U.S. patent application number 09/235477 was filed with the patent office on 2001-07-19 for decolorizable ink and printer.
Invention is credited to FUJIOKA, SAWAKO, MACHIDA, SHIGERU, NAITO, KATSUYUKI, OKUYAMA, TETSUO, SANO, KENJI, TAKAYAMA, SATOSHI.
Application Number | 20010008164 09/235477 |
Document ID | / |
Family ID | 27279516 |
Filed Date | 2001-07-19 |
United States Patent
Application |
20010008164 |
Kind Code |
A1 |
SANO, KENJI ; et
al. |
July 19, 2001 |
DECOLORIZABLE INK AND PRINTER
Abstract
A decoloring apparatus for an image forming material comprising
means for bringing a solvent into contact with an image forming
material formed on a paper sheet and containing a color former, a
developer and a decolorizer, and means for removing a residual
solvent from the paper sheet.
Inventors: |
SANO, KENJI; (TOKYO, JP)
; NAITO, KATSUYUKI; (TOKYO, JP) ; TAKAYAMA,
SATOSHI; (KAWASAKI-SHI, JP) ; FUJIOKA, SAWAKO;
(TOKYO, JP) ; OKUYAMA, TETSUO; (YOKOHAMA-SHI,
JP) ; MACHIDA, SHIGERU; (KAWASAKI-SHI, JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Family ID: |
27279516 |
Appl. No.: |
09/235477 |
Filed: |
January 22, 1999 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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09235477 |
Jan 22, 1999 |
|
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08900708 |
Jul 25, 1997 |
|
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5922115 |
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Current U.S.
Class: |
156/221 ; 118/61;
156/524 |
Current CPC
Class: |
Y10T 156/1043 20150115;
Y10T 156/1352 20150115; C09D 11/50 20130101 |
Class at
Publication: |
156/221 ;
156/524; 118/61 |
International
Class: |
B05C 011/00; B32B
031/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 25, 1996 |
JP |
8-196191 |
Jan 23, 1998 |
JP |
10-011653 |
Claims
1. A decoloring apparatus for an image forming material,
comprising: means for bringing a solvent into contact with an image
forming material formed on a paper sheet and containing a color
former, a developer and a decolorizer; and means for removing a
residual solvent from said paper sheet.
2. The apparatus according to claim 1, further comprising means for
transferring said paper sheet.
3. The apparatus according to claim 1, wherein said means for
removing a residual solvent from said paper sheet consists of
heating means.
4. The apparatus according to claim 1, further comprising means for
recovering a solvent.
5. The apparatus according to claim 4, wherein said means for
recovering a solvent includes an adsorbent of the solvent and
cooling means of the adsorbent.
6. The apparatus according to claim 5, wherein said cooling means
of the adsorbent includes a radiator, and the radiation from said
radiator is utilized for removal of the solvent.
7. A decoloring apparatus of an image forming apparatus,
comprising: means for decoloring the image forming material by
bringing a solvent containing a decolorizer into contact with the
image forming material formed on a paper sheet and containing a
color former and a developer; and means for removing a residual
solvent from the paper sheet.
8. A decoloring apparatus of an image forming apparatus,
comprising: means for decoloring an image forming material by
heating the image forming material formed on a paper sheet and
containing a color former, a developer and a decolorizer to a
temperature higher than the melting point of said decolorizer; and
means for roughening the surface of the image forming material
remaining on a surface of the paper sheet.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This is a Continuation-in-Part application of U.S. patent
application Ser. No. 08/900,708, filed Jul. 25, 1997, the entire
contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a decoloring apparatus for
a decolorizable image forming material.
[0003] In recent years, the amount of various kinds of information
has significantly increased by spread of office automation, and so
the level of information output has also increased. The information
output is represented by display output and hard copy output from a
printer onto paper sheets. The display output, however, requires a
large scale circuit board in a display unit. This brings about
problems of portability and cost. Regarding the hard copy output, a
large quantity of paper as a recording medium is being consumed
with increase in the information output amount. Therefore, the hard
copy output is expected to be a problem with respect to
conservation of natural resources. In addition, recycling of paper
sheets once printed by a printer or a copying machine is expensive,
since much of a bleaching agent and water are required for the
recycling and consumption of electric power is enormous. Under such
a situation, it is considered to decrease consumption of paper
substantially by using decolorizable image forming material to
print information on a paper sheet, restoring a blank sheet of
paper by decoloring the formed image, and reusing the paper
sheet.
[0004] Heretofore, ink which can be decolored on heating has been
proposed in, for example, Published Unexamined Japanese Patent
Application No. 7-81236. The ink includes a color former such as a
leuco dye, a developer, and a organophosphoric compound having a
decoloring power.
[0005] When such image forming material is used, however,
decoloring can be done insufficiently and, as a result, a paper
sheet is hard to return to the blank state. For this reason,
decolorizable image forming material cannot have been put into
practical use.
BRIEF SUMMARY OF THE INVENTION
[0006] It is, accordingly, an object of the present invention to
provide a decoloring apparatus which can easily decolor a
decolorizable image forming material and can maintain the decolored
state stably, thereby making it possible to reuse paper sheets.
[0007] According to an aspect of the present invention, there is
provided a decoloring apparatus for an image forming material
comprising means for bringing a solvent into contact with an image
forming material formed on a paper sheet and containing a color
former, a developer and a decolorizer, and means for removing a
residual solvent from the paper sheet.
[0008] According to another aspect of the present invention, there
is provided a decoloring apparatus of an image forming apparatus
comprising means for decoloring the image forming material by
bringing a solvent containing a decolorizer into contact with the
image forming material formed on a paper sheet and containing a
color former and a developer, and means for removing a residual
solvent from the paper sheet.
[0009] According to still another aspect of the present invention,
there is provided a decoloring apparatus of an image forming
apparatus comprising means for decoloring an image forming material
by heating the image forming material formed on a paper sheet and
containing a color former, a developer and a decolorizer to a
temperature higher than the melting point of the decolorizer, and
means for roughening the surface of the image forming material
remaining on a surface of the paper sheet.
[0010] Additional objects and advantages of the invention will be
set forth in the description which follows, and in part will be
obvious from the description, or may be learned by practice of the
invention. The objects and advantages of the invention may be
realized and obtained by means of the instrumentalities and
combinations particularly pointed out hereinafter.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING
[0011] The accompanying drawings, which are incorporated in and
constitute a part of the specification, illustrate presently
preferred embodiments of the invention, and together with the
general description given above and the detailed description of the
preferred embodiments given below, serve to explain the principles
of the invention.
[0012] FIG. 1 is a schematic view of a mechanism for decoloring the
decolorizable ink of the present invention;
[0013] FIG. 2 is a perspective view of an apparatus for decoloring
the decolorizable ink of the present invention;
[0014] FIG. 3 is a schematic view of another mechanism for
decoloring the decolorizable ink of the present invention;
[0015] FIG. 4A is a perspective view of an ink-jet printer of the
present invention, and FIG. 4B is a schematic view of a decoloring
mechanism used in the printer;
[0016] FIG. 5 is a schematic view of another ink-jet printer of the
present invention;
[0017] FIG. 6 is a perspective view of still another ink-jet
printer of the present invention;
[0018] FIG. 7 is a view illustrating a structure of still another
ink-jet printer;
[0019] FIG. 8 is a view illustrating a structure of a copy machine
of electrophotographic type of the present invention;
[0020] FIG. 9A is a sectional view of a sheet on which an ink of
the present invention is applied, and FIG. 9B is a sectional view
of a sheet on which a decolorizer of the present invention is
applied;
[0021] FIG. 10 is a graph showing a relationship between the TPH
power and the refractive density obtained in Example 7 of the
present invention;
[0022] FIG. 11 is a graph showing a relationship between the TPH
power and the reflection density obtained in Example 8 of the
present invention;
[0023] FIG. 12 is a graph showing a relationship between the TPH
power and the reflection density obtained in Example 9 of the
present invention;
[0024] FIG. 13 is a graph showing a relationship between the TPH
power and the reflection density obtained in Example 10 of the
present invention;
[0025] FIG. 14 shows a heating type image decoloring apparatus of
the present invention;
[0026] FIG. 15 shows a solvent type image decoloring apparatus of
the present invention;
[0027] FIG. 16 shows another solvent type image decoloring
apparatus of the present invention;
[0028] FIG. 17 shows another solvent type image decoloring
apparatus of the present invention;
[0029] FIGS. 18A to 18C show another solvent type image decoloring
apparatuses of the present invention; and
[0030] FIG. 19 shows still another solvent type image decoloring
apparatus of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0031] The present invention will be described in detail below.
[0032] The image forming material of the present invention uses a
color former and a developer in combination with a decolorizer to
enable decoloring after it is printed.
[0033] First, functions of basic components used in the image
forming material of the present invention will be described. A
color former is a precursor compound of a coloring matter which
forms colored information such as characters and graphics, a
developer is a compound which develops a color former by the
interaction (primarily, exchange of an electron or proton) between
the developer and the color former, and a decolorizer is a compound
having a property that preferentially dissolves one of the color
former and the developer when they are melted.
[0034] When the three-component system is in a solidified state, it
is possible for the system to assume one of the following two
particular states:
[0035] (1) A colored state in which the decolorizer is mixed with
the color former and the developer in an amount that corresponds to
the equilibrium solubility, and the excessive color former and
developer over the equilibrium solubility are phase-separated from
the decolorizer, with the result that the interaction between the
color former and the developer is increased to develop a color.
[0036] (2) A decolored state in which the decolorizer dissolves a
larger amount of the color former and the developer than the
equilibrium solubility, with the result that the interaction
between the color former and the developer is decreased to lose the
color.
[0037] Changes between colored and decolored states of the
three-component system are effected in accordance with a principle
described below. It is assumed in the following description that,
when the above mentioned three-component system is melted into a
fluidized condition, the decolorizer preferentially dissolves the
developer. At room temperature, a condition in which a phase of the
color former and the developer is separated from a phase of the
decolorizer is close to equilibrium. In this condition, the system
is in a colored state, since the color former and the developer
interact with each other. When the three-component system in the
colored state is heated up to the melting point or higher to be a
fluidized condition, the developer is preferentially dissolved into
the decolorizer. As a result, the interaction between the developer
and the color former is lost, leading to decoloring. When the
three-component system is forcedly solidified by cooling rapidly
from the molten state, the decolorizer takes the developer into
itself in a large amount exceeding the equilibrium solubility. As a
result, the system is turned amorphous and colorless at room
temperature. Although the amorphous three-component system is under
a non-equilibrium state in a relative sense, the amorphous system
exhibits a sufficiently long life at temperatures not higher than a
glass transition point Tg. Therefore, if Tg is not lower than room
temperature, the system does not easily converted from the
amorphous state to the equilibrium state.
[0038] Next, compounds used as components of the image forming
material of the present invention are described below.
[0039] The color former used in the present invention includes
electron-donating organic substances such as leucoauramines,
diarylphtalides, polyarylcarbinoles, acylauramines, arylauramines,
Rohdamine B lactams, indolines, spiropyrans and fluorans.
[0040] To be more specific, the color former includes Crystal
Violet lactone (CVL), Malakite Green lactone,
2-anilino-6-(N-cyclohexyl-N-methyl- amino)-3-methylfluoran,
2-anilino-3-methyl-6-(N-methyl-N-propyl-amino)fluo- ran,
3-[4-(4-phenylaminophenyl)aminophenyl]-amino-6-methyl-7-chlorofluoran-
, 2-anilino-6-(N-methyl-N-isobutylamino)-3-methylfluoran,
2-anilino-6-(dibutylamino)-3-methylfluoran,
3-chloro-6-(cyclohexylamino)f- luoran,
2-chloro-6-(diethylamino)fluoran, 7-(N,N-diethylamino)-3-(N,N-diet-
hylamino)fluoran, 3, 6-bis(diethylamino) fluoran,
.gamma.-(4'-nitroanilino- )lactam, 3-diethylaminobenzo[a]-fluoran,
3-dietylamino-6- methyl-7-aminofluoran, 3-diethylamino-7-xylidino-
fluoran, 3-(4-diethylamino-2-ethoxyphenyl)-3-
(1-ethyl-2-methylindole-3-yl)-4-azap- hthalide,
3-(4-diethylaminophenyl)-3-(l-ethyl-2-methylindole-3-yl) phthalide,
3-diethylamino-7-chloroanilinofluoran, 3-diethylamino-7,
8-benzofluoran, 3,3-bis(1-n-butyl-2-methylindole-3-yl)phthalide,
3,6-dimethylethoxyfluoran,
3,6-diethylamino-6-methoxy-7-aminofluoran, DEPM, ATP, ETAC,
2-(2-chloroanilino)-6-dibutylaminofluoran, Crystal Violet carbinol,
Malachite Green carbinol, N-(2,3-dichlorophenyl)leucoaur- amine,
N-benzoylauramine, Rhodamine B lactam, N-acetylauramine,
N-phenylauramine,
2-(phenyliminoethanedilydene)-3,3-dimethylindoline,
N,3,3-trimethylindolinobenzospiropyran,
8'-methoxy-N,3,3-trimethylindolin- obenzospiropyran,
3-diethylamino-6-methyl-7-chlorofluoran,
3-diethylamino-7-methoxyfluoran, 3-diethyamino-6-benzyloxyfluoran,
1,2-benzo-6-diethyaminofluoran,
3,6-di-p-toluidino-4,5-dimetylfluoran,
phenylhydrazide-.gamma.-lactam, and 3-amino-5-methylfluoran. The
color former compounds exemplified above can be used singly or in a
combination of two or more species. If color formers are selected
properly, a variety of colored states can be obtained, and thus
formation of multicolor image can be attained.
[0041] The developer used in the present invention includes acidic
compounds, such as phenols, metal phenolates, metal carboxylates,
benzophenones, sulfonic acids, sulfonates, phosphoric acids, metal
phosphates, acidic phosphoric esters, acidic phosphoric ester metal
salts, phosphorus acids, and metal phosphites. The developer
compounds can be used singly or in a combination of two or more
species.
[0042] The decolorizer used in the present invention should
desirably have a good colorlessness in an amorphous state. If the
decolorizer is more colorless and transparent in the amorphous
state, a paper sheet is turned white closer to the original paper
sheet when the image forming material on the paper sheet is
decolored. The decolorizer shows such characteristics should
preferably have a high molecular weight and a small enthalpy change
of melting .DELTA.H of the crystal per weight and, thus, should be
low in maximum crystallization velocity (MCV). If the crystal of
decolorizer has a small enthalpy change of melting .DELTA.H, the
heat energy required for melting the crystal is decreased, which is
desirable in regard to energy saving. In order to increase
solubility of the developer in the decolorizer, it is desirable
that the decolorizer has a high affinity with the developer.
Therefore, the decolorizer should desirably be a compound having,
for example, an alcoholic hydroxyl group. From a view point of a
storage stability of the three-component system in a decolored
state, a glass transition point Tg of the three-component system
should be not lower than room temperature (25.degree. C.), and
preferably be not lower than 50.degree. C. In order to satisfy the
above condition, the glass transition point Tg of the decolorizer
should also be not lower than room temperature (25.degree. C.), and
preferably be not lower than 50.degree. C. On the other hand, the
crystallization temperature of a decolorizer is in the range of the
glass transition point Tg to the melting point Tm of the
three-component system. Therefore, in order to accelerate
decoloring, the glass transition point Tg of a decolorizer should
preferably be not higher than 150.degree. C.
[0043] As a preferable decolorizer that satisfies above conditions,
the following compounds classified in the groups (a) to (c) are
enumerated.
[0044] (a) Sterol compounds: Specific examples are cholesterol,
stigmasterol, pregnenolone, methylandrostenediol, estradiol
benzoate, epiandrostene, stenolone, .beta.-sitosterol, pregnenolone
acetate, .beta.-chorestanol, 5,16-pregnadiene-3.beta.-ol-20-one,
5.alpha.-pregnen-3.beta.-ol-20-one,
5-pregnen-3.beta.,17-diol-20-one 21-acetate, 5-pregnen-3.beta.,17
-diol-20-one 17-acetate, 5-pregnen-3.beta., 21-diol-20-one
21-acetate, 5-pregnen-3.beta.,17-diol diacetate, rockogenin,
thigogenin, esmiragenin, heckogenin, diosgenin and their
derivatives. These decolorizers can be used singly or in a
combination of two or more species. Particularly preferable
decolorizer which can give a stable decolored state includes
methylandrostenediol, heckogenin, rockogenin, thigogenin, diosgenin
and esmiragenin.
[0045] When a three-component system containing the decolorizer
selected from the above group in an amorphous state is heated to a
temperature higher than a glass transition point, a diffusion
velocity of a developer is rapidly increased and a motion of phase
separation between the developer and the decolorizer is accelerated
in a direction of returning to a equilibrium. If the
three-component system heated to a temperature higher than the
crystallizing temperature and lower than the melting point is then
slowly cooled down to room temperature, the system reaches to a
stable phase separated state closer to a equilibrium, at which the
system returns to a colored state. Therefore, the three-component
system including the decolorizer of the (a) group can repeat
reversible changes between colored and decolored states. In this
sense, the decolorizer classified in the (a) group is sometimes
referred to, hereinafter, as a "reversible decolorizer". A
rewritable recording medium which utilizes such reversible changes
has been proposed. However, the present invention has an object to
provide decolorizable image forming material whose color is removed
after printed, and therefore the reversibility between colored and
decolored states is not substantially required in the present
invention with the exception of some special applications.
[0046] (b) Cholic acid, lithocholic acid, testosterone, cortisone
and their derivatives: Specific examples are cholic acid, methyl
cholate, sodium cholate, lithocholic acid, methyl lithocholate,
sodium lithocholate, hydroxycholic acid, methyl hydroxycholate,
hyodeoxycholic acid, methyl hyodeoxycholate, testosterone,
methyltestosterone, 11.alpha.-hydroxymethyltestosterone,
hydrocortisone, cholesterol methyl carbonate, and
.alpha.-cholestanol. Among them, compounds having two or more
hydroxyl groups are especially preferred.
[0047] The decolorizer of the (b) group, compared to that of the
(a) group, has a stronger affinity to the developer when they are
melted, in other words, has a very high compatibility thereto. In
addition, the decolorizer of the (b) group has a higher inclination
of being amorphous, and therefore a phase separation is hard to
occur even after the three-component system is solidified. In this
sense, the decolorizer classified in the (b) group is sometimes
referred to as a "compatible decolorizer" hereinafter. For this
reason, the three-component system including the decolorizer of the
(b) group can maintain a stabler decolored state. (c) Non-aromatic
cyclic compounds of a five-membered or larger ring having one or
more hydroxyl groups: The decolorizer of the (c) group should have
a melting point of 50.degree. C. or higher. Specific examples are
alicyclic monohydric alcohols such as cyclododecanol; alicyclic
dihydric alcohols such as 1,4-cyclohexandiol, 1,2-cyclohexandiol
and 1,2-cyclododecandiol; saccharides and their derivatives such as
glucose and saccharose; alcohols having a ring structure such as
1,2:5,6-diisopropylidene-D-mannitol.
[0048] The decolorizer of the (c) group functions effectively when
it is used together with the decolorizer of the (a) group, although
it may be used singly. That is, the decolorizer of the (c) group
has a strong affinity with the decolorizer of the (a) group, and
therefore a phase separation is hard to occur even after the system
is solidified. In this sense, the decolorizer of the (c) group is
sometimes referred to as a "phase separation inhibiting
decolorizer" or "phase separation inhibitor" hereinafter. The
system including the decolorizer of the (c) group can also maintain
a stabler decolored state.
[0049] The decolorizer of the (c) group, i.e., the phase separation
inhibitor, can be further classified into two types:
[0050] (c1) A type having a relatively high melting point and a
relatively high glass transition point and, thus, likely to become
amorphous at room temperature. Typical examples of the decolorizer
of the (c1) type are saccharides and their derivatives. The
decolorizer of this type is hereinafter referred to as a highly
amorphous phase separation inhibitor.
[0051] (c2) A type having a relatively low melting point and a
relatively low glass transition point and, thus, unlikely to become
amorphous at room temperature with possiblity to form
microcrystals, but having high compatibility with the developer
under a fluidized state. Typical examples of the decolorizer of the
(c2) type are alicyclic alcohols. The decolorizer of this type is
hereinafter referred to as a slightly amorphous phase separation
inhibitor.
[0052] Let us describe the behavior of an image forming material
containing a color former, a developer and a highly amorphous phase
separation inhibitor when it is heated and cooled. If an image
forming material which develops a color at room temperature is
heated to a temperature higher than a melting point of the highly
amorphous phase separation inhibitor, the developer is dissolved in
the highly amorphous phase separation inhibitor so as to lose
interaction with the color former and, thus, to present a decolored
state. If the image forming material under a molten state is
solidified by cooling, the highly amorphous phase separation
inhibitor takes in the developer in an amount exceeding an
equilibrium solubility so as to be made amorphous and decolored at
room temperature. In this fashion, the highly amorphous phase
separation inhibitor functions as a decolorizer even when used
singly. In addition, since the highly amorphous phase separation
inhibitor is likely to become amorphous at room temperature, the
decolored state can be maintained over a long period of time. It
should be noted, however, that, where the phase separation
inhibitor under a fluidized state fails to exhibit a sufficiently
high compatibility with the developer at room temperature, a
satisfactory difference in image density may not be obtained
between the developed state and the decolored state.
[0053] Let us describe the behavior of an image forming material
containing a color former, a developer and a slightly amorphous
phase separation inhibitor when it is heated and cooled. If the
image forming material, which develops a color under room
temperature, is heated to a temperature higher than the melting
point of the slightly amorphous phase separation inhibitor, a
considerably large amount of the developer is dissolved in the
slightly amorphous phase separation inhibitor so as to lose
interaction with the color former and, thus, to be decolored.
However, even if the image forming material under a molten state is
solidified by cooling, the slightly amorphous phase separation
inhibitor is unlikely to become amorphous. Also, it is possible for
the inhibitor to be microcrystallized. It follows that the image
forming material is brought back to the original color-developed
state. In this fashion, the slightly amorphous phase separation
inhibitor does not function as a decolorizer when used singly.
[0054] In the present invention, the highly amorphous phase
separation inhibitor and the slightly amorphous phase separation
inhibitor are used in combination as a decolorizer so as to utilize
the merits of both phase separation inhibitors. Let us describe the
behavior of an image forming material containing a color former, a
developer, a highly amorphous phase separation inhibitor and a
slightly amorphous phase separation inhibitor when it is heated and
cooled. At room temperature Tr, an image is formed under a state
that a mixed phase of the color former, developer and slightly
amorphous separation inhibitor is separated from a phase of the
highly amorphous phase separation inhibitor. If the composition
system is heated to a temperature higher than a melting point Tm1
of the slightly amorphous phase separation inhibitor, the developer
is dissolved in a fluidized slightly amorphous phase separation
inhibitor so as to lose interaction with the color former and,
thus, to be decolored. If the composition system is further heated
to a temperature higher than a melting point Tm2 of the highly
amorphous phase separation inhibitor, the developer and the
slightly amorphous phase separation inhibitor are dissolved in the
highly amorphous phase separation inhibitor. If the composition
system in the molten state is solidified by cooling, the highly
amorphous phase separation inhibitor causes the slightly amorphous
phase separation inhibitor to take in the developer in an amount
exceeding an equilibrium solubility, resulting in decoloration at
room temperature. It should be noted that the highly amorphous
phase separation inhibitor, which is highly amorphous, inhibits the
crystallization of the slightly amorphous phase separation
inhibitor so as to suppress the phase separation of the composition
system. It follows that the decolored state of the image forming
material is maintained with a very high stability.
[0055] Cyclic sugar alcohols can be used in the present invention
as a suitable highly amorphous phase separation inhibitor. The
specific compounds of the cyclic sugar alcohols used in the present
invention include, for example, D-glucose, D-mannose, D-galactose,
D-fructose, L-sorbose, L-rhamnose, L-fucose, D-ribodesose,
.alpha.-D-glucose pentaacetate, acetoglucose, diacetone-D-glucose,
D-glucuronic acid, D-galacturonic acid, D-glucosamie,
D-fructosamine, D-isosaccharic acid, vitamin C, erutorubic acid,
trehalose, saccharose, maltose, cellobiose, gentiobiose, lactose,
melibiose, raffinose, gentianose, melizitose, stachyose, methyl
.alpha.-glucopyranoside, salicin, amygdalin, and euxanthic acid.
These compounds can be used singly or in the form of a mixture of
at least two compounds.
[0056] The slightly amorphous phase separation inhibitor adapted
for use in the present invention includes, for example,
non-aromatic cyclic compounds other than cyclic sugar alcohols,
said non-aromatic cyclic compounds having a five-membered or larger
ring and having a hydroxyl group, and derivatives of cyclic sugar
alcohols, the typical examples being terpene alcohols. To be more
specific, the slightly amorphous phase separation inhibitor used in
the present invention includes, for example, alicyclic monohydric
alcohols such as cyclododecanol, hexahydrosalicylic acid, menthol,
isomenthol, neomenthol, neoisomenthol, carbomenthol,
.alpha.-carbomenthol, piperithol, .alpha.-terpineol,
.beta.-terpineol, .gamma.-terpineol, 1-p-menthene-4-ol, isopulegol,
dihydrocarveol and carveol; alicyclic polyhydric alcohols such as
1,4-cyclohexanediol, 1,2-cyclohexanediol, phloroglucitol,
quercitol, inositol, 1,2-cyclododecane diol, quinic acid,
1,4-terpene, 1,8-terpene, pinol hydrate, and betulin; polycyclic
alcohol derivatives such as borneol, isoborneol, adamantanol,
fenchol, camphor, and isosorbide; and derivatives of cyclic sugar
alcohols such as 1,2:5,6-diisopropylidene-D-m- annitol. Further, it
is possible to use materials of a molecular structure having a
large steric hindrance, which is obtained by the reaction between
the cyclic alcohols exemplified above and another compound having a
cyclic molecular structure. In the case of using the particular
material, it is possible to improve the temperature stability of
the image forming material under a decolored state. For example,
the ester between isosorbide and cyclohexane dicarboxylic acid can
be used as a suitable material of the slightly amorphous phase
separation inhibitor. The compounds exemplified above can be used
singly or in the form of a mixture of at least two compounds.
[0057] In terms of the effects given to the environment, it is
desirable for the image forming material of the present invention
to contain as a decolorizer biodegradable sterol compounds, cyclic
sugar alcohols or derivatives thereof, which are extracted from
animals, plants or fungi.
[0058] The biodegradable sterols extracted from animals, plants or
fungi include, for example, various animal sterins, plant sterins,
and fungi sterins. To be more specific, the animal sterins used in
the present invention include, for example, cholesterol,
lanosterol, agnosterol, cholestanol, coprostanol, ostreasterol,
actiniasterol, spongosterol, and clionasterol. The bile acid used
in the present invention includes, for example, cholanoic acid,
cholic acid, hyodeoxycholic acid, and lithocholic acid. The plant
sterins used in the present invention include, for example,
stegmasterol, .alpha.-sitosterol, .beta.-sitosterol,
.gamma.-sitosterol, brassicasterol, and vitamin D. Further, the
fungi sterins used in the present invention include, for example,
ergosterol. These sterol compounds can be used singly or in the
form of a mixture of at least two compounds. It is also possible to
use, for example, lanolin alcohol which is originally a
mixture.
[0059] On the other hand, it is not desirable to use toxic
materials such as digilanide, digoxigenin, digitoxin,
digitoxigenin, bufotalin, bufotoxin, strophanthin, strophanthidin
and scillaren.
[0060] Preferable mixing ratio of the color former, the developer
and the decolorizer in the image forming material of the present
invention is as follows. It is desirable to use the developer in an
amount of 0.1 to 10 parts by weight, preferably 1 to 2 parts by
weight, relative to 1 part by weight of the color former. If the
amount of the developer is smaller than 0.1 parts by weight,
coloring of the image forming material by the interaction between
the color former and the developer becomes insufficient. If the
amount of the developer exceeds 10 parts by weight, it becomes
difficult to decrease sufficiently the interaction between these
compounds. It is desirable to use the decolorizer in an amount of 1
to 200 parts by weight, preferably 10 to 100 parts by weight,
relative to 1 part by weight of the color former. If the amount of
the decolorizer is smaller than 1 part by weight, changes between
the colored and decolored states cannot occur easily. If the amount
of decolorizer exceeds 200 parts by weight, coloring of the image
forming material becomes insufficient.
[0061] The image forming materiel of the present invention can be
used various form. For example, it can be used as ink for thermal
printer; ink for an ink-jet printer; a toner for plain paper copier
(PPC) and laser beam printer, etc.; printing ink for screen
printing and typographic printing; ink for writing implements such
as ball-point pens and fountain pens. The ink for thermal printer
comprises a color former, a developer, a decolorizer and wax, and
is applied to a plastic sheet. The ink for an ink-jet printer
comprises a color former, a developer and a decolorizer, which are
dispersed in a solvent. The toner is prepared by pulverizing a
composition containing a color former, a developer, a decolorizer
and a binder. In this case, typical binders are polystyrene,
styrene acrylate copolymer, polyester and epoxy resin. The image
forming material of the present invention can be printed onto
various types of paper sheet. The medium for forming an image is
not restricted to a paper sheet. The image forming material can be
printed onto, for example, a sheet for a overhead projector,
etc.
[0062] The image forming material of the present invention can be
applied to uses in which decoloring is simply required without
reusing paper sheets. For example, the image forming material is
applicable to processing post cards in post offices, wherein the
addresses handwritten on post cards are read with an image reader
to obtain bar code corresponding to the reading in a post office,
bars are then printed on the post cards with the image forming
material of the present invention, the post cards are classified
with a machine according to the bar code, the classified post cards
are sent to another post offices, the post cards are sorted in
order of postal delivery in each post office, and then the bars are
decolored by heating. In such a manner, post cards can be delivered
without any trace of the processing in the post offices. In a
manner similar to this, the decolorizable image forming material of
the present invention can generally be used for physical
distribution. In this purpose, substances other than paper may be
printed.
[0063] For decoloration of the color developed image forming
material, used are a method of decoloring by heating and melting
the image forming material and a method of decoloring by bringing
the image forming material into contact with a solvent.
[0064] In the method of decoloring by heating, the decoloration is
performed according to the principle as described above. A heating
means for decoloring the image forming material may have any form.
More specifically, a thermal printer head (TPH), a thermal bar, a
hot stamp and a heat roller can be used. Alternatively, heating may
performed by a infrared lamp or hot air.
[0065] In the method of decoloring by a solvent, the decoloration
is performed according to the following principle. When the image
forming material in a color developed state is brought into contact
with a solvent, the developer is mixed with a slightly amorphous
phase separation inhibitor, and further these components are mixed
with a highly amorphous phase separation inhibitor. The developer
loses interaction with the color former and, thus, the image
forming material is decolored. When the solvent is removed, the
highly amorphous phase separation inhibitor causes the slightly
amorphous phase separation inhibitor to take in the developer in an
amount exceeding an equilibrium solubility, so that the decolored
state of the image forming material is fixed. This decolored state
is very stable at room temperature.
[0066] If the image is decolored by using a solvent, quality of the
paper sheet after decoloration is improved. The reason is as
follows. That is, when the image forming material is decolored by
contact with a solvent and then the solvent which has been
contained in the binder is evaporated, the binder is made porus.
Since light is scattered on the surface of the porus binder,
reflection on the binder is diminished. In addition, the binder and
the other components are spread out widely, so that the boundary
between portions where the image forming material is present and is
not present becomes unclear. Therefor, the remaining image forming
material is hardly recognized either by eye or hand.
[0067] By any of the above methods, there are no needs for a
bleaching agent and water for recycling of paper, and therefore
recycling cost is decreased. At the same time, decrease in paper
consumption contributes to conservation of forest resources.
[0068] Where the image forming material of the present invention is
used as ink, a composition containing the color former, developer
and decolorizer, which is in a colored state, is dispersed in a
solvent. Such decolorizable ink can be used as ink for ball-point
pens and fountain pens, printer ink for ink-jet printer, and
printing ink for screen printing and typographic printing. The
solvent used in the decolorizable ink is preferably water. Although
the ink composition may be dispersed in the solvent by the help of
a surfactant, it is preferred that microcapsules having a structure
in which the ink composition is covered by a polymer shell are
dispersed in the solvent. In order to improve weather resistance
and ultraviolet resistance, it is preferable to add a ultraviolet
absorber to the ink composition contained in the microcapsules or
to use a ultraviolet absorbing polymer as a shell material of
microcapsule. In preparing microcapsules, it is desirable to use
the polymer in an amount of 0.01 to 100 parts by weight, preferably
0.1 to 5% parts by weight, relative to 1 part by weight of the
decolorizer.
[0069] The concentration of the ink composition in the solvent is
preferably in the range of 0.1 to 10 wt. %, although the
concentration varies depending on purposes. If the concentration is
smaller than 0.1 wt. %, sufficient print density cannot be
obtained. If the concentration exceeds 10 wt. %, the viscosity of
the ink becomes too high to use, for example, as ink for a ink-jet
printer. The ink composition dispersed in the solvent should
preferably be in the form of particles of sub-micron in size not
including particles of 10 .mu.m or more.
[0070] Where the image forming material of the present invention is
used as a toner, the color former, developer and decolorizer are
dispersed in a binder. It is desirable to control appropriately the
binder content of the image forming material in accordance with the
average molecular weight of the binder in the toner use. It should
be noted that, where an image is decolored by using a solvent, the
affinity between the solvent and the binder is decreased with
increase in the average molecular weight of the binder, making it
desirable to control the binder content in accordance with the
average molecular weight of the binder.
[0071] Where polystyrene is used as a binder, it is desirable to
control the binder content depending on the average molecular
weight of the binder as follows:
Average molecular weight Binder content
[0072] 1,000 to 200,000 . . . 30 to 90% by weight.
[0073] 200,000 to 600,000 . . . 30 to 80% by weight.
[0074] 600,000 to 1,000,000 . . . 30 to 70% by weight.
[0075] The acrylate monomers constituting the styrene-acrylate
copolymer include, for example, n-butyl methacrylate, isobutyl
methacrylate, ethyl acrylate, n-butyl acrylate, methyl
methacrylate, glycidyl methacrylate, dimethylaminoethyl
methacrylate, diethylaminoethyl methacrylate, diethylaminopropyl
acrylate, 2-ethylhexyl acrylate, butylacrylate-N-(ethoxymethyl)
acrylamide, ethyleneglycol methacrylate, and 4-hexafluorobutyl
methacrylate. These acrylate monomers can be used singly or in the
form of a mixture of at least monomers. It is also possible to use,
for example, butadiene, maleic ester, chloroprene, etc., in
addition to styrene and acrylate monomer for the polymerization. In
this case, it is desirable to set the amount of the additive
component such as butadiene at 10% by weight or less. It is also
desirable for the binder polymer to contain the styrene in an
amount of 50% by weight or more. Where styrene-acrylate copolymer
is used as a binder, it is desirable to control the binder content
of the image forming material depending on the average molecular
weight of the binder polymer as follows:
Average molecular weight Binder content
[0076] 1,000 to 200,000 . . . 30 to 95% by weight.
[0077] 200,000 to 400,000 . . . 30 to 85% by weight.
[0078] 400,000 to 1,000,000 . . . 30 to 75% by weight.
[0079] A blend polymer consisting of polystyrene and acrylic resin
can also be used as a binder. In this case, it is possible for the
blend polymer to contain a single or a plurality of acrylic resins.
It is also possible to use a copolymer containing at most 10% by
weight of butadiene, maleic ester, chloroprene, etc. The
polystyrene content of the binder is desirably 50% by weight or
more. Where a blend polymer consisting of polystyrene and acrylic
resin is used as a binder, it is desirable to control the binder
content of the image forming material depending on the average
molecular weight of the polymer as follows:
Average molecular weight Binder content
[0080] 1,000 to 200,000 . . . 30 to 95% by weight.
[0081] 200,000 to 400,000 . . . 30 to 85% by weight.
[0082] 400,000 to 1,000,000 . . . 30 to 75% by weight.
[0083] The carboxylic acids and the polyhydric alcohols used as
starting materials of the polyester are not particularly limited.
For example, the carboxylic acids include terephthalic acid,
fumaric acid, maleic acid, succinic acid, glutaric acid, adipic
acid, pimelic acid, suberic acid, azelaic acid, sebacic acid,
brasylic acid, pyromellitic acid, citraconic acid, glutaconic acid,
mesaconic acid, itaconic acid, teraconic acid, phthalic acid,
isophthalic acid, hemimellitic acid, mellophanic acid, trimesic
acid, prehnitic acid, and trimellitic acid. These carboxylic acids
can be used singly or in the form of a mixture of at least two of
these compounds. The polyhydric alcohols used in the present
invention include, for example, bisphenol A, hydrogenated bisphenol
A, ethylene glycol, propylene glycol, butanediol, neopentyldiol,
hexamethylenediol, heptanediol, octanediol, pentaglycerol,
pentaerythritol, cyclohexanediol, cyclopentanediol, pinacol,
glycerin, etherified diphenol, catechol, resorcinol, pyrogallol,
benzenetriol, phloroglucinol, and benzenetetraol. These polyhydric
alcohols can be used singly or in the form of a mixture of at least
two compounds. It is also possible to use a blend polymer
consisting of at least two polyesters. Where the polyester is used
as a binder of a toner, it is desirable to control the binder
content of the image forming material in accordance with the
average molecular weight of the polyester as follows:
Average molecular weight Binder content
[0084] 1,000 to 5,000 . . . 30 to 95% by weight.
[0085] 5,000 to 10,000 . . . 30 to 90% by weight.
[0086] 10,000 to 20,000 . . . 30 to 87% by weight.
[0087] 20,000 to 100,000 . . . 30 to 85% by weight.
[0088] 100,000 to 1,000,000 . . . 30 to 80% by weight.
[0089] Where polyester is used as a binder of a thermal transfer
ink, paraffin is used as a wax component. Therefore, it is
desirable for the polyester content to fall within a range of
between 2 to 50% by weight.
[0090] Epoxy resin is synthesized by using as raw materials
epichlorohydrin and a compound having a polyhydric phenolic
hydroxyl group. The polyhydric phenolic compounds used in the
present invention include, for example, bisphenol A, hydrogenated
bisphenol A, bisphenol S, etherified diphenyl, catechol, resorcin,
pyrogallol, benzenetriol, phloroglucinol, and benzenetetraol. These
compounds can be used singly or in the form of a mixture of at
least two compounds. Also, it is possible to add 15% by weight or
less of phenolic resin, urea resin, melamine resin, alkyd resin,
acrylic resin, polyester, polyamide or polyurethane to the epoxy
resin. Where an epoxy resin is used as a binder of a toner, it is
desirable to control the resin content in accordance with the
average molecular weight of the resin as follows:
Average molecular weight Binder content
[0091] 1,000 to 5,000 . . . 30 to 95% by weight.
[0092] 5,000 to 10,000 . . . 30 to 90% by weight.
[0093] 10,000 to 20,000 . . . 30 to 87% by weight.
[0094] 20,000 to 100,000 . . . 30 to 85% by weight.
[0095] 100,000 to 1,000,000 . . . 30 to 80% by weight.
[0096] Where the epoxy resin is used as a binder of a thermal
transfer ink, paraffin is used as a wax component. Therefore, it is
desirable for the polyester content to fall within a range of
between 2 and 50% by weight.
[0097] Where polyester or epoxy resin is used as a binder, the
unreacted carboxylic acid or phenol remaining within the binder
possibly causes the image not to be decolored satisfactorily or
possibly impairs the stability of the decolored state.
[0098] A basic compound is used in the present invention in order
to avoid having the decoloration of the image adversely affected by
the unreacted carboxylic acid or phenol. In the case of using a
basic compound, it is possible to avoid having the decoloration of
the image affected, even if the image is formed on a paper sheet
having a pH value smaller than 8. The basic compound used in the
present invention is not particularly limited. Both inorganic and
organic basic compound can be used in the present invention.
[0099] Suitable inorganic basic compounds used in the present
invention include, for example, calcium chloride, potassium
hydroxide, calcium hydroxide, sodium hydroxide, barium hydroxide,
magnesium hydroxide, ammonium carbonate, potassium carbonate,
calcium carbonate, sodium carbonate, magnesium carbonate, ammonium
hydrogencarbonate, potassium hydrogencarbonate, sodium
hydrogencarbonate, alkaline metal borates, tripotassium phosphate,
dipotassium hydrogenphosphate, calcium phosphate, trisodium
phosphate, and disodium hydrogenphosphate.
[0100] Suitable organic compounds used in the present invention
include, for example, primary to tertiary amines and quaternary
ammonium salt. The counter ions of the quaternary ammonium salt
include, for example, hydroxyl ion, halogen ion and alkoxide
ion.
[0101] The non-aromatic organic basic compounds used in the present
invention include, for example, compounds having aliphatic
hydrocarbon group having 1 to 50 carbon atoms or having alicyclic
hydrocarbon group having 1 to 50 carbon atoms. It is possible for
these hydrocarbon groups to be substituted by at least one
substituent selected from the group consisting of vinyl group,
ethynylene group, ethynyl group, oxy group, oxycarbonyl group,
thiocarbonyl group, dithiocarbonyl group, thio group, sulfinyl
group, sulfonyl group, carbonyl group, hydrazo group, azo group,
azido group, nitrilo group, diazoamino group, imino group, urea
bond, thiourea bond, amide bond, urethane bond, and carbonyldioxy
group.
[0102] The aromatic organic basic compounds used in the present
invention include, for example, those having an aromatic ring such
as benzene ring, biphenyl ring, naphthalene ring, tetralone ring,
phenanthrene ring, indene ring, indan ring, pentalene ring, azulene
ring, heptalene ring and fluorene ring. It is possible for an
aliphatic hydrocarbon group having 1 to 50 carbon atoms or an
alicyclic hydrocarbon group having 1 to 50 carbon atoms to be
substituted in these aromatic rings. Further, it is possible for
the substituents given above to be substituted in these hydrocarbon
groups.
[0103] The cyclic amines used in the present invention include, for
example, aziridine, azetidine, pyrroline, pyrrolidine, indoline,
pyridine, piperidine, hydropyridine, quinoline, isoquinoline,
tetrahydroquinoline, tetrahydroisoquinoline, acridine,
phenanthridine, phenanthroline, pyrazole, benzimidazole,
pyridazine, pyrimidine, pyrazine, imidazole, histamine,
decahydroquinoline, pyrazoline, imidazoline, piperazine, cinnoline,
phtharazine, quinazoline, quinoxaline, dihydrophenazine, triazole,
benzotriazole, triazine, tetrazole, pentamethylenetetrazole,
tetrazine, purine, pteridine, carboline, naphthyridine, indolizine,
quinolizine, quinuclidine, oxazole, benzoxazole, isoxazole,
anthranil, oxazine, oxazoline, thiazole, thiazolidine,
benzothiazole, benzothiazoline, isothiazole, thiazine, azoxim,
furazan, oxadiazine, thiadiazole, benzothidiazole, thiadiazine,
dithiazine, morpholine, hexamethylenetetramine, and
diazabicycloundecene.
[0104] The additional organic basic compounds used in the present
invention include, for example, guanidine, aminoguanidine, urea,
thio urea, semicarbazide, and carbonohydrazide.
[0105] In the present invention, the basic compounds can be mixed
as they are with the other components of the image forming
material. Also, it is desirable to mix the basic compounds, which
are sealed in microcapsules, with the other components of the image
forming material.
[0106] For a shell material of maicrocapsules, selected is a
material which can be broken when the image forming material is
heated to be decolored and can release the basic compounds sealed
in the microcapusules. The temperature where the maicrocapsules are
broken should preferably be 120 to 200.degree. C. Examples of
suitable shell material are polyether sulfone, polyether ketone,
epoxy resin, polyethylene, polypropylene, polyphenylene ether,
polyphenylene sulfite, polyalkylene oxide, polystyrene, polyphenol
ether, nylon, polyamide, polyurethane, gelatin, polymethacrylic
acid, polyimide, melamine resin, polyester, polyacrylic acid,
polysiloxane, polysulfide, gum arabic, polyvinyl pyrrolidone,
polycarbonate, polysulfone, polyisocyanate and polypyrrole. These
compounds can be used singly or in combination of two or more
species. Also, a copolymer of these compounds may be used.
[0107] Next, an apparatus used for decoloring the decolorizable ink
of the present invention and an ink-jet printer using the
decolorizable ink are described below.
[0108] An apparatus used for decoloring the decolorizable ink of
the present invention to recycle paper sheets by heat process may
be in any form, as long as the apparatus has a mechanism capable of
heating and rapid cooling a paper sheet. A specific example of such
an apparatus is a thermal head having a heating resistor. A thermal
bar, which is one kind of thermal head, having a heating resistor
capable of heating the paper sheet across a large area can be used.
In this case, a heating area on a paper sheet may be adjusted by
controlling current in the thermal bar so as to decolor only a
desired area of the paper sheet. If a heating apparatus such as a
heat roller is used, a large quantity of printed paper can be
decolored for recycling. In the case where printing on the surface
of an article not having sheet-like form is to be decolored, the
surface of the article is heated with an infrared lamp or by hot
air and then rapidly cooled by cold air or with a heat sink having
a large heat capacity.
[0109] For example, as shown in FIG. 1, a thermal bar 13 whose
heating area is adjusted to a proper area is located between a pair
of feed rollers 11, 11 and a pair of transport rollers 12, 12, and
a paper sheet 10 already printed with the decolorizable ink of the
present invention is passed through the thermal bar 13. When
electric current is made to flow through the thermal bar 13,
heating up to 300.degree. C. can be effected instantly. The paper
sheet 10 is heated with the thermal bar 13, and then comes out of
the apparatus to be cooled rapidly, so that the print on the paper
sheet can be decolored. FIG. 2 shows a decoloring apparatus
(recycling apparatus) 21 of a hand-feed type which incorporates the
decoloring mechanism of FIG. 1.
[0110] FIG. 3 shows a mechanism with which decoloring of print on a
paper sheet and recycling of the paper sheet can be carried out in
a more reliable manner than that in the mechanism of FIG. 1. As
shown in FIG. 3, in addition to the mechanism of FIG. 1, a pair of
pressing rollers 14, 14 is disposed to smooth wrinkles on the paper
sheet, and also a UV source 15 and a humidifier 16 are disposed
between the transport rollers 12, 12 and the pressing rollers 14,
14. In this mechanism, the coloring matter is decomposed completely
to be colorless on exposure by radiation from the UV source 15, the
wrinkles on the paper sheet 10 can effectively be smoothed by the
pressing rollers 14, 14 after proper humidity is given by the
humidifier 16. When such a mechanism is used, the number of
repeating use of the same paper sheet can be increased. Degradation
of the paper sheet does not become a problem, if a high-grade paper
sheet such as plastic-coated paper is used for a special
purpose.
[0111] A printer using the decolorizable ink of the present
invention is most preferably an ink-jet printer. When ink
containing a reversible decolorizer is used, it is especially
preferable to use an ink-jet printer that injects ink without any
heating. Accordingly, the most preferable means for injecting the
ink is one that uses vibration of a piezoelectric element or
supersonic waves. If ink containing a decolorizer of the (b) group
and the (c) group or ink containing components having high Tg is
used, a bubble-jet printer in which ink is heated may be used.
[0112] FIGS. 4A and 4B show an ink-jet printer having the
decoloring mechanism of FIG. 1. In this printer 31, paper sheets to
be printed are stored in the feed tray 32. A paper sheet is printed
by way of a printing mechanism similar to that of a common ink-jet
printer and finally comes out from the outlet 33. Upon recycling, a
printed paper sheet 10 is inserted through the inlet 34, the paper
sheet 10 travels through the decoloring mechanism equipped with the
feed rollers 11, transport rollers 12 and the thermal bar 13 as
shown in FIG. 1, and finally the paper sheet 10 is received into
the recovery tray 35. In this case, the printing tray 32 and the
recovery tray 35 are in the same shape so as to be
exchangeable.
[0113] FIG. 5 shows an ink-jet printer capable of printing on both
new paper sheets and printed paper sheets. In this printer 41,
trays 42, 43 for respectively accommodating new and printed paper
sheets are mounted on a side of the printer 41. The tray 42 is also
used as a tray for recovering recycled paper after the printed
information on the printed paper is decolored. A new paper sheet is
fed from the tray 42, printed with a printer head 45 while passing
through a printing mechanism of a common ink-jet printer, and then
discharged. On the other hand, a printed paper sheet is fed from
the tray 43, decolored with the thermal bar 13, and then recovered
in the tray 42 or fed again toward the printer head 45 so as to be
printed and then discharged. Switching between both transport
courses is conducted by a switching mechanism 44.
[0114] FIG. 6 shows an ink-jet printer having a head for printing
with the decolorizable ink of the present invention and another
head for printing with a normal ink. In this printer 51, the head
52 for printing with the decolorizable ink and the head 53 for
printing with the normal ink are equipped. Printing information is
instructed to the printer 51 from an application software executed
on the computer 61. An image of a paper sheet to be printed is
displayed on the computer display. Input to a fixed information
region 62 and a variable information region 63 is conducted on the
display. In the printer 51, both heads 52 and 53 for the
decolorizable ink and the normal ink are actuated according to the
instructions from the application software, thereby carrying out
printing on a paper sheet 50 as instructed. With this type of
printer, only variable information possibly be rewritten can be
repeatedly decolored and printed again many times.
[0115] FIG. 7 shows an ink-jet printer having a decoloring
mechanism consisting of a heat roller. In this printer 71, paper
sheets placed in the cassette 72 in the bottom are fed by a
transport roller, printed by the printer head 73 and discharged
through the outlet 74. When a printed paper is recycled, the
printed paper sheet is fed through the inlet 75, decolored by
heating with the heat roller 76, and then discharged through
another outlet 77.
[0116] In the present invention, toner for electrophotographic
prepared by pulverizing a composition containing a color former, a
developer, a decolorizer and a binder may be used to decolor a
printed paper sheet. In the electrophotographic application, toner
transferred on the paper sheet is fixed by heating, and therefore
it is preferable to use a compatible or phase-separation inhibiting
decolorizer.
[0117] FIG. 8 shows a copy machine of electrophotographic type
having a decoloring mechanism consisting of a heat roller. In this
copy machine 81, paper sheet are accommodated in the cassette 82 in
the bottom. The photosensitive drum 83 locating in the central
portion of the machine is irradiated with light from the LED head
84, thereby forming a latent image on the surface of the drum 83.
To the drum 83, charged toner 86 is attached with the developing
apparatus 85 by an electrostatic force to form a toner image. A
paper sheet is, in a timely manner with the development,
transported between the drum 83 and the transfer roller 87, thereby
transferring the toner to the paper sheet. The toner transferred on
the paper sheet is fixed by the fixing roller 88 and then
discharged through the outlet 89. When a printed paper sheet is
recycled, the paper sheet is fed through the inlet 90, heated by a
heat roller 91 to decolor and then discharged through the outlet
92. Temperatures of the fixing roller 88 and the heat roller 91 are
so set, for example, 140.degree. C. and 190.degree. C., that the
temperature of the heat roller 91 is higher than that of the fixing
roller 88.
[0118] In the copy machine of electrophotographic type, printing
toner comprising a color former and a developer and decoloring
toner comprising a decolorizer may be used.
[0119] Components of the ink of the present invention can be
applicable to a thermal printer. In this case, a sheet (or ribbon)
for printing and a sheet (or ribbon) for decoloring are preferably
used to effect printing and decoloring. The sheet or ribbon is made
of a heat-resistant resin such as polyethyleneterephthalate
(PET).
[0120] For example, an ink composition comprising a color former
and a developer is applied on a sheet substrate to prepare a
printing sheet. The ink composition may be applied together with
wax in order to facilitate transfer to the paper. Another
composition including a decolorizer is applied on another sheet
substrate to prepare a decoloring sheet. Using a thermal printer,
the ink composition on the printing sheet is thermally transferred
to a paper sheet to effect printing and, when necessary, the
composition including the decolorizer on the decoloring sheet is
thermally transferred to the printed paper sheet to effect
decoloring. As to the decolorizer, those categorized in the
compatible decolorizer or the phase-separation inhibiting
decolorizer are preferred. In the decoloring operation, a power of
the thermal printer head is raised so as to operate at a higher
temperature as compared with that in the printing operation.
[0121] FIG. 9A shows an example of a printing sheet, and FIG. 9B
shows an example of a decoloring sheet. The printing sheet 100 in
FIG. 9A has a structure that the release layer 103, the ink layer
104 and the lubricant layer 105 are formed on the PET sheet 101 on
the back of which the back coating layer 102 is formed. Note that,
the release layer 103 and the lubricant layer 105 are not
necessarily required. The decoloring sheet 200 in FIG. 9B has a
structure that the release layer 203, the barrier layer 204 and the
decolorizer layer 205 are formed on the PET sheet 201 on the back
of which the back coating layer 202 is formed. With the barrier
layer 204 inserted, the decolorizer can be prevented from spreading
wide over a medium. Note that, the release layer 203 and the
barrier layer 204 are not necessarily required.
[0122] In the above case, it may be used an ink composition in
colored state which comprises a color former, a developer and a
decolorizer having a relatively low glass transition point. When
the ink composition is thermally transferred to a paper sheet and
the printed paper sheet is temporarily decolored by heating and
then the paper sheet is left at room temperature, the decolored
printing can be restored to be visible. Such a function is
applicable, for example, to judgment of storage conditions of fresh
foods to be refrigerated. That is, if a label on which warning is
printed with the above ink composition is attached on the package
of fresh foods and then the label is decolored, the warning appears
on the label when the package is left at room temperature.
[0123] In addition, when it is desired that an ink composition has
a reversibility, a phase-separation accelerator, which is a
compound that accelerates phase separation of a color former and a
developer from a decolorizer, may be added in order to raise a
coloring speed. Preferred phase-separation accelerator is a low
molecular weight organic compound, which is highly crystallizable,
having a long chain alkyl group with eight or more carbon atoms and
a polar group such as OH, CO and COOH. Examples of phase-separation
accelerator are linear higher monohydric alcohols, linear higher
polyhydric alcohols, linear higher fatty acids, linear higher
polyvalent fatty acids, esters and ethers thereof, linear higher
fatty acid amides and linear higher polyvalent fatty acid
amides.
[0124] To be more specific, the phase-separation accelerator
includes: linear higher monohydric alcohols such as 1-docosanol,
1-tetracosanol, 1-hexacosanol and 1-octacosanol; linear higher
polyhydric alcohols such as 1,12-dodecanediol, 1,12-octadecanediol,
1,2-tetradecanediol and 1,2-hexadecanediol; linear higher fatty
acids such as behenic acid, 1-docosanic acid, 1-tetracosanic acid,
1-hexacosanic acid and 1-octacosanic acid; linear higher polyhydric
fatty acids such as dodecanedioic acid and
1,12-dodecanedicarboxylic acid; linear higher ketons such as
stearone; linear higher fatty acid alcohol amides such as
isopropanolamide stearate, isopropanolamide behenate and
hexanolamide behenate; and linear higher fatty acid dioldiesters
such as ethyleneglycol dilaurate, catechol dilaurate and
cyclohexanediol dilaurate. These compounds can be used singly or in
combination of two or more species. Examples of a mixture which can
be used as the phase-separation accelerator are ester-base waxes,
alcohol-base waxes and urethane-base waxes.
[0125] Combinations of components applied on a printing sheet and a
decoloring sheet are modified from the above mentioned
combinations. For example, a printing sheet applied with an ink
composition comprising a color former, a developer and a
phase-separation inhibiting decolorizer (or a compatible
decolorizer) and a decoloring sheet applied with a composition
including a reversible decolorizer may be used. Further, only a
printing sheet applied with an ink composition comprising a color
former, a developer, a reversible decolorizer and a
phase-separation inhibiting decolorizer (or compatible decolorizer)
in a state where the reversible decolorizer and the
phase-separation inhibiting decolorizer (or compatible decolorizer)
are phase-separated may be used.
[0126] In the present invention, two kinds of printing method may
be used together. For example, a paper sheet is printed with toner
including a color former and a developer in electrophotography and
then a decolorizer may be thermally transferred from a decoloring
sheet to the printed paper sheet for decoloring.
[0127] Further, printing and decoloring may be carried out in the
following manner. Upon printing, first toner including a color
former and a developer is transferred on a heat-resistant sheet in
electrophotography, and then the first toner on the heat-resistant
sheet is thermally transferred to a paper sheet. Upon decoloring,
second toner including a decolorizer is transferred on a
heat-resistant sheet in electrophotography, and then the second
toner on the heat-resistant sheet is thermally transferred to the
printed paper sheet. In this case, too, decoloring is carried out
at a higher temperature than printing. In this method, partial
correction can be made in a printed region. In normal
electrophotography, since a paper sheet is entirely heated in the
fixing process, if a part of printed paper sheet is decolored and
subsequently re-printed and then a different part of the re-printed
paper is decolored, the re-printed part is likely to be decolored
in the fixing process. On the contrary, in the above method,
correction can be repeated two or more times, since there is no
need for the fixing process.
[0128] It is desirable for the solvent used in the method in which
an image forming material is brought into contact with the solvent
to satisfy requirements A and B given below:
[0129] A. The solvent should desirably be effective for assisting
the formation of hydrogen bond between the developer and the
decolorizer.
[0130] B. The solvent should desirably exhibit a high affinity with
the binder so as to permeate deep inside the image forming
material.
[0131] The solvent satisfying requirement A given above can be used
singly. Also, it is possible to use a plurality of solvents in
combination to allow the mixed solvents to satisfy requirements A
and B.
[0132] The solvents satisfying both requirements A and B include,
for example, ethers, ketones and esters. To be more specific, the
solvents satisfying requirements A and B include, for example,
saturated ethers such as ethyl ether, ethyl propyl ether, ethyl
isopropyl ether, isopentyl methyl ether, butyl ethyl ether,
dipropyl ether, diisopropyl ether, ethyl isopropyl ether, dibutyl
ether, dipentyl ether, diisopentyl ether, and dihexyl ether;
unsaturated ethers such as ethyl vinyl ether, aryl ethyl ether,
diaryl ether, and ethyl propargyl ether; ethers of dihydric
alcohols such as ethyleneglycol monomethyl ether, ethyleneglycol
monoethyl ether, ethyleneglycol monobutyl ether, ethyleneglycol
dimethyl ether, and ethyleneglycol diethyl ether; cyclic ethers
such as oxetane, tetrahydrofuran, tetrahydropyran, dioxolane,
dioxane, and trioxane; saturated ketones such as acetone, methyl
ethyl ketone, methyl propyl ketone, isopropyl methyl ketone, butyl
methyl ketone, ethyl propyl ketone, isobutyl methyl ketone,
pinacolone, methyl pentyl ketone, butyl ethyl ketone, dipropyl
ketone, diisopropyl ketone, hexyl methyl ketone, isohexyl methyl
ketone, heptyl methyl ketone, and dibutyl ketone; unsaturated
ketones such as ethylidene acetone, allyl acetone, and mesityl
oxide; cyclic kotones such as cyclopentanone, cyclohexanone, and
cyclooctanone; and esters such as ethyl formate, propyl formate,
butyl formate, isobutyl formate, pentyl formate, isopentyl formate,
ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate,
isobutyl acetate, pentyl acetate, isopentyl acetate, sec-amyl
acetate, hexyl acetate, allyl acetate, 2-methoxyethyl acetate,
2-ethoxyethyl acetate, 1,2-diacetoxy ethane, methyl propionate,
ethyl propionate, propyl propionate, isopropyl propionate, butyl
propionate, pentyl propionate, isopentyl propionate, sec-amyl
propionate, 2-methoxypropyl acetate, 2-ethoxypropyl acetate, methyl
butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate,
butyl butyrate, pentyl butyrate, isopentyl butyrate, sec-amyl
butyrate, methyl isobutyrate, ethyl isobutyrate, propyl
isobutyrate, isopropyl isobutyrate, butyl isobutyrate, pentyl
isobutyrate, isopentyl isobutyrate, sec-amyl isobutyrate, methyl
valerate, ethyl valerate, propyl valerate, isopropyl valerate,
butyl valerate, methyl hexanoate, ethyl hexanoate, propyl
hexanoate, isopropyl hexanoate and ethyl ladate. Additional
solvents used in the present invention include, for example,
methylene chloride, .gamma.-butyrolactone, .beta.-propyolactone,
N-methylpyrrolidinone, dimethyl formamide, dimethyl acetoamide and
dimethyl sulfoxide. These solvents can be used singly or in the
form of a mixture of at least two compounds. In the case of using
mixed solvents, the mixing ratio can be determined arbitrarily (the
first group).
[0133] The solvents satisfying requirement A, though the affinity
with the binder is low, include, for example, water, methyl
alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl
alcohol, isobutyl alcohol, pentyl alcohol, 2-pentyl alcohol,
3-pentyl alcohol, isopentyl alcohol, 1-hexanol, 2-hexanol,
3-hexanol, cyclopentanol, cyclohexanol, ethylene glycol, propylene
glycol, butylene glycol, and glycerin (the second group).
[0134] On the other hand, the solvents having a high affinity with
the binder but failing to satisfy requirement A include, for
example, toluene, ethylbenzene, propylbenzene, cumene,
butylbenzene, isobutylbenzene, sec-butylbenzene, pentylbenzene,
diethylbenzene, mesitylene, xylene, cresol, dimethoxybenzene,
dimethoxytoluene, benzyl alcohol, tolyl carbinol, cumyl alcohol,
acetophenone, propiophenone, hexane, pentane, heptane, octane,
cyclohexane, cyclopentane, cycloheptane, cyclooctane, and petroleum
fractions such as petroleum ether and benzene (the third
group).
[0135] The first group of the solvents given above can be used
singly satisfactorily. The second group of the solvents, which can
certainly be used singly, should desirably be mixed with the first
group of the solvents. Since each of these first and second groups
of the solvents exhibits a decoloring capability, these solvents
can be mixed at an arbitrary mixing ratio. Where a solvent of the
second group is mixed with a solvent of the third group, the mixing
ratio is not particularly limited as far as the mixed solvents
exhibit a sufficient decoloring capability. However, it is
desirable for the mixing amount of the third group solvent to fall
within a range of between 20 and 80% by weight. It is also possible
to use the third group solvent together with the first group
solvent. In this case, the mixing amount of the third group solvent
should be 90% by weight or less. Further, it is possible to use the
first, second and third group solvents together. In this case, it
is desirable for the mixing amount of the third group solvent to be
80% by weight or less.
[0136] For efficiently decoloring the image forming material, it is
desirable to heat in advance the solvent. In this case, the solvent
temperature should desirably fall within a range of between
40.degree. C. and 150.degree. C.
[0137] In the case of employing a decoloring method using a
solvent, a decolorizer may be added to the solvent. For example,
the image can be formed and decolored by the methods exemplified
below:
[0138] 1. An image is formed by using an image forming material
containing a color former, a developer and a highly amorphous phase
separation inhibitor, and the image forming material in a color
developed state is brought into contact with a solvent containing a
slightly amorphous phase separation inhibitor so as to achieve
decoloration.
[0139] 2. An image is formed by using an image forming material
containing a color former, a developer and a slightly amorphous
phase separation inhibitor, and the image forming material in a
color developed state is brought into contact with a solvent
containing a highly amorphous phase separation inhibitor so as to
achieve decoloration.
[0140] 3. An image is formed by using an image forming material
containing a color former and a developer, and the image forming
material in a color developed state is brought into contact with a
solvent containing a highly amorphous phase separation inhibitor
and a slightly amorphous phase separation inhibitor so as to
achieve decoloration.
[0141] In the methods exemplified above, it is desirable to use at
least one decolorizer selected from the group consisting of a
biodegradable sterol compound extracted from an animal, plant or
fungi, cyclic sugar alcohols or derivatives thereof, said
decolorizer being mixed with the solvent for decoloring the image.
A plurality of these decolorizers can be used together in the form
of a mixture.
[0142] In the present invention, an image may be formed by using an
image forming material containing a color former, a developer, a
decolorizer and a binder consisting of a polyester or an epoxy
resin. In decoloring the image, a solvent containing a basic
compound can be brought into contact with the image forming
material. In bringing the solvent containing a basic compound into
contact with the image forming material, the solvent may be sprayed
onto a paper sheet bearing the image. Alternatively, the paper
sheet may be immersed in a solution. Further, after contact with
the solvent containing a basic compound, the image forming material
may be heated.
[0143] The solvent used for preparing a solution of a basic
compound is not particularly limited as far as the basic compound
can be dissolved in the solvent. The solvents used for this purpose
include, for example, water, methyl alcohol, ethyl alcohol,
isopropyl alcohol, acetone, methylene chloride, ethyl acetate,
ethyl lactate, ethyl butyrate, n-pentyl butyrate, ethyl ether,
tetrahydrofuran, ethyleneglycol dimethyl ether, ethyleneglycol
diethyl ether, cellosolve acetate, .gamma.-butyrolactone,
.beta.-butyrolactone, N-methyl pyrrolidinone, dimethyl formamide,
dimethyl acetamide, dimethyl sulfoxide, methyl ethyl ketone, methyl
isopropyl ketone, toluene, xylene, hexane, pentane, heptane,
petroleum fractions such as petroleum ether and benzine. It is
desirable for the basic compound solution to have a concentration
of 1 to 40% by weight.
[0144] For bringing the image forming material which has developed
color on a paper sheet into contact with a solvent, it is possible
to use a roller for immersing the paper sheet in a solvent housed
in a container, a spray nozzle for spraying the solvent onto the
paper sheet, a nozzle for dripping the solvent onto the paper
sheet, and a gravure roller for supplying the solvent onto the
paper sheet. On the other hand, the solvent can be removed from the
paper sheet by using, for example, a hot air, an infrared ray lamp,
a heat roller, a hot press, a thermal printer head (TPH) and a
thermal bar. Where the solvent used is likely to be evaporated, the
paper sheet may be subjected to a natural drying. Further, it is
desirable to use a solvent recovery means used in the apparatus of
the present invention.
EXAMPLES
[0145] Examples of the present invention will be described
below.
[0146] Example 1
[0147] One part by weight of Crystal Violet lactone (CVL) as a
color former, two parts by weight of 2,4,4'-trihydroxybenzophenone
as a developer and 10 parts by weight of methylandrostenediol as a
decolorizer were homogeneously mixed in a mixture solvent of
toluene and cyclohexane, and then the solvent was evaporated off to
obtain powder. After the powder was heated up to 150.degree. C., it
was cooled down to room temperature in 10 minutes to develop blue
color. One gram of the powder was put into 50 cc of water added
with 0.5 grams of sodium stearate as surfactant, and the ink
composition powder was pulverized to a particle size of a micron
order in a pulverizer to prepare ink with dispersed fine powder
therein.
[0148] Using the ink thus prepared, characters were written on a
paper sheet of A4 size with pen. After drying, a thermal bar set at
200.degree. C. was passed above the paper sheet in two seconds. As
a result, the characters completely disappeared and a blank paper
sheet was obtained. When writing and decoloring were repeated 30
times, also a blank paper sheet was finally obtained. The optical
density (OD) of the blank paper sheet finally obtained was
0.15.
[0149] Example 2
[0150] One part by weight of ETAC as a color former, one part by
weight of 2,4,4'-trihydroxybenzophenone as a developer, five parts
by weight of heckogenin as a decolorizer were homogeneously mixed
in a mixture solvent of toluene and cyclohexane, and then the
solvent was evaporated off to obtain powder. After the powder was
heated up to 150.degree. C., it was cooled down to room temperature
in 10 minutes to develop black color. One gram of the powder was
put into 50 cc of water added with 0.5 grams of sodium stearate as
surfactant, and the ink composition powder was pulverized to a
particle size of a micron order in a pulverizer to prepare ink with
dispersed fine powder therein.
[0151] The ink was used in an ink-jet printer equipped with a
piezoelectric element (MJ800C manufactured by Epson Co.), and
printing was carried out on a paper sheet of A4 size. After the
printing, a thermal bar was passed above the paper sheet to decolor
the printed information. When the recycled paper was stored at
60.degree. C. for 30 hours, the printed information did not appear
again, which revealed that the recycled paper sheet had a good
storage stability. After the paper sheet was printed again, the
printed surface was irradiated with light at 5000 lux for 300
hours. In this case, decrease in printing density was not higher
than 10%.
[0152] Example 3
[0153] One part by weight of PSD-HR (available from Nippon Soda Co.
Ltd.) as a color former, one part by weight of .alpha., .alpha.,
.alpha.'-tris(4-hydroxyphenyl)-1-ethyl-4-isoproylbenzene as a
developer and 20 parts by weight of pregnenolone as a decolorizer
were melted to form a mixture, and then the mixture was gradually
cooled to obtain a red solid product. The product dissolved in an
aqueous solution containing 8 wt. % of gum arabic was pulverized
with a ball mill to a particle size of the order of 10 .mu.m so
that the powder was dispersed in the aqueous solution. The
dispersed product was mixed with an aqueous solution of gelatin at
40.degree. C., the mixture was stirred for 1 hours, and then water
was added dropwise while stirring to dilute the mixture. Next, an
aqueous solution containing 10 wt. % of acetic acid was added to
adjust pH of the mixture to be 3.9, and then 37% formalin was added
to adjust pH of the mixture to be 7.0. The liquid thus prepared was
cooled to 5.degree. C., left at room temperature for 3 days, and
then the liquid was subjected to a centrifugal separator to
separate microcapsules. In this way, microcapsules for red color
were prepared. The microcapsules were dispersed in water at a
concentration of 8 wt. % to prepare ink.
[0154] The ink was used in a ink-jet printer equipped with a
piezoelectric element (MJ800C, manufactured by Epson Corp.), and
printing was carried out on a paper sheet of A4 size. After the
printing, a thermal bar was passed above the paper sheet to decolor
the printed information. When the recycled paper was stored at
60.degree. C. for 30 hours, the printed information did not appear
again, which revealed that the recycled paper sheet had a good
storage stability. After the paper sheet was printed again, the
printed surface was irradiated with light at 5000 lux for 300
hours. In this case, decrease in printing density was not higher
than 10%.
[0155] Example 4
[0156] Microcapsules obtained in a similar method to that of the
example 3 was dispersed in water at a concentration of 15 wt. % to
prepare ink for typographic printing.
[0157] A paper sheet of A4 size was printed with this ink in a
common typographic printing process. Thereafter, a heat roller kept
at 200.degree. C. was made to contact with the sheet for two
seconds to decolor the printed information. When printing and
decoloring were repeated 30 times, also a blank paper sheet was
finally obtained. The optical density (OD) of the blank paper sheet
finally obtained was 0.15.
[0158] Example 5
[0159] Microcapsules were prepared in a similar method to that the
example 3 except that one part by weight of Crystal Violet lactone
(CVL) as a color former, two parts by weight of
2,4,4'-trihydroxybenzophenone as a developer and 20 parts by weight
of pregnenolone as a decolorizer were used. The microcapsules were
dispersed in water at a concentration of 8 wt. % to prepare
ink.
[0160] This ink was used in a ink-jet printer equipped with a
piezoelectric element (MJ800C manufactured by Epson Corp.) to print
on a paper sheet of A4 size. After the printing, a thermal bar was
passed above the paper to decolor the printed information. When the
recycled paper was stored at 60.degree. C. for 30 hours, the
printed information did not appear again, which revealed that the
recycled paper sheet had a good storage stability. After the paper
sheet was printed again, the printed surface was irradiated with
light at 5000 lux for 300 hours. In this case, decrease in printing
density was not higher than 10%.
[0161] Example 6
[0162] Two parts by weight of a colored composition consisting of
PSD-150 (available from Nippon Soda Co. Ltd.) as a color former and
2,3,4,4'-tetrahydroxybenzophenone as a developer at a ratio of 1 to
1, seven parts by weight of D-glucose as a decolorizer, three parts
by weight of gelatin as a binder, and small amounts of isopropyl
alcohol and a mildew inhibitor were added to water to prepare ink
with a solid content of 10%. The color of the ink was black.
[0163] A paper sheet was printed with the ink with an ink-jet
printer, and then the printed paper sheet was dried. When the paper
sheet was heated by means of a thermal printer head (TPH) at a
power of 0.35 mJ/dot or more, the printed information was able to
be decolored. The decolored state was kept for 1000 hours at
40.degree. C. without any change.
[0164] Examples 7 to 11
[0165] In the following Examples 7 to 11, 4.5 .mu.m-thick PET film
back-coated with thermosetting silicone-acrylic resin at a
thickness of about 0.2 .mu.m was used as a sheet substrate to
prepare a printing sheet and a decoloring sheet. Printing and
decoloring were carried out by using a thermal printer head with a
pixel density of 8 dot/mm at a recording velocity of 10 ms/L.
[0166] Example 7
[0167] One part by weight of Crystal Violet lactone (CVL) as a
color former, one part by weight of propyl gallate as a developer,
15 parts by weight of wax as a thermal transferring agent and 3
parts by weight of polystyrene as a binder resin were mixed
followed by thermally melting to prepare an ink composition, and
then the melt was applied on a surface of a sheet substrate with a
bar coater at a thickness of about 2 .mu.m to prepare a printing
sheet.
[0168] One part by weight of 1,2-cyclohexanediol and one part by
weight of methyl cholate as a decolorizer were mixed followed by
thermally melting to prepare a decolorizer composition, and then
the melt was applied on a surface of another sheet substrate by a
bar coater at a thickness of about 3 .mu.m to prepare a decoloring
sheet.
[0169] Printing, decoloring and re-printing were carried out in the
following manner with changing a TPH power, during which the
reflection densities of a paper sheet were measured. The results
are shown in FIG. 10.
[0170] When the printing sheet was put on a paper sheet and the ink
composition was thermally transferred on the paper sheet by means
of TPH, printing was effected stably at a power of 0.15 mJ/dot or
more.
[0171] When the decoloring sheet was put on the printed paper sheet
and the decolorizer composition was thermally transferred on the
paper sheet by means of TPH, decoloring was effected at a power of
0.3 mJ/dot or more. This decolored state was maintained even for
longer than 300 hours at 40.degree. C.
[0172] When the printing sheet was put on the decolored paper sheet
and the ink composition was thermally transferred again on the
paper sheet by means of TPH, re-printing was effected at a power in
the range of 0.15 to 0.2 mJ/dot, but re-printing was not able to be
effected at a power of 0.3 mJ/dot or more.
[0173] Example 8
[0174] One part by weight of CVL as a color former, one part by
weight of 2,4,4'-trihydroxybenzophenone as a developer, five parts
by weight of metylandrostenediol as a reversible decolorizer, five
parts by weight of 1-docosanol as a phase-separation accelerator
and three parts by weight of styrene-methacrylic acid copolymer as
a binder were mixed followed by thermally melted to prepare an ink
composition, and then the melt was applied on a surface of a sheet
substrate by means of a bar coater at a thickness of 2 .mu.m to
prepare a printing sheet. A decoloring sheet was prepared in a
similar manner to that of the example 7.
[0175] Printing, reversible decoloring, complete decoloring and
re-printing were carried out in the following manner with changing
a TPH power, during which reflection densities of a paper sheet
were measured. The results are shown in FIG. 11.
[0176] When the printing sheet was put on a paper sheet and the ink
composition was thermally transferred on the paper sheet by means
of TPH, printing was effected stably at a power of 0.15 mJ/dot or
more.
[0177] When the printed portion on the paper sheet was heated by
means of TPH, the printed portion was decolored at a power of 0.35
mJ/dot or more. When the decolored paper sheet was left at room
temperature, the printed characters were restored to the originally
printed state after 72 hours had passed.
[0178] When the decoloring sheet was put on the printed paper sheet
and the decolorizer composition was thermally transferred on the
paper sheet by means of TPH, decoloring was effected at a power of
0.35 mJ/dot or more. This decolored state was maintained even for
longer than 1000 hours at 60.degree. C. without any change.
[0179] When the printing sheet was put on the decolored paper sheet
and the ink composition was thermally transferred again on the
paper sheet by means of TPH, re-printing was able to be effected at
a power in the range of 0.15 to 0.25 mJ/dot, but re-printing was
not able to be effected at a power of 0.35 mJ/dot or more.
[0180] Example 9
[0181] One part by weight of ETAC (available from Yamada Chemical
Co. Ltd.) as a color former, one part by weight of
2,4,4'-trihydroxybenzophen- one as a developer, five parts by
weight of methyl lithocholate as a compatible decolorizer and three
parts by weight of polystyrene as a binder were mixed at a
temperature where methyl lithocholate is not melted to prepare an
ink composition, and then the ink composition was applied on a
surface of a sheet substrate by means of a bar-coater at a
thickness of 2 .mu.m to prepare a printing sheet.
[0182] .beta.-Sitosterol as a reversible decolorizer and mixed
alcohols containing mainly myricyl alcohol as a phase-separation
accelerator were mixed at a ratio of 2 to 1 by weight followed by
thermally melting to prepare a decolorizer composition, and then
the melt was applied on a surface of another sheet substrate at a
thickness of 2 .mu.m by means of a bar-coater to prepare a
decoloring sheet.
[0183] Printing, decoloring and re-printing were carried out in the
following manner with changing a TPH power, during which the
reflection densities of the paper sheet were measured. The results
are shown in FIG. 12.
[0184] When the printing sheet was put on a paper sheet and the ink
composition was thermally transferred on the paper sheet, printing
was effected stably at a power of 0.10 mJ/dot or more. When the
printed portion of the paper sheet was heated by means of TPH, it
was not able to decolor the printed characters.
[0185] When the decoloring sheet was put on the printed paper sheet
and the decolorizer composition was thermally transferred on the
paper sheet by means of TPH, decoloring was effected at a power of
0.3 mJ/dot or more. The decolored state was not changed even after
300 hours had elapsed at 40.degree. C.
[0186] When the printing sheet was put on the decolored paper sheet
and the ink composition was thermally transferred again on the
paper sheet, re-printing was effected at a power in the range of
0.15 to 0.2 mJ/dot. However, re-printing was not effected at a
power of 0.3 mJ/dot or more.
[0187] Example 10
[0188] One part by weight of RED 40 (available from Yamada Chemical
Co., Ltd.) as a color former, one part by weight of
2,3,4,4'-tetrahydroxybenzo- phenone as a developer and 10 parts by
weight of 1,2-cyclohexanediol as a phase-separation inhibiting
decolorizer were mixed by melting, and then the solid mixture was
pulverized into fine powder with a particle size of 10 .mu.m or
less.
[0189] On the other hand, one part by weight of RED 40 as a color
former, 2,3,4,4'-tetrahydroxybenzophenone as a developer and 10
part by weight of cholesterol as a reversible decolorizer were
mixed by melting, and then the solid mixture was pulverized into
fine powder with a particle size of 10 .mu.m or less.
[0190] These two kinds of powder were mixed at a ratio of 1 to 1 by
weight and the mixture was dispersed in an aqueous solution
containing 5% gelatin at a solid content of 20% to prepare ink. The
ink was then applied on a surface of a sheet substrate with a
coating weight of about 3 g/m.sup.2 by means of a bar-coater to
prepare a printing sheet. In this example, no decoloring sheet was
used.
[0191] FIG. 13 shows a relationship between the TPH power and the
reflection density. When the printing sheet was put on a paper
sheet and the ink composition was thermally transferred on the
paper sheet by means of TPH, printing was effected at a power in
the range of 0.10 to 0.3 mJ/dot, but printing was not effected at a
power exceeding 0.3 mJ/dot.
[0192] When the printed portion of the printed paper was heated by
means of TPH, it was unable to decolor the printed portion at a
power in the range of 0.10 to 0.3 mJ/dot, but it was able to
decolor the printed portion at a power exceeding 0.3 mJ/dot. The
decolored state was maintained without any change for 300 hours at
40.degree. C.
[0193] Example 11
[0194] One part by weight of CVL as a color former, one part by
weight of propyl gallate as a developer and 10 parts by weight of
cholesterol as a reversible decolorizer were melted to prepare a
composition. Using a composition, microcapsules with a gelatin
shell were prepared. Three parts by weight of the microcapsules and
one part by weight of wax as a thermal transferring agent were
mixed and the mixture was applied on a sheet substrate by means of
a hot-melt coater to prepare a printing sheet.
[0195] The printing sheet was put on a paper sheet and then the ink
composition was thermally transferred on the paper sheet at a power
of 0.15 mJ/dot by means of TPH to print such a phrase as "STORAGE
POSSIBLY IMPROPER". The printed paper was heated at 60.degree. C.
to decolor the characters temporarily.
[0196] When the decolored paper was stored in a refrigerator at
10.degree. C., the printed characters did not appear even after 240
hours had passed. However, when the decolored paper was left in a
room at 25.degree. C., the printed characters appeared after 10
hours had passed. Similarly, in the condition of 35.degree. C., the
characters appeared after two hours had passed. Therefore, the ink
of the present invention can be applicable as a thermal history
sensor in the use such as quality control of fresh foods.
[0197] A temperature at which printing with an ink of the present
invention is restored, after it is printed and then decolored
temporarily, is controllable by selecting material having a proper
glass transition point. Glass transition point Tg and melting point
Tm of typical reversible decolorizers are shown in Table 1.
Moreover, coloring speed of ink in the vicinity of the above
mentioned temperatures were controlled by addition of a
phase-separation accelerator or selection of a proper
developer.
1TABLE 1 No. decolorizer Tg Tm 1 1,2:5,6-diisopropylidene-
2.degree. C. 106.degree. C. D-mannitol 2 pregnenolone acetate
15.degree. C. 140.degree. C. 3 .DELTA.-androstene- 22.degree. C.
130.degree. C. 3,17-dione 4 cholesterol 28.degree. C. 137.degree.
C. 5 lanosterol 33.degree. C. 131.degree. C. 6
5.alpha.-pregnan-3.beta.-ol- 37.degree. C. 182.degree. C. 20-one 7
pregnenolon 44.degree. C. 183.degree. C. 8 estradiol benzoate
50.degree. C. 188.degree. C. 9 5.alpha.-pregnen- 53.degree. C.
196.degree. C. 3.beta., 17-diol diacetate 10 methylandrostenediol
65.degree. C. 197.degree. C. 11 heckogenin 80.degree. C.
250.degree. C. 12 rockogenin 92.degree. C. 201.degree. C.
[0198] Example 12
[0199] One part by weight of CVL as a color former, one part by
weight of propyl gallate as a developer, 10 parts by weight of
cholesterol as a reversible decolorizer, three parts by weight of
wax as a thermal transferring agent, five parts by weight of
polystyrene as a binder, and small amounts of hydrophobic quartz
filler in the form of ultra-fine powder and a charge control agent
were melted and then solidified. The solid product was crushed and
further pulverized into fine particles with an average size of 10
.mu.m to prepare toner. A decoloring sheet was prepared in a
similar manner to that of the example 7.
[0200] The toner was fed to a copy machine (FC210 manufactured by
Cannon Inc.) and characters were copied on a paper sheet. They were
fixed stably.
[0201] When the decoloring sheet was put on the copied paper and
then the decolorizer was thermally transferred by means of THP,
decoloring was effected at a power of 0.3 mJ/dot or more. The
decolored state was unchanged even after 300 hours had elapsed at
40.degree. C.
[0202] Example 13
[0203] One part by weight of ETAC (made by Yamada Chemical Co.,
Ltd.) as a color former, one part by weight of
2,4,4'-trihydroxybenzophenone as a developer, 10 parts by weight of
heckogenin as a reversible decolorizer, three parts by weight of
mixed alcohols rich in myricyl alcohol as a phase-separation
accelerator, five parts by weight of styrene-methacrylic acid
copolymer as a binder, and small amounts of hydrophobic quartz
filler in the form of ultra-fine powder and a charge control agent
were melted and then solidified. The solid product was crushed and
further pulverized into fine particles with an average size of 10
.mu.m to prepare toner. A decoloring sheet was prepared in a
similar manner to that of the example 7.
[0204] The toner was fed into a copy machine (FC210 manufactured by
Canon Inc.) and characters were copied on a paper sheet. The
characters were fixed on the paper sheet stably.
[0205] When the copied portion of the paper sheet was heated by
means of TPH at a power of 0.35 mJ/dot or more, it was able to
decolor the copied characters. The decolored characters did not
appear at room temperature, but they appeared at 40.degree. C.
after 3 weeks had passed, and at 135.degree. C. at an elapsed time
of 0.2 seconds.
[0206] When the decoloring sheet was put on the copied paper and
then the decolorizer was thermally transferred by means of THP,
decoloring was effected at a power of 0.35 mJ/dot or more. The
decolored state was unchanged even after 1000 hours had elapsed at
60.degree. C.
[0207] In the following Examples 14 to 55, 500 BLATT (available
from Neusiedler, pH=9.4) was used as a plain paper sheet for
forming an image. This paper sheet has a reflection density of
0.07.
[0208] Example 14
[0209] FIG. 14 shows an example of heating type decoloring
apparatus. The apparatus comprises a pair of a heat roller 11a and
a counter roller 11b, another pair of a first surface roughening
roller 12a and a counter roller 12b, and still another pair of a
second surface roughening roller 13a and a counter roller 13b,
which are arranged in this order as seen from the inlet port. These
first and second surface roughening rollers 12a and 13a differ from
each other in the surface roughness. These surface roughening
rollers in the simplest form can be prepared by detachably mounting
a sand paper to the surface of each of these rollers. The surface
roughening roller of this type can be miniaturized so as to be used
in an office.
[0210] A paper sheet, which is fed into the apparatus with a
surface having an image formed thereon facing upward, is heated by
the heat roller 11a and, then, roughened by the first and second
surface roughening rollers 12a, 13a. As a result, light is
scattered on the surface of the image forming material so as to
decrease the light reflection, making it impossible to recognize
whether or not the image forming material remains on the surface of
the paper sheet.
[0211] Example 15
[0212] FIG. 15 shows an example of a solvent type decoloring
apparatus. A solvent container 101 and a solvent tank 103 for
supplying a solvent 102 (for example, ethyleneglycol diethyl ether)
into the solvent container 101 are arranged in a bottom portion of
the apparatus. Paper sheets each having an image formed thereon is
fed one by one with the formed image facing downward by a transfer
roller 104 into the apparatus and, then, transferred by carrier
rollers. The paper sheet is transferred through a clearance between
a immersing roller 105 and counter rollers 106. During the
transfer, the paper sheet is immersed in the solvent 102 housed in
the solvent container 101 so as to have the formed image decolored.
The paper sheet is further transferred into an upper region of the
apparatus by carrier rollers so as to be exposed to a hot air
generated from a radiator of an electronic cooler described herein
later and, then, heated by a heat roller 107 so as to be smoothed.
After removal of the solvent, the paper sheet is transferred by a
transfer roller 108 out of the apparatus so as to be housed in a
stocker. It is possible for the transfer rollers 104 and 108 to be
equipped with electric switches to permit these rollers to be
operated or stopped when the paper sheet is transferred into and
out of the decoloring apparatus. It is desirable for each roller to
be formed of a material resistant to a solvent and producing an
antistatic effect.
[0213] In the decoloring apparatus shown in FIG. 15, the paper
sheet is immersed in the solvent 102 housed in the solvent
container 101. Naturally, the solvent can be supplied in an amount
large enough to achieve the decoloring to the paper sheet
regardless of the amount of the image forming material on the paper
sheet. Also, the decolored state can be maintained stable, making
it possible to reuse the paper sheet effectively. It should also be
noted that, if the surface of the image forming material on the
paper sheet is roughened by the counter roller 108, the quality of
the decolored paper sheet can be improved.
[0214] The apparatus comprises a solvent recovery mechanism. The
recovery mechanism comprises mainly a recovery vessel in which are
housed an adsorbent 110, an electronic cooler 111, and a
circulation pump 114. The used solvent is recovered from the
solvent container 101 into a recovered solvent container 109. The
solvent evaporated in the recovered solvent container 109 is
adsorbed on the adsorbent 110 cooled by the electronic cooler 111,
e.g., a Peltier element. The temperature of the electronic cooler
111 is set to permit the vapor pressure of the solvent to be 100
ppm or less. The solvent adsorbed on the absorbent 110 is sucked by
a circulation pump 114 so as to be absorbed by an absorption filter
113. It is desirable to use an orifice pump excellent in resistance
to explosion as the circulation pump. It is possible to prevent the
pump material from being corroded by the solvent by arranging the
absorption filter 113 upstream of the circulation pump 114. It is
also possible to use a dehumidifier in order to prevent the water
within the atmosphere from entering the system. The hot air
generated from the radiator 112 of the electronic cooler 111 is
utilized for drying the paper sheet after immersing in the solvent
as described previously. The apparatus of the type shown in FIG. 15
can be miniaturized so as to be used in an office.
[0215] Example 16
[0216] FIG. 16 shows another example of a solvent type decoloring
apparatus. The decoloring apparatus shown in FIG. 16 is
substantially equal in construction to the apparatus shown in FIG.
15, except that a gravure roller 121 is used in the apparatus of
FIG. 16 for bringing a solvent into contact with the image forming
material on the paper sheet. The gravure roller 121 is rotated so
as to be immersed in the solvent 102 housed in the solvent
container 101 and, then, the amount of the solvent attached to the
surface is controlled by a blade 123. When the paper sheet fed into
the apparatus is passed through the clearance between the gravure
roller 121 and the counter roller 122, the solvent (for example,
n-pentyl lactate) is supplied by the gravure roller 121 to the
paper sheet so as to achieve decoloration.
[0217] In the apparatus shown in FIG. 16, the smallest amount of
the solvent required for the decoloration is supplied by the
gravure roller 121 onto the paper sheet, making it possible to
shorten the time required for removing the solvent from the paper
sheet. As a result, the process rate of the paper sheet is
improved. Also, since the image forming material remaining on the
paper sheet is roughened by the rubbing with the gravure roller,
the quality of the decolored paper sheet is improved.
[0218] Example 17
[0219] FIG. 17 shows another example of a solvent type decoloring
apparatus. The decoloring apparatus shown in FIG. 17 is
substantially equal in construction to the apparatus shown in FIG.
15, except that the apparatus shown in FIG. 17 comprises a pump 131
and a spray nozzle 132 as a means for bringing the solvent into
contact with the image forming material on the paper sheet, and a
lamp heater 133 for removing the solvent from the paper sheet. In
the apparatus shown in FIG. 17, the solvent 102 is pumped out by
the pump 131 from the solvent container 101 so as to be sprayed
onto the paper sheet from the nozzle 132, thereby to achieve
decoloration. Then, the paper sheet is dried by a hot air and, at
the same time, heated by the lamp heater 133 so as to remove the
solvent from the paper sheet.
[0220] In the apparatus shown in FIG. 17, a sufficiently large
amount of the solvent can be supplied by the pump 131 onto the
paper sheet. In addition, the lamp heater 133 permits improving the
solvent removing rate from the paper sheet. It follows that the
apparatus shown in FIG. 17 is superior to the apparatus shown in
FIG. 15 or 16 in the paper sheet processing rate. What should also
be noted is that the solvent flows down along the surface of the
paper sheet so as to spread the image forming material. As a
result, the quality of the decolored paper sheet is improved.
[0221] Example 18
[0222] FIGS. 18A to 18C collectively exemplifies a batch type
decoloring apparatuses. FIG. 18A is a plan view of the apparatus,
with FIGS. 18B and 18C being side views. As shown in the drawings,
a solvent 202 is housed in a solvent tank 201 arranged in a bottom
portion of the apparatus. A solvent immersing vessel 203 is
arranged in an upper portion of the apparatus. A chemical pump 204
and a pipe 205 connected to the chemical pump 204 are arranged
between the solvent tank 201 and the solvent immersing vessel 203.
Further, an electronic cooler 206, e.g., a Peltier element, is
arranged below the solvent immersing vessel 203 such that a
radiator of the electronic cooler 206 faces upward. An electric
power is supplied from a power source 207 to the electronic cooler
206.
[0223] For performing the decoloration, a lid of the solvent
immersing vessel 203 is opened, and a bundle of, for example, 100
paper sheets is put in the vessel 203. Under this condition, the
chemical pump 204 is operated to supply the solvent 202 from the
solvent tank 201 into the solvent immersing vessel 203 so as to
immerse the paper sheets in the solvent for the decoloring purpose.
Then, the chemical pump 204 is operated again to cause the solvent
to flow from the solvent immersing vessel 203 back to the solvent
tank 201. Further, the solvent is removed from the paper sheet by
utilizing the heat radiated from the electronic cooler 206. The
paper sheets thus decolored can be used again effectively. It is
also possible to use the recovered paper sheets for manufacturing
regenerated paper sheets. Further, the evaporated solvent can be
cooled by the electronic cooler 206 for recovering the solvent.
Incidentally, a heat exchanger can be used in place of the
electronic cooler shown in FIG. 18. The apparatus shown in FIG. 18
is capable of processing the paper sheets on the order of 100
kg/day.
[0224] Example 19
[0225] FIG. 19 exemplifies an in-line type large plant using a
solvent. In this plant, bundles 301 of paper sheets are transferred
by a belt conveyor 302 into a solvent processing vessel 303 so as
to be immersed in a solvent 304 for the decoloring purpose. The
bundles 301 of the paper sheets are taken out of the solvent
processing vessel 303 by a belt conveyor 305 so as to be
transferred into a primary drying station in which these paper
sheets are exposed to a hot air generated from a heater 306 and
blown by a fan 307. As a result, these paper sheets are scattered
and dried and, then, transferred into a secondary drying station in
which these paper sheets are transferred by a belt conveyor 308.
During the transfer in the secondary drying station, the scattered
paper sheets are completely dried by an infrared heater 309. The
dried paper sheets are stored in a stock room 310. In this
apparatus, the recovered paper sheets can be effectively used
again. It is also possible to use the recovered paper sheets for
manufacturing regenerated paper sheets. It should be noted that the
evaporated solvent generated from the entire plant is recovered in
a fractionator (not shown) so as to be used again as a decoloring
solvent in the solvent processing vessel. The apparatus of this
type is capable of processing paper sheets in an amount of scores
of tons/day.
[0226] In a plant of the type shown in FIG. 19, it is desirable to
use a solvent for its own use. For example, it is desirable to use
a mixed solvent consisting of a ketone type solvent exhibiting a
high decoloring rate and toluene that is a good solvent for the
binder. Further, a decolorizer should desirably be added to the
mixed solvent noted above.
[0227] Additional advantages and modifications will readily occur
to those skilled in the art. Therefore, the invention in its
broader aspects is not limited to the specific details and
representative embodiments shown and described herein. Accordingly,
various modifications may be made without departing from the spirit
or scope of the general inventive concept as defined by the
appended claims and their equivalents.
* * * * *