U.S. patent number 3,895,173 [Application Number 05/332,881] was granted by the patent office on 1975-07-15 for dichromatic thermo-sensitive recording paper.
This patent grant is currently assigned to Matsushita Electric Industrial Co., Ltd.. Invention is credited to Kinichi Adachi.
United States Patent |
3,895,173 |
Adachi |
July 15, 1975 |
Dichromatic thermo-sensitive recording paper
Abstract
Recording paper which forms, for example, a red color when
scratched with a thermal pen or head at a certain temperature and
which forms, for example, a blue color when scratched with a
thermal head at a higher temperature, said dichromatic
thermo-sensitive paper having first and second layers formed from a
dispersion in a film-forming binder of discontinuous particles of a
leuco base of triphenylmethane or fluoran type dye and a phenolic
acidic substance or an organic acid; and, disposed therebetween an
inter layer capable of being thermally fused to dilute as well as
to exclude the color formed in the first layer.
Inventors: |
Adachi; Kinichi (Takarazuka,
JA) |
Assignee: |
Matsushita Electric Industrial Co.,
Ltd. (Kadoma, JA)
|
Family
ID: |
27519885 |
Appl.
No.: |
05/332,881 |
Filed: |
February 15, 1973 |
Foreign Application Priority Data
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|
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Feb 17, 1972 [JA] |
|
|
47-17063 |
Jul 31, 1972 [JA] |
|
|
47-77219 |
Oct 20, 1972 [JA] |
|
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47-105440 |
Oct 20, 1972 [JA] |
|
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47-105441 |
Oct 20, 1972 [JA] |
|
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47-105442 |
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Current U.S.
Class: |
503/204; 428/913;
503/214; 503/226; 503/205; 503/221 |
Current CPC
Class: |
B41M
5/42 (20130101); B41M 5/34 (20130101); B41M
5/3275 (20130101); B41M 5/323 (20130101); Y10S
428/913 (20130101); B41M 5/327 (20130101); B41M
5/44 (20130101); B41M 5/423 (20130101) |
Current International
Class: |
B41M
5/34 (20060101); B41M 5/40 (20060101); B41M
5/42 (20060101); B41M 5/30 (20060101); B41m
005/18 () |
Field of
Search: |
;117/36.9,36.8,36.7 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Herbert, Jr.; Thomas J.
Attorney, Agent or Firm: Stevens, Davis, Miller &
Mosher
Claims
What is claimed is:
1. A dichromatic thermo-sensitive recording paper comprising: a
first layer formed from a dispersion in a film-forming binder of
discontinuous particles of a leuco base of triphenylmethane or
fluoran type dye and a phenolic substance or an organic acid, said
first layer capable of forming a first color upon application of
heat; a second layer formed from a dispersion in a film-forming
binder of discontinuous particles of a leuco base of
triphenylmethane or fluoran type dye and a phenolic substance or an
organic acid, said second layer capable of forming a second color
upon application of heat, said second color distinguishable from
the first color formed in the first layer; and, disposed between
the first and second layers, an inter layer capable of being
thermally fused to dilute as well as to exclude the first color
formed in the first layer from the second color formed in the
second layer.
2. A dichromatic thermo-sensitive recording paper according to
claim 1, wherein the heat capacity A necessary to form the first
color of the first layer, the heat capacity B necessary to form the
second color of the second layer, and the heat capacity C necessary
to fuse the thermo-fusible inter layer, satisfy the inequality A
< C .ltoreq. B.
3. A recording paper according to claim 1, wherein the inter layer
comprises a dispersion in a film-forming binder of discontinuous
particles of a phenolic substance or an organic acid.
4. A recording paper according to claim 1, wherein the inter layer
comprises a dispersion in a film-forming binder of discontinuous
particles of at least one member selected from the group consisting
of acetamide, stearamide, phthalonitrile, m-nitroaniline and
.beta.-naphthylamine.
5. A recording paper according to claim 4, wherein the dispersion
additionally contains discontinuous particles of a phenolic
substance or an organic acid.
6. A recording paper according to claim 1, wherein the first layer
and/or the second layer additionally contain as a sensitizer at
least one member selected from the group consisting of stearamide,
acetamide, phthalonitrile, nitroaniline and
.beta.-naphthylamine.
7. A recording paper according to claim 1, wherein the dye ratio of
the first layer to the second layer is in the range from 1:5 to
1:20.
8. A recording paper according to claim 1, wherein said first
layer, inter layer, and second layer are coated on the same side of
a substrate.
Description
This invention relates to dichromatic thermosensitive paper for use
in information terminal machines, e.g., facsimiles, telexes,
electronic computers, etc., various metrological appliances and
copying machines.
Recording materials, which have heretofore been utilized for the
above-mentioned uses, are represented by conventional photographic
recording papers, electrophotographic recording papers,
electrostatic recording papers, electrolytic recording papers and
diazo type recording papers. All these recording papers, however,
have had such drawbacks that the supply of toners, developers,
fixers and the like chemicals is necessarily required in the
image-forming process. Furthermore, inks are used in recording
machines employed at present. Accordingly, there have been such
disadvantages for users that the recording papers are stained with
the inks, or ink-flowing holes of pens are clogged with solids
formed by vaporization of solvents of the inks, with the result
that figures to be recorded are not recorded clearly or, in extreme
cases, cannot be recorded. With an aim to overcome the
above-mentioned drawbacks and disadvantages, pressure-sensitive
papers have come to be used chiefly. At present, however, these
recording papers are limited in uses to copying papers and
teletyping papers which are used in place of carbon papers.
Heretofore, thermo-sensitive recording materials of various types
have been proposed. Among these recording materials, those which
have already been put into practical use and those which will be
put into practical use in the near future are as follows:
1. A thermo-sensitive recording paper prepared by coating carbon or
the like colored pigment or dye powder on a substrate, and then
coating a white, opaque thermofusible substance on the resulting
pigment or dye powder layer. This recording sheet is of such a type
that the thermofusible substance on the surface is scratched with a
thermal stylus to expose and make visible the lower colored layer.
The recording material of this type has such drawbacks that scums
are formed and multi-color recording is impossible.
2. A recording material which forms a color by forming a complex
compound of an electron donor with an electron acceptor. This
recording material is of such a type that ferric stearate and
pyrogallol, for example, are independently dispersed in a binder,
and the binder is softened by application of heat, thereby reacting
the two compounds with each other to form a visible complex
compound. The color formed in this case is dark brown.
3. A recording material of such a type that Crystal Violet Lactone
and a phenolic substance are dispersed as discontinuous particles
into a thermo-softening substance such as polyvinyl alcohol, and
the thermo-softening substance is softened by application of heat
to give a record. The color obtained in this case is brilliant
cobalt blue. This type of recording material suggests the promising
future of thermo-sensitive recording materials, but has a question
in how to solve the recording of two or more colors.
As mentioned above, a recording material for use in information
terminal machines is required to satisfy such conditions as that it
can give a clear record and can be recorded by use of a recording
machine which is simple in maintenance. Considering the said
conditions, the thermo-sensitive recording material of the
aforesaid item (3) is a preferable recording material since it can
give a clear image by mere heating with a thermal head. With
progress of society, however, high density informations have come
to be required, and there is a strong need for a thermo-sensitive
recording material which can give a two- or more-colored
record.
The present invention provides a dichromatic thermo-sensitive paper
which is free from the drawbacks of this kind of thermo-sensitive
recording material and which satisfies the above-mentioned
requirements.
That is, the invention provides a recording paper which forms, for
example, a red color when scratched with a thermal pen or head at a
certain temperature, and which forms, for example, a blue color
when scratched with a thermal head at a higher temperature.
With reference to the drawings attached hereto,
FIG. 1 show the basic construction of the recording sheet of this
invention;
FIG. 2A and 2B show the relation between reflection density and
width of lines of image obtained in accordance with this
invention;
FIGS. 3, 4 and 5 show the relation between temperature of recording
stamp and reflection density of image obtained; and
FIGS. 6 A and 6 B and 7 A and 7 B show the relation between
reflection density and width of lines of image obtained.
The thermo-sensitive recording paper of the present invention will
be explained in detail below with reference to FIG. 1. As shown in
FIG. 1, the recording paper is composed of a first color-forming
layer 1, and inter layer 3, a second color-forming layer 2, and a
base paper 4. In FIG. 1, 1.1 is a color-forming dye, 1.2 is a
color-forming agent, 1.3 is a sensitizer, 2.1 is a color-forming
dye different in hue from the color-forming dye 1.1, 2.2 is a
color-forming agent, 2.3 is a sensitizer, and 3.1 is a crystalline
organic substance.
In the first color-forming layer 1, the color-forming dye 1.1 and
the color-forming agent 1.2 have dispersed separately from each
other in a thermo-softening substance which is solid at normal
temperature. However, when a certain quantity of heat is applied to
the surface of the recording paper, the color-forming dye reacts
with teh color-forming agent to form the first color. In this case,
the sensitizer acts to promote the reaction of the color-forming
dye with the color-forming agent so as to form the color quickly.
In the second color-forming layer 2, the color-forming dye 2.1 and
the color-forming agent 2.2 have dispersed separately from each
other in a thermo-softening substance which is solid at normal
temperature. However, when a certain quantity of heat is applied to
the surface of the recording paper, the color-forming dye reacts
with the color-forming agent to form a color different in hue from
the first color. In this case, the sensitizer 2.3 acts to promote
the reaction of the color-forming dye with the color-forming agent.
Further, when a certain quantity of heat is applied to the surface
of the recording paper, the crystalline organic substance contained
in the inter layer fuses to dilute as well as to push aside the dye
which has formed the first color in the first layer, and when heat
is further applied, the organic substance so acts that the dye,
which has formed the second color in the second layer, does not mix
with the dye, which has formed the first color in the first
layer.
The above-mentioned first and second color-forming layers have
individually been well known as thermo-sensitive recording
materials of this kind. However, the recording paper of the present
invention is characterized in that the first layer, the inter layer
and the second layer have been so combined that among the
quantities of heat applied to the surface of the recording paper,
the quantity of heat necessary to cause color formation of the
first color-forming layer (hereinafter referred to as "heat Q.sub.1
"), the quantity of heat necessary to fuse the inter layer
(hereinafter referred to as "heat Q.sub.2 "), and the quantity of
heat necessary to cause color formation of the second color-forming
layer (hereinafter referred to as "heat Q.sub.3 ") are in such a
relation as to satisfy the inequality Q.sub.1 < Q.sub.2 .ltoreq.
Q.sub.3, and in that the recording paper has been so designed that
at a temperature attained when heat Q.sub.3 is applied to the paper
surface, the first and second layers form colors, but the dye,
which has formed the color in the first layer, is diluted and
pushed aside by means of the inter layer and is surrounded by the
dye, which has formed the color in the second layer, to be brought
into such a state that, apparently, it has formed no color, and
only the second layer is made visible, whereby the recording paper
can form two brilliant colors.
The quantity of heat applied to each of the color-forming layers is
dependent on the temperature of a thermal head contacted with the
paper surface to give a record on the recording paper, the contact
time of the thermal head with the paper surface, and the thermal
conductivity of the recording paper from the surface to each layer.
For example, in case the thermal head is applied from the above to
the surface of recording paper having such structure as shown in
FIG. 1, the quantity of heat applied to the first color-forming
layer 1 is greater than the applied to the second color-forming
layer, even if the temperature of the thermal head and the contact
time thereof with the paper surface are definite. In this case, the
temperature of the first color-forming layer is higher than that of
the second color-forming layer, and hence is not always required to
be made higher than a temperature at which the second color-forming
layer forms a color.
Now, the color formation mechanism of the recording paper according
to the present invention will be explained in detail below.
It has been clarified by O. Fischer, et al., [Berichte der Deutchen
Chemischen Gesellschaft, 42 2934-2935 (1909)] that a leuco dye base
of the triphenylmethane type, e.g., Crystal Violet Lactone, forms a
color by reaction with a phenolic substance such as phenol or
cresol and an organic acid. Further, a leuco dye base of the
fluoran type also exhibits the same property as mentioned above. It
is said that the color formation mechanism of the said reaction is
such that the electron attractive acid attracts the electrons of
amine of the leuco dye base to bring about ionization of the dye
base. Generally, this kind of color-forming dye and color-forming
agent are mixed or contacted with each other either as they are or
in the form of solutions, whereby the color-forming dye forms a
color due to electron transfer. However, no color is formed in case
the said two components are dispersed individually in a non-solvent
therefor by use of a binder and are then contacted with each other.
This is ascribable to the fact that the binder separates the two
components from each other to inhibit the contact thereof. If the
binder which has separated the two components from each other is
fused, or either the color-forming agent or the color-forming dye
is fused to bring the two into contact with each other, there is
formed a color.
Generally, when heat Q.sub.1 is applied to a recording paper having
first and second color-forming layers containing the
above-mentioned thermo-sensitive substances, the first
color-forming layer forms a color according to the aforesaid color
formation principle, and when heat Q.sub.2 is then applied to the
recording paper, the second color-forming layer forms a color.
However, if the color-forming dye in the first color-forming layer
does not substantially differ in amount from that in the second
color-forming layer, and if no inter layer has been disposed
between the two layers, the color formed in the first color-forming
layer is mixed with the color formed in the second color-forming
layer to make it impossible to form two brilliant colors. For
example, if the recording paper is subjected to a dot printer, two
colors, which are to be formed, become mere shade and light, and
thus the recording paper cannot be used as a two color recording
paper. However, in case the color-forming dye in the first
color-forming layer is smaller in amount than that in the second
color-forming layer, and in case a thermofusible crystalline
organic substance is present in the inter layer, the first and
second color-forming layers form colors at the same time by
application of heat Q.sub.3. In this case, the crystalline organic
substance present in the inter layer fuses to dilute as well as to
push aside the first color formed in the first layer, whereby the
recording paper can form two brilliant colors. When the recording
paper is used as a dichromatic recording paper for high efficiency
recorder or printer, it is advantageous if the density of each
color formed becomes maximum due to slight temperature difference.
That is, the greater the value of .gamma., the more advantageous.
(In the present invention, the value of .gamma. is defined by the
formula .gamma. = (D.sub.2 -D.sub.1)/(T.sub.2 -T.sub.1), wherein
T.sub.2 is a maximum density-reaching temperature; T.sub.1 is a
temperature when "fog" is +0.1; and D.sub.2 and D.sub.1 are
reflection densities at temperatures of T.sub.2 and T.sub.1,
respectively. The greater the value of .gamma., the shorter the
time to reach the maximum density.) The aforesaid color-forming dye
and color-forming agent form a color according to color formation
mechanism based on ionization of the color-forming dye due to
contact of the said two components with each other. In preparing
the recording paper by use of the said two color-forming
components, the two components are separated from each other by
means of a binder so as to inhibit the occurrence of color
formation reaction at normal temperature. When heat is applied to
the recording paper, the two components are swelled or activated
and initiate to react with each other. In this case, the density of
the formed color reaches maximum when the two components have
completely mixed with each other. It is therefore ordinary that the
color forming temperature T.sub.s is 90.degree.C., the maximum
density-reaching temperature T.sub.D-max is 150.degree.C., and the
value of .gamma. is small. When such recording paper is used for
copying, it gives a half tone image high in gradation. However,
when used in a line printer or the like machine required to be
particularly high in speed, it is preferable that the recording
paper is greater in .gamma. value. Further, if the value of .gamma.
is small in the case of dichromatic recording paper, the resulting
image is blurred due to thermal diffusion from the head, with the
result that the image shows a somewhat stained appearance and no
brilliant two colors can be formed.
In the present invention, the recording paper is made greater in
.gamma. value by introduction of a third substance (referred to as
"sensitizer" in the present invention) in addition to the
color-forming dye and the color-forming agent, so that the
recording paper can form brilliant two colors. The sensitizer is a
crystalline organic substance having a sharp melting point, and has
such action that when fused by application of heat, it dissolves at
least one of the color-forming agent and the color-forming dye to
quickly contact and mix the two with each other. Accordingly, the
value of .gamma. can be made greater. Further, when a substance
having a suitable melting point is selected as the sensitizer, it
is possible to establish the temperature at which the color
formation is initiated. The sensitizer used in the present
invention is thermofusible by itself, so that it is not preferable
to use as the sensitizer a substance which fuses at the storage
temperature of the recording paper or which does not fuse at an
ordinary color formation temperature of the color-forming
components. In this sense, it is preferable that the sensitizer has
a melting point in the range from 70.degree.C. to 180.degree.C.
Materials used in the present invention are exemplified below.
a. Color-forming dyes:
As the color forming dyes, there are used, in general, leuco bases
of triphenylmethane type dyes represented by the general formula
(1) or leuco bases of fluoran type dyes represented by the general
formula (2). ##SPC1##
wherein R.sub.x, R.sub.y and R.sub.z are individually hydrogen, a
hydroxyl group, a halogen, an alkyl group, an aryl group, a nitro
group, an amino group, a dialkylamino group, a monoalkylamino group
or an alkoxy group; and Z is an atom necessary to form a
heterocyclic group, and represents O or S.
i. Compounds belonging to (1):
3,3-Bis(p-dimethylaminophenyl)-phthalide
3,3-Bis(p-dimethylaminophenyl)-6-dimethylaminophthalide
3,3-Bis(p-dimethylaminophenyl)-6-nitrophthalide
3,3-Bis(p-dimethylaminophenyl)-6-monoethylaminophthalide
3,3-Bis(p-dimethylaminophenyl)-6-chlorophthalide
3,3-Bis(p-dimethylaminophenyl)-6-ethoxyphthalide
3,3-Bis(p-dimethylaminophenyl)-6-diethylaminophthalide
ii. Compounds belong to (2):
3-Dimethylamino-6-methoxyfluoran
7-Acetamino-3-dimethylaminofluoran
3-Dimethylamino-5,7-dimethylfluoran
3,6-Bis-.beta.-methoxyethoxyfluoran
3,6-Bis-.beta.-cyanoethoxyfluoran
iii. Other lactam compounds:
9-p-nitroamino-3,6-(diethylamino)-9-xanthenoyl-6-benzoic acid
lactam, (Rhodamine Lactam)
9-p-Nitroamino-3,6-bis(dimethylamino)-9-thioxanthenoyl-6-benzoic
acid lactam
The above-mentioned dye bases are effective as the color-forming
dyes. They are scarcely soluble in non-polar or substantially
non-polar solvents such as, for example, n-hexane, xylene, ligroin,
benzene and toluene, and in water, and can be pulverized to fine
particles of less than 10 microns.
b. Color-forming agents:
Preferable as the color-forming agents, which form dyes by chemical
reaction with the color-forming dyes mentioned in (a) are phenolic
compounds or organic acids. It is desirable for dye formation that
the color-forming agents are solid at normal temperature and are
liquefied or gasified at above 50.degree.C.
i. Phenolic substances:
4-tertiary-Butylphenol
4-Phenylphenol
4-Hydroxy-di-phenol
.alpha.-Naphthol
Methyl-4-hydroxybenzoate
.beta.-Naphthol
4-Hydroxyacetophenone
4-tertiary-Octylcatechol
2,2'-Dihydroxydiphenol
2,2'-Methylenebis(4-chlorophenol)
4,4'-Isopropylidene-di-phenol=(Bisphenol A)
4,4'-isopropylidenebis(2-chlorophenol)
4,4'-Isopropylidenebis(2,6-dibromophenol)
4,4'-Isopropylidenebis(2,6-dichlorophenol)
4,4'-Isopropylidenebis(2-methylphenol)
4,4'-sec-Isobutylidenediphenol
4,4'-Cyclohexylidenediphenol
2,2'-Thiobis(4,6-dichlorophenol)
Hydroquinone
Pyrogallol
Phloroglucine
Phloroglucinolcarboxylic acid
ii. Organic acids:
p-Hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic
acid, boric acid, tartaric acid, oxalic acid, maleic acid, succinic
acid, gallic acid, 1-hydroxy-2-naphthenic acid and
2-hydroxy-p-tolyl acid.
c. Binders:
In case the aforesaid color-forming dye and color-forming agent are
merely dispersed in water or in a non-polar or substantially
non-polar organic solvent and the dispersion is coated on a
substrate, the resulting layer is not only great in fog but also
comes off and thus is low in practicality. It is therefore
necessary to use a binder which can disperse and fix the two as
discontinuous particles at normal temperature. Due to its inherent
property, the binder softens or melts on heating, whereby the dye
formation is promoted. Examples of the binder are as shown
below.
i. Water soluble binders:
Polyvinyl alcohol, polyacrylic acid, hydroxyethyl cellulose,
polyacrylamide, carboxymethyl cellulose, methoxy cellulose,
polyvinyl pyrrolidone, gelatin and starch are preferable binders
which provide tackiness when dissolved in or swelled with
water.
ii. Binders soluble in non-polar or substantially non-polar organic
solvents:
As this kind of binders, there are natural rubber, synthetic
rubbers, chlorinated rubbers, alkyd resins, styrene-butadiene
copolymers and polybutyl methacrylates. These binders can disperse
and fix the color-forming dyes and color-forming agents as
discontinuous particles at temperatures below the thermal recording
temperature and, at the same time, play the role of adhering them
onto substrates. Those which do not simply discolor are
preferable.
d. Sensitizers and crystalline organic substances to be
incorporated into the inter layer:
As the sensitizers, there are used colorless or pale-colored
crystalline organic substances having a melting point of 70.degree.
to 180.degree.C. which, when fused, can dissolve at least one of
the color-forming dyes and color-forming agents. Effective as such
substances are organic compounds having nitrogen in the molecules
of nitro, amino and the like groups. Further, it has been found
that acetamide, stearamide, phthalonitrile, m-nitroaniline and
.beta.-naphthylamine are most suitable as the binders used in the
present invention.
The substances to be incorporated into the inter layer may be the
aforesaid phenolic substances or organic acids. Favorable results
are obtained when the said substances are used together with the
aforesaid sensitizers.
In addition thereto, talc, clay, titanium oxide, zinc oxide or
calcium carbonate may be incorporated with an aim to improve the
recording paper in whiteness and printability and to prevent the
paper from adhering to a thermal head.
Procedures for examining and evaluating the effect of the recording
paper according to the present invention were carried out in the
following manner:
It is convenient, for the purpose of comparison, to express in
terms of optical density (hereinafter abbreviated to "O.D.") an
image formed by scratching a thermo-sensitive recording paper with
a metal stamp head capable of being adjusted to and maintained at a
definite temperature.
For evaluation of the present recording paper, the recording was
conducted by use of a column-shaped stainless steel stamp having a
tip diameter of 10 mm. which had a heating portion disposed
therein, and a thermal head having a silicon resistor as the
heating element. The O.D. value was measured by means of an
automatic specular densitometer NLM-VI manufactured by Narumi Co.,
and a microdensitometer manufactured by Konishiroku Co., Ltd. The
filter used was a gelatin filter produced by Kodak Co.
The present invention is illustrated in detail below with reference
to examples.
EXAMPLE 1
35 Parts by weight of Rhodamine Lactam as a color-forming dye was
mixed with 200 parts by weight of a 5 wt% aqueous solution of
polyvinyl alcohol (PVA 107 produced by Kuraray Co., Ltd.), and the
resulting mixture was ground for at least 2 hours in a ball mill
having an inner volume of 500 liters to prepare a dispersion A. In
the dispersion A, the color-forming dye had scarcely dissolved but
had dispersed in the form of fine particles of less than several
microns.
Separately, 35 parts by weight of p-hydroxybenzoic acid as a
color-forming agent was mixed with 200 parts by weight of a 5 wt%
aqueous polyvinyl alcohol solution, and the resulting mixture was
ground for at least 2 hours in a ball mill to prepare a dispersion
B. In the dispersion B, the color-forming agent had dispersed in
the form of fine particles of less than several microns.
In the next place, 35 parts by weight of Crystal Violet Lactone as
a color-forming dye was mixed with 200 parts by weight of a 5 wt%
aqueous solution of polyvinyl alcohol (PVA 205 produced by Kuraray
Co., Ltd.), and the resulting mixture was ground for at least 2
hours in a ball mill to prepare a dispersion C. The particle size
of the color-forming dye after dispersion was less than several
microns.
Further, 35 parts by weight of bisphenol A was mixed with 200 parts
by weight of a 5 wt% aqueous solution of polyvinyl alcohol (PVA 205
produced by Kuraray Co., Ltd.), and the resulting mixture was
ground for at least 2 hours in a ball mill to prepare a dispersion
D. The particle size of the bisphenol A after dispersion was less
than several microns.
Separately, 50 parts by weight of bisphenol A and 10 parts by
weight of stearamide were mixed with 200 parts by weight of a 3 wt%
aqueous solution of polyvinyl alcohol (PVA 205 produced by Kuraray
Co., Ltd.), and the resulting mixture was ground for at least 2
hours in a ball mill to prepare a dispersion E. The particle size
of the bisphenol A and stearamide after grinding was less than
several microns.
Further, 20 parts by weight of stearamide was mixed with 200 parts
by weight of a 3 wt% aqueous solution of polyvinyl alcohol (PVA 205
produced by Kuraray Co., Ltd.), and the resulting mixture was
ground for at least 2 hours in a ball mill to prepare a dispersion
F. The particle size of the stearamide after grinding was less than
several microns.
Subsequently, 1 part by weight of the dispersion A and 15 parts by
weight of the dispersion B were weighed and were mixed together by
means of a homogenizing mixer. In the resulting mixed dispersion,
the color-forming dye and the color forming agent had dispersed in
the form of fine particles surrounded by the PVA. It may therefore
be said that there was no direct contact between the two particles.
The said mixed dispersion was coated by means of a wire bar on a
white paper having a basis weight of 60 g/m.sup.2. The weight of
the coated dispersion after air-drying was 4 g/m.sup.2. The thus
coated paper was subjected to calendering to make the surface
thereof uniform, and then the dispersion E was coated on said
surface. The amount of the coated dispersion E after air-drying was
3 g/m.sup.2. On the thus formed layer of dispersion E was coated a
mixed dispersion comprising 1 part by weight of the dispersion C,
25 parts by weight of the dispersion D and 15 parts by weight of
the dispersion F. The amount of the coated mixed dispersion after
air-drying was 1 g/m.sup.2. In the above-mentioned manner, a
recording paper was obtained.
The thus obtained recording paper was subjected to recording by use
of a recorder which had been so controlled that a definite quantity
of heat could always be applied to the recording paper from a
silicon semiconductor used as the heating element. As the result, a
blue color was formed when the quantity of heat was 2 mj. (at a
recording speed of 200 mm/sec.) while a brilliant red color was
formed when the quantity of heat was 3.5 mj., and thus a two
colored record could be obtained. Characteristics of the thus
obtained record were as shown in FIGS. 2-A and 2 B. Densities of
the two colors formed were measured by means of a microdensitometer
manufactured by Konishiroku Co. In measuring the density of the
first color (FIG. 2-A), the red component was made invisible by use
of a red filter (Kodak Ratten No. 25), while in measuring the
density of the second color (FIG. 2-B), the blue component was made
invisible by use of a blue filter (Kodak Ratten No. 47B).
In FIG. 2-A, the solid line shows the formation state of the blue
color, and the dotted line 2 shows that of the blue color at that
time. In FIG. 2-B, the solid line 1 shows the formation state of
the red color (measured by use of the blue filter), and the dotted
line 2 shows that of the blue color at that time. FIG. 2-B
indicates that in the formation of the second color (red), the blue
component has substantially been pushed to both sides of the line
and has been diluted in density.
The effect of the sensitizer used in the present invention is
explained below with reference to Referential Example.
Referential Example 1
A 1:20 mixture of dispersions C and D prepared in Example 1 was
coated on a white paper in a proportion of 4 g/m.sup.2, and was
then sufficiently dried to prepare a paper (a). On the other hand,
a 1:20 mixture of the dispersions C and E prepared in Example 1 was
coated on a white paper in a proportion of 4 g/m.sup.2, and was
then sufficiently dried to prepare a paper (b). The thus prepared
papers (a ) and (b) were individually investigated in color
formation characteristics by means of the aforesaid stamp type
color formation tester under the conditions of a stamp contact
pressure of 4 kg/cm.sup.2 and a contact time of 1 second. The
results obtained were as shown in FIG. 3. In FIG. 3, a is the color
formation characteristic curve of the paper (a), and b is that of
the paper (b) incorporated with the sensitizer stearamide. That is,
the color formation characteristics of the paper (a) are
Ts=105.degree.C., D-max=1.05 and .gamma.=0.03, while those of the
paper (b) are Ts=85.degree.C., D-max=1.0 and .gamma.=0.08. From the
above results, it is understood that the use of the sensitizer
increases the sensitivity of the paper to make the .gamma. value
higher. As is clear from FIG. 3, the paper (b) incorporated with
the sensitizer is small in difference between the color formation
temperature and the maximum density-reaching temperature, and shows
sufficient efficiency as a recording paper for high speed
recording.
Subsequently, the paper (a) and the paper (b) incorporated with the
sensitizer were individually recorded by means of a printer using a
silicone resistor having 7 dots per line. As the result, the paper
(b) incorporated with the sensitizer could be recorded at a speed
of 95 cha./sec. to give a blue-free record. However, the paper (a)
incorporated with no sensitizer could not give the same record as
in the paper (b) unless it was recorded at a speed of 22
cha./sec.
EXAMPLE 2
A mixed dispersion comprising 3-dimethylamino-5,7-dimethylfluoran
as a color-forming dye and p-hydroxybenzoic acid as a color-forming
agent was prepared in the same manner as in Example 1. This mixed
dispersion was coated on a white paper of 70 g/m.sup.2 in basis
weight in a proportion of 7 g/m.sup.2, and was then sufficiently
dried to form a layer on the paper. On the thus formed layer, a
mixed dispersion comprising bisphenol A and phthalonitrile was
coated in a proportion of 3 g/m.sup.2, and the dispersion was
sufficiently dried to form an inter layer. On the thus formed inter
layer, a mixed dispersion comprising Crystal Violet Lactone as a
color-forming dye and bisphenol A as a color-forming agent was
coated in a proportion of 1 g/m.sup.2, and the dispersion was
sufficiently dried to obtain a recording paper (c). The thus
obtained recording paper (c) is a dichromatic type recording paper
having a first color-forming layer which forms a blue color (cobalt
blue) by the reaction of Crystal Violet Lactone with bisphenol A,
and a second color-forming layer which forms a red color by the
reaction of 3-dimethylamino-5,7-dimethylfluoran with
p-hydroxybenzoic acid.
On the other hand, a recording paper (d) was obtained in the same
manner as above, except that stearamide having a melting point of
109.degree.C. was incorporated as a sensitizer into the first
color-forming layer and phthalonitrile having a melting point of
141.degree.C. was incorporated as a sensitizer into the second
color-forming layer.
Characteristics of these recording paper (c) and (d) were as set
forth in Table 1.
Table 1 ______________________________________ Recording paper
Characteristics (c) (d) ______________________________________
Color formation First color 95.degree.C. 82.degree.C. temperature
Second color 125.degree.C. 95.degree.C. .gamma. First color 0.015
0.050 Second color 0.030 0.070 D-max *1 First color 0.30 0.60
Second color 1.05 1.00 Energy required for color forma- First color
6 mj. 5 mj. tion using a Second color 13 mj. 8 mj. thermal head *2
______________________________________ *1 The D-max value of the
first color is the density measured when the density of the second
color became 0.1. (The densities of the first and second colors
were measured by use of, respectively, the red and blue filters
used in Example 1.) *2 The energy in Table 1 is an energy per dot
which was required when eac recording paper was recorded at a speed
of 45 cha./sec. by means of a thermal printer using a thermal head
formed 7 dots per line.
FIGS. 4 and 5 show color formation characteristic curves of the
recording papers (c) and (d), respectively, as measured by use of
the aforesaid stamp type color formation tester under the
conditions of a contact pressure of 4 kg/cm.sup.2 and a contact
time of 1 second with varying stamp temperature. In each of FIGS. 4
and 5, the first color (blue) is represented by the curve 1, and
the second color (red) is represented by the curve 2. For the
measurement of reflection densities, a microdensitometer
manufactured by Konishiroku Co. was used. In measuring the density
of the first color, the red component was made invisible by use of
a red filter (Ratten No. 25, a gelatin filter produced by Kodak),
while in measuring the density of the second color, the blue
component was made invisible by use of a blue filter (Ratten No.
47B, a gelatin filter produced by Kodak).
FIGS. 6 and 7 show color formation states per dot of the recording
papers (c) and (d), respectively, when the recording papers were
individually recorded by means of a thermal printer using as a head
a silicon resistor having 7 dots (each 0.4 .times. 0.4 mm. in size)
per dot. In each of FIGS. 6 and 7, A shows the color formation
state at the time when the first color was formed in the first
color-forming layer, and B shows the color formation state at the
time when the second color was formed in the second color-forming
layer, in which the curve 1 represents the color formation state of
the blue component of the first color, and the curve 2 represents
the color formation state of the red component of the second
color.
As is clear from FIGS. 6 and 7, the color formation state of the
recording paper (c) containing no sensitizers is such that at the
time of color formation of the first color-forming layer, there is
formed a blue color which has been mixed with the second color,
i.e. red, (FIG. 6-A), and at the time of color formation of the
second color-forming layer, there is formed a red color which has
considerably been mixed with the first color, i.e. blue, (FIG.
6-B), whereas the color formation state of the recording paper (d)
containing the sensitizers is such that at the time of color
formation of each color-forming layer, there is formed a color
which has not been mixed with the other component, with the result
that a brilliant dichromatic recording can be obtained. Such effect
of sensitizers is particularly marked in the case of a dichromatic
type recording paper, and a clear record can be obtained by making
great the difference in melting point between the two sensitizers
to be incorporated into the individual layers.
EXAMPLE 3
Recording papers incorporated with sensitizers were prepared in the
same manner as in Example 2, except that the ratio in amount of the
color-forming dye in the first color-forming layer to that in the
second color-forming layer was varied. These recording papers were
compared in characteristics with each other to obtain the results
as set forth in Table 2. The amount of the inter layer was made 3
g/m.sup.2, and the total amount of components constituting the
thermo-sensitive layers was made definite to 9 g/m.sup.2. The
recording was carried out according to Example 2, while applying
input energies of 2 mj. and 4 mj., and the measurement of
reflection density was conducted according to Example 2.
Table 2
__________________________________________________________________________
Input energy 2 mj. Input energy 4 mj. Areal ratio of Areal ratio of
Dye ratio Density of first color Density of first color Sample No.
First layer: first component to second component to Second layer
color second color color second color component * component*
__________________________________________________________________________
1 1:1 0.95 95:5 0.65 75:25 2 1:4 0.90 90:10 0.84 50:50 3 1:5 0.85
90:10 1.05 25:75 4 1:7 0.80 90:10 1.10 20:80 5 1:10 0.75 85:15 1.15
20:80 6 1:15 0.70 80:20 1.15 15:85 7 1:20 0.58 70:30 1.20 15:85 8
1:30 0.35 65:35 1.20 10:90
__________________________________________________________________________
* The areal ratio of first color component to second color
component is the ratio of the area surrounded by the density curve
of the first color to the area surrounded by the density curve of
the second color, as seen in FIG. 7.
This kind of dichromatic thermo-sensitive paper is such that in
case a record of the first color is intended to be obtained by
applying heat Q.sub.1 (2 mj. in this example) to the paper surface,
the second color is also formed to a certain extent. Accordingly,
it is necessary that the density of the first color and the ratio
of the first color component to the second color component are
within certain ranges, so that the first color formed can be
visually distinguished from the second color formed by application
of heat Q.sub.2 (4 mj. in this example). considering the above, it
is desirable that the density of the first color is at least 0.50,
and the areal ratio of the first color component to the second
color component is greater than 70:30. Further, in case a record of
the second color is intended to be obtained, the first color is
necessarily formed as well. In this case, therefore, it is
desirable that the ratio of the first color component to the second
color component is smaller than 30:70. If the ratio is greater than
said value and if the recording paper is subjected to a dot
printer, the second color formed merely differs in shade and light
from the first color. In view of the above, the color-forming dye
ratio of the first layer to the second layer should be within the
range from 1:5 to 1:20.
EXAMPLE 4
A thermo-sensitive dichromatic recording paper having a first layer
comprising 3-dimethylamino-5,7-dimethylfluoran as a color-forming
dye, 4-hydroxyacetophenone as a color-forming agent, and
m-nitroaniline as a sensitizer; an inter layer comprising bisphenol
A; and a second layer comprising
3,3-bis(p-dimethylaminophenyl)-6-aminophthalide as a color-forming
dye and p-hydroxybenzoic acid as a color-forming agent was
prepared. This recording paper was subjected to recording by use of
the aforesaid recorder, whereby a red color could be recorded by
application of an input energy of 1.8 mj., and a brilliant blue
color could be recorded by application of an input energy of 2.8
mj.
EXAMPLES 5 - 10
Example 1 was repeated, except that the constructions of the first,
inter and second layers were varied as set forth in Table 3, to
prepare thermosensitive two color recording papers. The total
amount of components constituting the layers was 8 g/m.sup.2, in
which the amount of the inter layer was 2.5 g/m.sup.2. The thus
prepared recording papers were subjected to recording by use of the
same recorder as in Example 1 to obtain records having such colors
as shown in Table 3.
Table 3
__________________________________________________________________________
Dye ratio First Second Construction Construction Construction of
first color color Example of first of inter of second layer to
formation formation layer layer layer second layer Color Energy
Color Energy
__________________________________________________________________________
5 Crystal Rhodamine Violet Bisphenol A Lactam Lactone 1:10 Blue 1.6
mj. Red 3.0 mj. Naphthol Phthalo- Phlorogluci- nitrile
nolcarboxylic Stearamide acid Rhodamine Stearamide Crystal 6 Lactam
Violet Lactone 1:7 Red 1.5 mj. Blue 3.0 mj. Bisphenol A p-Hydroxy-
Acetamide benzoic acid Rhodamine Bisphenol A Crystal 7 Lactam
Violet Stearamide Lactone Bisphenol A 1:8 Red 1.6 mj. Blue 2.6 mj.
Bisphenol A Stearamide .beta.-Naphthyl- amine Crystal Salicylic
Rhodamine 8 Violet acid Lactam Lactone Hydroquinone 1:10 Blue 1.5
mj. Red 2.8 mj. 4-Hydroxy- Acetamide diphenol .beta.-Naphthyl-
amine Acetamide 3,6-Bis-.beta.- Bisphenol A 9 methoxy- do. ethoxy-
Acetamide Ye- fluoran 1:8 llow 1.6 mj. Red 2.8 mj. Bisphenol A
Stearamide
__________________________________________________________________________
* * * * *