INDIGOID & THIOINDIGOID

PIGMENTS
INDIGOID PIGMENTS
Indigo itself (C.I. Vat Blue 1, C.I. 73000) has a
certain amount of interest as a pigment
because of its insolubility in most solvents and
its very good fastness to light and heat (in spite
of its tendency to sublimation). That is why it is
still used, notably in rubber and for mass coloration of rayon in a navy
blue shade, although it has the drawback of
Figure 1: C.I. Vat Blue 1
being sensitive to the reducing action of
viscose.

Halogenated derivatives of indigo have also been used as blue pigments,

6 halogenated
5
but today they are obsolete.
On the contrary, several
7 valuable pigments.
4
derivatives of thioindigo have
been recognized as

Figure 2: Thioindigo

They are reds and violets, three of which are also textile vat dyes of
importance. These pigments are shown below:

Figure 3: Pigment Red 86

Figure 4: Pigment Red 87 Figure 5: Pigment Red 88

Table 1: Thioindigo Pigments

CI name

CI Constitution No.

Thioindigo derivatives

Pigment Red 86

73375

6,6-Dibromo-4,4-dimethyl

Pigment Red 87

73310

7,7-Dichloro

Pigment Red 88

73312

4,4,7,7-Tetrachloro

Vat Red 1

73360

6,6-Dichloro-4,4-dimethyl

Vat Red 198

73390

4,4-Dichloro-7,7-dimethyl

Vat Violet 2

73385

5,5-Dichloro-7,7-dimethyl

Vat Violet 3

73395

5,5-Dichloro-4,4,7,7-tetramethyl

Figure 6: Vat Red 1

Figure 7: Vat Red 198

Figure 8: Vat Violet 2

Figure 9: Vat Violet 3

These pigments are all appreciated for their brilliance of shade.

The most used at the present time are:
i.
ii.

Thioindigo Red Violet RH (C.I. Vat Violet 2), and

Thioindigo Pink (C.I. Vat Red 1)

They are not, however, the best, since they bleed slightly in solvents and
have only moderate fastness to light in pale tints.
The fastest are the derivatives substituted in the 4,4,7,7 positions:
i.
ii.

Thioindigo Red Violet Y or Maroon (C.I. 73390), and especially

Thioindigo Red Violet B or Bordeaux (C.I. Pigment Red 88).

The latter is shown as non-migrating and exceptionally fast to light, even

in pastel shades.
2

4,4,7,7-Tetrachlorothioindigo with a reddish violet shade reigns supreme

as a pigment among the derivatives of this indigo.
It can be used for Bordeaux shades in automotive refinishes.
Thioindigo pigments are generally used in industrial coatings and plastics
for their good lightfastness and weather-fastness in deeper shades.

CHEMISTRY & MANUFACTURE

Thioindigo pigments have the following general structure:
O
S
Rn

Rn
S
O

In commercially important products,

R typically represents a Cl atom or a CH3 group, and n stands for 2 or 3.
The compounds assume the trans-structure.

The synthesis is performed in two steps:

i.
ii.

attaching the 5-membered ring to the benzene ring, and

oxidatively linking two molecules of the resulting thionaphthenone3

The most important route involves cyclization of appropriately substituted

phenylthioglycolic acids:
O

OH

O
HOC
CH2
S

Suitable agents are ClSO3H, monohydrate, or conc. H2SO4.

Other methods include cyclization of phenylthioglycolic acid chlorides,

which is afforded by Friedel-Crafts reaction with AlCl3, possibly in the
presence of H2SO4/NaCl. The acid chloride is obtained from
phenylthioglycolic acid with SOCl2 or PCl3.

There are more routes to cyclization.

The synthetic route to tetrachlorothioindigo may serve as an example for
an industrial scale synthesis:
Cl

SO2Cl

Cl

Red.

Cl

ClSO3H

Cl

Cl

KSCOC2H5

SCOC2H5

N
Cl

Hydrolysis

SH

Cl

Cl

2,5-dichlorothiophenol

Na2S2

Red.
Cl

Cl

S
Cl

S
Cl

Cl

Cl

ClSO3H, 35oC

ClCH2COOH

CH2
S

SCH2COOH

SH
Cl

Cl

Cl

Cl

Br2/ ClSO3H (directly)

or O2/ alkali
(after intermediate isolation)

Cl

Cl

O
S
C

S
Cl

Cl

AFTER-TREATMENT
In most cases, it is necessary to modify the crude thioindigo derivative by
appropriate after-treatment in order to develop the desired pigment
properties.
The list of options include milling the crude product with salt or dispersing
agents or reprecipitation from H2SO4 orClSO3H, followed by after-treatment
with organic solvents.
Tinctorially strong transparent pigment grades, for instance, are obtained
by milling the crude pigment suspension in the presence of an aqueous
base.
The same result is achieved by oxidizing the leuco form of
tetrachlorothioindigo in the presence of sodium dithionite with air while
applying shearing forces (for instance in a pearl mill).

PROPERTIES
Thioindigo pigments provide a range of hues from red violet and maroon
to brown shades.

The type and position of the substituents affects the shade:

i.

Electron donating substituents (methyl groups) in 5-position cause

the most drastic bathochromic shift, which decreases in the
following order:
4- > 7- > 6- position

ii.

The reverse is also true in the case of electron acceptors (such as

chlorine): they cause more of a bathochromic shift in 6-position than
in 5-position.

As a class, tetrachlorothioindigo pigments exhibit good to excellent

lightfastness and weather-fastness as well as solvent stability and
migration fastness.
4,4,7,7-substituted derivatives demonstrate highest fastness to solvents.
Cl substitution has a better effect in this respect than CH3 substitution.
Shifting only one of the substituents on 4,4,7,7-tetrachlorothioindigo, for
instance, will adversely affect the migration resistance of the parent
compound (fastness to bleeding).

COMMERCIALLY AVAILABLE TYPES & THEIR APPLICATION

GENERAL:
Of the two remaining thioindigo pigments, only Pigment Red 88, the
4,4,7,7-tetrachlorothioindigo, has been able to maintain interest
throughout the pigments industry. It is broad in scope. The other type,
Pigment Red 181, is a special-purpose type for a limited number of
applications. The following table lists the chemical constitutions of both
pigments.

R4

R7'

R5

R6'

S
S

R6

R5'
O

R7

R4'

Table 2: Commercially available thioindigo pigments

CI Constitution
CI name
P.R. 88
P.R. 181

No.
73312
73360

R4

R5

R6

R7

Shade

Cl
CH3

H
H

H
Cl

Cl
H

red-violet
bluish red

Unsubstituted thioindigo, which is marketed as

Vat Red 41, 73 300, is used in rigid PVC,
polystyrene, and a number of other plastics.
Dissolved in its medium, the pigment affords
fluorescent bluish
red10:
shades.
Figure
Vat Red 41

Unsubstituted indigo is marketed as Pigment Blue

66, 73 000. It is a suitable pigment for spin dyeing
of synthetic viscose rayon and spun rayon, to
which it lends navy blue shades. The pigment
provides good lightfastness. However, Pigment
Figure 11: Pigment
Blue 66
performs poorly regarding a number
Blue 66
of textile
fastnesses, especially in terms of
bleaching with chlorite, and vat resistance.

INDIVIDUAL PIGMENTS:
Pigment Red 88

It is a suitable colorant especially for industrial

coatings, including automotive (O.E.M.) finishes
and automotive refinishes.
Its red-violet shade is used frequently to
produce opaque dark shades of red, bordeaux,

Figure 12: Pigment Red

88

and maroon, for which purpose the pigment is typically used in

combination with inorganic pigments, such as Iron Oxide Red or
Molybdate Red.
P.R.88 is both very lightfast and weather-fast.
P.R.88 shows good stability to organic solvents.
Its fastness to over-coating is good, but not reliable at baking
temperatures above 140C.
Paints containing P.R.88 are acid and alkali resistant.
P.R.88 is one of the standard red-violet pigments for use in plastics.
It is particularly suitable for use in PVC, including PVC plastisols and
PUR coatings.
Transparent polyolefin systems containing P.R.88 are stable up to 260
to 300C, depending on the type and on the pigment content.
P.R.88 is recommended for use in PP spin dyeing, special-purpose
grades are used for polyacrylonitrile spin dyeing.
The resulting fibres are completely fast to perspiration, dry and wet
crocking, perchloroethylene, and other important solvents, as well as to
dry heat fixation.
Used in the spin dyeing of polyester, the pigment dissolves in the fibre.
Both sublimation and migration fastness are excellent in this medium.
Depending on the temperature, the pigment dissolves in this polymer
and accordingly changes its colour and fastness properties. This
presents major difficulties in trying to match a defined shade.
Incorporated in methacrylate and unsaturated polyester cast resins,
P.R.88 not only withstands several hours of thermal exposure during
processing but is also resistant to the peroxides which are used as
catalysts.
P.R.88 is also used for printing inks.
Its red-violet shade is especially used for printing inks which are to be
targeted for packaging, posters, and other special purposes.
The prints are entirely fast to organic solvents, plasticizers, and
packaged goods, such as butter and soap.
P.R.88 prints are fast to alkali and acid, heat stable up to 200C, and
fast to sterilization.
P.R.88 is also used in wood stains, for instance in combination with
yellow pigments, such as P.Y.83, or carbon black to produce shades of
brown.

PIGMENT RED 181

P.R.181 is a special-purpose product for

polystyrene and similar polymers.
Figure 13: Pigment Red
181
8

P.R.181 largely dissolves in its medium at the high temperatures at

which these polymers are processed.
The pigment affords brilliant, bluish shades of red. It possesses
excellent lightfastness and satisfies the application requirements.
Another important market is in toothpaste, for which the pigment has
been approved worldwide.
It also lends colour to lipstick and other decorative cosmetics. In the
US, it is registered by FDA as D&C Red 30, in Germany as C-Rot 28
according to the DFG Catalogue for Cosmetic Colorants, in Japan as Red
No. 226.

REFERENCES:

The Chemistry of Synthetic Dyes Volume II by K. Venkataraman

Industrial Organic Pigments by W. Herbst, K. Hunger