Dyes and Pigments 66 (2005) 103e108

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New developments in the stabilization of leuco dyes:

effect of UV absorbers containing an amphoteric
counter-ion moiety on the light fastness of color formers
Hironori Oda*
Faculty of Education, Osaka Kyoiku University, 4-698-1 Asahigaoka, Kashiwara, Osaka 582-8582, Japan
Received 28 June 2004; received in revised form 3 September 2004; accepted 23 September 2004
Available online 17 November 2004

Abstract

Color formers are extensively used in information recording systems or thermochromic systems for textiles, but their light
fastness properties are poor. The improvement of light fastness is therefore being sought at the present time. Various kinds of
stabilizers have been synthesized to prolong the life of colored species derived from color formers. The suppressing effect of these
compounds towards photofading was investigated on cellulose. It was found that the UV absorbers bearing the groups capable of
acting as an amphoteric counter-ion play very important role in improving the light fastness of colorants for imaging and data
recording systems. Zinc and nickel 2,4-dihydroxybenzophenone-3-carboxylates have been proposed as effective stabilizers against
the fading of color formers.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: Color former; Counter-ion effect; UV absorber; Photofading; Improvement

1. Introduction intermolecular acid-base equilibrium reaction. Thus, the

coloration occurs when basic color formers react with
The chemistry of color formers has recently become acidic developments, e.g. bisphenol-A [2].
of importance, particularly in connection with the rapid In addition, the color formers are also employed in
development of information recording systems and the making use of thermochromism. Examples of the use
thermochromic systems for a diverse range of applica- of these materials include temperature indicator for
tions [1e3]. Thermal recording systems using heat- children’s food by color change plastic mugs, indicator
sensitive paper have been widely used in facsimiles, stripes on beer to indicate correct chilling, and on milk
word-processors, printers and point of sale labels, etc. cartons to indicate that they have been refrigerated. In
because of its workable properties. Moreover, a heat- the novelty area, logos on mugs and printed textiles such
sensitive recording method has been used in prepaid as ski wear or promotional T-shirts are common uses.
cards. These information recording systems have re- Such pigments are actually composites formulated from
cently become more and more common in our daily life three components, the color former, an acidic catalyst
[1]. In the systems, the image is recorded by the color- and a non-polar co-solvent medium. The thermochrom-
forming reactions upon heating. This process is an ism centers around the interaction of color former and
developer which occurs in a low-melting hydrophobic
medium: the color of pigment changes when heated
* Tel./fax: C81 729 78 3405. above its melting point and returns instantaneously on
E-mail address: [email protected] cooling and solidification [3]. However, functional dyes

0143-7208/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2004.09.009
104 H. Oda / Dyes and Pigments 66 (2005) 103e108

R2N NR2 R2N NR2

X
R X
O R
Y
C=O
CO2 Y
X = OH
Y = CO2Zn1/2 or Ni1/2
NR2 R = Aromatic Compound NR2 n
I II
Scheme 1

of this type gradually fade and so improved light ethanol in the usual way. 2,4-dihydroxybenzophenone-
fastness is currently being sought [1]. 3-carboxylic acid (mp 203-4
C) was synthesized by
In previous papers [4e8], the photofading behaviors Friedel-Crafts reaction of benzoylchloride with 2,6-
of Crystal Violet lactone and related compounds were dimethoxybenzoic acid ethyl ester in anhydrous di-
investigated in solution and in the adsorbed state. Zinc chloromethane solution containing aluminum chloride
or nickel salts of 1-hydroxy-2-naphthoic acid and its according to the procedure described in the literature [9].
derivatives provided more marked improvements in the The compound was recrystallized from methanol-2-
light fastness of color formers than did conventional propanol after the column chromatography and identi-
stabilizers. It was found that the amphoteric counter-ion fied by 1H NMR, Mass, IR and elemental analyses.
effect plays a very important role in the photostability of Metal carboxylates were prepared and purified as
color formers. Therefore, it is of interest to prepare a described previously [5,10].
series of compounds capable of acting as the amphoteric The formulas of dye 7 and these materials are shown
counter-ion (X-R-Y) in complex II with color former in Figs. 1 and 2.
(see Scheme 1). An UV absorber with attached
amphoteric counter-ion residues is particularly note- 2.2. General procedure for photofading of color
worthy. formers and related colorant
In this paper, the influence of a functional UV ab-
sorber containing an amphoteric counter-ion moiety on According to the procedure described in the previous
the photofading behavior of color formers was investi- papers [5e8], a solution of 1 (8!103 mol dm3) in
gated on cellulose, and a novel approach for improving 10 cm3 of a mixture of pyridine and water (4:1 v/v) with
the light fastness of colorants for imaging and data or without additive (4!102 mol dm3) such as carbox-
recording systems is now reported. ylic acids, metal salts, HMBT, HBP or NMC, was
prepared in the presence of bisphenol-A (54.8 mg), and
then stirred at 80
C for 1 h.
2. Experimental Portions of the solutions (1!102 cm3) were spotted
on cellulose TLC plates using a micro-syringe and dried
2.1. Materials at 150
C. The plates were held at a distance of ap-
proximately 5 cm from the light source (100 W high-
Crystal Violet lactone (1), 3-diethylamino-7,8-benzo- pressure mercury lamp; Ushio Electric Inc., UM-102
fluoran (3),3-(N-ethylisobutylamino)-6-methyl-7-anili-
nofluoran (5) and tetrachlorophthalic acid mono
(ethylene glycol ester) zinc salt (PEG-Zn) were obtained Cl
from a commercial source. The chloride of Crystal
Violet (CI Basic Violet 3, lH 2O Me2N NMe2
max 586 nm) (7), 2,2-bis
(4-hydroxyphenyl)propane (bisphenol-A), nickel
dimethyldithiocarbamate (NMC), 2-(2#-hydroxy-5#-
methylphenyl)benzotriazole (HMBT) and 2-hydroxy-
benzophenone (HBP) were purchased from Tokyo
Chemical Ind. Co., Ltd. Cellulose TLC plates (0.1 cm
thickness) were purchased from Merk Co., Ltd. 2,6- NMe2
dimethoxybenzoic acid ethyl ester was obtained by
treating 2,6-dimethoxybenzoic acid with anhydrous Fig. 1. Chemical structure of dye 7.
 H. Oda / Dyes and Pigments 66 (2005) 103e108 105

OH CO2X H H
O O O O
OH UV
CO2X -∆
8a: X=H 9a: X=H
Scheme 3
8b: X=Zn1/2 9b: X=Zn1/2
8c: X=Ni1/2 9c: X=Ni1/2 a poor fastness to light, and an improvement of the
property is requested.
A number of different types of UV absorbers,
O OH CO2X containing absorbing groups, are available for protect-
CO2X ing dyes on fabrics, but only 4 fundamentally different
classes have achieved commercial significance. These are
OH the derivatives of cinnamic acids, phenyl esters, hydroxy-
10a: X=H phenylbenzotriazoles and 2-hydroxybenzophenone. The
10b: X=Zn1/2 11b: X=Zn1/2 latter type of compound, which is used in this work,
10c: X=Ni1/2 11c: X=Ni1/2 protect the dye by preferentially absorbing the harmful
UV radiation and converting it into heat energy by
Fig. 2. Carboxylate additives used in the present study. means of rapid tautomerism (see Scheme 3) [11].
In preliminary studies [5e8], the effect of various
counter-ions on the photofading of color materials
type) and exposed to light (l>300 nm) in air. The
derived from color formers was investigated on cellulose
apparatus was kept at 30G2
C. After irradiation for
plate or heat-sensitive recording paper. It was found
3 h, the plates were developed with 60% acetic acid. The
that the amphoteric counter-ion effect plays a very
spot of separated color was scanned using a Shimadzu
important role not only in the photostability but also in
thin-layer chromatoscanner (CS-920 type). The percent-
the image stability of color formers. It is therefore of
age conversion was calculated by comparison with
interest to investigate benzophenone type UV absorber
unirradiated color. A similar procedure was also used
bearing a built-in amphoteric counter-ion moiety as
for dyes 3, 5 and 7. The irradiation times were 5 h in the
a means of improving the light fastness of phthalide-
case of 3 or 5, and 23 h in the case of 7.
type color former. Various types of related stabilizers
were prepared, and the effectiveness of these compounds
was examined on cellulose plate. The formulas of dye 7
3. Results and discussion and the stabilizers used in this study are shown in Figs. 1
and 2. The influence of various additives on the photo-
3.1. Improvement of the light fastness of Crystal fading of dye 2 on cellulose was investigated in air on
Violet lactone exposure to filtered radiation (l>300 nm) from a 100 W
high-pressure mercury lamp, and the results are shown
Dye 1 is a chromogenic compound in its colorless in Table 1.
form. Acidic catalysts, e.g. acidic clay, open the lactone When dye 2 adsorbed on cellulose was exposed for
ring, thereby allowing a violet triarylmethane dye (2, 3 h to filtered radiation, it showed 84% conversion,
l95%AcOH
max 605 nm) to form, as illustrated in Scheme 2 while in the presence of 2-hydroxybenzoic acid (8a) or
[2]. Generally, the dye derived from the color former has 2-hydroxy-1-naphthoic acid (9a) showed 70 and 72%

Me2N NMe2
Me2N NMe2

O
H
C=O
CO2H

NMe2
NMe2
95 AcOH
1: Colorless 2:λmax = 605 nm

Scheme 2
106 H. Oda / Dyes and Pigments 66 (2005) 103e108

Table 1 these zinc salts had little influence on the rate of fading
Effect of various additives on the photostability of colorants on of dye 7 which contains no lactone ring [5].
cellulose
Furthermore, the influence of UV absorbers on the
Additivea Conversion (%) photofading of dye 2 was also examined on cellulose.
2 7 When 2-hydroxybenzophenone (HBP), benzophenone
None 84 61 (68)b type UV absorber, or 2-(2#-hydroxy-5#-methylphenyl)-
8a 70 e benzotriazole (HMBT), benzotriazole type UV absorber,
8b 20 65b was added to the photofading system, dye 2 showed
8c 17 53b
9a 72 e
66 and 43% conversion respectively. Benzophenone type
9b 40 68b UV absorber behaved in a very slightly inferior way to
9c 19 58b benzotriazole type UV absorber. A similar stabilizing
10a 63 e effect was also observed in the presence of 2,4-
10b 12 54 dihydroxybenzophenone-3-carboxylic acid (10a). How-
10c 0 47
11b 82 57
ever, when zinc 2,4-dihyroxybenzophenone-3-carboxyl-
11c 62 37 ate (10b) was added to the photofading system, dye 2
HBPc 66 35 showed only 12% conversion. The nickel salt (10c)
HMBTd 43 33 completely retarded the rate of photofading of dye 2
PEG-Zne 82 e under the condition employed. Such an excellent degree
NMCf 64 e
of protection against the fading of dye 2 may be caused
a
For key see Fig. 2. by combined function of amphoteric counter-ion effect
b
Exposed for 24 h.
c such as 12 and UV absorbing ability by UV absorber,
2-Hydroxybenzophenone.
d
2-(20 -Hydroxy-50 -methylphenyl)benzotriazole. since these salts had little influence on the fading of dye
e
Tetrachlorophthalic acid mono(ethylene glycol ester) zinc salt. 7 which contains no lactone ring [4] (see Scheme 4).
f
Nickel dimethyldithiocarbamate. The process of formation of complex 12 is now being
studied and will be reported later. Moreover, the retard-
ing effects provided by the nickel salts were generally
conversion respectively. These carboxylic acids are superior to those of the zinc salts. Since the contribution
incapable of acting as amphoteric counter-ions, and so of singlet oxygen to the photofading of Crystal Violet
had little influence on the rate of photofading. However, lactone has been proposed in recent years [12], this may
the addition of zinc salts of these acids (8b, 9b) in the result from the singlet oxygen quenching effects caused
photofading system remarkably retarded the fading. A by nickel salts [5]. This hypothesis is supported by
similar stabilization effect was also observed in the the fact that the retardation effect afforded by NMC,
presence of nickel salts (8c, 9c). The retardation effect well-known singlet oxygen quencher [14], is somewhat
provided by these compounds (8b, c, 9b, c) were sig- superior to that of PEG-Zn, a conventional stabilizer for
nificantly better than those of the monofunctional zinc color former. Consequently, these observations suggest
and nickel benzoates (11b, c), and the conventional that the introduction of the groups capable of acting as
stabilizers PEG-Zn and NMC. Such an enhanced an amphoteric counter-ion into UV absorber plays a
photochemical stability may be due to the contribution very important role in the photostabilization of phtha-
of an intermolecular amphoteric counter-ion effect, since lide type color formers.

Me2N NMe2 O NMe2

O OH HO M
O CO2M
C=O +
O2C OH
CO2
OH
Me2N
NMe2 M=Zn1/2 or Ni1/2
NMe2
n
1 12
Scheme 4
 H. Oda / Dyes and Pigments 66 (2005) 103e108 107

3.2. Effect of UV absorbers on the photofading Table 2

of fluoran dyes Effect of various stabilizers on the photofading of fluoran dyes
Additivea Conversion (%)
Fluoran dyes 3 and 5 together with dye 1 are 4 6
extensively used for technical reproduction, e.g. business None 87 86
forms for resisters or computers, or thermochromic 8a 66 63
systems for textiles. The colored materials 4 and 6 8b 41 14
derived from color formers 3 and 5 shows a red color 8c 38 14
9a 66 63
(l95%AcOH
max 490, 522 and 555 nm) and a black color 9b 41 20
(l95%AcOH
max 446 and 586 nm) respectively, as illustrated in 9c 37 9
Scheme 5, but their light fastness properties are as poor 10a 57 26
as dye 1 [1]. 10b 30 13
In the above section, it was found that metal 10c 11 0
HMBT 63 36
hydroxyarylcarboxylates were highly effective for photo- HBP 60 30
stabilizing the colored material derived from Crystal a
For key see Fig. 2 and Table 1.
Violet lactone. Particularly, functional UV absorbers
(10b, c) were effective in preventing fading. Following
this, it was considered of interest to further investigate
the protecting effects of these stabilizers in connection 2-hydroxybenzoic acid zinc salt (8b) or 2-hydroxy-1-
with improving the light fastness of fluoran dyes. The naphthoic acid zinc salt (9b) in the photofading system
influence of various stabilizers on the photostability of remarkably retarded the fading. A similar stabilizing
fluoran dyes was examined using dyes 4 and 6 in the effect was also observed in the presence of these nickel
same manner as above; the results are shown in Table 2. salts (8c, 9c). Such an enhanced photochemical stability
When dye 4 on cellulose was exposed for 5 h to filtered may be due to the contribution of amphoteric counter-
radiation, it showed 87% conversion, while in the ions as well as in the case of dye 1.
presence of 2-hydroxybenzoic acid (8a) or 2-hydroxy- On the other hand, dye 4 showed 57% conversion by
1-naphthoic acid (9a) showed 66% conversion respec- adding 10a, which must be capable of acting as an UV
tively. These behaviors may be supported by the fact absorber. The protecting effect was almost equal to that
that the carboxylic acids, such as 2-hydroxybenzoic acid, of HBP or HMBT, good UV absorbers. The use of 10b
capable of forming intramolecular hydrogen bonds gave or 10c, however, showed higher inhibition against the
little protection against the fading of color formers in fading of dye 4 compared with 10a. Similar behavior
solution and on silica gel [13]. However, the addition of was also observed in the case of dye 6. When dye 6,

Et2N O
Et2N O

O H
O=C
HO2C

95 AcOH
3: Colorless 4:λmax = 490, 522 and 555 nm

Et
N O Me Et
i-Bu N O Me
i-Bu
O NHPh H NHPh
C=O
CO2H

95 AcOH
6:λmax = 446 and 586 nm
5: Colorless
Scheme 5
108 H. Oda / Dyes and Pigments 66 (2005) 103e108

adsorbed on cellulose, was exposed for 5 h to filtered these have been shown to offer some degree of
radiation (l>300 nm) and air, it showed 86% con- improvement, the most positive protection was given
version, and in the presence of 8a and 9a showed 63% by the presence of UV absorber bearing a built-
conversion, respectively. When HBP or HMBT was in amphoteric counter-ion moiety. The functional UV
added to the photofading system, dye 6 still showed 30 absorbers discovered in this study may be applied
and 36% conversion respectively. Similar incomplete as effective stabilizers against photofading of color
protection has also been observed in the presence of 10a. formers.
This fact implies that the application of simple UV
absorbers is not necessarily useful for improving the
light fastness of color formers. References
On the contrary, the addition of 8b, c significantly
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[10] Clark GL, Kao H. A versatile technique for X-ray singlet crystal
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[13] Oda H, Kitao T. Role of counter-ions in the photofading reaction
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