U.S. patent application number 10/472125 was filed with the patent office on 2004-10-07 for recording material and recording sheet.
Invention is credited to Kawakami, Tadashi, sato, Shinichi.
Application Number | 20040198603 10/472125 |
Document ID | / |
Family ID | 26613091 |
Filed Date | 2004-10-07 |
United States Patent
Application |
20040198603 |
Kind Code |
A1 |
Kawakami, Tadashi ; et
al. |
October 7, 2004 |
Recording material and recording sheet
Abstract
A recording material and a recording sheet free from surface
fogging and excellent in dynamic coloring sensitivity, wet heat
resistance, heat resistance, light resistance, plasticizer
resistance, and water resistance. A recording material comprising a
composition containing at least one kind of a compound (1) and at
least one kind of a compound (2) and/or at least one kind of a
compound (3), and a recording sheet having a recording layer formed
from the recording material. Compound (1), Compound (2), Compound
(3) (in the formulae, R.sup.1, R.sup.2, R.sup.6, R.sup.7, R.sup.11,
R.sup.12 indicate hydrogen atom or alkyl radical, a.sup.1-a.sup.3
integer of 1-6, n.sup.1-n.sup.3 0, 1 or 2, m.sup.1, m.sup.4 and
m.sup.7 0, 1, 2, or 3. R.sup.3, R.sup.4, R.sup.8, R.sup.9,
R.sup.13, R.sup.14 indicate alkyl radical or the like, m.sup.2,
m.sup.3, m.sup.5, m.sup.6, m.sup.8, and m.sup.9 0, 1 or 2,
Y.sup.1-Y.sup.3 Co or NRCO (R indicates hydrogen atom or the
like)). 1
Inventors: |
Kawakami, Tadashi; (Chiba,
JP) ; sato, Shinichi; (Chiba, JP) |
Correspondence
Address: |
MASON LAW, PL
17757 US HWY 19 N.
CLEARWATER
FL
33764
US
|
Family ID: |
26613091 |
Appl. No.: |
10/472125 |
Filed: |
September 16, 2003 |
PCT Filed: |
March 29, 2002 |
PCT NO: |
PCT/JP02/03159 |
Current U.S.
Class: |
503/218 |
Current CPC
Class: |
B41M 5/3375 20130101;
B41M 5/155 20130101; B41M 5/3336 20130101; B41M 5/3333 20130101;
B41M 2205/04 20130101 |
Class at
Publication: |
503/218 |
International
Class: |
B41M 005/20; B41M
005/24 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 4, 2001 |
JP |
2001-106364 |
Aug 10, 2001 |
JP |
2001-244785 |
Claims
1. A composition including: at least one type of a compound
represented by Formula (1); wherein 11R.sup.1 and R.sup.2 each
independently represent hydrogen or C1-C6 alkyl, a.sup.1 represents
an integer of 1 to 6, n.sup.1 represents 0, 1 or 2, m.sup.1
represents 0 or an integer in the range 1 to 3, R.sup.3 and R.sup.4
each independently represent nitro, carboxyl, halogen, C1-C6 alkyl
or C2-C6 alkenyl, m.sup.2 and m.sup.3 each independently represent
0, 1 or 2; R.sup.3 and R.sup.4 may be different to each other when
m.sup.2 and m.sup.3 represent each 2, Y.sup.1 represents CO or
NR.sup.5CO (in the equation, R.sup.5 represents hydrogen or C1-C6
alkyl); at least one type of a compound represented by Formula (2);
wherein 12R.sup.6 and R.sup.7 each independently represent hydrogen
or C1C6 alkyl, a.sup.2 represents an integer of 1 to 6, n.sup.2
represents 0, 1 or 2, m.sup.4 represents 0 or an integer in the
range 1 to 3, R.sup.8 and R.sup.9 each independently represent
nitro, carboxyl, halogen, C1-C6 alkyl or C2-C6 alkenyl, m.sup.5 and
m.sup.6 each independently represent 0, 1 or 2; R.sup.8 and R.sup.9
may be different to each other when m.sup.5 and m.sup.6 represent
each 2, Y.sup.2 represents CO or NR.sup.10CO (in the equation,
R.sup.10 represents hydrogen or C1-C6 alkyl); and/or at least one
type of a compound represented by Formula (3); wherein 13R.sup.11
and R.sup.12 each independently represent hydrogen or C1-C6 alkyl,
a.sup.3 represents an integer of 1 to 6, n.sup.3 represents 0, 1 or
2, m.sup.7 represents 0 or an integer in the range 1 to 3, R.sup.13
and R.sup.14 each independently represent nitro, carboxyl, halogen,
C1-C6 alkyl or C2-C6 alkenyl, m.sup.8 and m.sup.9 each
independently represent 0, 1 or 2; R.sup.13 and R.sup.14 may be
different to each other when m.sup.8 and m.sup.9 represent each 2,
Y.sup.3 represents CO or NR.sup.15CO (in the equation, R.sup.15
represents hydrogen or C1-C6 alkyl).
2. A recording material comprising: at least one type of a compound
represented by Formula (1); wherein 14R.sup.1 and R.sup.2 each
independently represent hydrogen or C1-C6 alkyl, a.sup.1 represents
an integer of 1 to 6, n.sup.1 represents 0, 1 or 2, m.sup.1
represents 0 or an integer in the range 1 to 3, R.sup.3 and R.sup.4
each independently represent nitro, carboxyl, halogen, C1-C6 alkyl
or C2-C6 alkenyl, m.sup.2 and m.sup.3 each independently represent
0, 1 or 2; R.sup.3 and R.sup.4 may be different to each other when
m.sup.2 and m.sup.3 represent each 2, Y.sup.1 represents CO or
NR.sup.5CO (in the equation, R.sup.5 represents hydrogen or C1-C6
alkyl); at least one type of a compound represented by Formula (2);
wherein 15R.sup.6 and R.sup.7 each independently represent hydrogen
or C1-C6 alkyl, a.sup.2 represents an integer of 1 to 6, n.sup.2
represents 0, 1 or 2, m.sup.4 represents 0 or an integer in the
range 1 to 3, R.sup.8 and R.sup.9 each independently represent
nitro, carboxyl, halogen, C1-C6 alkyl or C2-C6 alkenyl, m.sup.5 and
m.sup.6 each independently represent 0, 1 or 2; R.sup.8 and R.sup.9
may be different to each other when m.sup.5 and m.sup.6 represent
each 2, Y.sup.2 represents CO or NR.sup.10CO (in the equation,
R.sup.10 represents hydrogen or C1-C6 alkyl); and/or at least one
type of a compound represented by Formula (3); wherein 16R.sup.11
and R.sup.12 each independently represent hydrogen or C1-C6 alkyl,
a.sup.3 represents an integer of 1 to 6 n.sup.3 represents 0, 1 or
2, m.sup.7 represents 0 or an integer in the range 1 to 3, R.sup.13
and R.sup.14 each independently represent nitro, carboxyl, halogen,
C1-C6 alkyl or C2-C6 alkenyl, m.sup.5 and m.sup.9 each
independently represent 0, 1 or 2; R.sup.13 and R.sup.14 may be
different to each other when m.sup.8 and m.sup.9 represent each 2,
Y.sup.3 represents CO or NR.sup.15CO (in the equation, R.sup.15
represents hydrogen or C1-C6 alkyl).
3. A recording material according to claim 2 wherein the compound
represented by Formula (2) according to claim 2 and/or the compound
represented by Formula (3) according to claim 2 each have a content
quantity in the range 5 to 500 parts by weight relative to 100
parts by weight of the compound represented by Formula (1)
according to claim 2.
4. A recording sheet comprising a base sheet and a recording
material layer made from a recording material according to claim 2
on the said base sheet.
5. A recording sheet according to claim 4, wherein the compound
represented by Formula (2) according to claim 2 and/or the compound
represented by Formula (3) according to claim 2 each have a content
quantity in the range 5 to 500 parts by weight relative to 100
parts by weight of the compound represented by Formula (1)
according to claim 2.
Description
TECHNICAL FIELD OF INVENTION
[0001] The present invention relates to a composition having an
excellent dynamic sensitivity in recording as well as an excellent
image stability and, particularly, having excellent resistance for
heat and humidity, heat, light, plasticizer and water, relates to a
recording material made from the composition and relates to a
recording sheet comprising a base sheet and a recording material
layer made from the recording material on the base sheet.
BACKGROUND ART
[0002] A recording material making use of color development based
on a chemical reaction between a color forming dye and a developer
is capable of carrying out a recording process in a relatively
simple apparatus and within a short period of time without
performing complicated processing such as development fixing. Thus,
such recording material is used in a wide range of applications
including pressuresensitive copying materials or thermal recording
materials of output-recording units employed in facsimile machines
or printers.
[0003] The capability to develop colors quickly and maintain the
whiteness of the portion with no developed colors is demanded of
these recording materials. The portion with no developed colors is
hereafter referred to as the background. In addition, high
durability of background and image is demanded of these recording
materials. In recent years, particularly, a large amount of
recording material is being used in a field where the reliability
of a recorded image is considered to be of high importance. As a
result, there is an increase in the demand for a recording material
having an excellent image stability such as heat and humidity,
heat, light, water and plasticizer (included in a macromolecular
material) resistance.
[0004] With one kind of developer, however, it is difficult to
provide a recording material satisfying all the demands described
above. In addition, while attempts have been made to use a mixture
consisting of a developer exhibiting a good heat and humidity
resistance and a developer having a good light resistance, a
recording material that sufficiently satisfies all the requirements
has not yet been invented. As described earlier, the requirements
include an excellent sensitivity in recording, heat and humidity,
heat, light, plasticizer and water resistance. When a recording
material does not satisfy all the requirements, a phenomenon called
background fogging typically occurs after the creation of a piece
of thermal recording paper. A background fogging is a phenomenon in
which color is generated on the thermal recording paper.
DISCLOSURE OF THE INVENTION
[0005] In accordance with a first aspect of the present invention,
there is provided a composition including:
[0006] at least one type of a compound represented by Formula (1);
wherein 2
[0007] R.sup.1 and R.sup.2 each independently represent hydrogen or
C1-C6 alkyl,
[0008] a.sup.1 represents an integer of 1 to 6,
[0009] n.sup.1 represents 0, 1 or 2,
[0010] m.sup.1 represents 0 or an integer in the range 1 to 3,
[0011] R.sup.3 and R.sup.4 each independently represent nitro,
carboxyl, halogen, C1-C6 alkyl or C2-C6 alkenyl,
[0012] m.sup.2 and m.sup.3 each independently represent 0, 1 or
2;
[0013] R.sup.3 and R.sup.4 may be different to each other when
m.sup.2 and m.sup.3 represent each 2,
[0014] Y.sup.1 represents CO or NR.sup.5CO (in the equation,
R.sup.5 represents hydrogen or C1-C6 alkyl);
[0015] at least one type of a compound represented by Formula (2);
wherein 3
[0016] R.sup.6 and R.sup.7 each independently represent hydrogen or
C1-C6 alkyl,
[0017] a.sup.2 represents an integer of 1 to 6,
[0018] n.sup.2 represents 0, 1 or 2,
[0019] m.sup.4 represents 0 or an integer in the range 1 to 3,
[0020] R.sup.8 and R.sup.9 each independently represent nitro,
carboxyl, halogen, C1-C6 alkyl or C2-C6 alkenyl,
[0021] m.sup.5 and m.sup.6 each independently represent 0, 1 or
2;
[0022] R.sup.8 and R.sup.9 may be different to each other when
m.sup.5 and m.sup.6 represent each 2,
[0023] Y.sup.2 represents CO or NR.sup.10CO (in the equation,
R.sup.10 represents hydrogen or C1-C6 alkyl); and/or
[0024] at least one type of a compound represented by Formula (3);
wherein 4
[0025] R.sup.11 and R.sup.12 each independently represent hydrogen
or C1-C6 alkyl,
[0026] a.sup.3 represents an integer of 1 to 6,
[0027] n.sup.3 represents 0, 1 or 2,
[0028] m.sup.7 represents 0 or an integer in the range 1 to 3,
[0029] R.sup.13 and R.sup.14 each independently represent nitro,
carboxyl, halogen, C1-C6 alkyl or C2-C6 alkenyl,
[0030] m.sup.8 and m.sup.9 each independently represent 0, 1 or
2;
[0031] R.sup.13 and R.sup.14 may be different to each other when
m.sup.8 and m.sup.9 represent each 2,
[0032] Y.sup.3 represents CO or NR.sup.15CO (in the equation,
R.sup.15 represents hydrogen or C1-C6 alkyl);
[0033] In accordance with a second aspect of the present invention,
there is provided a recording material including at least one type
of the compound represented by the said Formula (1), at least one
type of the compound represented by the said Formula (2) and/or at
least one type of the compound represented by the said Formula
(3).
[0034] It is desirable to provide the recording material according
to the second aspect of the present invention wherein the compound
represented by the said Formula (2) and/or the compound represented
by the said Formula (3) each have a content quantity in the range 5
to 500 parts by weight relative to 100 parts by weight of the
compound represented by the said Formula (1).
[0035] In accordance with a third aspect of the present invention,
there is provided a recording sheet comprising a base sheet and a
recording material layer made from the recording material according
to the second aspect of the present invention on the said base
sheet.
[0036] The recording material layer made from the recording
material according to the second aspect of the present invention
has an excellent dynamic sensitivity in recording as well as an
excellent image stability and, particularly, has excellent property
such as heat and humidity, heat, light, plasticizer and water
resistance. In addition, there is no generation of the background
fogging phenomenon, which is commonly observed in conventional
methods that use a mixture of the developers. In the present
invention, dynamic sensitivity is defined as a sensitivity obtained
as a optical density measured by instantaneously applying thermal
energy generated by a thermal head (employed in a thermal printer)
in the form of an ordinary pulse having a duration in the range 0.2
to 1.8 msec to a piece of thermal recording paper.
[0037] As described above, the composition provided by the present
invention comprises at least one type of the compound represented
by the said Formula (1), at least one type of the compound
represented by the said Formula (2) and/or at least one type of the
compound represented by the said Formula (3). While the weight
ratios among the compounds are arbitrary, the compound represented
by the said Formula (2) and/or the compound represented by the said
Formula (3) normally each have a content quantity in the range 5 to
500 parts by weight relative to 100 parts by weight of the compound
represented by the said Formula (1). It is desirable, however, to
adjust the weight ratios so that the compound represented by the
said Formula (2) and/or the compound represented by the said
Formula (3) each have a content quantity in the range 10 to 300
parts by weight relative to 100 parts by weight of the compound
represented by the said Formula (1). It is even more desirable to
adjust the weight ratios so that the compound represented by the
said Formula (2) and/or the compound represented by the said
Formula (3) each have a content quantity in the range 20 to 250
parts by weight relative to 100 parts by weight of the compound
represented by the said Formula (1).
[0038] The compounds represented by the said Formula (1), wherein
the portion of S(O)n.sup.1 is S, to be used in the present
invention can be obtained by the reaction of the compound
represented by Formula (4); 5
[0039] wherein R.sup.1, R.sup.2, R.sup.3, Y.sup.1, a.sup.1 and
m.sup.2 each have the same meaning as the one previously described,
and X represents halogen, such as a chlorine or bromine, with a
compound represented by Formula (5); 6
[0040] wherein R.sup.4, m.sup.1 and m.sup.3 each have the same
meaning as the one previously described, in an organic solvent such
as methanol with the presence of a base such as a potassium
hydroxide.
[0041] Compounds represented by the said Formula (1), wherein the
portion of S(O)n.sup.1 is SO or SO.sub.2, may be obtained by
oxidizing the compound obtained by the reaction herein above with
an oxidizing agent, such as aqueous solution of hydrogen peroxide
and m-chloroperbenzoic acid in an organic solvent such as acetic
acid.
[0042] Compounds represented by the said Formula (4), wherein the
portion of Y.sup.1 is NR.sup.5CO, can be obtained by the reaction
of the compound represented by Formula (6); 7
[0043] wherein R.sup.3, R.sup.5 and m.sup.2 each have the same
meaning as the one previously described, with the compound
represented by Formula (7); 8
[0044] wherein R.sup.1, R.sup.2, X and a.sup.1 each have the same
meaning as the one previously described, in an organic solvent such
as acetonitrile, and water with the presence of a base such as
potassium bicarbonate.
[0045] Compounds represented by the said Formula (4), wherein the
portion of Y is CO, can be obtained by the reaction of the compound
represented by Formula (8); 9
[0046] wherein R.sup.3 and m.sup.2 each have the same meaning as
the one previously described, with a compound represented by the
said Formula (7), in an organic solvent such as dichloromethane
with the presence of a Lewis acid such as aluminum chloride.
[0047] A compound represented by the said Formula (2) and a
compound represented by the said Formula (3) can each be
synthesized in the same way as a compound represented by the said
Formula (1).
[0048] As methods of mixing a compound represented by Formula (1)
with a compound(s) represented by
[0049] Formulas (2) and/or (3), it is possible to adopt a method of
mixing powders of the compounds, a fusion-mixing method, a method
of adding and mixing of the compounds during crystallization of the
compound represented by Formula (1) and a method of having a
chemical reaction using a mixture such as o-hydroxyaniline,
m-hydroxyaniline or p-hydroxyaniline as hydroxyaniline of the raw
materials and synthesizing/including compounds of at least two or
three types at the same time.
[0050] In Formula (1), R.sup.1 and R.sup.2 each independently
represent hydrogen; C1-C6 alkyl such as methyl, ethyl, n-propyl,
isopropyl, n-butyl and tert-butyl.
[0051] a.sup.1 represents an integer of 1 to 6;
[0052] n.sup.1 represents 0, 1 or 2;
[0053] m.sup.1 represents 0 or an integer of 1 to 3.
[0054] R.sup.3 and R.sup.4 each independently represent nitro;
carboxyl; halogen such as fluorine, chlorine, bromine and iodine;
C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl and
tert-butyl; C2-C6 alkenyl such as propenyl, isopropenyl and
butenyl.
[0055] m.sup.2 and m.sup.3 each independently represent 0, 1 or 2,
and
[0056] Y.sup.1 represents CO or NR.sup.5CO.
[0057] R.sup.5 represents hydrogen; C1-C6 alkyl such as methyl,
ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
[0058] Compounds represented by Formula (1) particularly include a
preferred compound in which Y.sup.1 represents NR.sup.5CO and a
more preferred compound in which Y.sup.1 represents NHCO. Examples
of compounds represented by Formula (1) are
N-(2'-hydroxyphenylthio)acetyl-2- -hydroxyaniline,
N-(3'-hydroxyphenylthio)acetyl-2-hydroxyaniline,
N-(4'-hydroxyphenylthio)acetyl-2-hydroxyaniline and the like.
[0059] Another recording material provided by the present invention
includes at least one type of the compound represented by Formula
(2) and at least one type of the compound represented by Formula
(3).
[0060] In Formula (2), R.sup.6 and R.sup.7 each independently
represent hydrogen; C1-C6 alkyl such as methyl, ethyl, n-propyl,
isopropyl, n-butyl and tert-butyl.
[0061] a2 represents an integer of 1 to 6, and
[0062] n represents 0, 1 or 2.
[0063] m.sup.4 represents 0 or an integer of 1 to 3.
[0064] R.sup.8 and R.sup.9 each independently represent nitro;
carboxyl; halogen such as fluorine, chlorine, bromine and iodine;
C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl and
tert-butyl; C2-C6 alkenyl such as propenyl, isopropenyl and
butenyl.
[0065] m.sup.5 and m.sup.6 each independently represent 0, 1 or 2,
and
[0066] Y.sup.2 represents CO or NR.sup.10CO.
[0067] R.sup.10 represents hydrogen; C1-C6 alkyl, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
[0068] Compounds represented by Formula (2) particularly include a
preferred compound in which Y.sup.2 represents NR.sup.10CO and a
more preferred compound in which Y.sup.2 represents NHCO.
[0069] Examples of the compounds represented by Formula (2) are the
N-(2'-hydroxy phenyl thio)acetyl-4-hydroxy aniline, the
N-(3'-hydroxy phenyl thio)acetyl-4-hydroxy aniline, the
N-(4'-hydroxy phenyl thio)acetyl-4-hydroxy aniline and the
like.
[0070] In Formula (3), R.sup.11 and R.sup.12 each independently
represent hydrogen; C1-C6 alkyl such as methyl, ethyl, n-propyl,
isopropyl, n-butyl and tert-butyl.
[0071] a.sup.3 represents an integer of 1 to 6, and
[0072] n.sup.3 represents 0, 1 or 2, and
[0073] m.sup.7 represents 0 or an integer of 1 to 3.
[0074] R.sup.13 and R.sup.14 each independently represent nitro;
carboxyl; halogen such as fluorine, chlorine, bromine and iodine;
C1-C6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl and
tert-butyl; C2-C6 alkenyl such as propenyl, isopropenyl and
butenyl.
[0075] m.sup.8 and m.sup.9 each independently represent 0, 1 or 2,
and
[0076] Y.sup.3 represents CO or NR.sup.15CO.
[0077] R.sup.15 represents hydrogen; C1-C6 alkyl such as methyl,
ethyl, n-propyl, isopropyl, n-butyl and tert-butyl.
[0078] Compounds represented by Formula (3) particularly include a
preferred compound in which Y.sup.3 represents NR.sup.5CO and a
more preferred compound in which Y.sup.3 represents NHCO.
[0079] Examples of the compounds represented by Formula (3) are the
N-(2'-hydroxy phenyl thio)acetyl-3-hydroxy aniline, the
N-(3'-hydroxy phenyl thio)acetyl-3-hydroxy aniline, the
N-(4'-hydroxy phenyl thio)acetyl-3-hydroxy aniline and the
like.
[0080] Preferred examples of the composition comprising a compound
represented by the said Formula (1) and a compound represented by
the said Formula (2) and/or (3) are items (a) to (c) listed as
follows.
[0081] (a) N-(4'-hydroxyphenylthio)acetyl-2-hydroxyaniline and
N-(4'-hydroxyphenylthio)acetyl-4-hydroxyaniline.
[0082] (b) N-(4'-hydroxyphenylthio)acetyl-2-hydroxyaniline and
N-(4'-hydroxyphenylthio)acetyl-3-hydroxyaniline.
[0083] (c) N-(4'-hydroxyphenylthio)acetyl-2-hydroxyaniline,
N-(4'-hydroxyphenylthio)acetyl-4-hydroxyaniline and
N-(4'-hydroxyphenylthio)acetyl-3-hydroxyaniline.
[0084] The recording material provided by the present invention
includes at least one type of a color forming dye and a compound
represented by the said Formula (1) in addition to compounds
represented by the said Formula (2) and/or Formula (3). That is to
say, the recording material provided by the present invention may
include both compounds represented by the said Formula (2) and
Formula (3) or include only a compound represented by either the
said Formula (2) or Formula (3).
[0085] In the recording material provided by the present invention,
the compound represented by Formula (1) normally has a content
quantity in the range 10 to 500 parts by weight relative to 100
parts by weight of the color forming dye. It is desirable, however,
to adjust the weight ratio so that the compound represented by
Formula (1) has a content quantity in the range 50 to 300 parts by
weight relative to 100 parts by weight of the color forming dye. It
is even more desirable to adjust the weight ratio so that the
compound represented by Formula (1) has a content quantity in the
range 50 to 200 parts by weight relative to 100 parts by weight of
the color forming dye. If the compound represented by Formula (1)
has a relative content quantity of 10 parts by weight or smaller, a
sufficient saturated density will not be achieved. If the compound
represented by Formula (1) has a relative content quantity greater
than 500 parts by weight, on the other hand, the general content
quantity of the developer is considered to be excessively large
even though there is no conceivable bad effect in particular. An
excessively large content quantity is not desirable because such a
content quantity raises the cost of the thermal recording
paper.
[0086] In addition, the compound represented by Formula (2) and the
compound represented by Formula (3) normally have a total content
quantity in the range 5 to 500 parts by weight relative to 100
parts by weight of the compound represented by Formula (1). It is
desirable, however, to adjust the weight ratios so that the
compound represented by Formula (2) and the compound represented by
Formula (3) have a total content quantity in the range 10 to 300
parts by weight relative to 100 parts by weight of the compound
represented by Formula (1). It is even more desirable to adjust the
weight ratios so that the compound represented by Formula (2) and
the compound represented by Formula (3) have a total content
quantity in the range 20 to 250 parts by weight relative to 100
parts by weight of the compound represented by Formula (1). If the
compound represented by Formula (2) and the compound represented by
Formula (3) have a total relative content quantity of 5 parts by
weight or smaller, it is feared that the heat and humidity
resistance and plasticizer resistance of the image will
deteriorate. If the compound represented by Formula (2) and the
compound represented by Formula (3) have a total relative content
quantity greater than 500 parts by weight, on the other hand, it is
feared that the light resistance of the image will deteriorate.
[0087] In addition, the compound represented by Formula (1) and the
compound represented by Formula (2) and/or the compound represented
by Formula (3) normally have a total content quantity in the range
100 to 1,000 parts by weight relative to 100 parts by weight of the
color forming dye. It is desirable, however, to adjust the weight
ratios so that the compound represented by Formula (1) and the
compound represented by Formula (2) and/or the compound represented
by Formula (3) normally have a total content quantity in the range
150 to 500 parts by weight relative to 100 parts by weight of the
color forming dye.
[0088] The composition and recording material of the present
invention may include same compounds of a different degree of
crystallinity as well as a variable crystalline form, those in an
amorphous state and an adduct of the solvent. By properly selecting
and using compounds with different crystalline forms, the
background and sensitivity of the recording material can probably
be improved. In addition, if the particle diameter of the compounds
in a coating solution is made smaller, the sensitivity may be
improved. In particular, the substance having a high degree of
crystallinity results in a background with excellent brightness and
an excellent heat resistance in comparison with a substance put in
an amorphous state.
[0089] Methods of mixing the compound represented by the said
Formula (1) and the compound represented by the said Formula (2)
and/or the compound represented by the said Formula (3) include a
method of mixing particles of the compounds, an additive method
implemented during liquid mixture adjustment/dispersion time and an
additive method implemented in a state of an dispersion. In
addition, by selecting a process to produce compounds, a mixture of
the compound represented by the said Formula (1) and the compound
represented by the said Formula (2) and/or the compound represented
by the said Formula (3) can be obtained in the process and used as
it is.
[0090] The recording material of the present invention may also
contain one or more of a known developer, an image stabilizer, an
antioxidant, a desensitizer, an antitack agent, an antifoamer, a
photo stabilizer and a fluorescent dye. These additional agents may
be contained either in the color forming layer, or in an arbitrary
layer, for example a protecting layer when the recording material
is configured by a multi-layer structure. In particular, in the
case of a structure including an overcoat layer and an undercoat
layer respectively over and under the color forming layer, an
antioxidant and a photo stabilizer may be included in the overcoat
and undercoat layers by being contained in microcapsules if
necessary.
[0091] Examples of the color forming dye used for the recording
material of the present invention include leuco dyes based on
fluoran, phthalide, lactam, triphenyl methane, fenothiazine, and
spiropyran. However, the color forming dyes are not limited to
these leuco dyes, and any color forming dyes may be used as far as
it forms color by contacting with a developer of an acidic
substance.
[0092] Examples of the color forming dyes based on fluoran include
3-diethylamino-6-methyl-7-anilino fluoran,
[0093] 3-dibutylamino-6-methyl-7-anilinofluoran,
[0094] 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluoran,
[0095] 3-(N-methyl-N-propylamino)-6-methyl-7-anilino fluoran,
[0096] 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluoran,
[0097] 3-diethylamino-7-(o-chloroanilino)fluoran,
[0098] 3-dibutylamino-7-(o-chloroanilino)fluoran
[0099] 3-(N-ethyl-p-toluidino)-6-methyl-7-anilinofluoran,
[0100]
3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran,
[0101] 3-pyrrolidino-6-methyl-7-anilinofluoran,
[0102] 3-piperidino-6-methyl-7-anilinofluoran,
[0103] 3-dimethylamino-7-(m-trifluoromethylanilino)fluoran,
[0104] 3-dipentylamino-6-methyl-7-anilinofluoran,
[0105]
3-(N-ethoxypropyl-N-ethylamino)-6-methyl-7-anilinofluoran,
[0106] 3-dibutylamino-7-(o-fluoroanilino)fluoran,
[0107] 3-diethylaminobenzo[a]fluoran,
[0108] 3-dimethylamino-6-methyl-7-chlorofluoran,
43-diethylamino-5-methyl-- 7-dibenzylaminofluoran,
[0109] 3-diethylamino-7-dibenzylaminofluoran,
[0110] 3-diethylamino-5-chlorofluoran,
[0111] 3-diethylamino-6-(N,N'-dibenzylamino)fluoran,
[0112] 3,6-dimethoxyfluoran,
[0113] and 2,4-dimethyl-6-(4-dimethylaminophenyl)aminofluoran.
[0114] Examples of the color forming dyes based on phthalide
include
3-{4-[4-(4-anilino)-anilino]anilino}-6-methyl-7-chlorofluoran,
[0115]
3,3-bis[2-(4-dimethylaminophenyl)-2-(4-methoxyphenyl)vinyl]-4,5,6,7-
-tetrachlorophthalide,
[0116]
3,6,6'-tris(dimethylamino)spiro(fluorine-9,3'-phthalide),
[0117] and
3,3-bis(4'-diethylaminophenyl)-6-diethylaminophthalide.
[0118] In particular, it is desirable to use color forming dyes
pertaining to fluoran such as
3-diethylamino-6-methyl-7-anilinofluoran,
[0119] 3-dibutylamino-6-methyl-7-anilinofluoran,
[0120] 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluoran,
[0121] 3-(N-methyl-N-propylamino)-6-methyl-7-anilinofluoran,
[0122] 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluoran,
[0123] 3-diethylamino-7-(o-chloroanilino)fluoran,
[0124] 3-dibutylamino-7-(o-chloroanilino)fluoran,
[0125] 3-(N-ethyl-p toluidino)-6-methyl-7-anilinofluoran,
[0126]
3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran,
[0127] 3-pyrrolidino-6-methyl-7-anilinofluoran,
[0128] 3-piperidino-6-methyl-7-anilinofluoran,
[0129] 3-dimethylamino-7-(m-trifluoromethylanilino)fluoran,
[0130] 3-dipentylamino-6-methyl-7-anilinofluoran,
[0131]
3-(N-ethoxypropyl-N-ethylamino)-6-methyl-7-anilinofluoran,
[0132] 3-dibutylamino-7-(o-fluoroanilino)fluoran,
3-diethylbenzo[a]fluoran- ,
[0133] 3-dimethylamino-6-methyl-7-chlorofluoran,
[0134] 3-diethylamino-5-methyl-7-dibenzylaminofluoran,
[0135] 3-diethylamino-7-dibenzylaminofluoran,
[0136] 3-diethylamino-5-chlorofluoran,
[0137] 3-diethylamino-6-(N,N'-dibenzylamino)fluoran,
[0138] 3,6-dimethoxyfluoran and
2,4-dimethyl-6-(4-dimethylaminophenyl)amin- ofluoran.
[0139] It is even more desirable to use color forming dyes
pertaining to fluoran such as
3-diethylamino-6-methyl-7-anilinofluoran,
[0140] 3-dibutylamino-6-methyl-7-anilinofluoran,
[0141] 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluoran,
[0142] 3-(N-methyl-N-propylamino)-6-methyl-7-anilinofluoran,
[0143] 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluoran and
3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinofluoran.
[0144] Of course, these color forming dyes can each be used alone
to give a recording material of a color developed by the dye, or
two or more types of color forming dye can be mixed with each
other. For example, it is possible to mix the color forming dyes of
the elementary colors, namely, red, green and blue, or a black dye
to make a recording material develop the truly black color.
[0145] Other developers include those for thermal recording
materials and those for pressuresensitive recording materials.
Examples for the developer of thermal recording materials include
bisphenol compounds, such as bisphenol A,
[0146] 4,4'-sec-butylidenbisphenol,
[0147] 4,4'-cyclohexylidenbisphenol,
[0148] 2,2-dimethyl-3,3-bis(4-hydroxyphenyl)butane,
[0149] 2,2'-dihydroxydiphenyl,
[0150] pentamethylene-bis(4-hydroxybenzoate),
[0151] 2,2-dimethyl-3,3-di(4-hydroxyphenyl)pentane,
[0152] 2,2-di(4-hydroxyphenyl)hexane;
[0153] sulfur-containing bisphenol compounds, such as
4,4'-dihydroxydiphenylthio ether,
[0154] 1,7-di(4-hydroxyphenylthio)-3,5-dioxaheptane,
[0155] 2,2'-bis(4-hydroxyphenylthio)diethyl ether,
[0156] 4,4'-dihydroxy-3,3'-dimethyldiphenylthio ether;
[0157] 4-hydroxybenzoic esters, such as benzyl
4-hydroxybenzoate,
[0158] ethyl 4-hydroxybenzoate,
[0159] propyl 4-hydroxybenzoate,
[0160] isopropyl 4-hydroxybenzoate,
[0161] butyl 4-hydroxybenzoate,
[0162] isobutyl 4-hydroxybenzoate,
[0163] chlorobenzyl 4-hydroxybenzoate,
[0164] methylbenzyl 4-hydroxybenzoate and diphenylmethyl
4-hydroxybenzoate;
[0165] metal salts of benzoic acid, such as zinc benzoate and zinc
4-nitrobenzoate;
[0166] salicylic acids, such as
4-[2-(4-methoxyphenyloxy)ethyloxy]salicyli- c acid;
[0167] metal salts of salicylic acid, such as zinc salicylate and
bis[4-(octyloxycarbonylamino)-2-hydroxybenzoic acid]zinc;
[0168] hydroxysulfones, such as
[0169] 4,4'-dihydroxydiphenylsulfone,
[0170] 2,4'-dihydroxydiphenylsulfone,
[0171] 4-hydroxy-4'-methyldiphenylsulfone,
[0172] 4-hydroxy-4'-isopropoxydiphenylsulfone,
[0173] 4-hydroxy-4'-butoxydiphenylsulfone,
[0174] 4,4'dihydroxy-3,3'-diallyldiphenylsulfone,
[0175] 3,4-dihydroxy-4'-methyldiphenylsulfone,
[0176] 4,4'-dihydroxy-3,3',5,5'-tetrabromodiphenylsulfone;
[0177] 4-hydroxyphthalic diesters, such as dimethyl
4-hydroxyphthalate,
[0178] dicyclohexyl 4-hydroxyphthalate and diphenyl
4-hydroxyphthalate;
[0179] hydroxynaphtoic esters, such as
2-hydroxy-6-carboxynaphthalene;
[0180] trihalomethylsulfones, such as
tribromomethylphenylsulfone;
[0181] sulfonylureas, such as
4,4'-bis(p-toluenesulfonylaminocarbonylamino- )diphenylmethane;
[0182] tetracyanoqinodimethanes; hydroxyacetophenone;
p-phenylphenol;
[0183] benzyl 4-hydroxyphenylacetate; p-benzylphenol;
hydroquinonemonobenzyl ether;
[0184] 2,4-dihydroxy-2'-methoxydibenzanilide; and
[0185] diphenylsulfone bridged compounds represented by Formula (9)
given below; 10
[0186] wherein b is an integer of 0 to 6, and mixtures of the
compounds described above
[0187] And examples of the developer for pressure-sensitive
recording materials are:
[0188] inorganic acids, such as acid clay,
[0189] activated clay,
[0190] attapulgite,
[0191] bentonite,
[0192] colloidal silica,
[0193] aluminum silicate,
[0194] magnesium silicate,
[0195] zinc silicate,
[0196] tin silicate,
[0197] burned kaolin and talc;
[0198] aliphatic carboxylic acids, such as oxalic acid,
[0199] maleic acid,
[0200] tartaric acid,
[0201] citric acid,
[0202] succinic acid, and stearic acid;
[0203] aromatic carboxylic acids, such as benzoic acid,
[0204] p-t-butyl benzoate,
[0205] phthalic acid,
[0206] gallic acid,
[0207] salicylic acid, such as 3-isopropyl salicylate,
[0208] 3-phenyl salicylate,
[0209] 3-cyclohexyl salicylate,
[0210] 3,5-di-t-butyl salicylate,
[0211] 3-methyl-5-benzyl salicylate,
[0212] 3-phenyl-5-(2,2-dimethylbenzyl)salicylate,
[0213] 3,5-di-(2-methylbenzyl)salicylate and
2-hydroxyl-1-benzyl-3naphtate- ;
[0214] salts derived from these aromatic carboxylic acids through
displacement by such metals as zinc, magnesium, aluminum and
titanium;
[0215] developers of phenolic resin, such as
p-phenylphenol-formalin resin and p-butylphenol-acetylene resin,
and
[0216] mixtures of these developers of phenolic resin and the metal
salts of aromatic carboxylic acids described above.
[0217] Examples for the image stabilizer include
[0218] epoxycontaining diphenylsulfones, such as
4-benzyloxy-4'-(2-methylg- lycidyloxy)-diphenylsulfone, and
4,4'-diglycidyloxydiphenylsulfone; and
[0219] 1,4-diglycidyloxybenzene;
[0220]
4-[.alpha.-(hydroxymethyl)benzyloxy]-4'-hydroxydiphenylsulfone;
[0221] 2-propanol derivative;
[0222] salicylic acid derivative;
[0223] metal salts of oxynaphthoic acid derivatives (particulary,
zinc salt);
[0224] metal salts of 2,2-methylenebis(4,6-t-butylphenyl)phosphate
and other water-insoluble zinc-containing compounds.
[0225] Examples for the sensitizer include
[0226] higher fatty acid amides, such as the stearic amide;
[0227] benzamides;
[0228] anilide, such as stearic anilide, acetoacetic anilide and
thioacetoanilide;
[0229] dibenzyl oxalate, di(4-methylbenzyl)oxalate,
di(4-chlorobenzyl)oxalate, dimethyl phthalate, dimethyl
terephthalate, dibenzyl terephthalate, dibenzyl isophthalate, and
kinds of bis(t-butylphenol)s;
[0230] diphenylsulfone and its derivatives;
[0231] diethers of 4,4'-dihydroxydiphenylsulfone, such as
4,4'-dimethoxydiphenylsulfone,
[0232] 4,4'-diethoxydiphenylsulfone,
[0233] 4,4'-dipropoxydiphenylsulfone,
[0234] 4,4'-diisopropoxydiphenylsulfone,
[0235] 4,4'-dibutoxydiphenylsulfone,
[0236] 4,4'-diisobutoxydiphenylsulfone,
[0237] 4,4'-dipentyloxydiphenylsulfone and the
4,4'-dihexyloxydiphenylsulf- one;
[0238] diethers of 2,4-dihydroxydiphenylsulfone, such as
2,4'-dimethoxydiphenylsulfone,
[0239] 2,4'-diethoxydiphenylsulfone,
[0240] 2,4'-dipropoxydiphenylsulfone,
[0241] 2,4'-diisopropoxydiphenylsulfone,
42,4'-dibutoxydiphenylsulfone,
[0242] 2,4'-diisobutoxydiphenylsulfone,
[0243] 2,4'-dipentyloxydiphenylsulfone and
2,4'-dihexyloxydiphenylsulfone; and
[0244] 1,2-bis(phenoxy)ethane,
[0245] 1,2-bis(4-methylphenoxy)ethane,
[0246] 1,2-bis(3-methylphenoxy)ethane,
[0247] 2-naphtholbenzyl ether,
[0248] diphenyl amine,
[0249] carbazole,
[0250] 2,3-di-m-tolylbutane,
[0251] 4-benzylbiphenyl,
[0252] 4,4'-dimethylbiphenyl,
[0253] m-triphenyl,
[0254] di-.beta.-naphthylphenylene diamine,
[0255] phenyl 1-hydroxynaphthoate,
[0256] 2-naphthylbenzyl ether,
[0257] 4-methylphenyl-biphenyl ether,
[0258] 2,2-bis(3,4-dimethylphenyl)ethane,
[0259] 2,3,5,6-tetramethyl-4'-methyldiphenylmethane and diphenyl
carboxylate.
[0260] In particular, desirable sensitizers include;
[0261] Ethers, such as 1,2-bis(phenoxy)ethane,
[0262] 1,2-bis(3-methylphenoxy)ethane and 2-naphthylbenzyl
ether;
[0263] aromatic hydrocarbons, such as m-terphenyl,
[0264] 4-benzylbiphenyl and di(4-methylbenzyl)oxalate;
[0265] diphenylsulfone and derivatives of diphenylsulfone;
[0266] diethers of 4,4'-dihydroxydiphenylsulfone; and
[0267] diethers of 2,4'-dihydroxydiphenylsulfone.
[0268] As the filler, silica, clay, kaolin, burned kaolin, talc,
satin white, aluminum hydroxide, calcium carbonate, magnesium
carbonate, zinc oxide, titanium oxide, barium sulfate, magnesium
silicate, aluminum silicate, plastic pigment and the like may be
used. In the recording material of the present invention, salts of
alkaline earth metals are particularly preferable, and carbonates,
such as calcium carbonate and magnesium carbonate are further
preferable.
[0269] Examples for the dispersing agent include sulfosuccinic
esters, such as dioctylsodium sulfosuccinate,
[0270] sodium dodecylbenzene sulfonate,
[0271] and sodium salt and fatty acid salt of lauryl alcohol
sulfuric ester.
[0272] Examples for the antioxidant include
2,2'-methylenebis(4-methyl-6-t- -butylphenol),
[0273] 2,2'-methylenebis(4-ethyl-6-t-butylphenol),
[0274] 4,4'-propylmethylenebis(3-methyl-6-t-butylphenol),
[0275] 4,4'-butylidenebis(3-methyl-6-t-butylphenol),
[0276] 4,4'-thiobis(2-t-butyl-5-metylphenol),
[0277] 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane,
[0278] 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane and
4-{4-[1,1-bis(4-hydroxyphenyl)ethyl]-.alpha.,.alpha.-dimethylbenzyl}pheno-
l.
[0279] As the desensitizer, aliphatic higher alcohols, polyethylene
glycol, and guanidine derivatives and the like may be used.
[0280] Examples for the antitack agent include stearic acid, zinc
stearate, calcium stearate, camauba wax, paraffin wax and ester
wax.
[0281] Examples for the photostabilizing agent include salicylic
acid based ultraviolet radiation absorbents, such as phenyl
salicylate,
[0282] p-t-butylphenyl salicylate and p-octylphenyl salicylate;
[0283] Benzophenone based ultraviolet radiation absorbents, such as
the 2,4-dihydroxybenzophenone,
[0284] 2-hydroxy-4-methoxybenzophenone,
[0285] 2-hydroxy-4-benzyloxybenzophenone,
[0286] 2-hydroxy-4-octyloxybenzophenone,
[0287] 2-hydroxy-4-dodecyloxybenzophenone,
[0288] 2,2'-dihydroxy-4-methoxybenzophenone,
[0289] 2,2'-dihydroxy-4,4'-dimethoxoxybenzophenone,
[0290] 2-dihydroxy-4-metoxy-5-sulfobenzophenone and
bis(2-methoxy-4-hydroxy-5-benzoilphenyl)methane; and
[0291] benzotriazole based ultraviolet radiation absorbents, such
as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
[0292] 2-(2'-hydroxy-5'-t-buthylphenyl)benzotriazole,
[0293] 2-(2'-hydroxy-3',5'-di-t-buthylphenyl)benzotriazole,
[0294]
2-(2'-hydroxy-3'-t-buthyl-5'-methylphenyl)-5-chlorobenzotriazole,
[0295]
2-(2'-hydroxy-3',5'-di-t-buthylphenyl)-5-chlorobenzotriazole,
[0296] 2-(2'-hydroxy-3',5'-di-t-amylphenyl)benzotriazole,
[0297]
2-[2'-hydroxy-3'-(3",4",5",6"-tetrahydrophthalimidemethyl)-5'-t-met-
hylphenyl]benzotriazole,
[0298] 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,
2-[2'-hydroxy-3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)phenyl]-2H-benzotr-
iazole,
[0299] 2-(2'-hydroxy-3'-dodecyl-5'-methylphenyl)benzotriazole,
[0300] 2-(2'-hydroxy-3'-undecyl-5'-methylphenyl)benzotriazole,
[0301] 2-(2'-hydroxy-3'-tridecyl-5'-methylphenyl)benzotriazole,
[0302]
2-(2'-hydroxy-3'-tetradecyl-5'-methylphenyl)benzotriazole,
[0303]
2-(2'-hydroxy-3'-pentadecyl-5'-methylphenyl)benzotriazole,
[0304]
2-(2'-hydroxy-3'-hexadecyl-5'-methylphenyl)benzotriazole,
[0305] 2-[2'-hydroxy-4'-(2"-ethylhexyl)oxyphenyl]benzotriazole,
[0306] 2-[2'-hydroxy-4'-(2"-ethylhepthyl)oxy
phenyl]benzotriazole,
[0307] 2-[2'-hydroxy-4'-(2"-ethyloctyl)oxy
phenyl]benzotriazole,
[0308]
2-[2'-hydroxy-4'-(2"-propyloctyl)oxyphenyl]benzotriazole,
[0309]
2-[2'-hydroxy-4'-(2"-propylheptyl)oxyphenyl]benzotriazole,
[0310]
2-[2'-hydroxy-4'-(2"-propylhexyl)oxyphenyl]benzotriazole,
[0311] 2-[2'-hydroxy-4'-(1"-ethylhexyl)oxyphenyl]benzotriazole,
[0312]
2-[2'-hydroxy-4'-(1"-ethylheptyl)oxyphenyl]benzotriazole,
[0313] 2-[2'-hydroxy-4'-(1'-ethyloctyl)oxyphenyl]benzotriazole,
[0314]
2-[2'-hydroxy-4'-(1"-propyloctyl)oxyphenyl]benzotriazole,
[0315]
2-[2'-hydroxy-4'-(1"-propylheptyl)oxyphenyl]benzotriazole,
[0316]
2-[2'-hydroxy-4'-(1"-propylhexyl)oxyphenyl]benzotriazole,
[0317]
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole--
2-yl)]phenol and a condensate of polyethylene glycol and
methyl-3-[3-t-butyl-5-(2H-benzotriazole-2-yl)-4-hydroxyphenyl]propionate;
[0318] cyanoacrylate based ultraviolet radiation absorbents, such
as 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate and the
ethyl-2-cyano-3,3-diphenylacrylate; and
[0319] hindered amine based ultraviolet radiation absorbemts, such
as bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, succinic
acid-bis(2,2,6,6-tetramethyl-4-piperidyl)ester and
2-(3,5-di-t-butyl)
malonate-bis(1,2,2,6,6-pentamethyl-4-piperidyl)ester; and
[0320] 1,8-dihydroxy-2-acetyl-3-methyl-6-methoxy naphthalene.
[0321] Examples for the fluorescent dye include
4,4'-bis[2-anilino-4-(2-hy-
droxyethyl)amino-1,3,5-triazinyl-6-amino]stilbene-2,2'-disulfonic
acid disodium salt,
[0322]
4,4'-bis[2-anilino-4-bis(hydroxyethyl)amino-1,3,5-triazinyl-6-amino-
]stilbene-2,2'-disulfonic acid disodium salt,
[0323]
4,4'-bis[2-methoxy-4-(2-hydroxyethyl)amino-1,3,5-triazinyl-6-amino]-
stilbene-2,2'-disulfonic acid disodium salt,
[0324]
4,4'-bis[2-methoxy-4-(2-hydroxypropyl)amino-1,3,5-triazinyl-6-amino-
]stilbene-2,2'-disulfonic acid disodium salt,
[0325]
4,4'-bis[2-m-sulfoanilino-4-bis(hydroxyethyl)amino-1,3,5-triazinyl--
6-amino]stilbene-2,2'-disulfonic acid disodium salt,
[0326]
4-[2-p-sulfoanilino-4-bis(hydroxyethyl)amino-1,3,5-triazinyl-6-amin-
o]-4'-[2-m-sulfoanilino-4-bis(hydroxyethyl)amino-1,3,5-triazinyl-6-amino]s-
tilbene-2,2'-disulfonic acid tetrasodium salt,
[0327]
4,4'-bis[2-p-sulfoanilino-4-bis(hydroxyethyl)amino-1,3,5-triazinyl--
6-amino]stilbene-2,2'-disulfonic acid tetrasodium salt,
[0328]
4,4'-bis[2-(2,5-disulfoanilino)-4-phenoxyamino-1,3,5-triazinyl-6-am-
ino]stilbene-2,2'-disulfonic acid hexasodium salt,
[0329]
4,4'-bis[2-(2,5-disulfoanilino)-4-(p-methoxycarbonylphenoxy)amino-1-
,3,5-triazinyl-6-amino]stilbene-2,2'-disulfonic acid hexasodium
salt,
[0330]
4,4'-bis[2-(p-sulfophenoxy)-4-bis(hydroxyethyl)amino-1,3,5-triaziny-
l-6-amino]stilbene-2,2'-disulfonic acid tetrasodium salt,
[0331]
4,4'-bis[2-(2,5-disulfoanilino)-4-formalinylamino-1,3,5-triazinyl-6-
-amino]stilbene-2,2'-disulfonic acid hexasodium acid and
[0332]
4,4'-bis[2-(2,5-disulfoanilino)-4-bis(hydroxyethyl)amino-1,3,5-tria-
zinyl-6-amino]stilbene-2,2'-disulfonic acid hexasodium salt.
[0333] Different kinds of material used for making each element of
the color forming dye have been explained. The elements include the
developer, the image stabilizer, the sensitizer, the filler, the
dispersing agent, the antioxidant, the desensitizer, the antitack
agent, the antifoamer, the photostabilizing agent and the
fluorescent dye. In making each of the elements, every kind of
material can be utilized alone without mixing with others. As an
alternative, each kind of material can be utilized by mixing with
any of the other kinds. The ratio of each element to be used with
respect to a color forming dye is 0.1 to 15 parts by weight based
on 1 part by weight of a color forming dye, and preferably 1 to 10
parts by weight.
[0334] The recording sheet provided by the present invention has a
recording material layer created on a base sheet from a recording
material provided by the present invention. The base sheet can be a
paper base sheet, a synthetic resin film or a synthetic resin
sheet. Examples for the paper base sheet include thin leaf paper,
craft paper, titanium paper, linter paper, board paper, wood free
paper, coated paper, art paper, vegetable paper, glassine paper,
parchment paper, paraffine paper and recycled paper. Examples for
the synthetic resin film or the synthetic resin sheet include the
polyethylene, the polypropylene, the polyvinyl chloride, the
polyvinylidene chloride, the ethylene-vinyl acetate copolymer, the
ethylene-vinyl alcohol inter polymer, the polyethylene
terephthalate, the polybutylene terephthalate, the polyethylene
naphphthalate, the polymethyl methacrylate, the polymethyl
acrylate, the polyethyl methacrylate, the polystyrene, the
cellulose triacetate, the cellophane and the polycarbonate. In
particular, use of paper base sheets is desirable. There are no
particular limitations on the thickness of the base sheet. However,
the thickness of the base sheet normally has a value in the range 1
to 500 micrometers
[0335] Typically, the recording material layer is created by
coating the base sheet with a solution or a dispersion of the
recording material by adoption of a commonly known coating method.
The amount of coating is dependent on the concentration of the
solution or the dispersion liquid. However, it is 0.1 to 100
g/m.sup.2, desirably 1 to 20 g/m.sup.2 by dry weight.
[0336] Typical methods of coating the basic sheet with a solution
or a dispersion of the recording material provided by the present
invention include, but not limited to, a roll coat method, a
curtain flow coat method, a Mayer bar coat method, a reversed coat
method, a photogravure coat method, a photogravure reversed coat
method, an air knife coat method, a kiss coat method, a blade coat
method, a smooth coat method and a roll knife coat method.
[0337] In addition, the recording material layer may be created
directly on the base sheet. As an alternative, the recording
material layer may be created above the base sheet, with another
layer such as an anchor coat layer sandwiched between the recording
material layer and the base sheet. A protection layer may further
be created on the recording material layer. The anchor coat layer
and the protection layer may each be made from a solution or a
dispersion, including one or several kinds of commonly known
synthetic resin. If necessary, the solution or the dispersion may
include the other aforementioned elements of the developer, the
stabilizer, the sensitizer, the filler, the dispersing agent, the
antioxidant, the desensitizer, the antitack agent, the antifoamer,
the photo stabilizer and the fluorescent dye.
[0338] In particular, it is desirable to use thermal recording
paper and pressure-sensitive copying paper as a material for making
the recording sheet of the present invention. The thermal recording
paper can be manufactured by preparing a dispersion, coating the
upper surface of the base sheet with the dispersion and, then,
drying the base sheet and the dispersion. The dispersion is
prepared by dissolving, for example, fine particles of the color
forming dye and fine particles of the recording material into an
aqueous solution of an aqueous binding agent, such as polyvinyl
alcohol and the cellulose.
[0339] The pressure-sensitive copying paper can be manufactured by
combining a color forming dye sheet and a developer sheet. The
color formingdye sheet is made by coating the upper surface of a
first paper base sheet with a color forming dye dispersion, which
is prepared typically by dispersing microcapsules of a color
forming dye by adoption of a commonly known method using a proper
dispersion. On the other hand, the developer sheet is made by
coating the upper surface of a second paper base sheet with the
dispersion of a developer. During these processes, the recording
material provided by the present invention is dispersed into the
color forming dye dispersion or the dispersion of the developer, or
both the dispersions.
[0340] The pressure-sensitive copying paper can also be
manufactured as a unit comprising an upper sheet of paper and a
lower sheet of paper. The lower surface of the upper sheet of paper
is coated with microcapsules, each including the organic solvent
solution of the color forming dye and being retained on the
surface. The microcapsules also serve as a support material. The
upper surface of the lower sheet of paper is coated with the
developer (an acidic substances), which also is retained on the
surface. As another alternative, the pressure-sensitive copying
paper is manufactured as a piece of self content paper. One face of
the self content paper is coated with both the developer and
microcapsules each including the organic solvent solution of the
color forming dye. As the developer for the pressure-sensitive
copying paper, developers including, but not limited to, any of the
aforementionated typical developers for the pressure-sensitive
paper can be used.
BEST MODES FOR CARRYING OUT THE INVENTION
[0341] Preferred embodiments of the present invention are described
in detail as follows. However, the scope of the present invention
is not limited to these embodiments. It is to be noted that, unless
otherwise specified, the technical term `unit` used in the
following description means a `weight unit`. A image density
(Macbeth value) and a background density (Macbeth value) have been
measured by using a Macbeth reflection densitometer manufactured by
Macbeth Corporation with a model number of RD-514 and filter number
#106.
SYNTHESIS EXAMPLE 1
[0342] Synthesis of
N-(4'-hydroxyphenylthio)acetyl-2-hydroxyaniline
[0343] 109.1 g (1 mol) of 2-aminophenol, 84.1 g (1 mol) of sodium
bicarbonate, 900 mL of acetonitrile and 100 mL of water were added
under room temperature into a 2L flask with four inlets and
attached with a stirrer and a thermometer. The internal temperature
was cool down to 10.degree. C. and 112.9 g (1 mol) of chloroacetyl
chloride was added to the solution over a period of 3 hours and
stirred for 3 hours at room temperature. Following to the
completion of the reaction, 10 mL of methanol was added, and then
acetonitrile was distilled out under reduced pressure and the
resultant residue was subjected to recrystallization with toluene.
Then, salt was taken out in a cleaning process using water to
obtain 2-chloroacetyl-2-hydroxyaniline.
[0344] Then, 126.2 g (1 mol) of 4-mercaptophenol, 66 g (1 mol) of
potassium hydroxide and 1 L of methanol were added under room
temperature into a 3L flask with four inlets and attached with a
stirrer and a thermometer. After confirming that potassium
hydroxide added is completely dissolved, temperature inside the
resultant solution was cool down to 110.degree. C., then
2-chloroacetyl-2-hydroxyaniline obtained as a result of the
reaction described above was added to the solution and stirred at
room temperature for 3 hours. Following to the completion of the
reaction, 2 L of water was added and separated crystals was
filtered to give 210 g of
N-(4'-hydoxyphenylthio)acetyl-2-hydroxyaniline. The yield was 76%
and the melting point was in a range of 176 to 179.degree. C.
SYNTHESIS EXAMPLE 2
[0345] Synthesis of
N-(4'-hydroxyphenylthio)acetyl-4-hydroxyaniline
[0346] Synthesis example 2 was obtained according to the same
process as described in the synthesis example 1, except that,
4-aminophenol is replaced by 2-aminophenol. The melting point was
in a range 163 to 164.degree. C.
SYNTHESIS EXAMPLE 3
[0347] Synthesis of
N-(4'-hydroxyphenylthio)acetyl-3-hydroxyaniline
[0348] Synthesis example 3 was obtained according to the same
process as described in the synthesis example 1, except that,
3-aminophenol is replaced by 2-aminophenol. The melting point was
in a range 171 to 173.degree. C.
[0349] In addition to synthesis examples 1 to 3 described above, as
a method of mixing compositions provided by the present invention,
it is possible to adopt other methods such as a method of making
reactions using the hydroxy aniline compounds each as a raw
material as is the case with the following synthesis examples.
SYNTHESIS EXAMPLE 4
[0350] Synthesis of N-(4'-hydroxyphenylthio)acetyl-2-hydroxyaniline
and N-(4'-hydroxyphenylthio)acetyl-4-hydroxyaniline (mixing ratio
of 1:1)
[0351] 54.6 g (0.5 mol) of 2-aminophenol, 54.6 g (0.5 mol) of
4-aminophenol, 84.1 g (1 mol) of sodium bicarbonate, 900 mL of
acetonitrile and 100 mL of water were added under room temperature
into a 2L flask with four inlets and attached with a stirrer and a
thermometer. The internal temperature was cool down to 10.degree.
C. and 112.9 g (1 mol) of chloroacetyl chloride was added to the
solution over a period of 3 hours and stirred for 3 hours at room
temperature. Following to the completion of the reaction, 10 mL of
methanol was added, and then acetonitrile was distilled out under
reduced pressure and the resultant residue was subjected to
recrystallization with toluene. Then, salt was taken out in a
cleaning process using water to obtain a mixture of
2-chloroacetyl-2-hydroxyaniline and
2-chloroacetyl-4-hydroxyaniline.
[0352] Then, 126.2 g (1 mol) of 4-mercaptophenol, 66 g (1 mol) of
potassium hydroxide and 1 L of methanol were added under room
temperature into a 3L flask with four inlets and attached with a
stirrer and a thermometer. After confirming that potassium
hydroxide added is completely dissolved, temperature inside the
resultant solution was cool down to 10.degree. C., then a mixture
of 2-chloroacetyl-2-hydroxyaniline and
2-chloroacetyl-4-hydroxyaniline obtained as a result of the
reaction described above was added to the solution and stirred at
room temperature for 3 hours. Following to the completion of the
reaction, 2 L of water was added and separated crystals were
filtered to give 231 g of a mixture of
N-(4'-hydoxyphenylthio)acetyl-2-hydroxyaniline and
N-(4'-hydoxyphenylthio)acetyl-4-hydroxyaniline (a mixing ratio of
about 50%: 50%). The yield was 80% and the melting point was in a
range of 147 to 153.degree. C.
[0353] First Embodiment (Preparation of the Thermal Recording
Paper)
[0354] First of all, dispersion (liquids A to D) including
components described below were prepared. It is to be noted that
the components have each been well ground by using a sand
grinder.
[0355] Dye Dispersion (Liquid A)
[0356] The dye dispersion referred to as liquid A is a liquid
obtained as a result of dispersing
3-di-n-butylamino-6-methyl-7-anilinofluoran with a weight of 16
units in 84 units of an aqueous solution containing 10% polyvinyl
alcohol.
[0357] Developer Dispersion (Liquid B)
[0358] The developer dispersion referred to as liquid B is a liquid
obtained as a result of dispersing
N-(4'-hydroxyphenylthio)acetyl-2-hydro- xyaniline with a weight of
8 units and N-(4'-hydroxyphenylthio)acetyl-4-hy- droxyaniline with
a weight of 8 units in 84 units of an aqueous solution containing
10% polyvinyl alcohol.
[0359] Sensitizer Dispersion (Liquid C)
[0360] The sensitizer dispersion referred to as liquid C is a
liquid obtained as a result of dispersing di(4-methylbenzyl)oxalate
with a weight of 16 in 84 units of an aqueous solution containing
10% polyvinyl alcohol.
[0361] Filler Dispersion (Liquid D)
[0362] The filler dispersion liquid referred to as liquid D is a
liquid obtained as a result of dispersing calcium carbonate with a
weight of 27.8 units in 26.2 units of an aqueous solution
containing 10% polyvinyl alcohol and water with a weight of 71
units.
[0363] These dispersions were mixed at weight proportions of liquid
A:liquid B:liquid C:liquid D set at 1:2:1:4 in order to prepare a
coating liquid of a recording material for the thermal recording
paper.
[0364] Then, the surface of a piece of base paper was coated with
5.5 g/m.sup.2 (dry weight) of the coating liquid of the recording
material by using a wire rod manufactured by Wave Star Corporation
with a commodity name of Wire Bar and a commodity number of 12.
After a drying process, a calendaring process was carried out to
make the thermal recording paper. Visual observation of the
produced thermal recording paper confirmed that there is no
background fogging.
[0365] Second Embodiment
[0366] In accordance with a second embodiment, a recording material
was prepared in order to manufacture the thermal recording paper by
adoption of the same method as the first embodiment except that
liquid E described below was used as a substitute for the developer
dispersion referred to as liquid B.
[0367] Developer Dispersion (Liquid E)
[0368] A developer dispersion referred to as liquid E is a liquid
obtained as a result of dispersing
N-(4'-hydroxyphenylthio)acetyl-2-hydroxyaniline with a weight of 8
units and N-(4'-hydroxyphenylthio)acetyl-3-hydroxyanil- ine with a
weight of 8 units in 84 units of an aqueous solution containing 10%
polyvinyl alcohol.
[0369] Visual observation of the produced thermal recording paper
confirmed that there is no background fogging.
[0370] Third Embodiment
[0371] In accordance with a third embodiment, a recording material
was prepared in order to manufacture the thermal recording paper by
adoption of the same method as the first embodiment except that
liquid F described below was used as a substitute for the developer
dispersion liquid referred to as liquid B.
[0372] Developer Dispersion (Liquid F)
[0373] A developer dispersion referred to as liquid F is a liquid
obtained as a result of dispersing
N-(4'-hydroxyphenylthio)acetyl-2-hydroxyaniline with a weight of
5.3 units, N-(4'-hydroxyphenylthio)acetyl-3-hydroxyanili- ne with a
weight of 5.3 units and N-(4'-hydroxyphenylthio)acetyl-4-hydroxy-
aniline with a weight of 5.3 units in 84 units of an aqueous
solution containing 10% polyvinyl alcohol.
[0374] Visual observation of the produced thermal recording paper
confirmed that there is no background fogging.
COMPARISON EXAMPLE 1
[0375] In accordance with comparison example 1, a recording
material was prepared in order to manufacture the thermal recording
paper by adoption of the same method as the first embodiment except
that liquid K described below was used as a substitute for the
developer dispersion referred to as liquid B.
[0376] Developer Dispersion (Liquid K)
[0377] A developer dispersion referred to as liquid K is a liquid
obtained as a result of dispersing 2,4'-dihydroxydiphenylsulfone
with a weight of 16 units in 84 units of an aqueous solution
containing 10% polyvinyl alcohol.
COMPARISON EXAMPLE 2
[0378] In accordance with comparison example 2, a recording
material was prepared in order to manufacture the thermal recording
paper by adoption of the same method as the first embodiment except
that liquid L described below was used as a substitute for the
developer dispersion referred to as liquid B.
[0379] Developer Dispersion (Liquid L)
[0380] A developer dispersion referred to as liquid L is a liquid
obtained as a result of dispersing
N-(4'-hydroxyphenylthio)acetyl-2-hydroxyaniline with a weight of 16
units in 84 units of an aqueous solution containing 10% polyvinyl
alcohol.
EXPERIMENT EXAMPLE 1
Measurement of Dynamic Sensitivities
[0381] A portion of every piece of thermal recording paper made in
accordance with each of the first to third embodiments as well as
each of comparison examples 1 and 2 was cut out and used as an
experiment paper specimen. For each experiment paper specimen, a
coloring instrument for dynamic sensitivity was used. The apparatus
was manufactured by Ohkura Electric Corporation (model number
TH-PMD). Subsequently, heat energy was added under conditions of
0.38 and 0.50 m J per dot. Then, image density (Macbeth values) of
the experiment paper specimens were measured to give results of
measurement as shown in the first table. As is obvious from the
first table, the pieces of thermal recording paper, which were made
in accordance with the first to third embodiments, are known to
each have a high dynamic sensitivity of the same order as the
pieces of thermal recording paper, which were made in accordance
with comparison examples 1 and 2.
EXPERIMENT EXAMPLE 2
Heat & Humidity Resistance Tests of Image
[0382] A portion of every piece of thermal recording paper made in
accordance with each of the first to third embodiments as well as
each of comparison examples 1 and 2 was cut out and used as an
experiment paper specimen. Subsequently, heat energy was added to
get the state of saturated density of image. Each of the experiment
paper specimens in the state of saturated colored was then kept for
24 hours at a temperature of 50.degree. C. and a humidity of 80% in
a incubator controlled humidity and temperature manufactured by
Futaba Science Corporation (model number GL-42). Right after the
state of saturated colored and keeping after 24-hour in the
incubator controlled humidity and temperature, image density
(Macbeth values) of the experiment paper specimens were measured to
give results of measurement as shown in the first table. As is
obvious from the first table, the pieces of thermal recording
paper, which were made in accordance with the first to third
embodiments, are known to each have heat and humidity resistance
superior to the pieces of thermal recording paper, which were made
in accordance with comparison examples 1 and 2.
EXPERIMENT EXAMPLE 3
Heat Resistance Tests of Image
[0383] A portion of every piece of thermally sensitive recording
paper made in accordance with each of the first to third
embodiments as well as each of comparison examples 1 and 2 was cut
out and used as an experiment paper specimen. Subsequently, heat
energy was added to get the state of saturated density of image in
the same way as experiment example 1. Each of the experiment paper
specimens in the state of saturated colored was then kept for 24
hours at a temperature of 90.degree. C. in a constant temperature
oven manufactured by Yamato Science Corporation (model number
DK-400). Right after the state of saturated colored and keeping
after the 24--hour in the constant temperature oven, image density
(Macbeth values) of the experiment paper specimens were measured to
give results of measurement as shown in the first table. As is
obvious from the first table, the pieces of thermal recording
paper, which were made in accordance with the first to third
embodiments, are known to each have a heat resistance superior to
the pieces of thermal recording paper, which were made in
accordance with comparison examples 1 and 2.
EXPERIMENT EXAMPLE 4
Light Resistance Tests of Image
[0384] A portion of every piece of thermal recording paper made in
accordance with each of the first to third embodiments as well as
each of comparison examples 1 and 2 was cut out and used as an
experiment paper specimen. Subsequently, heat energy was added to
get the state of saturated density of image in the same way as
experiment example 1. Then, after an ultraviolet ray beam having a
wavelength of 380 nm was radiated to each of the experiment paper
specimens for 24 hours or 72 hours by using a UV auto-fade-mater
equipped with an Ultraviolet Carbon Arc lamp manufactured by Suga
Testing Equipment Corporation with a commodity name of ultraviolet
long-life fade meter and a model number of FAL-5, image density
(Macbeth values) of the experiment paper specimens were measured to
give measurement results and remaining rates (residual) summarized
as shown in the first table. A remaining rate (residual) expressed
in terms of percents is defined as a ratio of the post-experiment
image density to a pre-experiment image density. As is obvious from
the first table, the pieces of thermal recording paper, which were
made in accordance with the first to third embodiments, are known
to each have a light resistance of the same order as the pieces of
thermal recording paper, which were made in accordance with
comparison examples 1 and 2.
EXPERIMENT EXAMPLE 5
Plasticizer Resistance Tests of Image Part-I
[0385] A portion of every piece of thermal recording paper made in
accordance with each of the first to third embodiments as well as
each of comparison examples 1 and 2 was cut out and used as an
experiment paper specimen. Subsequently, heat energy was added to
get the state of saturated density of image. Then, a vinyl-chloride
wrap film including a plasticizer was stuck on to the
color-developing surface of each of the experiment paper specimens.
The experiment paper specimens were then kept in this state for
eight hours at a temperature of 25.degree. C.
[0386] Right after the state of saturated color development and
after the eight-hour storage period at the temperature of
25.degree. C., image density (Macbeth values) of the experiment
paper specimens were measured to give results of measurement as
shown in the first table. As is obvious from the first table, the
pieces of thermal recording paper, which were made in accordance
with the first to third embodiments, are known to each have a
plasticizer resistance superior to the pieces of thermal recording
paper, which were made in accordance with comparison examples 1 and
2.
EXPERIMENT EXAMPLE 6
Water Resistance Tests of Image Part-I
[0387] A portion of every piece of thermal recording paper made in
accordance with each of the first to third embodiments as well as
each of comparison examples 1 and 2 was cut out and used as an
experiment paper specimen. Subsequently, heat energy was added to
get the state of saturated density of image in the same way as
experiment example 1. Then, each of the experiment paper specimens
was submerged in pure water at a temperature of 25.degree. C. for
seven days. Right after the state of saturated colored and after
the seven-day submersion period at a temperature of 25.degree. C.,
image density (Macbeth values) of the experiment paper specimens
were measured to give results of measurement as shown in the first
table. As is obvious from the first table, the pieces of thermal
recording paper, which were made in accordance with the first to
third embodiments, are known to each have a water resistance
superior to the pieces of thermal recording paper, which were made
in accordance with comparison examples 1 and 2.
[0388] The results of experiment examples 1 to 6 prove that the
thermal recording paper provided by the present invention has an
excellent dynamic sensitivity as well as a heat and humidity
resistance, a heat resistance, a light resistance, a plasticizer
resistance and a water resistance, which are all also excellent as
well.
[0389] Then, as references, experiments were carried out on pieces
of thermal recording paper using a substitute for the sensitizer or
dye of the thermal recording paper made in accordance with the
first embodiment of the present invention.
[0390] Fourth Embodiment
[0391] In accordance with a fourth embodiment, a recording material
was prepared in order to manufacture the thermal recording paper by
adoption of the same method as the first embodiment except that
liquid G described below was used as a substitute for the
sensitizer dispersion referred to as liquid C.
[0392] Sensitizer Dispersion (Liquid G)
[0393] A sensitizer dispersion referred to as liquid G is a liquid
obtained as a result of dispersing 1,2-bis(phenoxy)ethane with a
weight of 16 units in 84 units of an aqueous solution containing
10% polyvinyl alcohol.
[0394] Visual observation of the produced thermal recording paper
confirmed that there is no background fogging.
[0395] Fifth Embodiment
[0396] In accordance with a fifth embodiment, a recording material
was prepared in order to manufacture the thermal recording paper by
adoption of the same method as the first embodiment except that
liquid H described below was used as a substitute for the
sensitizer dispersion referred to as liquid C.
[0397] Sensitizer Dispersion (Liquid H)
[0398] A sensitizer dispersion liquid referred to as liquid H is a
liquid obtained as a result of dispersing diphenylsulfone with a
weight of 16 units in 84 units of an aqueous solution containing
10% polyvinyl alcohol.
[0399] Visual observation of the produced thermal recording paper
confirmed that there is no background fogging.
[0400] Sixth Embodiment
[0401] In accordance with a sixth embodiment, a recording material
was prepared in order to manufacture the thermal recording paper by
adoption of the same method as the first embodiment except that
liquid I described below was used as a substitute for the dye
dispersion dispersion to as liquid A.
[0402] Dye Dispersion (Liquid I)
[0403] A dye dispersion referred to as liquid I is a liquid
obtained as a result of dispersing
3-(N-methyl-N-propylamino)-6-methyl-7-anilinofluoran with a weight
of 16 units in 84 units of an aqueous solution containing 10%
polyvinyl alcohol.
[0404] Visual observation of the produced thermal recording paper
confirmed that there is no background fogging.
[0405] Seventh Embodiment
[0406] In accordance with a seventh embodiment, a recording
material was prepared in order to manufacture the thermal recording
paper by adoption of the same method as the first embodiment except
that liquid J described below was used as a substitute for the dye
dispersion dispersion to as liquid A.
[0407] Dye Dispersion (Liquid J)
[0408] A dye dispersion referred to as liquid J is a liquid
obtained as a result of dispersing
3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilinoflu- oran with a
weight of 16 units in 84 units of an aqueous solution containing
10% polyvinyl alcohol.
[0409] Visual observation of the produced thermal recording paper
confirmed that there is no background fogging.
EXPERIMENT EXAMPLE 7
Heat Resistance Tests of Background
[0410] A portion of every piece of thermal recording paper made in
accordance with each of the first, fourth and fifth embodiments was
cut out and used as an experiment paper specimen. Subsequently,
each of the experiment paper specimens was put in a Constant
Temperature oven at temperatures of 90.degree. C. and 100.degree.
C. for 24 hours. The Constant Temperature oven was manufactured by
Yamato Corporation (model number DK-400).
[0411] After each of the experiment paper specimens was put in a
Constant Temperature oven for 24 hours, background density (Macbeth
values) of the experiment paper specimens were measured to give
results of measurement as shown in the second table. As is obvious
from the second table, by selecting a proper sensitizer, it is
known that the heat resistance of background, which are about equal
to each other at the temperature of 90.degree. C., can be further
improved at the temperature of 100.degree. C.
1TABLE 2 (Results of heat resistance tests of background)
Background density after heat resistance tests Macbeth value
(90.degree. C.) Macbeth value (100.degree. C.) First embodiment
0.11 0.26 Fourth embodiment 0.10 0.15 Fifth embodiment 0.11
0.17
EXPERIMENT EXAMPLE 8
Plasticizer Resistance Tests of Image Part-II
[0412] A portion of every piece of thermal recording paper made in
accordance with each of the first, sixth and seventh embodiments
was cut out and used as an experiment paper specimen. Subsequently,
heat energy was added to get the state of saturated density of
image in the same way as experiment example 1. Then, a
vinyl-chloride wrap film including a plasticizer was stuck to the
color-developing surface of each of the experiment paper specimens.
The experiment paper specimens were then kept in this state for
eight hours at a temperature of 25.degree. C.
[0413] Right after the state of saturated colored and keeping after
the eight-hour at 25.degree. C., image density (Macbeth values) of
the experiment paper specimens were measured to give results of
measurement as shown in the third table. As is obvious from the
third table, by selecting a proper dye, it is known that
plasticizer resistance of image can be further improved.
EXPERIMENT EXAMPLE 9
Water Resistance Tests of Image Part-II
[0414] A portion of every piece of thermal recording paper made in
accordance with each of the first, sixth and seventh embodiments
and used as an experiment paper specimen. Subsequently, heat energy
was added to get the state of saturated density of image in the
same way as experiment example 1. Then, each of the experiment
paper specimens was submerged in pure water at a temperature of
25.degree. C. for seven days. Right after the state of saturated
colored and after the seven-day submersion period at the
temperature of 25.degree. C., image density (Macbeth values) of the
experiment paper specimens were measured to give results of
measurement as shown in the third table. As is obvious from the
third table, by selecting a proper dye, it is known that the water
resistance of image can be further improved.
2TABLE 3 (Results of plasticizer resistance tests-part II and water
resistance tests-part II) Image density Image density after
plasticizer after water Original resistance test resistance test
Macbeth Macbeth Residual Macbeth Residual value value (%) value (%)
First 1.17 0.39 33 0.85 73 embodiment Reference 1.18 0.65 55 1.09
92 example 3 Reference 1.20 0.74 62 0.94 78 example 4 Residual
expressed in terms of percents is defined as a ratio of the
post-experiment image density to a pre-experiment image
density.
INDUSTRIAL APPLICATION POSSIBILITY
[0415] As described above, in accordance with the present
invention, it is possible to provide a recording material and a
recording sheet that cause no background fogging phenomenon and
have an excellent dynamic sensitivity as well as an excellent image
stability, particularly, such as a heat and humidity resistance, a
heat resistance, a light resistance, a plasticizer resistance and a
water resistance. In addition, it is possible to provide a
recording material and a recording sheet wherein, if necessary, by
selecting a sensitizer in applications of the recording material
and the recording sheet, their heat resistance of background can be
improved and, by selecting a proper dye in applications of the
recording material and the recording sheet, their plasticizer
resistance of image as well as their water resistance of image can
be improved.
3TABLE 1 (First Table) Dynamic sensitivity and Image stability Heat
and Humidity Light resistance resistance Heat resistance After test
After test After After for for Plasticizer resistance Water
resistance Dynamic sensitivity test test 24 hours 72 hours After
test After test 0.38 mJ/ 0.5 mJ/ <residual <Residual
<Residual <Residual <Residual <Residual dot dot
original %> Original %> Original %> %> Original %>
Original %> First 0.45 0.96 1.14 1.24 1.14 1.27 1.14 1.00 0.84
1.12 0.66 1.12 0.93 embodi- <109> <111> <88>
<74> <59> <83> ment Second 0.51 1.06 1.19 1.23
1.19 1.26 1.19 1.04 0.84 1.14 0.50 1.14 0.97 embodi- <104>
<106> <87> <71> <44> <85> ment Third
0.45 0.94 1.09 1.24 1.09 1.24 1.09 0.90 0.72 1.10 0.63 1.10 0.90
embodi- <114> <114> <83> <66> <58>
<82> ment Com- 0.78 1.23 1.27 1.17 1.27 1.05 1.27 1.00 0.82
1.23 0.50 1.23 0.96 parison <92> <83> <79>
<64> <41> <78> exam- ple 1 Com- 0.48 1.07 1.23
0.51 1.23 0.36 1.23 1.11 0.99 1.22 0.15 1.22 0.79 parison
<42> <30> <91> <80> <13> <65>
exam- ple 2
* * * * *