doi: 10.1111/j.1478-4408.2009.00204.

Industrial organic photochromic dyes

S Nigel Corns, Steven M Partington and Andrew D Towns*
James Robinson Ltd., PO Box B3, Leeds Road, Huddersfield, HD1 6BU, UK
Email: andy.towns@jamesrobinson.eu.com

Organic photochromic molecules are well established as colorants in the manufacture of niche products,
providing striking colour change effects when irradiated with light. This paper describes the industrially
important classes of photochromic dye in terms of their development and chemistries, the applications
in which their photochromism is employed commercially, and the technical features behind their
success. Photochromic systems form the subject of much industrially funded research into nascent high-
tech applications that have the potential to become the most commercially significant outlets for
photochromic dyes. Those types being scrutinised are therefore also discussed along with the directions
in which the industrial use of photochromic colorants may take.

Introduction
Now you see it – now you don’t… While most colorants
for surface coatings and plastics impart permanent colour,
commercially available photochromic dyes can be used to
create attention-grabbing effects involving the sudden
generation or disappearance of colour in response to light.
Such colour changes might appear magical, but the
science behind them is well established. Photochromism
forms the basis for what has become a global
multimillion-dollar business and a deep understanding of
the phenomenon has been fundamental to the growth of
the industries reliant upon it. Although comprehensive
surveys have been published concerning photochromism
[1] and a wide variety of organic photochromic materials
[2–4], relatively little has appeared that approaches the
subject from an industrial perspective. This review
therefore describes how photochromism has been
exploited commercially, placing emphasis on the
chemistries of those types of organic colorants that are
industrially important, as well as the properties that have
made them of interest. As ophthalmic lens technology is
by far the largest current application, particular attention
will be paid to the technical criteria that a commercially
viable photochromic molecule must meet in this context.
However, in addition to outlining existing industrial
applications, an insight will be given into how
photochromic dyes might play a crucial role in
technologies that are being developed for the markets of
the future. This review is not intended to be either an in-
depth market report on the industry or a detailed
academic account concerning the technical minutiae of
dye chemistry: it is instead meant to act as an
introduction to the design, manufacture and application of
industrial organic photochromic dyes, providing signposts
to further information on each of these aspects.
Photochromism
The phenomenon of photochromism is defined as a
reversible colour change induced in a compound driven
in one or both directions by the action of electromagnetic
radiation [1]. Many photochromic materials change colour
upon irradiation with ultraviolet (UV) or visible light and
then revert back to their original colour following removal
of the illuminant. This is known as T-type
photochromism when the back reaction is driven
thermally. If the photochromic material only returns to its
original state through irradiation with light of another
range of wavelengths, i.e. the change is photochemically
driven, then it is said to exhibit P-type photochromism.
In either case, the effect is reversible: loose terms such as
‘irreversibly photochromic’ are sometimes used in certain
fields, but such expressions are not strictly correct
because, by definition, they are oxymoronic.
The types of dye that dominate industrially are those
that exhibit what is essentially a thermally driven back
reaction, i.e. T-type photochromism; it is upon these
which this review will mainly focus. In addition, while
many examples of photochromic colorants are known
that switch between different coloured forms, such as
certain azo compounds, only photochromism that
involves reversible interconversion of colourless (or
almost colourless) to coloured species will be considered
in this review as it is this mode that has attracted most
industrial interest.
For the most important classes of photochromic dye,
the absorption of light causes a rearrangement of the
bonding between the atoms within a colourless or weakly
coloured molecule (photoisomerisation), creating a
structure that is intensely coloured (Figure 1). The
wavelengths of light that effect this conversion are dye-
dependent, but normally within the UV region for

ultraviolet
Colourless (or very light
Coloured
weakly coloured)
molecule
molecule
absence of
ultraviolet light

Figure 1 Behaviour of commercially important photochromic dyes

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Corns et al. Industrial organic photochromic dyes
commercial photochromic colorants. For example, certain
naphthopyrans respond best to UV-A radiation of
wavelengths 350–380 nm, while some spirooxazines can
be activated readily by blue light in the region of 410 nm.
Pronounced photochromism can therefore be produced
by sunlight with such dyes as it has a significant UV
component. Conversely, artificial light sources such as
tungsten filament bulbs, which emit relatively little light
at these wavelengths, are not very effective.
The nature of the reverse reaction, in which the
molecule returns to its original configuration, leading to
decolorisation, is also dependent on dye structure. For
commercial photochromic classes, the transformation is
primarily a thermal one, although visible light may also
contribute [5].
The photochromic properties outlined above which are
typical of industrially important colorants (high efficiency
photocoloration by near-UV radiation; moderately
efficient thermal fading; low efficiency photobleaching
with visible light) have been labelled ‘heliochromic’ [6,7].
This term, derived from the Greek word for sun, denotes
a specific type of photochromism whereby the dye’s
response is dependent on the intensity of incident
unfiltered sunlight. As the bulk of manufactured dyes are
used in the production of spectacle lenses, heliochromism
is commercially important. However, the general terms
photochromism and photochromic are far more
commonly encountered in both technical and commercial
literature when referring to colorants and products whose
behaviour falls within the definition of heliochromic.
Much time and money has been devoted over the last
half century into exploiting photochromism for a variety
of aesthetic and functional applications. Numerous
organic T-type photochromic molecules have been
commercialised along the way. While the ophthalmic
industry has primarily driven this development effort in
order to bring light-responsive plastic lenses to market,
photochromic compounds have been employed in a
diverse array of alternative applications, such as surface
coatings, to provide arresting visual effects.
Examples of dyes that fade solely through interaction
with light rather than heat, i.e. P-type photochromic
colorants, are relatively rare, but provide the opportunity
of controlled switching between colour and colourless
states, opening up applications for which commercial
T-types are unsuitable. P-type dyes, which include
members of the fulgide and diarylethene classes, have
therefore been subject to intense scrutiny during the last
two decades as molecular switches [8]. T-type
photochromism has however been more industrially
important over the past half century. This dominance
persists today with the main industrial outlet remaining
the application of T-type photochromic dyes in
ophthalmic lenses. Although considerable research is
being directed into making use of light-responsive
colorants in other ways, the next ‘killer app’ has yet to be
found [9]. The areas currently being explored lie
principally in the area of high technology in which P-type
photochromes offer promise as functional colorants for
electronics, communications and computing. This review
will also therefore briefly consider these types of dye and
the uses to which they could be put in future, but first
250 ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 249–261
the development of existing commercial photochromic
applications will be discussed.
Commercialisation of photochromic effects
While photochromism first attracted scientific attention at
the dawn of the modern chemical era in the mid-1800s,
nearly a century passed before the term itself was coined
[10] and the earliest ultimately successful attempts to
commercialise the effect were initiated. Systematic study
of organic photochromic molecules began in earnest in
the 1950s, but the first major commercial exploitation of
photochromism relied on inorganic materials. In 1966,
Corning (USA) marketed photochromic ophthalmic lenses
[11] that darkened reversibly in sunlight owing to silver
halide crystals trapped within the matrix of the glass
[12]. Millions of pairs of photochromic spectacles
incorporating this technology have been prescribed since
then. During this time, plastic lenses surpassed their glass
counterparts in general commercial importance, because
the former offer several advantages including greater
robustness and lighter construction [13]. Consequently,
lens manufacturers required photochromic systems
suitable for plastics as the existing inorganic technology
could not be transferred to polymeric organic matrices. It
was this necessity that primarily fuelled research into
organic photochromic dyes during the latter part of the
twentieth century. Commercial success was first achieved
in the 1990s by companies based in the USA, for
example, Transitions Optical (a subsidiary of PPG
Industries), in Europe, such as Rodenstock (Germany),
and in Japan [14]. Recent patent activity shows that
businesses involved in photochromic lens manufacture
are continuing to innovate in terms of dye structure and
lens formulation [e.g. 15–17]. The manufacture of plastic
photochromic lenses has spread worldwide with
producers obtaining their colorants by one or more
routes:
– in-house synthesis or contract manufacture;
– off-the-shelf purchase from independent photochromic
dye producers, such as James Robinson Ltd. [18]; or
– as part of photochromic lens formulation packages, for
instance those marketed by Corning [19], which are
used to cast or coat lenses.
The biggest consumer of photochromic dyes remains the
ophthalmic industry. Its desire to improve on existing
light-responsive lens systems still accounts for a
significant proportion of research into photochromism.
Advances in photochromic dye technology for lenses
have led to some crossover into the development of other
plastics coloration and surface coating applications in
terms of dye choice and usage. Despite this, achieving
commercially acceptable performance is by no means a
trivial matter for those unused to working with
photochromic colorants. They tend not to be as robust or
as easy to use as conventional dyes and pigments. In
addition, they are more expensive, cost being of the order
of thousands of dollars per kilogram of photochromic dye
as opposed to merely dollars per kilogram for commodity
colours. Nevertheless, photochromic effects with
satisfactory behaviour, durability and economy can be
created provided, as discussed in the next section,
 Corns et al. Industrial organic photochromic dyes

numerous technical factors peculiar to industrial matrix may actually inhibit photochromism: dyes tend to
photochromic compounds are taken into account. perform best in polymers like poly(ethylenes), which
have flexible chains and low glass transition temperatures
Properties of Commercial T-Type (Tg). Matrix polarity is another factor, which affects not
Photochromic Dyes only dye kinetics, but also helps determine the exact
shade produced as the coloured forms of commercial
Although many thousands of organic photochromic
types colorants are solvatochromic, i.e. their colour
molecules have been synthesised over the past 50 years,
changes with the polarity of their environment.
few have been commercialised owing to the formidable
The most commercially important lens shades are
technical and commercial challenges presented in
neutral colours such as greys and browns. These tertiary
developing a marketable product. Not only must the
shades usually call for mixtures of dyes, which poses the
candidate molecule be practical and economical to
problem that the photochromism of individual
manufacture, but also various aspects of its
components must match each other. Even within a closely
photochromism have to satisfy an array of criteria.
related set of photochromic dyes, each member will vary
Specific requirements and their relative importance will
subtly in terms of its intrinsic properties as well as its
vary according to application but may demand that the
responses to the various influences described above.
photochromic species should:
Consequently, combining photochromic colorants adds a
– activate rapidly from colourless to coloured forms so
further layer of complexity as individual components
that the photochromic effect is ‘on demand’;
must activate and fade in the chosen host matrix at the
– fade at the rate appropriate for the desired
same rates. If such molecular unison is not achieved then
application, often expressed as ‘half-life’ which is the
the photochromic mixture will not activate and ⁄ or fade on
time taken for absorbance to halve following removal
tone. Formulating acceptable mixtures is therefore not an
of the activating light – in the case of lenses, as short
easy task, especially when up to six dyes may be required.
as possible a half-life is desirable to prevent
One effective strategy to minimise complications
impairment of vision when light levels suddenly fall;
associated with the photochromic behaviour of individual
– change from its colourless to coloured forms
dyes varying with temperature is to use colorants drawn
efficiently, the latter being strongly absorbing, so that
from only a single class in a mixture and to select a type,
only a relatively low concentration of colorant
the naphthopyran class, whose members have relatively
produces a pronounced colour change effect: short
low temperature dependences [11]. Another commercially
half-lives and high observed intensities tend to be
successful approach has been to design dyes, again within
mutually exclusive, therefore a balance usually has to
the naphthopyran family, that exhibit neutral shades by
be struck between attaining sufficient depth of shade
modifying their molecular structure so that they produce
and ensuring bleaching is acceptably quick;
more than one absorption maximum in their visible
– possess low residual colour when not activated, but
spectrum when they are activated [24]. These single-
‘colour up’ to the desired hue when irradiated;
molecule greys and browns have been marketed since the
– show relatively little change in photochromic response
turn of the century for use as self-shades or in conjunction
with variation in temperature;
with one or two shading components to simplify
– not only exhibit sufficient photostability in both
formulation considerably. The naphthopyran class is
coloured and colourless forms, but also resist the
discussed in further detail, along with other industrially
tendency to ‘fatigue’, whereby, during activation, a
important T-type colorants, in the next section.
proportion of the dye is undesirably and irreversibly
converted to non-photochromic molecules, leading to
gradual weakening of colour upon repeated activation
Classes of Commercial T-Type
[1,20] – lens applications typically require a 2-year Photochromic Dyes
lifetime [13], so successful photochromics have Although many classes of photochromic molecule are
intrinsically low fatigue properties and respond well known, few have so far furnished commercially useful
to the presence of stabilisers; materials because of the stringency of the above criteria.
– be soluble in its immediate environment to give a true The following families are of greatest commercial
solution rather than a dispersion as most commercial importance:
classes do not exhibit useful photochromism as solids – spiropyrans;
[21,22]. – spirooxazines;
– naphthopyrans (also known as chromenes).
To complicate matters, the medium in which the
photochromic molecule is dissolved has a bearing on all Their chemistry and properties will be discussed in turn.
of the above criteria. In the case of polymeric matrices,
the rigidity of the system and the free volume available to Spiropyrans
the dye strongly influence the kinetics of the The first modern attempts to exploit photochromism in
photochromism [23]. These factors alter rates of commercial applications revolved around spiropyrans,
activation and fading because (as will be discussed later) because they could be readily synthesised and
commercial T-type colorants undergo substantial changes photochromed to deep colours that bleached at useful
in molecular shape when switching between colourless rates [25,26]. The class became the most intensively
and coloured states. If not chosen judiciously, the host studied group of organic photochromic molecules during

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Corns et al. Industrial organic photochromic dyes

the 1950s through to the 1970s with indolino-
spirobenzopyran systems 1 being particularly well
explored.
The photochromic properties of a spiropyran arise as a
consequence of the ability of the colourless form of the
compound to undergo a molecular rearrangement in
which the pyran ring opens, generating a coloured
photomerocyanine dye (Figure 2).
A dynamic equilibrium between the ring-closed and
ring-opened forms dictates the colour intensity of the
system. Each species coexists, there being constant
interconversion between the two forms at any given
moment. Irradiation with UV light facilitates the ring-
opening reaction, shifting the balance of the equilibrium
so that the concentration of the photomerocyanine form
increases, which is observed as an intensification of
colour. Removal of the light source has the opposite
effect. The equilibrium moves towards the colourless
pyran form of the dye, which is seen as fading. As ring
closure is driven thermally, a rise in temperature speeds
up decay of the photomerocyanine form to the pyran. The
equilibrium shifts further away from the ring-opened
side, leading to a perceived reduction in intensity of
colour. Consequently, the photochromic effect will be
weaker at higher temperatures: the photochromism of
spiropyrans therefore shows a temperature dependence.
As discussed earlier, other factors can influence
photochromism, such as the substrate into which the dye
is dissolved, by affecting the position of the pyran–
merocyanine equilibrium as well as the ease of
interconversion between the two forms.
The most common synthetic route to simple
indolinospirobenzopyrans is condensation of a Fischer’s
base analogue with a salicylaldehyde in refluxing alcohol
as solvent [25,26] (Figure 3). While product isolated from
the cooled reaction mass may be sufficiently pure for
certain end uses, purification can be effected if necessary
by recrystallisation or, as a last resort, column
chromatography.
The spiropyran products typically photochrome to
violets and blues, although this gamut can be expanded
by resorting to more exotic structures that may demand
alternative synthetic strategies. Replacing the oxygen of
the pyran ring with other chalcogens, such as sulphur
[27], affords derivatives that, when activated, absorb
beyond the visible region into the infrared, but at the cost
of stability. Intrinsically, the spiropyran class generally
has relatively poor photostability and has largely been
superseded by the more fatigue-resistant spirooxazine and
naphthopyran systems. Nevertheless, spiropyrans still
form the subject of research by biochemists, for example
as probes or controls [28–30], and by material scientists,
as in the case of tensile stress sensors [31] and photo-
switched magnetic systems [32], where light stability is
not a prerequisite.
Spirooxazines
During the four decades since the photochromism of this
class of molecules came to light, the research efforts of
academia and industry have borne fruit in the form of
indolinospirooxazine dyes [33]. These colorants are
similar to spiropyrans in terms of their molecular
structure and the mechanism behind their
photochromism, yet exhibit levels of fatigue that are
orders of magnitude lower [34]. As a consequence of their
relatively high stability, spirooxazines have achieved
industrial prominence since they were used in the
manufacture of the first commercial plastic photochromic
lenses in the early 1980s [35,36]. While this initial
product launch ultimately failed, lenses manufactured
with examples of this class were successfully marketed
from the beginning of the 1990s [13].
Two classes of spirooxazine of particular commercial
interest are those based on naphth[2,1-b][1,4]oxazines 2
and naphth[1,2-b][1,4]oxazines 3, which are generally
prepared by reaction of a Fischer’s base derivative with
either a 1-nitroso-2-naphthol or a 2-nitroso-1-naphthol,
respectively, in an alcoholic solvent (Figure 4). For

R' R'' R' R''

UV

X
N O heat and/or N
Y Y
R X light
R
O
Colourless spiropyran 1 Coloured photomerocyanine dye
R = alkyl; R', R'' = alkyl (usually both methyl) (mixture of isomers – others not shown)
X, Y = H, halogen, nitro, etc.

Figure 2 Photochromism of spiropyrans (with 1 as an example)

R' R'' O R' R''

H
+ X
N N O
Y HO Y
R R X

Fischer's base Salicylaldehyde R, X, Y = H; R', R'' = methyl

derivative derivative gives purple when activated

Figure 3 A commercial synthetic route to indolinospirobenzopyrans

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 Corns et al. Industrial organic photochromic dyes

NO R' R'' OH
OH ON
X + + A
N
Y
R

R = alkyl
R', R'' = alkyl (usually
R' R'' both methyl) R' R''
X = H, amino, hetaryl, etc. N
N X
Y = H, halogen, etc.
A = aryl
N O N O
Y Y
R R

2 3
Useful for violets and blues Useful for greenish–blues
A

Figure 4 Commercial synthetic routes to marketed spirooxazines

practically all end uses, purification by standard practices
such as recrystallisation or column chromatography is
essential, the latter being avoided if possible for economic
reasons.
The simplest examples give relatively fast-fading blue
photocoloration – however, by appropriate molecular
design, commercially viable dyes with red and purple
through to turquoise activated forms can be synthesised.
Careful selection of substituents enables kinetics, as well
as colour, to be fine-tuned. For example, placing bulky
alkyl groups on the indoline nitrogen of 2 and 3, i.e.
substituent R, produces industrially useful dyes with
increased colourability and slower fade [13,37]. Another
strategy involves locating either a tertiary amine function
or a nitrogen heterocycle, such as indoline [38], para to the
oxazine nitrogen atom in compounds of type 2 to furnish a
commercially successful subclass of general structure 4
(Figure 5; R = alkyl; X = tertiary [cyclo]alkylamino or N-
hetaryl) with good colourability that is shifted into the
bluish–red and purple regions. Such dyes have been
manufactured for at least the past 15 years [20], an
example being the spirooxazine 4 (R = methyl, X =
N-piperidino), which is currently marketed as Reversacol
Plum Red [24]. Its excellent photochromic properties are a
consequence of the amine function on the naphthalene
ring markedly increasing the extinction coefficient of the
photomerocyanine form as well as the quantum efficiency
of photoisomerisation [37].
Many other kinds of spirooxazines are known whose
structures have either or both of the nitrosonaphthol and
Fischer’s base components replaced with other synthons.
Examples are indolinospiropyridobenzoxazines 5 [11,39]
which are derived from 5-nitroso-6-hydroxyquinoline and
Fischer’s Base analogues. These compounds first attracted
industrial attention in the early 1980s [40] as they
combined relative ease of synthesis with useful properties
and were most successfully commercialised in the early
1990s [41]. While there are numerous examples of more
exotic spirooxazines in the patent literature, they do not
generally offer any advantages over simpler derivatives
because increases in cost and difficulty associated with
manufacture tend to outweigh any improvements in
performance.
Naphthopyrans
While neglected for many years since their discovery,
naphthopyrans have been much studied over the past two
decades [42] and are now the most commercially
important class of photochromic molecule. Like spiro-
pyrans and -oxazines, their photochromism relies on
light-induced ring opening (Figure 6). However, their
chemistry is such that many different types of functional
groups can be introduced cost-effectively, enabling a
more extensive gamut of colours that spans across the
visible spectrum from yellows through to oranges, reds,
purples and blues. Commercial naphthopyrans are
generally regarded as having stability properties that are
as good as any other known class and their
photochromism is less sensitive towards temperature than
spirooxazines. Consequently, all the major manufacturers
of plastic photochromic lenses have used naphthopyrans
in their formulations.
Two of the three possible naphthopyran subclasses,
namely 3H-naphtho[2,1-b]pyrans 6 and 2H-naphtho[1,2-
b]pyrans 7 (Figure 7), have commercially useful
properties.

H3C CH3 R''

R'''
N N
Y
N O N O N
R Z R'
X
4 5

Figure 5 Examples of some industrially useful spirooxazine types

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Corns et al. Industrial organic photochromic dyes

X Y

UV
Y
O
heat and/or
R light O
R
6
Colourless [2,1-b]naphthopyran
Coloured dye; typically yellow, orange or red
X, Y = H, alkoxy, amino, etc. (mixture of isomers – others not shown)
R = H, amino, etc.

Figure 6 Light-induced ring opening of naphthopyrans (using [2,1-b] derivatives as an example)

Y
X
X Y
OH
R'
OH
O
R +
R'

R 7
1-Naphthol
Diarylalkynol compound
derivative
Colourless [1,2-b]naphthopyran
X, Y = H, alkoxy, amino, etc. (typically gives red, purple or blue)
R, R' = H, alkyl, aryl, ester, amino, etc.

Figure 7 A commercial synthetic route to naphthopyrans (using [1,2-b] derivatives as an example)

Of several routes to such materials [43], a general and
important pathway for large-scale manufacture is reaction
of a suitable 2- or 1-naphthol, respectively, with a diaryl
alkynol. A non-polar solvent, such as toluene, is usually
used and always in the presence of an appropriate acidic
substance, for example, an aluminium oxide. In certain
instances, it may be possible to isolate a product of
sufficient purity directly from the reaction mass, but, as
with the spiro-pyrans and -oxazines, recrystallisation or
column chromatography is often necessary to obtain the
desired product quality.
Just as naphthopyran chemistry permits the economic
introduction of many different types of functional groups
in order to manipulate colour, structural changes can also
be employed to fine-tune the kinetics of photochromism
and improve photostability [43,44]. When making such
alterations, it must be borne in mind that their effects
tend to be inextricably linked with colour. These
considerations can be exemplified by examining the
structural features of a typical commercial dye,
Reversacol Berry Red, which is the naphtho[1,2-b]pyran 8
[45,46] (Figure 8).

Major kinetic and colour

X
effects
4'
H3CO 4' 4'' OCH3

O 4''
O Y
8
6
5 Z
CH3
6 9a X=Y=Z=H
CH3 9b X = Y = H; Z = amino
Major kinetic and 9c X = Y = OMe; Z = H
minor colour effects 9d X = Y = OMe; Z = amino
9e X = H; Y = Z = amino

Figure 8 Substituent effects in some commercial naphthopyrans

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The positions on the benzene systems para to the spiro
linkage (marked 4¢ and 4¢¢) are very effective sites to place
substituents for tuning the shade, intensity and speed of
fade of the activated colour. Electron donors, such as
alkoxy and amino functions, can be economically
introduced into these locations, furnishing substantial
bathochromic shifts, but at the cost of apparent intensity
owing to increases in the rate of the thermal fading.
However, substitution at the 5- and 6-positions on the
naphthalene ring is an effective way of manipulating
the rate of bleaching and can be used to compensate for
the effects of other features on kinetics. In the case of dye
8, the methoxy functions shift the very slow fading
parent orange dye into the red when activated, whilst the
5-methyl group is essential in shortening half-life by an
order of magnitude to give a fade rate that is of industrial
interest. The second methyl substituent is present to
further reduce half-life to a commercially useful level
without affecting shade.
Various strategies have been adopted by industry for
modifying the colour and kinetics within the naphtho[2,1-
b]pyran class. Some of these can be illustrated using the
dye series 9, whose members have all been
commercialised. The simplest possible derivative, 9a,
available as Reversacol Rush Yellow [47], produces a
relatively weak yellow coloration. One industrially
important means of boosting strength by slowing down
fade speed is to place an electron donor into the 6-position,
for example an amino function in the case of 9b. Although
doing so brings about a modest hypsochromic shift, this
dye is a much stronger yellow than the parent colorant. In
a similar manner to that discussed above for dye 8,
introducing electron-releasing methoxy functions into the
4¢- and 4¢¢-positions leads to red-shifting, making other
hues accessible. The bathochromism comes at the price of
an increase in fade rate, which tends to produce weaker
coloration. Consequently, dye 9c is orange but even weaker
than dye 9a. Use of a 6-amino group can offset this
outcome, but the hypsochromic shift it also confers works
against the intended effect: while dye 9d produces much
more intense photocoloration than dye 9c, it is yellow
rather than orange. A solution is to strike a balance
between the kinetic and colour effects of the 4¢- and
4¢¢-substituents with those of the donor function at the
6-position: this has been achieved, for instance, with
X Y
O
R2N
R
R1
confers extra
10 peak and
neutral colour
Figure 9 Some commercial naphtho[1,2-b]pyran types
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Corns et al. Industrial organic photochromic dyes
dye 9e, a commercially successful orange naphthopyran. In
combination with blue spirooxazines 5, pyrans of this type
and colour were utilised in the first true grey commercial
photochromic lenses in the early 1990s [35].
The utility of naphthopyrans for constructing
photochromic plastic lenses continues to drive much of
the research into this colorant class. Numerous esoteric
molecules have been patented, of which only a very small
proportion have been commercialised. While such
structures are claimed to offer technical advantages, it is
arguable that the primary motivating factor for the
appearance of the plethora of derivatives is simply the
need to avoid infringement of existing patents. However,
certain relatively complex substitution patterns have
proved industrially useful, for example, where an indeno
ring system has been fused to the 5- and 6-positions of
naphtho[1,2-b]pyrans as in the general structure 10
(Figure 9). Dyes of this kind have been used to create
lenses since the mid-1990s [41].
As touched on earlier, a significant innovation has been
the development of naphthopyrans that afford neutral
shades as a consequence of their coloured forms
exhibiting two or more broad absorption peaks of similar
intensity in the visible spectrum [24]. This property
simplifies the formulation of grey and brown colorations
by reducing the number of colorants required (thereby
lessening the difficulties involved in matching the
properties of the individual dyes) or even obviating the
need for shading components. Derivatives of general
structure 11 that give brown [48] and grey [49]
colorations have been marketed over the past decade. The
amino function at the 9-position of the naphthopyran ring
system induces additional absorption in the shorter
wavelength region of the visible spectra of their
photomerocyanines. Appropriate manipulation of
absorption at longer wavelengths, for example, by
adjusting the strength of the electron donor groups X and
Y, furnishes grey dyes as in the case of dye 11
(X = N-piperidino; Y = hydrogen, Z = carboxymethyl;
R = methyl) [38]. Dye selection is still important because
the medium in which the colorant is to be deployed will
influence the exact position and intensity of the
absorption peaks, which may alter the balance between
them and compromise neutrality of colour. However, not
only are neutral-colouring naphthopyrans of great benefit
varied to adjust
colour and kinetics
X Y
O
9
Z
11
selected to
tune kinetics
255
Corns et al. Industrial organic photochromic dyes

to lens formulators (and for this reason have been a inclusion of additives [50]. These latter materials may
commercial success), but they can also potentially comprise: hindered amine light stabilisers, antioxidants
simplify the effort of technologists working in other fields and thermal stabilisers whose mode of activation includes
like surface coatings. scavenging of free radicals that could attack colorants;
triplet state quenchers to deactivate reactive excited states
Industrial Applications of T-Type by channelling away their energy along thermal
Photochromic Molecules pathways, thereby inhibiting photochemical reactions
other than the desired photoisomerisation; UV absorbers
A diverse array of niche products has been created
which soak up excess radiation, shielding dyes from
with industrial photochromic dyes. The use made of
potentially destructive higher energy photons. Care must
photochromism in such items ranges from the purely
be exercised in selecting examples of the last-mentioned
aesthetic, as in artwork, to the functional. An example of
type of additive so that they do not absorb in the window
the latter is security printing where light-triggered change
of UV wavelengths required by the dyes for activation
is the key property of the system and its colour tends
and diminish the photochromic effect. Significant
to be incidental. The largest commercial application
interactions have been noted between additives, which
lies between these extremes: while variation in the
can complicate formulation of a stabiliser package, while
transmittance of sun lenses is crucial to their function of
instances of additives harming dye performance in terms
protecting spectacle wearers from excessive light levels,
of kinetics and residual colour are known. However,
activated colour is important both aesthetically and from
when used judiciously, additives can enhance the lifetime
the perspective of maintaining visual acuity. Despite these
of the photochromic molecule substantially without being
differences, product manufacture involves incorporating
deleterious to photochromism: extensions of over an
colorants into media in such a way that photochromic
order of magnitude in polyolefins have been claimed by
effects with the desired colour, kinetics and resilience are
means of a cocktail of the above additive types [50,51].
created. Implications for industrial dye application in
Given the right polymer selection and application
terms of medium are therefore discussed next.
techniques, striking and durable photochromic effects can
be achieved with low loadings of dye, varying in the
Non-ophthalmic thermoplastics
range 0.01–0.30% w ⁄ w depending on the colorant and
The photochromism of dye–polymer systems is heavily
medium. For example, in the case of poly(ethylene), an
dependent on the chemical and physical nature of both
inclusion level of just 0.05% by weight is typical. Too
components. An example is the application of dye by
great a concentration of dye can be detrimental to, or
injection moulding to a thermoplastic. Whether the
even destroy, the photochromic behaviour.
colorant is introduced in pure form or as a masterbatch,
Some of the difficulties described above can be
the process must produce a monomolecular dispersion of
obviated by conversion of dyes into forms that can be
dye in the polymer. The physical properties of the
processed like pigments through microencapsulation. A
medium are therefore of great importance in obtaining the
solution of the dye is encased in a polymer, giving a
desired photochromic effect or even permitting any
photochromic powder of particles with diameters of the
photochromism at all. Spirooxazines and naphthopyrans
order of 10)5–10)6 m that can be dispersed in a similar
work best in polymer matrices with relatively low
manner to a conventional pigment. Care is needed during
flexural moduli and Tg, like those of polyolefins and
application not to compromise the microcapsules and
plasticised polyvinyls, as they do not tend to restrict the
greater loadings of pigment are required than in the case
changes in conformation that the dyes undergo upon
of neat colorant. A significant benefit is that the
photoisomerisation. Materials with high rigidity are
performance of the dye is independent of the polymeric
therefore to be avoided with a typical commercial T-type
medium in which the microencapsulate is dispersed,
colorant as they tend to lock the dye in the non-coloured
enabling photochromism to be observed when it would
closed form and so inhibit photochromism. A reasonable
otherwise be inhibited using non-encapsulated dye.
rule of thumb is that a polymer with a flexural modulus
A more recently developed approach not only makes
of greater than two GPa will give a poor photochromic
possible the application of T-type dyes to polymers that
response, examples including polycarbonates and
are not conducive to photochromic effects, but also
styrene–acrylonitriles. Processing conditions must also be
improves the properties of dyes in well-used polymers.
borne in mind as many conventional commercial
Conventional spirooxazine and naphthopyran derivatives
photochromic dyes can only tolerate the elevated
are modified by attaching oligomeric chains or ‘tails’ that
temperatures involved in mass coloration for brief
provide a microenvironment for the dye by curling
periods. It is certainly the case that such colorants
around it when delivered to a polymeric matrix [52,53].
degrade excessively upon exposure to temperatures above
This in turn leads to kinetics that are more akin to those
250 C, causing discoloration and greatly reduced
observed when the tail-less dye analogue is dissolved in a
photochromic response.
solvent. In addition to providing more solution-like
Polymer choice will also influence photostability. The
performance, tailing can produce dyes that fade more
lifetime of the photochromic effect of a plastic is related
quickly and yet activate to more intense colours: these
to the cumulative amount of incident UV radiation rather
two properties are usually mutually exclusive. In
than the number of times the plastic is cycled between
addition, the tails tend to be protective of the dye,
colourless and coloured states. The type of plastic and
enabling application to polymers whose processing
dye employed can modify this dependency, as can the

256 ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 249–261

temperatures are too high for conventional dyes, like
polyamides, and also confer better photochromic
performance in relatively rigid thermoplastics. Recent
work has shown that the approach can be extended to
rigid thermosets by attaching longer tails, for example,
low Tg polymer chains to naphthopyrans [54].
All of the above techniques have been commercialised.
For example, mass coloration with photochromic
masterbatch and microencapsulate has been employed in
the production of items such as drinks bottles, Frisbees
and hair clips from poly(ethylene) as well as key fobs and
mobile phone accessories from plasticised poly(vinyl
chloride). Naphthopyrans and spirooxazines have been
employed in the manufacture of dolls that reversibly
develop ‘suntans’ when exposed to daylight and toy cars
[55] which give the impression of being spray-painted
when near-UV from an light emitting diode embedded in
a ‘spray gun’ is played over them. Photochromic crash
helmet visors for motorcyclists are available from several
manufacturers [56], with adhesive light-responsive film
being another option for riders [57]. Clever use of
photochromism has been made in fishing line, which
consists of a clear colourless polymeric fluorocarbon
impregnated with photochromic dye [58]. Below the
water, the line is well concealed from fish owing to its
refractive index and lack of light absorption as
insufficient UV is able to penetrate below the surface to
activate the dye. However, this is not the case out of the
water: the line colours up and thus becomes readily
visible to anglers.
Photochromic dyes have also been combined with other
special effects colorants, like pearlescents and metallics,
to generate unusual looks, for example, in mobile phone
covers.
Ophthalmic lenses
As has already been indicated, photochromic lens
manufacture accounts for by far the greatest volume
usage of T-type dyes. Considerable intellectual property
exists concerning the ways in which the dyes are
incorporated into lenses [13].
– In mass: dyes are injection-moulded in a
thermoplastic or are dissolved in a monomer or resin
system which is then thermally or UV-cured into a
semi-finished lens that can be ground to the desired
prescription.
– Coating: the colorants are coated onto the front or the
back face of a lens in solution along with a resin by a
technique like spin- or dip-coating.
– Imbibition – a photochromic layer ca. 0.2 mm thick is
formed in the lens surface by allowing dye to diffuse
into the polymer matrix.
– Lamination: a film containing the photochromic dyes
is sandwiched between two sides of a lens.
When employing the in-mass and imbibition techniques,
the formulation of the prepolymer system is of crucial
importance in obtaining a lens that not only has the
desired physical properties, such as impact resistance,
but also allows dye molecules to function within the
matrix. Conventional plastic lens materials such as
polycarbonates are too rigid, which has necessitated the
ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 249–261
Corns et al. Industrial organic photochromic dyes
development of proprietary systems to achieve a
compromise. The approaches of coating and lamination
sidestep this problem through use of a photochromic
layer that is separate from the main body of the lens,
widening the choice of polymer vehicles for the colorants.
However, in-mass lenses possess an advantage with
respect to countering fatigue. They effectively have a
reservoir of dye to draw upon in the body of the lens
when colorant nearer to the surface is photochemically
destroyed during use.
Much effort has been devoted to creating lenses that
activate and fade on tone through the use of dyes with
neutral colours and ⁄ or cocktails of carefully matched
components. In contrast, one recent innovation to be
commercialised centres around a lens for drivers that
changes to different hues depending upon whether or not
the sunlight to which it is exposed has been filtered
through a car windscreen [59]. The lens turns from a
greenish–yellow base colour to dark brown upon direct
exposure to bright daylight outside of a vehicle, but
becomes only copper-coloured under a windscreen,
assisting the driver by removing excess light while not
hindering traffic signal recognition. This two-stage
activation is achieved by use of a combination of
photochromic colorants with different spectral
sensitivities [60]. Those that can be activated when
irradiated with just visible light are used to provide the
in-car photochromic response, while those that are
sensitive to UV wavelengths furnish the supplementary
darkening when outside of the vehicle.
Surface coatings
Photochromic inks and varnishes for application to a
variety of substrates are a commercial reality [61,62]. In
addition to aesthetic uses, like photochromic nail varnish,
their colour-change properties have been exploited for
more functional applications. For instance, security
printers can produce optically variable marks that allow
document authentication in a manner that is difficult to
copy [63]. An example is the claim that photochromic
material has featured in the US passport [47].
There are a variety of means of applying photochromic
colorants to surface coating formulations. The simplest
method takes advantage of the solvent solubility of
certain commercial photochromic dyes: a colour-change
effect can be obtained simply by dissolving them in a
commercially available solvent-based gloss varnish. These
dyes are, however, not water soluble, so, when working
with aqueous vehicles, alternative approaches must be
employed [64]. One such technique that has already been
mentioned in the context of thermoplastics involves
dispersion of photochromic microencapsulates into
surface coatings in a similar manner to conventional
pigments. Microencapsulated dye for this purpose is
supplied commercially in powder or aqueous slurry form,
comprising micron-scale droplets of photochromic dye
solution that are enclosed in a polymer shell. This
conversion is necessary in order to produce photochromic
ink from spirooxazine and naphthopyran dyes that are
water insoluble when the ink vehicle is aqueous as the
colorants must be in solution to photochrome. An
alternative practice entails micronising a solid solution of
257
Corns et al. Industrial organic photochromic dyes
photochromic dye in a polymer and dispersing the
resultant photochromic pigment into the surface coating
medium.
Inclusion levels of colorant are dependent on the form
in which the dye is added as well as the application. For
example, printing techniques such as lithography,
flexography and gravure produce relatively thin films of
ink, typically 2- to 7-lm dry thickness, and require more
neat colorant (1–3% w ⁄ w dye ⁄ ink) than those giving
thicker films, like conventional screen printing (ca. 12-lm
dry film thickness) where only 0.5–1% w ⁄ w dye may be
needed. As is the case with other media, photochromic
effects will not be generated if the concentration of
colorant is too high. In addition, care must be taken to
ensure that the photochromic dye is not damaged during
formulation or application and is provided with the right
environment to function once the surface coating has
been applied to a substrate.
Textiles
The interest shown in photochromic colorants as a
means of producing novel effects in apparel has not
been matched by commercial success in this sector.
Major technical factors for this state of affairs are the
difficulties encountered when applying industrial
photochromic dyes by conventional textile coloration
techniques as well as their poor performance in terms of
the effect produced and its durability [65]. For the most
commercially important hydrophobic polymers such as
polyester and nylon, there are several problems
associated with the use of conventional T-type colorants.
They are relatively delicate molecules that do not
respond well to the conditions of exhaustion dyeing.
The relative bulk of the colorants (when compared with
conventional disperse dyes) does not favour diffusion
into the fibre and the polymers themselves tend to
inhibit photochromism. The combined consequences
have been illustrated in the case of spirooxazines as
disperse dyes for nylon [66] and other substrates [67,68].
They are also evident in members of this photochromic
dye class that have been equipped with reactive
functionality for nylon [69] or conferred with water
solubility for silk [70].
Marketable photochromic textile effects can be
achieved, however, by application of screen-printing
pastes incorporating dye onto fabric. While this technique
obviates the snags associated with exhaustion dyeing and
colorant–substrate incompatibility, print photostability is
sufficiently low that consumer expectations must be
managed appropriately [62]. A different approach for
imparting photochromic detail to garments is to use mass-
coloured thread, such as poly(propylene) melt-spun with
photochromic dye. Application of a commercial
spirooxazine derivative to wool fibre by means of a silica-
based sol-gel coating process has recently been
demonstrated to give a photochromic effect [71].
However, it appears that, if the application of extant
industrial colorant types to fabrics by conventional
dyeing techniques is ever to become commercially viable,
then tailoring of dye structure and ⁄ or coloration process
design will be necessary to give cost-efficient, durable
effects of acceptable intensities and kinetics.
258 ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 249–261
Other uses and future developments
A great deal of interest has been shown by academic,
governmental, military and industrial organisations over
the last half-century in examining T-type photochromic
dyes for a plethora of uses. While some of these
applications have come to fruition as discussed earlier,
others remain to be commercialised as they have not yet
surmounted technical, economic and ⁄ or regulatory
hurdles. The way in which each application utilises
photochromism has been split into one of three broad
classifications of dependency [72,73]:
– reversibility, for example, adaptation of transmittance
as in sun lenses and flash protection;
– sensitivity to radiation, for example, production of
colour change effect in toys and artwork;
– functionality, for example, overt or covert light-driven
property changes for security purposes;
but it is arguable that there is overlap in many cases. For
example, photochromic dyes have been proposed as
covert markers to combat the laundering of fuel [74]:
their presence is only revealed during a field test which
involves irradiation with UV light, causing a measurable
change in colour. While reversibility may not be critical
to the application, both sensitivity and functionality are
key properties. Other potential means of defeating fraud
and counterfeiting include the marking of currency [75]
and woven merchandise labels [76].
Numerous other opportunities await the development
of systems that give a commercially acceptable level of
robustness before they can be marketed. These
applications include smart windows and agricultural
films that enable the amount of light transmitted to be
automatically regulated, for example, in the latter case
shielding of crops from excessive light levels. The lifetime
for activity of at least 10 years demanded of architectural
windows [47] is beyond current photochromic
technology, hence the exploration of electrochromism and
thermochromism as potential solutions [77].
Another manufacturing sector that has taken an interest
in photochromism is personal care. Intellectual property
has been developed concerning photo-responsive colora-
tion effects, for example, in cosmetics, hair dye formu-
lations and sunscreen lotions [e.g. 78–81]. Photochromic
inks have even been patented for the creation of tattoos
that are invisible until exposed to sunlight [82].
There are numerous outlets of great potential
importance that demand photochromic behaviours which
T-types simply cannot provide: these are outlined in the
following sections.
P-Type Photochromic Dyes
As mentioned earlier, P-type photochromic dyes have
received increasing attention over the past decade as a
consequence of industry and academia seeking to make
new applications based on photochromism a commercial
reality. These technologies rely on controlled light-driven
switching between molecular states [8,83], which is a
mode of action that, by definition, is not possible with
T-types. For example, all-optical circuitry would free
computers of the need to shunt electrons around during

processing, leading to step changes in speed and power
consumption. Consequently, there is great interest in
finding optical equivalents to electronic components,
such as switches and logic gates, based on P-type dyes
[84,85]. Optically-switchable molecules have also formed
part of the drive to develop next-generation memory
technologies because they can in theory offer much
greater data storage densities than existing systems
[86,87]. For instance, numerous novel materials of
interest in information technology have been created by
covalently linking P-type dyes to non-photochromic
systems so that the properties of the latter, such as
fluorescence, can be photo-regulated [88,89].
The two most studied dye types for the applications
described above are drawn from the fulgide and
diarylethene families so they will be discussed in turn
next.
Fulgides
In contrast to the previously discussed commercial types
of photochromic dye, the photochromism of fulgides
relies upon UV light provoking ring closure as opposed to
ring opening [90,91] (Figure 10). The reverse reaction
does not occur thermally, but requires the absorption of
certain wavelengths of visible light. Consequently, unlike
pyran- and oxazine-derived colorants, activated fulgides
are reluctant to bleach in the dark. A further difference
exists in that, whereas the spiro compounds must be in
solution for them to exhibit useful photochromism,
fulgides also photochrome as solids [22]. A wide gamut of
colours can be obtained: while simpler derivatives give
transitions from nearly colourless to yellows and reds,
absorption into the infrared region is possible with
appropriate molecular design.
Although fulgides have been used in conventional
coloration areas such as textiles and printing inks [92],
they are of more interest for functional applications [93].
O O
UV light
O O
O visible O Conclusions
light
O O
Pale yellow Red
12
Figure 10 Structural change associated with photochromism of
fulgides as illustrated by the furyl fulgide ‘Aberchrome 540’ (12)
F F
F F
UV light
F F
X Y visible
light
S S
Colourless
13
Figure 11 Photoisomerism of diarylethenes as illustrated by the dithienylhexafluorocyclopentene class (13)
ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 249–261
Corns et al. Industrial organic photochromic dyes
For example, dye 12, which was once commercially
available as Aberchrome 540, has been widely employed
in chemical actinometry [94]. Fulgides and related
systems continue to attract attention as candidates for
optical switch and memory applications [95,96].
Diarylethenes
The photochromism of this class, like that of the fulgides,
involves photocyclisation to a coloured isomer and ring
opening to the colourless form [97,98]. When
appropriately structured, the coloured cyclised material is
thermally stable, furnishing useful P-type photochromic
dyes, examples of which have been found to be more
resilient and readily synthesised than fulgides [99,100].
Derivatives that have attracted particular industrial
attention over the past two decades for these reasons
include members of the dithienylhexafluorocyclopentene
subclass 13 as shown in Figure 11.
Materials of this type have been investigated for their
potential as optical switches [98], both for photonics
[101] and multiple state memory elements capable of
shifting between more than one coloured form [102].
Dihetarylethenes have been targeted for use in
nanotechnology, for example, by exploiting the
remarkable photo-induced shape change in dye crystals
that certain members exhibit [103,104] as the basis for
light-driven actuators [105]. They have also been
investigated in connection with the control of polymer
surface properties, for example, water repellency through
reversible dye-moderated microfibril formation [106,107].
Despite all the effort being expended on this class,
including the study of continuous microflow reactor
techniques to improve selectivity and yield [108], it is not
clear which, if any, of these avenues will bear fruit in the
long term. However, owing to the potential impact that
some of the technologies could have if they ever do
eventually become commercial reality, their successful
development and introduction would signal the end of
the dominance of T-type dyes in terms of industrial
importance.
Photochromic dyes occupy a niche position within the
coloration industry, but nevertheless underpin a
multimillion-dollar manufacturing sector in the form of
the photochromic ophthalmic lens business. The vision of
the chemists and technologists who set out over 30 years
ago to commercialise lightweight, lightfast, mechanically
F F
F F
F F X, Y = H, R1-2, Ph,
fused (het)aryl,
X etc.
Y
S S
Coloured
259
Corns et al. Industrial organic photochromic dyes
strong photochromic plastic lenses of the desired
activation and fade rates has, to a large extent, been
achieved with great strides being made over the last two
decades. Despite this, the search for both minor and step-
change improvements in the technology is still a major
driving force for the continued instigation of
investigations into photochromic colorants. Other
incentives for such research efforts are the financial
rewards that could be realised by whoever successfully
brings to market one of several high-tech applications
based on photochromism. These nascent technologies
place quite different sets of demands on dyes compared
with ophthalmic requirements, resulting in much recent
attention being focused onto colorant classes whose
chemistries and properties differ markedly from those
already exploited industrially. There is no lack of
technological challenges and commercial obstacles to be
surmounted in each case, ensuring that the design,
application and manufacture of industrial organic
photochromic dyes will be the subject of research and
development work for many years to come.
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The corresponding author, Dr Andrew Towns, is
research manager at James Robinson Ltd, a
subsidiary of Vivimed Labs Limited. During his eight
years at the company, he has been involved with
research into, and manufacture of, many colorant-
related materials including photochromic dyes and
their intermediates.
Dr Steven Partington has served over twenty years
with James Robinson Ltd, spending the majority of
this time as product research manager. He has been
heavily involved in the development of the company’s
photochromic dye business since its inception, driving
much of the research that has led to its expansion.
Dr Nigel Corns is a research chemist and the safety
co-ordinator at James Robinson Ltd. As well as
undertaking photochromic dye research and
development during part of his fourteen years at the
company, he has much experience of the kilo-scale
manufacture of these colorants and their
intermediates.
261