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Accepted Manuscript Structural comparison of two bisphenol S derivatives used as colour developers in high -performance thermal paper Saori Gontani, Tatsuya Ohashi, Kyohei Miyanaga, Takaaki Kurata, Yoshiki Akatani, Shinya Matsumoto PII:
S0143-7208(16)31071-3
DOI:
10.1016/j.dyepig.2016.12.049
Reference:
DYPI 5675
To appear in:
Dyes and Pigments
Received Date: 28 October 2016 Revised Date:
15 December 2016
Accepted Date: 15 December 2016
Please cite this article as: Gontani S, Ohashi T, Miyanaga K, Kurata T, Akatani Y, Matsumoto S, Structural comparison of two bisphenol S derivatives used as colour developers in high -performance thermal paper, Dyes and Pigments (2017), doi: 10.1016/j.dyepig.2016.12.049. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Structural comparison of two bisphenol S derivatives used as colour developers in high -performance thermal paper
RI PT
Saori Gontani, Tatsuya Ohashi, Kyohei Miyanaga, Takaaki Kurata, Yoshiki Akatani, Shinya
SC
Matsumoto*
AC C
EP
TE D
M AN U
[Graphical abstract]
ACCEPTED MANUSCRIPT
Structural comparison of two bisphenol S derivatives used as colour developers in high
2
-performance thermal paper
3
Saori Gontania, Tatsuya Ohashia, Kyohei Miyanagab, Takaaki Kuratab, Yoshiki Akatanic, Shinya
4
Matsumotoa,*
5
a
6
Tokiwadai 79-7, Hodogaya-ku, Yokohama 240-8501, Japan.
7
b
8
Kita-ku, Tokyo 115-8588, Japan.
9
c
M AN U
SC
Graduate School of Environment and Information Sciences, Yokohama National University,
Functional Chemicals R&D Laboratories, Nippon Kayaku Corporation Limited, Shimo 3-31-2,
Color Materials Division in Functional Chemicals Group, Nippon Kayaku Corporation
TE D
Limited, Shimo 3-31-2, Kita-ku, Tokyo 115-8588, Japan.
11
12
EP
10
RI PT
1
Keywords
14
Thermal paper, Colour developer, Bisphenol S, Crystal structure, Hydrogen bonding network,
15
Fluoran dye
AC C
13
16
17
Abstract
18
The crystal structure of a new bisphenol S derivative, 3,3'-diallyl-4,4'-dihydroxydiphenyl
1
ACCEPTED MANUSCRIPT
sulfone was analyzed. This compound is used as colour developer in high-performance thermal
20
paper, because of its high colour sensitivity and excellent image stability. In the crystalline
21
phase, each molecule of this derivative is linked to four neighbouring molecules by O-H…O=S
22
intermolecular hydrogen bonds. In order to understand the solid-state properties of the new
23
derivative, its hydrogen bonding features were compared to those of the parent bisphenol S
24
compound. The hydrogen bonding network of the new derivative forms two-dimensional square
25
lattice sheets stacked along the b axis. This stacking arrangement, which is different from that of
26
the unsubstituted compound, results in a lower number of hydrogen bonds per unit volume. This
27
structural feature was considered to be correlated with the considerably lower melting point of
28
the new derivative compared to that of the unsubstituted one. This property would result in a
29
good coloration sensitivity of the new derivative when used as colour developer.
30
Introduction
AC C
31
EP
TE D
M AN U
SC
RI PT
19
32
Thermal paper is employed for various printing purposes such as receipts, tickets, and labels
33
because of the compact printing system and high printing speed associated to it[1]. The versatile
34
printing ability of thermal printing systems is another key factor for their market growth. The
35
thermal printing technology is based on the coloration reaction of fluoran dyes from their
36
colourless leuco form to the coloured form. The chemical structure of the leuco form of a
2
ACCEPTED MANUSCRIPT
common fluoran dye for black colour is shown in Fig. 1[2]. Fluoran dyes are reacted with an
38
acidic substrate to produce their ring-opened coloured form. The ring-opened form of the fluoran
39
dyes used for imparting black colour exhibits two absorption bands in the visible region,
40
corresponding to the complementary colours[3-5].
M AN U
42
SC
41
RI PT
37
43
The printing system based on the coloration reaction of fluoran dyes is very simple. Unprinted
45
thermal paper incorporating leuco fluoran dyes is heated by a thermal head to form a printed
46
image. The thermal paper is prepared by depositing a thermosensitive layer on a paper substrate.
47
The thermosensitive layer generally consists of a fluoran dye, a developer, and other additives,
48
such as a sensitizer. The developer consists of an acidic compound that can promote the
49
ring-opening reaction of the fluoran dyes. The developers are also known to significantly
50
influence the properties of thermosensitive paper, such as colour fastness, density, and
51
sensitivity[6-8]. Bisphenol A (BPA; 2,2'-bis(4-hydroxyphenyl)propane) is a typical colour
52
developer used for thermal printing. BPA has recently been suspected to have an
53
endocrine-disrupting activity [9, 10]; another issue that needs improvement is the low stability of
54
images printed using BPA. In order to address these issues, bisphenol S (BPS;
AC C
EP
TE D
44
3
ACCEPTED MANUSCRIPT
4,4'-sulfonyldiphenol) and its derivatives have been developed as alternatives to BPA[11].
56
Compound 1, 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone, shown in Fig. 2, is one of the latest
57
BPS derivatives[12]. This compound provides higher coloration sensitivity and colour density in
58
a printed image compared to the unsubstituted BPS. The long-term stability of coloured images
59
developed by compound 1 is less affected by the addition of various sensitizers. Therefore, 1 is
60
now used in thermal paper for high-reliability purposes, such as air tickets and receipts.
M AN U
SC
RI PT
55
61
62
Despite its widespread use, the reasons behind the good performance of 1 as developer and its
64
role in the coloration of fluoran dyes are still unclear. In this paper, we report the crystal structure
65
of 1 and compare it with that of BPS, as reported by Gidwell and Ferguson[13], in order to
66
understand their different colour development properties on thermal paper. This study is the first
67
in a series of investigations on the mechanism of coloration of fluoran dyes using BPS-based
68
developers.
EP
AC C
69
TE D
63
70
Experimental
71
Compound 1 was prepared according to a previously reported methods[12]. Single crystals of 1
72
were grown by a liquid-liquid diffusion method using tetrahydrofuran (THF) as good solvent and
4
ACCEPTED MANUSCRIPT
73
petroleum ether as poor solvent at 298 K. Colourless needle-shaped crystals suitable for X- ray
74
diffraction were obtained within several weeks. Diffraction data were collected at room
75
temperature
76
graphite-monochromated Cu-Kα radiation (λ = 1.54187 Å) at 40 kV and 30mA. The structure
77
was solved by the direct SHELXS-97 method[14] and refined by a least-squares calculation using
78
the program SHELXL-2014/7[14]. All calculations were performed using the Crystal Structure
79
4.2 program[15]. Hydrogen atoms were placed at the calculated positions and refined using a
80
riding model. Due to the uncertainty in the position of the hydroxyl H atoms for this system, the
81
hydrogen bonds formed in the crystal structure were discussed on the basis of the interaction
82
between the heteroatoms. All atoms were refined anisotropically except for the disordered allyl
83
groups which were refined isotropically. The disordered groups were refined on the basis of two
84
sets of positions, each one with approximately 50% occupancy for the disordered C atoms. The
85
crystallographic data and details of the refinement procedure are presented in Table 1. The
86
crystallographic data reported in this paper have been deposited in the Cambridge
87
Crystallographic Data Centre (CCDC) under deposition number CCDC 1502569. These data can
88
be
89
https://summary.ccdc.cam.ac.uk/structure-summary-form.
Rigaku
R-AXIS
RAPID
imaging
plate
area
detector
with
RI PT
a
AC C
EP
TE D
M AN U
SC
using
obtained
free
of
charge
via
the
Internet
at
90
5
ACCEPTED MANUSCRIPT
S0143-7208(16)31071-3
DOI:
10.1016/j.dyepig.2016.12.049
Reference:
DYPI 5675
To appear in:
Dyes and Pigments
Received Date: 28 October 2016 Revised Date:
15 December 2016
Accepted Date: 15 December 2016
Please cite this article as: Gontani S, Ohashi T, Miyanaga K, Kurata T, Akatani Y, Matsumoto S, Structural comparison of two bisphenol S derivatives used as colour developers in high -performance thermal paper, Dyes and Pigments (2017), doi: 10.1016/j.dyepig.2016.12.049. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT
Structural comparison of two bisphenol S derivatives used as colour developers in high -performance thermal paper
RI PT
Saori Gontani, Tatsuya Ohashi, Kyohei Miyanaga, Takaaki Kurata, Yoshiki Akatani, Shinya
SC
Matsumoto*
AC C
EP
TE D
M AN U
[Graphical abstract]
ACCEPTED MANUSCRIPT
Structural comparison of two bisphenol S derivatives used as colour developers in high
2
-performance thermal paper
3
Saori Gontania, Tatsuya Ohashia, Kyohei Miyanagab, Takaaki Kuratab, Yoshiki Akatanic, Shinya
4
Matsumotoa,*
5
a
6
Tokiwadai 79-7, Hodogaya-ku, Yokohama 240-8501, Japan.
7
b
8
Kita-ku, Tokyo 115-8588, Japan.
9
c
M AN U
SC
Graduate School of Environment and Information Sciences, Yokohama National University,
Functional Chemicals R&D Laboratories, Nippon Kayaku Corporation Limited, Shimo 3-31-2,
Color Materials Division in Functional Chemicals Group, Nippon Kayaku Corporation
TE D
Limited, Shimo 3-31-2, Kita-ku, Tokyo 115-8588, Japan.
11
12
EP
10
RI PT
1
Keywords
14
Thermal paper, Colour developer, Bisphenol S, Crystal structure, Hydrogen bonding network,
15
Fluoran dye
AC C
13
16
17
Abstract
18
The crystal structure of a new bisphenol S derivative, 3,3'-diallyl-4,4'-dihydroxydiphenyl
1
ACCEPTED MANUSCRIPT
sulfone was analyzed. This compound is used as colour developer in high-performance thermal
20
paper, because of its high colour sensitivity and excellent image stability. In the crystalline
21
phase, each molecule of this derivative is linked to four neighbouring molecules by O-H…O=S
22
intermolecular hydrogen bonds. In order to understand the solid-state properties of the new
23
derivative, its hydrogen bonding features were compared to those of the parent bisphenol S
24
compound. The hydrogen bonding network of the new derivative forms two-dimensional square
25
lattice sheets stacked along the b axis. This stacking arrangement, which is different from that of
26
the unsubstituted compound, results in a lower number of hydrogen bonds per unit volume. This
27
structural feature was considered to be correlated with the considerably lower melting point of
28
the new derivative compared to that of the unsubstituted one. This property would result in a
29
good coloration sensitivity of the new derivative when used as colour developer.
30
Introduction
AC C
31
EP
TE D
M AN U
SC
RI PT
19
32
Thermal paper is employed for various printing purposes such as receipts, tickets, and labels
33
because of the compact printing system and high printing speed associated to it[1]. The versatile
34
printing ability of thermal printing systems is another key factor for their market growth. The
35
thermal printing technology is based on the coloration reaction of fluoran dyes from their
36
colourless leuco form to the coloured form. The chemical structure of the leuco form of a
2
ACCEPTED MANUSCRIPT
common fluoran dye for black colour is shown in Fig. 1[2]. Fluoran dyes are reacted with an
38
acidic substrate to produce their ring-opened coloured form. The ring-opened form of the fluoran
39
dyes used for imparting black colour exhibits two absorption bands in the visible region,
40
corresponding to the complementary colours[3-5].
M AN U
42
SC
41
RI PT
37
43
The printing system based on the coloration reaction of fluoran dyes is very simple. Unprinted
45
thermal paper incorporating leuco fluoran dyes is heated by a thermal head to form a printed
46
image. The thermal paper is prepared by depositing a thermosensitive layer on a paper substrate.
47
The thermosensitive layer generally consists of a fluoran dye, a developer, and other additives,
48
such as a sensitizer. The developer consists of an acidic compound that can promote the
49
ring-opening reaction of the fluoran dyes. The developers are also known to significantly
50
influence the properties of thermosensitive paper, such as colour fastness, density, and
51
sensitivity[6-8]. Bisphenol A (BPA; 2,2'-bis(4-hydroxyphenyl)propane) is a typical colour
52
developer used for thermal printing. BPA has recently been suspected to have an
53
endocrine-disrupting activity [9, 10]; another issue that needs improvement is the low stability of
54
images printed using BPA. In order to address these issues, bisphenol S (BPS;
AC C
EP
TE D
44
3
ACCEPTED MANUSCRIPT
4,4'-sulfonyldiphenol) and its derivatives have been developed as alternatives to BPA[11].
56
Compound 1, 3,3'-diallyl-4,4'-dihydroxydiphenyl sulfone, shown in Fig. 2, is one of the latest
57
BPS derivatives[12]. This compound provides higher coloration sensitivity and colour density in
58
a printed image compared to the unsubstituted BPS. The long-term stability of coloured images
59
developed by compound 1 is less affected by the addition of various sensitizers. Therefore, 1 is
60
now used in thermal paper for high-reliability purposes, such as air tickets and receipts.
M AN U
SC
RI PT
55
61
62
Despite its widespread use, the reasons behind the good performance of 1 as developer and its
64
role in the coloration of fluoran dyes are still unclear. In this paper, we report the crystal structure
65
of 1 and compare it with that of BPS, as reported by Gidwell and Ferguson[13], in order to
66
understand their different colour development properties on thermal paper. This study is the first
67
in a series of investigations on the mechanism of coloration of fluoran dyes using BPS-based
68
developers.
EP
AC C
69
TE D
63
70
Experimental
71
Compound 1 was prepared according to a previously reported methods[12]. Single crystals of 1
72
were grown by a liquid-liquid diffusion method using tetrahydrofuran (THF) as good solvent and
4
ACCEPTED MANUSCRIPT
73
petroleum ether as poor solvent at 298 K. Colourless needle-shaped crystals suitable for X- ray
74
diffraction were obtained within several weeks. Diffraction data were collected at room
75
temperature
76
graphite-monochromated Cu-Kα radiation (λ = 1.54187 Å) at 40 kV and 30mA. The structure
77
was solved by the direct SHELXS-97 method[14] and refined by a least-squares calculation using
78
the program SHELXL-2014/7[14]. All calculations were performed using the Crystal Structure
79
4.2 program[15]. Hydrogen atoms were placed at the calculated positions and refined using a
80
riding model. Due to the uncertainty in the position of the hydroxyl H atoms for this system, the
81
hydrogen bonds formed in the crystal structure were discussed on the basis of the interaction
82
between the heteroatoms. All atoms were refined anisotropically except for the disordered allyl
83
groups which were refined isotropically. The disordered groups were refined on the basis of two
84
sets of positions, each one with approximately 50% occupancy for the disordered C atoms. The
85
crystallographic data and details of the refinement procedure are presented in Table 1. The
86
crystallographic data reported in this paper have been deposited in the Cambridge
87
Crystallographic Data Centre (CCDC) under deposition number CCDC 1502569. These data can
88
be
89
https://summary.ccdc.cam.ac.uk/structure-summary-form.
Rigaku
R-AXIS
RAPID
imaging
plate
area
detector
with
RI PT
a
AC C
EP
TE D
M AN U
SC
using
obtained
free
of
charge
via
the
Internet
at
90
5
ACCEPTED MANUSCRIPT