solvent fastness artists' paints, plastics PR179, PR194. PR224
napthalene-l.4,s.8-tetra
carboxylic acid (perinones)

Triarylcarbonium Ion triary1carbonium cations with moderate lightfastness patented 1913 printing inks PR81 , PV3, PV27
complex anions

Isoindolinone and contain the isoindoline ring excellent lightfastness, introduced mid 1960s automotive and industrial P061, P066, P069
Isoindoline excellent solvent fastness paints PY109. PY110. PY130

Diketopyrrolo-pyrrole based on 1,4-diketopyrrolo excellent lightfastness, introduced 1980s automotive and artists' PR254
(3,4c)pyrrole ring system excellent solvent fastness paints, plastics

Thioindigo structurally related to indigo excellent lightfastness. ftrst discovered 1907 automotive and other PR88
excellent solvent fastness paints, plastics. textiles

Dioxazine Violet dioxazine type structure excellent lightfastness, fIrst synthesized 1928 automotive and artists' PV23
moderate solvent fastness patented as pigment 1952 paints, plastics, inks

Indanthrone Blue from oxidative dimerization of excellent lightfastness, introduced in early 1950s automotive and artists' PB60
2-aminoantbraquinone excellent solvent fastness paints, plastics. inks

Flavantbrone Yellow polycyclic pigment darkens on light exposure introduced in early 1950s automotive and artists' PY24 (formerly PY112)
paints. wood stains.
plastics

3.1.2 Diarylide Yellows and Oranges

Diarylide yellows and oranges are disazo products

0 of 3,3' -dichlorobenzidine with two equivalents of
acetoacetarylide. A representative structure is shown
):~ .....
H
N-N in figure 3. Although the first diarylide was patented
'" in 1911 (Herbst and Hunger 2004), they were not
Fig. 1. Hydroxyazo-ketohydrazone tautomerism, an isomer- widely used as pigments until the 1930s. The delay
ization found in many azo pigments was due to the simultaneous introduction of the more

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A REVIEW OF THE CLASSES,STRUCTURES, AND METHODS OF ANALYSIS

OF SYNTHETIC ORGANIC PIGMENTS

a) Though they have about twice the tIntIng

strength of the arylide yellows, diarylide yellows are
not as lightfast. However, the diarylide yellows have
better heat and solvent fastness;the increased solvent
fastness is primarily due to their higher molecular
weight. PY12 and PY14 are the two most widely
used synthetic organic pigments in this class and
PO 16 is the only commercially important orange in
this class.PY12 is commonly called Benzidine Yellow,
while PY14 is often referred to as Diarylide Yellow
AAOT. These pigments do not have widespread use
in paints.

b) 3.1.3 B-Naphthol Pigments

The B-naphthol pigments are a group of red azo

pigments, which encompass a large percentage of
synthetic organic red pigments. The B-naphthol
pigments are based on the coupling of a substituted
aniline with B-naphthol (fig. 4), and are among the
oldest of synthetic organic pigments. They are rela-
tively inexpensive pigments, and their color ranges
from yellowish orange to bluish red. B-naphthol
Fig. 2. Structure of arylide yellow pigments, showing pigments are of relatively low tinting strength and are
members of the two main types: a) PY1, (acetoacetic arylide not extremely solvent fast.
type), and b) PY10 (pyrazolone type) These synthetic organic pigments may be neutral
species or may be salts formed from sulfonate or
lightfast arylide yellows. Currently, the diarylide
carboxylate groups. The neutral pigments include
yellows are widely used pigments in the printing ink
PRl (12070), PR3 (12120), PR4 (12085), PR6
industry. They are the largest group by volume of
(12090), P02 (12060), and P05 (12075). The B-
synthetic organic yellows. Diarylide yellows range in
naphthol salts (sometimes called lakes) include the
color from greenish to reddish yellow: Important
BON pigments (see definition below): PR48
members of this class include PY12 (21090), PY13
(21100), PY14 (21095), PY16 (20040), PY17 (21105),
PY55 (21096), PY81 (21127), PY83 (21108), PY106
(21102), PYl13 (21126), PYl14 (21092), PY126
(21101), PY127 (21102), PY152 (21111), P014 CI~
(21165), P015 (21130), P016 (21160), and P034
(21115). PY16 and PY155 (200310), which are disazo
yellow pigments, have a slightly different structure
than other members of this class,and can be referred
to as bisacetoacetarylide pigments.
+ HCI

R == H, N02, CH3, CI

Fig. 4. Coupling reaction to form B-naphthol pigments. The

Fig. 3. Structure ofPY12, a commonly used diarylide yellow diazonium salt generated in situ is reacted with B-naphthol
pigment to form the synthetic organic pigment

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SUZANNE QUILLEN LOMAX AND TOM LEARNER

(15865), PR52 (15860), PR52:2 (15860:2), PR57 o

(15850) and PR63 (15880), and the non-BON
pigments PR49 (15630), PR53 (15585), PR60 HO
o
(16105), and P046 (15602).
P05 (dinitroaniline orange), first patented in
1909 (Lewis 1988a), is an extremely widely used
H
3
C)C(N"N Ca++
orange synthetic organic pigment. It does not have
CI 803-
outstanding lightfastness and has a tendency to bleed
in certain solvents. It is used extensively in latex-
Fig. 5. Structure of PR52:1 (BON Lake Red), an example
based paints (Lewis 1988a) and in printing inks. P02 of a B-naphthol pigment
(orthonitroaniline orange), first patented in Germany
in 1895 (Lewis 1988a), is used in the printing ink discovered in 1910, it did not have extensive use as a
industry. pigment until the 1950s (Lewis 1988a). PR63 (BON
PR3 (toluidine red), first patented in 1905 (Lewis maroon), patented in 1907 (Lewis 1988a), exists with
1988a),was at one time an extremely widely used red a variety of cations, the most important being
synthetic organic pigment. It has poor lightfastness in manganese and calcium. PR49 (lithol red) is a
tint and poor resistance to a variety of organic synthetic organic pigment first prepared in 1899
solvents including esters and ketones. It is used (Lewis 1988a). It is usually sold as the calcium or
primarily for industrial coatings. PRl (para red) was barium salt, which are bright red pigments with fair
the first azo red pigment synthesized in 1895 (Lewis lightfastness at masstone and poor lightfastness in tint.
1988a). It is an intense, bluish red pigment, with poor PR53 (red lake C), first prepared in 1902 (Lewis
lightfastness and poor resistance to solvents.The chlo- 1988a), is a yellowish red pigment used extensively in
rinated para reds include PR 4 (chlorinated para red) the printing ink field. It is also found in inexpensive
and PR6 (parachlor red). These two isomeric colored pencils and paints. P046 (Clarion Red), is a
pigments were first manufactured in the early 1900s chemically related structure and has poor solvent fast-
(Lewis 1988a). The lightfastness of both of these ness and lightfastness. PR60 (pigment scarlet) has
pigments is unsatisfactory in tints and they are both moderate lightfastness and is used in the printing ink
sensitive to solvents.PR 4 has been used extensively in industry and for the coloration of plastics.
artists' materials, including paints, colored pencils, and
wax crayons.
The BON pigments were so named because of 3.1.4 Naphthol Reds
the use of the coupling component BON (3-
hydroxy-2-napthoic acid-beta-oxynaphthoic acid). The Naphthol Reds are a large class of red azo
This acid has been used as a coupling component pigments, and are also called the Naphthol AS
since 1893 (Herbst and Hunger 2004). PR57 (lithol pigments. The AS means that they are derivatives of
rubine) is a salt first prepared in 1903 (Lewis 1988a). 2-hydroxy-3-naphthoic acid (fig. 6), where AS stands
The most common form is the calcium salt, and this for Amid einer Saure. Naphtol AS is the trade name
blue-shade pigment has a high tinting strength and is of these syntheJic organic pigments as sold by
used mostly in industrial finishes. PR57 has poor

(r"NSA
lightfastness but good solvent resistance, and is used

~ ~*.
R ~ I.
extensively in the printing ink industry.
N H R
PR48 (Permanent Red 2B) is made with a
number of different counter ions, including barium, j
R~ HO I
calcium, and manganese.They were introduced in the R 0 h R
1920s (Lewis 1988a), and are used mostly for indus- R
trial coatings. PR52:2 (Yellow BON Maroon), a
R = H, CI, CH 3, OCH3, OC2Hs, N02, NHCOCH3, S02N(C2Hsh,
manganese salt, is a relatively lightfast BON pigment.
CONHPh, C02CH3
PR52 (BON Lake Red, but also known as Red 2G)
is usually produced as a calcium or manganese salt Fig. 6. General structure of Naphthol AS pigments. The
(see structure in fig. 5). The manganese salt is of coupling component of these pigments is the anilide of 2-
excellent lightfastness in masstone. Although first hydroxy-3-naphthoic acid.

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A REVIEW OF THE CLASSES, STRUCTURES, AND METHODS OF ANALYSIS

OF SYNTHETIC ORGANIC PIGMENTS

Hoechst AG. These pigments are referred to

Naphthol AS pigments in the United States.
The original method for the synthesis of these
pigments was discovered in 1911 in Germany (Herbst
and Hunger 2004).These pigments were initially called
Grela Reds, and there are no common names for
members of this class. Important members of this
group include: PR2 (12310), PR5 (12490), PR7
(12420), PR8 (12335), PR9 (12460), PR10 (12440),
PRll (12430), PR12 (12385), PR13 (12395), PR14
(12380), PR15 (12465), PR16 (12500), PR17 (12390),
PR18 (12350), PR21 (12330), PR22 (12315), PR23
(12355), PRl12 (12370), PRl14 (12351), PR146
(12485), PR147 (12433), PR170 (12475), PR187
(12486), PR188 (12567), PR253 (12375), PR256
(124635), and PR258 (12318).They are an extremely
important classof synthetic organic pigments, and they Fig. 7. Structure of benzimidazolones, showing representa-
vary in hue from yellowish to bluish red. A number of tive members of the two main types: a) PY151 (yellow and
the pigments exist in multiple crystalline forms. orange series), and b) PR175 (red and brown series)
The lightfastness of the Naphthol Reds is supe-
rior to that of the B-naphthol class,but not as good as (13980), PY154 (11781), PY156, PY175 (11784),
other red pigments such as the quinacridones. They PY180 (21290), PY181 (11777), and PY194 (11785);
are, however, synthetic organic pigments of high tint- the oranges: P036 (11780), P060 (11782) and P062
ing strength, and their cost is much less than the (11775); and the reds:PR171 (12512), PR175 (12513),
quinacridones. They have been used in automotive, PR176 (12515), PR185 (12516), and PR208 (12514).
architectural and artists' paints, and for the coloration Benzimidazolones have excellent lightfastness
of plastics. Members of the class that have an addi- properties and excellent resistance to solvents (Lewis
tional amide functionality on the diazo grouping have 1988a). They are much more lightfast than represen-
improved lightfastness. These members include tative arylide or Naphthol AS pigments.
PR170, PR187, and PR188. The carbonamide group Benzimidazolones vary substantially in their tinctor-
also improves solvent fastness,as does the sulfonamide ial strength (Herbst and Hunger 2004). Although
grouping (found on PR5, PR253, and PR258). many of these synthetic organic pigments are poly-
morphic, only one crystalline form is typically
marketed. They are extremely stable pigments and are
3.1.5 Benzimidazolones used in automotive and artists' paints, especially
PY154, PY175, PR175, P036, P060, and P062.
The benzimidazolones are a class of yellow, Benzimidazolones are also used for the coloration of
orange, and red synthetic organic pigments that were plastics and for high grade printing inks.
first patented in the 1960s (Hunger 1988). They are
characterized as containing the 5-aminocarbonyl
benzimidazolone grouping (fig. 7). This functionality 3.1.6 Disazo condensation pigments
imparts significant lightfastness. Benzimidazolones are
of two general structures: the Hansa type and the Disazo condensation pigments are a class of
Naphthol AS type. The Hansa types are derived from synthetic organic pigment first synthesized in the
acetoacetarylamides while the Naphthol AS are 1950s by Ciba (Herbst and Hunger 2004), which
derived from 2-hydroxy-3-naphthoic acid anilide. became available in the United States in 1960. As a
The Hansa type spans the color range from greenish- class,they were manufactured purposely to be of high
yellow to orange, while the Naphthol AS types are molecular weight, thereby reducing their solubility.
red and violet. The yellows were not commercially They are composed of two monoazo units that are
introduced until 1969 (Lewis1988a). Members of this connected by an aromatic diamino carbonamide link-
class include the yellows: PY120 (11783), PY151 age (fig. 8). Red disazocondensation pigments are of

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SUZANNE QUILLEN LOMAX AND TOM LEARNER

the Naphthol AS type, derived from 2-hydroxy-3- a)

naphthoic acid anilide, while yellow disazo condensa-

tion pigments are of an arylide yellow type, derived
from acetoacetarylamides. Important members of this
class include PY93 (20710), PY94 (20038), PY95
(20034), PY128 (20037), PY166 (20035), P031
(20050), PR144 (20735), PR166 (20730), PR214
(200660), PR220 (20055), PR221 (20065), PR242
(20067), and PBr23 (20060). No members of the class
are known by common names.
b)
Disazo condensation pigments have excellent
fastness to solvents, good heat resistance, and excellent
lightfastness (Richter 1979). These pigments are
expensive to manufacture, and are usually used in Cl
high-end applications including the plastics industry,
and also for automotive, industrial, architectural, and
artists' paints.
Fig. 8. Structure of disazo condensation pigments, showing
representative members of the two main types: a) PYl28
3.1.7 Pyrazolone Pigments (yellow series), and b) PBr23 (orange/red/brown series)

The pyrazolone pigments encompass two general

structural types-the arylide yellow type and the
disazo type (Shapiro 1988). The arylide type uses the
acetoacetylanilide of an arylide as a heterocycle. The
disazopyrazolones are more similar in structure to
diarylide pigments, but they incorporate a pyrazolone
ring. Pyrazolone pigments span the color range of
yellow, orange, and red. The structure of pyrazolone Fig, 9. Structure ofPOl3, pyrazolone orange
pigment P013 is shown in figure 9. The first pyra-
zolone pigment was PYI00 (tartrazine yellow),' a 3.1.8 Nickel Azo Yellow
pyrazolone lake, first manufactured in 1884 (Herbst
and Hunger 2004). It has been used as a pigment and Nickel azo yellow (PGI0, 12775) is a very green
also as a food colorant (FD&CYellow No.5). shade of yellow. It was developed in 1945 by two
Many pyrazolone pigments have been intro- DuPont researchers, Woodward and Kvalnes (Lewis
duced, but only a few are commercially important 1988a), and was commercially introduced in 1947.
today. These include P013 (21110), P034 (21115), The structure of nickel azo yellow is shown in figure
PR37 (21205), PR38 (21120), PR41 (21200), and 10. It is an extremely lightfast pigment, although it
PR 111. Pyrazolones have good lightfastness and does not have an extremely high tinting strength.
reasonable solvent fastness.The exception is PYI00, Nickel azo yellow has good solvent resistance and is
which has poor solvent fastness, and lightfastness used in automotive and artists' paints and for the
similar to the diarylide yellows. P013, known as coloration of textiles.
pyrazolone orange in the United States, is widely
used in artists' paints. It was first introduced in 1910
(Lewis 1988a) and is used in printing inks due to its 3.2 NON-AZO PIGMENTS
excellent solvent fastness.P034 is also used in print-
ing ink applications and for the coloration of plastics.
3.2.1 Phthalocyanines

Copper phthalocyanines are the predominant

blue and green organic pigments used in artists' paints

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OF SYNTHETIC ORGANIC PIGMENTS

Fig.10.StructureofPG10, nickelazo yellow Fig. 11. Copper porphyrin ring systemof phthalocyanines.
As shown,the pigmentis copperphthalocyanineblue.

as well as in the coloration of plastic and printing inks. pigment. The unmetallized phthalocyanine is known
In 1988, these synthetic organic pigments represented as PB 16 and exists in an unstable ex form.
more than fifteen percent of the organic pigment The phthalocyanine greens vary from blue-green
market (Smith 1988). Half of the halogenated to yellow-green. The shade is a function of the degree
phthalocyanine green pigments are used in the paint of halogenation. PG7, the chlorinated pigment is a
industry (Pascoe 1988). Unhalogenated copper green-blue while PG36, the chlorinated and bromi-
phthalocyanines are blue whereas halogenated copper nated phthalocyanine is yellow-green. The phthalocya-
phthalocyanines are green. This pigment classincludes nine greens do not exist in multiple crystalline forms.
the metallized blues PB15 (74160), PB15:1, PB15:2, As evidenced by their widespread use, the copper
PB15:3, PB15:4, PB15:5, PB15:6; the unmetallized phthalocyanines have outstanding lightfastness, heat
blue PB 16 (74100); the chlorinated copper phthalo- stability,and solvent resistance.The ASTM (1995) lists
cyanine PG7 (74260); and the chlorinated and bromi- PB15, PB16, PG7, and PG36 on their list of suitable
nated copper phthalocyanine PG36 (74265). pigments for use as artists' materials.
Copper phthalocyanines are organometallic
compounds with a porphyrin ring structure (fig. 11).
Their name derives from their origin (a phthalic 3.2.2 Quinacridones
compound) and their color (cyan, or bluish green).
Copper phthalocyanine was patented by the Scottish Quinacridones are polycyclic synthetic organic
Dye Works in 1929 (British Patent 322,169, cited in pigments that span the color range of gold, orange,
Dahlen 1935), and the pigments were commercially maroon, scarlet, red, magenta, and violet. This
introduced in 1935.The firstchlorinated phthalocyanine pigment classincludes P048, P049 (564800), PR122
was prepared in 1938, and the first bromochloroph- (73915), PR192 (739155), PR202 (73907), PR206
thalocyanine was commercially introduced in 1959 (US (73903, also mixture of 73900 and 73920), PR207
Patent 2,247,752, cited in Lenoir 1971). (73904, also mixture of 73900 and 73906), PR209
The parent phthalocyanine blue exists in five (73905), PV19 (73900), and PV42. Quinacridones
crystalline polymorphs. In general, available forms of have been prepared in four different forms (two
the pigment are either the ex or the B. These forms angular and two linear), but it is only the linear trans
can be unstabilized, or stabilized to flocculation. form that is of commercial importance.
PB15:1 is the stabilized ex copper phthalocyanine, The name quinacridone derives from an assumed
while the noncrystallizing, nonflocculating stabilized reaction product of a quinoline and an acridine
ex copper phthalocyanine is PB15:2. PB15:3, a residue. The history of this pigment class has been
turquoise blue, is the unstabilized B copper phthalo- summarized by de Keijzer (1990). The first linear
cyanine. Since the B form of copper phthalocyanine trans-quinacridone was reported by Liebermann in
has a tendency to flocculate; the nonflocculating 1935, and Struve of DuPont recognized the commer-
stabilized B copper phthalocyanine is PB15:4. The E cial importance of quinacridones as pigments in 1955
modification, marketed as PB15:6, is a reddish blue (Liebermann 1935). About 3,400 tons of

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SUZANNE QUILLEN LOMAX AND TOM LEARNER

quinacridone pigments are manufactured yearly Gaffe PR224 (71127), and PV29 (71129). Perylenes are used
2002). The parent linear trans-quinacridone is the in automotive, industrial, and artists' paints, and for the
pigment PV19 (fig. 12), which exists in four different coloration of plastics.Perylenes have excellent solvent
crystalline modifications. Two are commercially fastness and lightfastness.
important as pigments, and PV19 is sold as the red- Perinone pigments were also originally intro-
violet B form and the red 'Yform. Substitution of the duced as dyestuffs,and then as pigments beginning in
ring system produces a variety of pigments of varying 1950 (Herbst and Hunger 2004). Perinones are made
shade.These substituents are usually either methyl or from naphthalene-1,4,5,8-tetracarboxylic acid or its
chloro groups. PV19 IS commonly called monohydride. They perform in much the same
quinacridone red or quinacridone violet depending manner as perylenes. The two commercial pigments
on the crystalline form. in this class are P043 (71105) and PR194 (71100).
Quinacridones also exist as solid solutions, either They are used in automotive, architectural, and indus-
with other quinacridones or with quinacridone trial paints, printing inks, and stains. Perinone
quinones. Binant and Lautie (1989) have studied pigments have excellent light and solvent fastness.
these solid solutions that broaden the color range The structures of two common members of these
available for the quinacridone pigments. pigment classesare shown in figure 13.
Quinacridones have excellent lightfastness,
solvent fastness,and heat resistance.Their resistance to
solvent is partially a feature of the strong hydrogen 3.2.4 Triarylcarbonium Ion Pigments
bonding that occurs between the carbonyl and the
imino groups in the crystal. The ASTM (1995) lists Triary1carbonium ion pigments began as dyes for
P048, P049, PR122, PR192, PR207, and PV19 textiles.They consist of two different types, one called
(both crystalline forms), on their list of suitable the alkali blue type and the other containing complex
pigments. Because of their excellent fastness proper- anions.The alkali blue types have a history dating back
ties, quinacridones are used in automotive paints, to the beginning of dye chemistry, and they span the
printing inks, for the coloration of plastics, and in color range of reddish blue to violet. The complex
artists' oil, watercolor, and acrylic paints. anion group also spans the red and violet shades. Due
to their polar nature, this classof pigments is not stable
to polar solvents, including alcohols, ketones and
3.2.3 Perylene and Perinone Pigments

Perylene reds are sometimes described as vat

pigments (Lewis 2001). They are diimides of perylene
tetracarboxylic acid. They have been used as dyestuffs
beginning in 1913 and as pigments beginning in 1950
(Herbst and Hunger 2004). They exist in the colors
red, bordeaux, violet, and brown. Important members b)
of this classinclude PR123 (71145), PR149 (71137),
PR178 (71155), PR179 (71130), PR190 (71140),

NhN
Q
o I ":: "::
~ ~
~
NY' N

o
N
I
H 0°
Fig. 12.StructureofPV19, a quinacridone Fig. 13. Structure of perylene and perinone pigments:a)
PR149, a perylene,and b) P043, a perinone

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A REVIEW OF THE CLASSES, STRUCTURES, AND METHODS OF ANALYSIS

OF SYNTHETIC ORGANIC PIGMENTS

ethylene glycol. Important members of this class

include PV3 (42535:2), PV27 (42535:3), and PR81
(45160:1).The structure ofPV3 is shown in figure 14.
The major use of these pigments is in the printing ink
industry.They have moderate lightfastness.

3.2.5 Isoindolinone and Isoindoline

Pigments

Isoindolinone and isoindoline pigments were

introduced in the mid 1960s, although they were first Fig. 14. Structure of PV3, a commonly used triarylcarbo-
nium ion pigment
patented in the 1940s (Herbst and Hunger 2004).
These pigments have the isoindoline ring in
a
common. The tetrachloroisoindolinone, or azome-
thine type pigments span the color range from yellow
to orange to red. These pigments include PY109
(56284), PYll0 (56280), PY173 (561600), and P061
(11265). The isoindoline pigments, or methine type,
include PY139 (56298), PY185 (56280), P066
(48210), P069 (56292), and PR260 (56295). These
pigments are characterized by excellent fastness prop-
erties, and are used in automotive and industrial paint b
applications. Representative structures of these
pigments are shown in figure 15.

3.2.6 Diketopyrrolo-Pyrrole Pigments

The diketopyrrolo-pyrrole (DPP) pigments Fig. 15. Isoindolinone and isoindoline pigments: a) PY109,
are a class of red pigments introduced by Ciba- an isoindolinone (azomethine type), b) PY139, an isoindo-
line (methine type)
Geigy in the 1980s (Herbst and Hunger 2004).
They have very good fastness properties. The
most important pigment in this class is PR254
(56110) (fig. 16). It is used in automotive paints,
artists' paints, and for the coloration of plastics.
This pigment was first introduced as Irgazin
DPP.

3.2.7 Thioindigo Pigments

Thioindigo pigments are related to indigo, one of

the oldest of natural dyestuffs.After the synthesis of
mauve, dyestuff chemists targeted the synthesis of
indigo. Bayer first described the structure of indigo in
1883 (Herbst and Hunger 2004). In the 20th century,
several thioindigo derivatives were introduced as
synthetic organic pigments. The only commercially
=
significant member of this class is PR88 (73312) (fig.
R2 =
17), which is a reddish violet pigment having excel- Fig. 16. General structure of DPP (diketopyrrolo-pyrrole)
lent lightfastness and good resistance to organic pigments

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SUZANNE QUILLEN LOMAX AND TOM LEARNER

solvents.This pigment is used in automotive finishes,

paints, and for the coloration of plastics and textiles.

3.3 MISCELLANEOUS

3.3.1 Dioxazine Violet

PIGMENTS
Ni:f
....
....::~\
o
CI

::::--.....

Cl
N

Dioxazine violet (PV23, 51319), also known as

Carbazole Violet, is a very important pigment; its
structure is shown in figure 18. Synthetic organic Fig. 18. Structure ofPV23, Dioxazine Violet
pigments that derive from a dioxazine type structure
have been known since the late 1920s (Herbst and known as PYl12, but is now listed in the Colour
Hunger 2004). PV23 has a very high tinting strength Index as PY24. The structure of the pigment is shown
and is bluish violet, a shade that is difficult to approx- in figure 20. This reddish yellow pigment tends to
imate with other colorants. Its lightfastness is excel- darken upon light exposure at masstone, although this
lent, and it is resistant to many organic solvents. PV23 effect is not a problem in light tints (Herbst and
is used in automotive, architectural, and artists' paints, Hunger 2004). PY24 is used in automotive finishes,
crayons, fiber tip pens, printing inks, and for the artists' colors, wood stains, and for the coloration of
coloration of plastics. plastics.

3.3.2 Indanthrone Blue 4. METHODS OF ANALYSIS

Indanthrone blue, or PB60 (69800), is a vat It is often difficult to identify synthetic organic
pigment with the structure shown in figure 19. It is a pigments. Due to their high tinting strength, they are
red-shade blue with excellent fastness properties, and frequently present in relatively small quantities. Large
has been used as a pigment for many years.Indanthrone amounts of fillers and extenders can make analysis
blue is more expensive than phthalocyanine blue, particularly difficult. These fillers and extenders,
which limits its applications. However, it is frequently frequently calcium carbonate or barium sulfate,compli-
encountered in artists' paints, as well as automotive cate infrared analysis or x-ray powder diffraction. In
finishes,printing inks, and for the coloration of plastics. addition, identification is often impossible by traditional
techniques used for mineral pigments, such as polarized
light microscopy. Many synthetic organic pigments
3.3.3 Flavanthrone Yellow differ in structure by the position of substituents on an
aromatic ring, making definitive analysis difficult.
Flavanthrone yellow is a pigment that also origi-
nated as a vat dye.This pigment, 70600, was formally o

CI

CI 0

o CI

CI o
Fig. 17. Structure of thioindigo pigment, PR88 Fig. 19. Structure ofPB60, Indanthrone Blue

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OF SYNTHETIC ORGANIC PIGMENTS

has been suggested as a good technique for the iden-

tification of quinacridones in paints (Rioux 1995).
A number of researchers have examined synthetic
organic pigments using infrared spectroscopy. Christie
et al. (1988) have examined a number of dry pigment
samples of monoazoacetacetanilides, including PYl
and PY74. Infrared spectroscopy was used to identify
synthetic organic pigments in works by Alfred Pellan
(Corbeil et al. 1994).These include PY1, PY3, POlS,
PR1, PR3, and PR 4. Dry pigment samples of phthalo-
o
cyanines, including unmetallized, copper uncWori-
Fig. 20. Structure of PY24 (formerly PY112), Flavanthrone
nated, and cWorinated forms have also been examined
Yellow
by infrared spectroscopy (Shurvell and Pinzuti 1966).
However, in spite of, or perhaps due to these Another study examined the infrared spectra of cWo-
difficulties, a number of different analytical tech- rinated phthalocyanines as a function of cWorine
niques have been applied to the analysis of synthetic content (Starke and Wagner 1969). Learner used FTIR
organic pigments. McKay (1992) has applied trans- to identify the arylide yellow pigment PYl in an
mission electron microscopy to dry pigment samples acrylic paint film (1998), as well as the organic
of the arylide yellows PYl and PY74. Although they pigments PY3, PY73, PR9, PR122, PR170, PB15, and
cannot be distinguished, the authors found the parti- PG7 from a variety of paint samples (1996,2004). The
cle size of arylide yellows to be large compared to spectra from a number of pure synthetic organic
other monoazo yellow pigments. Electron micro- pigments were also published. Two techniques shown
graphs were also recorded of dry pigments of the to be capable of dramatically increasing the sensitivity
arylide yellow class (Schaefer and Wallisch 1981). of infrared spectroscopy in detecting synthetic organic
Again, the authors focused on the particle size distri- pigments from paint samples are solvent immersion,
bution of the pigments. used to extract soluble organic pigments, and acid
De Keijzer (1990) successfully used microchemi- immersion to convert calcium carbonate to calcium
cal tests for various blue, green, orange, violet, and oxide (Jonsson and Learner 2004).
brown synthetic organic pigments. These tests involve Raman spectroscopy has also been used for the
color changes when the samples are exposed to sulfu- identification of synthetic organic pigments. Davey
ric or nitric acids or alcoholic potassium hydroxide. et. al. (1994), applying this technique to artwork, have
He found that microrecrystallizations can also be used identified PYl in the lithographic ink on Abstract
to identify the synthetic organic pigments. The Design for a Poster by Victor Pasmore, dating from
author applied the microchemical tests to paint cross 1948. PR49:1 was detected in a lithographic poster
sections (de Keijzer 1987). designed by Leonetto Cappiello and printed in Paris
Whitaker (1983, 1986a,1986b, 1986c, 1988) has in 1929 (Wise and Wise 2004). Raman spectroscopy
reviewed the application of x-ray powder diffraction has also been used to identify phthalocyanine blue
to the analysis of synthetic organic pigments and dyes, and green, a Hansa yellow and two B-naphthol reds
including dry samples of the arylide yellows. The from a supposed 13th-century BC papyrus (Burgio
author was able to determine that these azo pigments and Clark 2000). Twenty-one different dry azo
exist in the hydrazone tautomer rather than in an azo pigments were also analyzed by Raman spectroscopy
form. The unit cells of organic pigments are usually (Vandenabeele et al. 2000). Copper phthalocyanines
much larger than inorganic pigments, leading to low- have been examined by Raman spectroscopy (Smith
angle diffraction lines. and Rospendowski 1992; Massonnet and Stoecklein
Phthalocyanines have also been studied by x-ray 1999; Vandenabeele et al. 2001). They have been
powder diffraction (Honigmann 1964; Whitaker recorded in different environments and with different
1977).These include low- and high-chlorine-content excitation frequencies. The Raman spectra of blue
green pigments, which were examined as solids. x- and green copper phthalocyanines often are charac-
ray powder diffraction spectra were reported for the terized by luminescence or thermal degradation
ex, B, and 'Y forms of linear trans-quinacridone problems that can sometimes be remedied by chang-
(Spengeman 1970;Whitaker 1986c). X-ray diffraction ing the excitation wavelength of the laser.

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SUZANNE QUILLEN LOMAX AND TOM LEARNER

Synthetic organic pigments in artists' paints have Nine different tattoo dyes were also analyzed by
been identified by solution spectrophotometry, thin-layer chromatography (Lehmann and Pierchalla
including tube paints dating from 1977 to 1980 1988). Inorganics were removed by filtration. Other
(Billmeyer et al. 1981; Luke et al. 1994). Whitmore analyses such as nuclear magnetic resonance, ultravi-
(1988) used solution spectrometry to identify the olet-visible, and infrared spectroscopies were also
fugitive red pigment on Mark Rothko's Harvard performed. Pigments identified include PY74, PY83,
Murals as PR49 Lithol Red. Christie et al. (1988) P016, PR22, and PV19.
have used ultraviolet-visible spectroscopy in a study Examination of synthetic organic pigments has
of solid monoazoacetoacetanilides dissolvedin cyclo- been carried out using other chromatographic tech-
hexane. Vagi.(1963a, 1963b) examined the electronic niques. High-performance liquid chromatography
spectra of dry phenylazoacetanilides dissolved in using diode array detection was used to identify
hexane. Talksy and Ristic Solajic (1987) used fourth- synthetic organic colorants used in cosmetics
derivative ultraviolet visible spectroscopy to examine (Wegener et al. 1987). A number of azo pigments
twenty-two colorants used in artists' paints. The were included in the study. The colorants were
samples were neat pigments as well as commercial extracted from the cosmetics with DMF and then
tube paints. The fourth-derivative spectra were filtered prior to analysisusing a reverse phase system.
considered to be of sufficient resolution for most Synthetic organic pigments have been examined
analyses. Compounds of similar chemical structure using pyrolysis gas chromatography (PyGC). Sonoda
were found to have different fourth-derivative spec- et al. (1993) and Sonoda (1998, 1999) have used
tra.This technique was also used in combination with PyGC and pyrolysis gas chromatography/mass spec-
thin-layer chromatography (TLC) to examine paint trometry (PyGC-MS) to study a variety of binders
samples consisting of two or more pigments. and pigments in synthetic media, including poly(vinyl
Home et al. (1982) used TLC to identify acetate), acrylic, and alkyd. Pure synthetic organic
synthetic organic pigments in household gloss paints. pigments as well as pigments in commercial paints
Normal phase separation was performed with a were examined. Azo pigments, nitroso, quinacridones,
mixture of chlorobenzene, toluene, and 1, 2- and phthalocyanines were characterized. A variety of
dichloroethane as the mobile phase. Strauss (1984) has techniques including x-ray fluorescence, x-ray
used TLC in conjunction with infrared analysis to powder diffraction, and infrared spectroscopy were
identify synthetic organic pigments in a collection of used to examine samples from paintings by Yves
commercial paints in the Doerner Institute. Baier Klein, Jean Dubuffet, and Bernard Rancillac. X-ray
(1974) used TLC with a variety of solvent systems to powder diffraction was found to be a useful comple-
examine synthetic organic pigments. Silica gel was mentary technique in order to characterize the
used for the stationary phase, and solvent systems pigments. Quinacridones (PR122) and phthalocya-
included a mixture of hexane, benzene, and pyridine, nine PB 15 were initially found not to pyrolyze under
a mixture of chloroform and xylene, and, finally, the conditions utilized. In another study, however,
benzene. Most of the pigments examined were simple phthalocyanine blue pyrolyzed to give a very small
naphthol and mono- and di-arylide pigments. quantity of benzene-l, 2-dicarbonitrile.
Milovanoic et al. (1982) used silica gel thin-layer Learner (1996, 2004) used PyGC-MS to look at
chromatography for the separation and identification a number of synthetic organic pigments. Yellow,
of commercial oil and acrylic paints containing orange, and red azo pigments gave characteristic
synthetic organic pigments. The pigments included pyrograms. Dry pigments examined included PR5,
azo yellows, naphthols, perinones, quinacridones, PR9, PRl12, PRl70, PRl7l, PY1, PY3, PY73,
benzimidazolones, dioxazine, metal salts,and phthalo- PY74, PY83, and PY97. Paints containing these
cyanines. Dimethylsulfoxide was used as solvent for pigments were also examined. Infrared spectra were
most of the paints. The metal azo salts, the isoin- also recorded of these pigments and also P05 and
dolinones, perinones, quinacridones, monoazobenz- P036, as well as the phthalocyanines PB15 and PG7,
imidazolones, dioxazines, and phthalocyanines were and the quinacridone PR122.
very difficult to chromatograph due to their poor Mass spectral techniques have sometimes proven
solubility and poor chromatographic characteristics. useful in the analysis of synthetic organic pigments.
The authors required six different solvent systems for Boon and Learner (2002) used direct temperature-
the analysis of the paints. resolved mass spectrometry (DTMS) to examine an

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OF SYNTHETIC ORGANIC PIGMENTS

acrylic paint contaInIng PY3 and one contaInIng dioxazine violet PV23; and the phthalocyanines PB15
PY73. In addition, a green paint was found to contain and PG7.
PY3 and the phthalocyanine PG7. The medium and Binant and coworkers characterized dry samples
the pigments were well resolved. Using the same of quinacridones using a variety of techniques
instrumental set-up, DTMS spectra have been (Binant and Lautie 1989; Binant 1990; Binant et al.
published from a larger selection of pure synthetic 1990). P048 and PR206 were examined by reso-
organic pigments, including PR5, PR9, PR122, nance Raman microspectrometry and were found to
PR170, PR207, PY3, PY73, PY74, PB15 and PG7; be solid solutions of linear trans-quinacridone and
and PR3, PR170, PY1, PY3, PY73, and PY97 from linear trans-quinacridonequinone. Electronic (visible
various commercial paints (Learner 2004). absorption and fluorescence emission), infrared, and
Wyplosz (2003) examined a series of reference Raman spectroscopy were used to study six
dry synthetic organic pigments including azos, quinacridone pigments. The quinacridone color was
phthalocyanines, quinacridones, dioxazines, correlated to the crystal structure rather than being
perylenes, and DPP pigments by laser desorption due to substituent effects. The pigments examined
mass spectrometry. Several acrylic and oil paints were were PV19 (B, "I, and "I' forms), PR122, PR202, and
also examined.Analyses were performed with a nitro- PR209. Binant (1990) has also used x-ray diffraction,
gen laser (337 nm) which selectively desorbs the differential thermal analysis,electron microscopy, and
organic pigment in the presence of the binder. This visible diffuse reflection spectroscopy to examine this
selectivity is of great benefit for pigment analysis. class of materials. The technique of visible diffuse
Under the conditions used, laser desorption ioniza- reflection spectroscopy was found extremely useful in
tion produces molecular ions from the pigment with characterizing these synthetic organic pigments. It is
little or no fragmentation. The author also used the most applicable technique to see the variation in
matrix-assisted laser desorption ionization (MALDI) shade of the components. The pigments were illumi-
to examine the pigments and paints using 2, 5-dihy- nated with a tungsten lamp (Amax emission, 520 nm),
droxybenzoic acid as the matrix. In addition, cross and the emission was recorded from 400 to 700 nm.
sections prepared with layers of phthalocyanine blue The wavelength maxima between 500 and 600 nm
and green acrylic paints were examined by spatially are characteristic of the pigments while the envelope
resolved laser desorption mass spectrometry. Each of the band characterizes the quinacridone family.
layer was approximately 100 micrometers in thick-
ness. The phthalocyanine blue pigment could be 5. CONCLUSIONS
identified. Spatial resolution was estimated to be
twenty to fifty micrometers. The spatially resolved Synthetic organic pigments occupy. a largepropor-
technique was also used to identifY PV19 in a sample tion of the output of the pigment industry.Thousands
removed from the sculpture Dunstable Reel by Phillip of these pigments have been introduced in the last
King (Tate, T01361). A sample from the painting 150 years, and hundreds have been used and are
Interior with a Picture by Patrick Caulfield (Tate, continuing to be used in artists' paints and products.
T07112) was also examined, and PY3 and PR170 This paper has served to review the major classes of
were found. However, the estimated diameter of the synthetic organic pigments. Many of these pigments
laser beam overlapped several of the paint layers. are azos, which span the color range of yellow,
Baumler et al. (2000).used a variety of analytical orange, and red. Members of some of the early azo
techniques in the analysis of forty-one tattoo pigment classessuch as the diarylides and the B-naph-
colorants. These were found to consist of sixteen thols are not of sufficient lightfastness for today's
different pigments. A variety of techniques were used, more stringent requirements, and they have been
including absorption spectroscopy, infrared spec- discontinued or are used in less permanent applica-
troscopy, electron microscopy, x-ray powder diffrac- tions. Other azo pigment classes,including the arylide
tion, and mass spectrometry using a direct insertion yellows, Naphthol AS pigments, benzimidazolones,
probe. The synthetic organic pigments identified and disazo condensation pigments have good light-
include the diarylide yellows PY14, PY55, PY83, and fastness properties.
PY87; the monoarylide yellow PY74; the disazopyra- Other synthetic organic pigment classes have
zolone P013; the Naphthol AS pigments PR5, PR9, been introduced in the 20th century, including the
PR22, PRl12, and PR170; the quinacridone PR122; phthalocyanines, quinacridones, perylenes and peri-

JAIC 45 (2006):107-125
122

SUZANNE QUILLEN LOMAX AND TOM LEARNER

nones, indolinones and isoindolines, DP:p'and triaryl- application of electronic and vibration spectroscopic
carbonium colorants. Many of these pigments have techniques to the identification of quinacridone
become extremely popular due to the ease of manu- pigments in vehicle paint systems.Journal of the Society
facture or due to their superior fastness properties, of Dyers and Colourists 106:187-90.
and they are used to color a variety of materials.
Due to their unique properties, synthetic organic Binant C., and A. Lautie. 1989. Identification of
pigments may be difficult or impossible to analyze quinacridone pigment mixtures using resonance
using techniques suited to the analysis of mineral Raman microspectroscopy. Applied Spectroscopy
pigments, such as polarized light microscopy, x-ray 43:851-55.
diffraction, or x-ray fluorescence. Their high tinting
strength, small particle size and similarity of structure Boon, J., and T. Learner 2002. Analytical mass spec-
among members of a series can make identification trometry of artists' acrylic emulsion by direct temper-
difficult. This paper has discussed various methods ature-resolved mass spectrometry and laser
that have been applied to the analysis of these desorption ionization mass spectrometry. Journal of
pigments, focusing on spectroscopic and chromato- Analytical and Applied Pyrolysis 64:327-44.
graphic techniques.
Boyd, S. N. 1955. Mechanisms of the diazotization
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OF SYNTHETIC ORGANIC PIGMENTS

in cosmetic products by high-performance liquid SUZANNE QUILLEN LOMAX received her PhD
chromatography. Chromatographia 24: 865-75. in Organic Chemistry from the University of
Maryland in 1984. Her thesis explored the photo-
Whitaker, A. 1977. X-ray powder diffraction. In The chemistry of iminium salts. She performed postdoc-
analytical chemistry of synthetic dyes) ed. K. toral research in organic photochemistry at
Venkataraman. New York:Academic Press. 280-85. Northwestern University. In 1986, she joined the
Scientific Research Department of the National
Whitaker,A. 1983. Crystal data for C.l. pigment PY3. Gallery of Art as organic chemist. Her main areas of
journal of the Society of Dyers and Colourists 99:121-23. work include identification of paint binders,
varnishes, waxes, and synthetic organic pigments.
Whitaker, A. 1986a. Crystal data for C.l. pigment Address: Scientific Research Department, National
Yellow 65.journal of the Society of Dyers and Colourists Gallery of Art, 2000B South Club Drive, Landover,
102:136-37. MD 20785; [email protected]

Whitaker, A. 1986b. Crystal data for C.l. pigment TOM LEARNER is a senior conservation scientist at
Yellow 74.journal of the Society of Dyers and Colourists Tate in London. He received his MA in Chemistry
102:109-10. from Oxford University in 1988 and a Diploma in the
Conservation of Easel Paintings from the Courtauld
Whitaker, A. 1986c. The value of x-ray powder Institute of Art, University of London, in 1991. He
diffraction analysis in colour chemistry.journal of the spent a year as a Getty intern in the Painting
Society of Dyers and Colourists 102:66-76. Conservation and Scientific Research Departments at
the National Gallery of Art, Washington, DC. Since
Whitaker, A. 1988. Crystal structure of azo pigments joining the Tate Gallery in 1992 he has been principally
derived from acetoacetanilide,journal of the Society of researching analytical techniques for the characteriza-
Dyers and Colourists 104:294-300. tion of 20th-century painting materials and the effects
of conservation treatments. He received his PhD in
Whitmore, :P. 1988.Appendix: Notes on the technical Chemistry from Birkbeck College, University of
analysis. In Mark Rothko's Harvard Murals) ed. M. B. London, in 1997. Address: Conservation Department,
Cohn. Cambridge, Mass.: Harvard University Art Tate Gallery, Millbank, London, SW1P 4RG UK;
Museums. 61-62. [email protected]

Wise, D., and A. Wise. 2004. Application of Raman

microspectroscopy to problems in the conservation,
authentication and display of fragile works of art on
paper.journal of Raman Spectroscopy 35:710-18.

Wyplosz, N. 2003. Laser desorption mass spectromet-

ric studies of artists' organic pigments. PhD diss.,
University of Amsterdam.

Yagi,Y 1963a. Studies of the absorption spectra of azo

dyes and their metal· complexes: 1. The absorption
spectra of phenylazoacetoacetanilide and its related
compounds. Bulletin of the Chemical Society of japan
36:487-91.

Yagi,Y 1963b. Studies of the absorption spectra of azo

dyes and their metal complexes: 2. The absorption
spectra of phenylazoacetoacetanilide and its deriva-
tives. Bulletin of the Chemical Society of japan
36:492-99.

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