U.S. patent number 3,792,481 [Application Number 05/270,195] was granted by the patent office on 1974-02-12 for method of recording by heat sensitive multicolor indication.
This patent grant is currently assigned to Canon Kabushiki Kaisha. Invention is credited to Shinichiro Nagashima, Toshio Watanabe.
United States Patent |
3,792,481 |
Nagashima , et al. |
February 12, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
METHOD OF RECORDING BY HEAT SENSITIVE MULTICOLOR INDICATION
Abstract
Heat sensitive recording to produce a multicolor indication is
effected by bringing a heating element close to or in contact with
a heat sensitive recording material for multicolor indication, the
recording material has two or more heat sensitive recording layers.
The temperature of the heating element is controlled to produce
patterns having different colors depending upon the heat sensitive
temperature of each heat sensitive layer.
Inventors: |
Nagashima; Shinichiro (Tokyo,
JA), Watanabe; Toshio (Kawasaki, JA) |
Assignee: |
Canon Kabushiki Kaisha (Tokyo,
JA)
|
Family
ID: |
12901085 |
Appl.
No.: |
05/270,195 |
Filed: |
July 10, 1072 |
Foreign Application Priority Data
|
|
|
|
|
Jul 13, 1971 [JA] |
|
|
46/51948 |
|
Current U.S.
Class: |
503/204; 427/144;
503/226; 347/172; 250/316.1; 430/348 |
Current CPC
Class: |
G06K
1/126 (20130101); B41M 5/34 (20130101) |
Current International
Class: |
B41M
5/34 (20060101); G06K 1/12 (20060101); G06K
1/00 (20060101); G01d 015/10 () |
Field of
Search: |
;346/46,76R,135
;250/65T,316-319 ;117/36.9,36.7,36.8 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Hartary; Joseph W.
Attorney, Agent or Firm: Fitzpatrick, Cella, Harper &
Scinto
Claims
We claim:
1. A method of recording by heat sensitive multicolor indication
which comprises the steps of: providing a heat sensitive recording
member for multicolor indication having a plurality of heat
sensitive recording layers, wherein each said heat sensitive
recording layer contains a material which changes color above a
predetermined temperature, and wherein the respective resultant
colors and predetermined temperatures are different for each said
layer; bringing a heating element into contact with or near to said
heat sensitive recording member; and developing a desired color on
said recording member by controlling the temperature of the heating
element in relation to said predetermined temperatures to change
the color of a desired one or more of said layers of the recording
member.
2. A method of recording by heat sensitive multicolor indication
according to claim 1 in which said step of providing said heat
sensitive recording member is performed by laminating said layers
on a support layer in the order of their respective predetermined
temperatures, wherein said predetermined temperatures increase
toward said support layer.
3. A method of recording by heat sensitive multicolor indication
according to claim 1 in which said color changing material of one
of said recording layers comprises at least one phenol compound and
a color forming material capable of reacting with the phenol
compound to form a conjugated system.
4. A method of recording by heat sensitive multicolor indication
according to claim 3 in which the color forming material is a basic
material having a color forming group.
5. A method of recording by heat sensitive multicolor indication
according to claim 4 in which the basic material is selected from
the group consisting of diarylphthalides, leuco auramines,
acrylauramines, .alpha., .beta.-unsaturated arylketones, basic
monoazo dyes, rhodamine B lactams, polyarylcarbinols,
benzoindolinospirophyrans, phthalans and spirophthalans.
6. A method of recording by heat sensitive multicolor indication
according to claim 1 in which the predetermined heat sensitive
temperatures range from 60.degree.C to 160.degree.C.
7. A method of recording by heat sensitive multicolor indication
according to claim 1 in which plural heating elements having
different temperatures are used.
8. A recording member for providing a heat sensitive multicolor
indication which comprises a laminate having at least two heat
sensitive recording layers, wherein each said layer contains a
material which changes color above a predetermined temperature; and
wherein the respective resultant colors and predetermined
temperatures are different for each said layer.
9. A recording member for providing a heat sensitive multicolor
indication according to claim 8 in which said heat sensitive
recording layers are laminated on a support layer, and the color
forming temperatures of the heat sensitive recording layers
increase from the surface side to the support layer side.
10. A recording member for providing a heat sensitive multicolor
indication according to claim 8 in which the material of at least
one said recording layer comprises at least one phenol compound and
a color forming material capable of reacting with the phenol
compound to form a conjugated system.
11. A recording member for providing a heat sensitive multicolor
indication according to claim 10 in which the color forming
material capable of reacting with the phenol compound to form a
conjugated system is selected from the group consisting of
diarylphthalides, leuco auramines, acrylauramines, .alpha.,
.beta.-unsaturated arylketones, basic monoazo dyes, rhodamine B
lactams, polyarylcarbinols, benzoindolinospirophyrans, phthalans
and spirophthalans.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method of recording by heat sensitive
multicolor indication and a heat sensitive recording material used
in said method.
2. Description of the Prior Art
Heretofore, it has been well known that the components of a heat
sensitive recording system are usually a basic color forming
material and an acidic material such as diphenol at a colorless
state; and, upon application of a heat pattern the system causes
liquefication or vaporization of the acidic material such as
diphenol and then the acidic material thus liquefied or vaporized
contacts with the basic color forming material to form color. The
colorless components of the recording system are usually contained
in a single supporting sheet referred to as a "self containing
system." Another type of heat sensitive recording system is that
composed of two sheets, i.e. one sheet having the first component
and the other sheet having the second component. Each component is
placed face to face and thereby one component, liquefied or
vaporized by application of a heat pattern, transfers to the other
component to form a recording. This latter system is known as a
"transferring system."
These heat sensitive recording materials have been widely used in
the reproduction of documents. A heating element utilizing a
miniature semiconductor has been recently developed and arranged
into a desk top calculator as a recording head or into a high speed
printer as a recording head. As the result, the heat sensitive
recording material attracts attention again as a recording material
for such recording head.
As the heat sensitive recording material for such a new recording
method, there may be used a conventional heat sensitive recording
material for usual copying when it is appropriately improved.
However, for such recording head different from usual copying field
it is particularly preferable to make the important data and
numbers distinct from the other ones by using a different
color.
It is difficult to form indications of two or more colors on a
single sheet by employing conventional heat sensitive materials for
prior art copying. In addition, it is not possible to form
multicolor indication in view of the reproduction process.
SUMMARY OF THE INVENTION
An object of this invention is to provide a method of multicolor
indication of figures such as letters, numbers and the like by
using a heating element.
Another object of this invention is to provide a mechanically
silent printing method.
A further object of this invention is to provide a multicolor heat
sensitive recording material suitable for the above mentioned
process.
Still another object of this invention is to provide a recording
material for indicating printed letter recording of different color
tone on the same recording sheet or tape.
A still further object of this invention is to provide a multicolor
recording material capable of producing a permanent print.
The method of recording by heat sensitive multicolor indication
according to the present invention can be attained by combining a
heating element and a heat sensitive recording material for
multicolor indication.
As a heating element in the present invention, there may be used,
for example, a heating head as described in U.S. Pat. No. 3,496,333
to E.G. Alexander. Particularly, there is preferred a heat element
device having a control circuit containing a current control device
capable of switching between a low temperature heating element and
a high temperature heating element.
This heating element can control the heat amount and thereby the
heating temperature by controlling the current flowing in the
heating unit. The heat sensitive material for multicolor indication
of the present invention is fundamentally composed of a multilayer
heat sensitive recording layer overlying a support, e.g. paper or
film, but, if desired, a self-supporting layer may be employed
which is produced by admixing a color forming main agent or a color
forming auxiliary agent with the support material or making the
support layer therefrom.
The heat sensitive recording material for multicolor indication
comprises a heat sensitive recording layer of multilayer type
overlying a support, and the laminating is effected in an order of
heat sensitive temperatures ranging from about 60.degree.C to about
160.degree.C. Different colors are formed depending each specific
heat sensitive temperature of the layers in a direction from the
outermost layer to the support layer or in the opposite
direction.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows a cross sectional view of a heat sensitive material
according to the present invention;
FIG. 2 is a graph showing temperature characteristic of each heat
sensitive layer;
FIG. 3 diagrammatically shows application of a heat element to a
heat sensitive material; and
FIG. 4 diagrammatically shows a heat element provided with a
current control circuit.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, a heat sensitive material is composed of a
support 1 such as paper and film, a heat sensitive layer II 2
overlying the support and a heat sensitive layer I 3 overlying the
heat sensitive layer II.
Referring to FIG. 2, there is illustrated heat color forming
characteristics of the above mentioned heat sensitive material. The
heat sensitive layer I forms color at a temperature of T.sub.1 (low
temperature) while the heat sensitive layer II does not form color
at all at T.sub.1 but forms color at T.sub.2 when the temperature
is raised from T.sub.1 to T.sub.2. Naturally, in the latter case
the heat sensitive layer I has already formed color. For example,
assuming that the formed color of heat sensitive layer I is magenta
and that of heat sensitive layer II is cyanic, the color of the
heat sensitive recording multilayer is magenta at a temperature
T.sub.1 and violet at a temperature T.sub.2 since magenta and
cyanic colors are mixed.
Referring to FIG. 3, a heat element for low temperature 5 and a
heat element for high temperature 6 which are connected with
control circuits (not shown) come in contact with or approach the
heat sensitive recording multilayer, and the heat element for low
temperature 5 causes a magenta color indication and the heat
element for high temperature 6 causes a purple color
indication.
When at least one layer in the multilayer of the heat sensitive
material of FIG. 1 is dyed to yellow, the color at low temperature
(T.sub.1) is red as a result of combination of magenta and yellow
and the color at high temperature (T.sub.2) is black as a result of
combination of magenta, cyanic and yellow. Thus, red and black
printings can be effected on a yellow background.
Now referring to FIG. 4, the device is different from that in FIG.
3 and only one heat element 4 is used, and current in each portion
of the heat element 4 is controlled by a control circuit 7 to
indicate figures, letters and other patterns with two different
colors. When two or more heat sensitive layers are used, the
performance is similar to the above one and different colors
corresponding to the number of layers can be employed for
indication.
The heat sensitive material for multicolor indication is composed
of heat sensitive recording layers laminated in an order depending
upon the heat sensitive temperatures thereof.
The layer of heat sensitive recording material of the present
invention essentially comprises a color forming main agent and a
color forming auxiliary agent and if desired, additionally contains
a softening point adjusting agent, a binder and other
additives.
The color forming main agent is a basic material having a color
forming group. Representative color forming main agents are: diaryl
phthalides such as 3-3 bis (p-dimethyl amino phenol)-6-dimethyl
amino phthalide (Crystal Violet Lactone), 3-3 bis (p-dimethyl amino
phenol) phthalide (Malachite Green Lactone) and the like; leuco
auramines such as N-halophenyl derivatives, N-alkyl halophenyl
derivatives, N-(2,5-dichlorophenyl) leuco auramine and the like;
acryl auramines such as N-benzoyl auramine, N-acetyl auramine and
the like; .alpha.,.beta.-unsaturated arylketones such as
dianisylidene acetone, dibenzylidene acetone, anisylidene acetone
and the like; basic mono azo dyes such as p-dimethyl amino azo
benzene-O-carboxylic acid (Methyl Red), 4-amino azo benzene (Oil
yellow-AAB), 4-phenyl azo-1-naphthyl amine and the like; Rhodamine
B lactams such as N(p-nitrophenyl) rhodamine B lactam, 3,6'-diamino
rhodamine B lactam, 3,6'-diethyl amino rhodamine B lactam,
3,6'-dimethyl amino rhodamine B lactam and the like; polyaryl
carbinols such as bis(p-dimethyl amino phenyl) methanol (Michler's
hydrol), Crystal Violet carbinol, Malachite Green carbinol and the
like; benzoindolino spiropyrans such as 8'-methoxy benzoindolino
spiropyran, 4,7,8'-trimethoxybenzoindolino-spiropyran,
6'-chloro-8'-methoxy benzoindolino-spiropyran and the like;
phthalans such as 1,1-bis(p-aminophenyl) phthalan, 1,1
-bis(p-benzylaminophenyl) phthalan, 1,1-bis(p-dibenzylaminophenyl)
phthalan, 1,1-bis(p-N-methyl anilino phenyl) phthalan and the like;
and spiro phthalans such as 6,6'-diamino spiro
(phthalan-1,9'-xanthene), 6,6'-diethyl amino spiro (phthalan,
1,9'-xanthene), 6,6'-dimethyl amino spiro (phthalan-1,9'-xanthene)
and the like.
The color forming auxiliary agents used in this invention are a
material capable of thermally reacting with the color forming main
agent to form a conjugated system such as, for example, phenolic
compounds, phenol derivatives, phenolic resins and the like.
Representative color forming auxiliary agents suitable for the
above mentioned color forming main agents are:
4-tertiary butyl phenol, 4-tertiary amylphenol, 4-phenyl phenol,
4-4'-isopropylidene bis (2-chlorophenol), 4,4'-isopropylidene bis
(2-methyl phenol), 4,4-isopropylidene bis (2-tertiary butyl
phenol), 4,4'-secondary butylidene bis (2-methyl phenol),
2,2'-dihydroxydiphenyl, 4,4'-seconary butylidene diphenol,
4-tertiary octyl cathechol, bis phenols, 4'-hydroxyacetophenone,
methyl-4-hydroxy-benzoate, 4-hydroxy diphenoxide, .alpha.-naphthol,
.beta.-naphthol and novolac type phenol formaldehyde condensation
products, resol type phenol formaldehyde condensation products and
modified phenolic resin and the like. These phenolic materials have
melting points ranging from 60.degree. to 150.degree.C. It is
preferable to use the material of lower melting point or softening
point in a heat sensitive layer close to the heating element and
the material of higher melting point or softening point in a heat
sensitive layer far from the heating element.
A softening point adjusting agent may be employed for controlling
the color forming temperature range. The softening point adjusting
agent should be mutually soluble with the color forming main agent
and/or color forming auxiliary agent to lower the softening point.
They are, for example, low melting point materials, higher fatty
acids and crystalline solid plasticizers.
Representative materials of low melting point are:
(a) Amides such as 9,12-octadecane amide, 9-octadecane amide,
octadecane amide hexadecane amide, tetradecane amide, dodecane
amide, decane amide, octane amide, hexane amide and the like; (b)
Paraffines such as chlorinated paraffin; (c) derivatives of fatty
acid such as methyl hydroxy stearate, glycerol tri-1,2-hydroxy
stearate, partially hydrogenated castor oil.
Representative higher fatty acids are those having 12-20 carbon
atoms and 50.degree.-150.degree.C of melting point, such as lauric
acid, palmitic acid, stearic acid, myristic acid and the like.
Representative crystalline solid plasticizers are diphenyl
phthalate (DPP), dichlorohexyl phthalate (DCHP), ethylene glycol
dibenzoate (EGDB), dimethyl isophthalate (DMIP) and the like.
As binders used in the present invention, there may be mentioned
methyl cellulose, arabian gum, gelatine, sodium alginate, casein,
zinc caseinate, sodium carboxymethyl cellulose, polyvinyl alcohol,
pectine, polyvinyl pyrrolidone, starch and its derivatives,
copolymer of styrene and maleic anhydride, copolymer of
polyethylene and maleic anhydride, copolymer of polyvinyl
pyrrolidone and maleinic anhydride, polyacrylate and its copolymer,
copolymer of styrene and butadiene, emulsions of polyvinyl
chloride, polymethyl methacrylate and polyvinyl acetate and the
like. Among them, arabian gum, zinc caseinate, copolymer of styrene
and maleic anhydride, and copolymer of styrene and butadiene, are
particularly effective.
Color formation caused by combining the representative color
forming main agents is as shown in Table 1 below. ##SPC1##
A feature of this invention resides in the fact that recordings of
different colors can be formed on one and the same recording sheet
or tape by controlling the heating temperature of a heating
element. For example, according to the present invention, it is
possible in a desk top calculator to indicate the calculating
procedure with blue color and the answer and sum with red color,
and further in a thermal printer an important sentence can be
printed with red color while an unimportant sentence can be printed
with blue color. In conventional typewriters there are also
employed two color indications, but mechanical typewriters are
noisy and only predetermined numbers or letters can be printed. On
the contrary, color of a part or a half of each letter or number
can be changed according to the present invention.
For example, a heating element is employed which is composed of a
linear matrix containing many minor heating portions arranged on
one line, and the heating element is moved in a direction
perpendicular to the linear matrix and the current supplied to each
minor heating portion is controlled corresponding to a pattern. As
the result, there can be recorded a multicolor pattern divided into
each dot in place of a full letter or number. Such multicolor dot
pattern can not be produced by conventional mechanical
typewriters.
The following examples are given as being illustrative of the
invention, but it will be understood that the invention is not
limited thereto. In the examples, parts are by weight unless
otherwise specified.
EXAMPLE 1
High temperature color forming layer:
Twenty parts of Crystal Violet Lactone (CVL) and 10 parts of a
copolymer of styrene and maleic anhydride were mixed and ground for
one hour until CVL particles became 0.5-2 microns in size. 60 parts
of phenolic resin and 10 parts of a copolymer of styrene and maleic
anhydride in a solution form were mixed and ground for one hour
until particles of the phenolic resin became 2-3 microns in size.
Then, the above two compositions were mixed and coated on a support
(60 microns thick) in 2-5 microns thick (when dried) by a wire
bar.
Low temperature color forming layer:
Twenty parts of Rhodamine lactone (RL) and 10 parts of a copolymer
of styrene and maleic anhydride were mixed and ground for one hour
until particles of RL became 0.5-2 microns in size. A mixture of 55
parts of phenolic resin, 10 parts of a copolymer of styrene and
maleic anhydride and 5 parts of myristic acid were ground for one
hour until the phenolic resin became 1-2 microns in size. Then, the
two compositions obtained above were mixed and coated on the high
temperature color forming layer as obtained above in 2-5 microns
thick (when dried) by a wire bar to produce a heat sensitive
recording material for two color indication.
Printing was effected on the resulting heat sensitive material for
two color indication by using a heating element at a relatively low
temperature (about 60.degree.-110.degree.C) to produce a red
pattern. On the contrary when printing was effected at relatively
high temperature (110.degree.-160.degree.C) there was obtained
clear violet pattern. Current flow was applied for 5-20 m.sec. in
each case.
EXAMPLE 2
High temperature color forming composition:
Twenty parts of CVL and 10 parts of a copolymer of styrene and
maleic anhydride were mixed and ground for one hour until the
particle size became 0.5-2 microns. On the other hand, 60 parts of
bisphenol A and 10 parts of a copolymer of styrene and maleic
anhydride were mixed and ground for one hour until particle size of
the bisphenol A became 1-3 microns. The resulting two compositions
were mixed with stirring and coated on a paper (60 microns in
thickness) in 2-5 microns thick (when dried) by a wire bar.
Low temperature color forming composition:
Twenty parts of RL and 10 parts of a copolymer of styrene and
maleic anhydride were mixed and ground for one hour until the RL
particle became 0.5-2 microns.
55 parts of bisphenol A, 10 parts of a copolymer of styrene and
maleic anhydride and 5 parts of myristic acid were mixed and ground
until particle size of the bisphenol A became 1-2 microns.
The resulting two compositions were mixed thoroughly and coated on
the high temperature color forming layer as obtained above in
thickness of 2-5 microns (when dried) by a wire bar. The resulting
heat sensitive recording material was subjected to printing test as
mentioned in Example 1 above to produce clear bluish violet
color.
EXAMPLE 3
High temperature color forming composition:
The high temperature color forming layer as obtained in Example 1
was employed.
Low temperature color forming composition:
Twenty parts of RL and 10 parts of a copolymer of styrene and
maleic anhydride were mixed and ground for one hour until particle
size of the RL became 0.5 to 2 microns.
55 parts of phenolic resin, 10 parts of a copolymer of styrene and
maleic anhydride and 5 parts of ethylene glycol dibenzoate (EGDB)
were mixed and ground unti particle size of the phenolic resin
became 1-3 microns.
The resulting two components were mixed by stirring and coated on
the high temperature color forming layer in 2-5 microns thick (when
dried) by a wire bar.
The resulting heat sensitive sheet for multicolor formation which
is of low adhesivity was subjected to a printing test as mentioned
in Example 1 to produce a clear two color formation.
EXAMPLE 4
High temperature color forming composition:
The high temperature color forming layer as obtained in Example 2
was used.
Low temperature color forming composition:
Twenty parts of RL and 10 parts of a copolymer of styrene and
maleic anhydride were mixed and ground for one hour until particle
size of RL became 0.5-2 microns.
55 parts of bisphenol A, 10 parts of a copolymer of styrene and
maleic anhydride and 5 parts of EGDB were mixed and ground until
particle size of the bisphenol A became 1-3 microns.
The resulting two compositions as mentioned above were mixed with
stirring and coated on the high temperature color forming layer as
obtained above in 2-5 microns thick (when dried) by a wire bar. The
resulting heat sensitive sheet had an adhesivity similar to that in
Example 3 and was subjected to a printing test in a way similar to
Example 1 to produce a clearer and more bluish violet pattern than
that obtained in Example 3.
EXAMPLE 5
High temperature color forming layer:
Twenty parts of CVL and 10 parts of a copolymer of styrene and
butadiene were mixed and ground for one hour until particle size of
the CVL became 0.5-2 microns.
60 parts of phenolic resin and 10 parts of a copolymer of styrene
and butadiene were mixed and ground for one hour until particle
size of the phenolic resin became 1-3 microns.
The resulting two compositions were mixed by stirring and coated in
a way similar to Example 1.
Low temperature color forming composition:
Twenty parts of RL and 10 parts of a copolymer of styrene and
butadiene were mixed and ground for one hour until particle size of
RL became 0.5-2 microns.
55 parts of phenolic resin, 10 parts of a copolymer of styrene and
butadiene and 5 parts of myristic acid were mixed and ground for
one hour until particle size of the phenolic resin became 0.1-5
microns.
The resulting two compositions were mixed by stirring and coated on
the high temperature color forming layer as obtained above and then
subjected to a printing test as in Example 1 to produce a sharp and
highly transparent pattern was obtained.
EXAMPLE 6
High temperature color forming layer:
Twenty parts of CVL and ten parts of a copolymer of styrene and
butadiene were ground for one hour until CVL particles became 0.5-2
microns in size. 60 parts of bisphenol A and ten parts of copolymer
of styrene and butadiene were mixed and ground until bisphenol
particles became 1-2 microns in size. Then the above two
compositions were mixed and coated in accordance with Example
1.
Low temperature color formation layer:
Twenty parts of RL and ten parts of a copolymer of styrene and
butadiene were mixed and ground for one hour until particles of RL
became 1-2 microns in size. A mixture of 55 parts of bisphenol A
and 10 parts of a copolymer of styrene and butadiene and 5 parts of
myristic acid were mixed and ground until bisphenol A particles
became 0.5-2 microns. Then the two compositions obtained above were
mixed and stirred and coated on the high temperature color forming
layer. Printing was held as in Example 1, and then was obtained
clear red pattern.
EXAMPLE 7
High temperature color forming layer:
The high temperature color forming layer as obtained in Example 5
was used.
Low temperature color forming layer:
Twenty parts of RL and ten parts of a copolymer of styrene and
butadiene were mixed and ground for one hour until RL particles
became 0.5-2 microns in size. 55 parts of phenolic resin and 10
parts of a copolymer of styrene and butadiene and 5 parts of EGDB
were mixed and ground until phenolic resin particles became 1-2
microns in size. Then the two compositions obtained were mixed and
stirred and coated on the high temperature color forming layer and
printed in accordance with Example 1. The resulting printing was
non-sticky and well.
EXAMPLE 8
The high temperature color forming layer:
The high temperature color forming layer as obtained in Example 6
was used.
The low temperature color forming layer:
20 parts of RL and 10 parts of a copolymer of styrene and butadiene
were mixed and ground for one hour until RL particles became 0.5-2
microns in size. 55 parts of bisphenol A and 10 parts of a
copolymer of styrene and butadiene and 5 parts of EGDB were mixed
and ground until bisphenol A became 1-2 microns in size. Then the
two compositions obtained above were mixed and stirred and coated
on the high temperature color forming layer in accordance with
Example 1.
As the result of printing test by the method of Example 1 a good
two color sheet of red and violet was obtained.
EXAMPLE 9
High temperature color forming layer:
20 parts of Malachite Green Lactone (MGL) and 10 parts of a
copolymer of styrene and maleic anhydride were ground for one hour
until MGL particles became 0.5-2 microns in size. 60 parts of a
phenolic resin and 10 parts of a copolymer of styrene and maleic
anhydride were mixed and ground for one hour until the phenolic
resin particles became 1-2 microns in size. Then the two above
obtained were mixed and coated on a film support (60 microns thick)
in 2-5 microns thick (when dried) by a wire bar.
Low temperature color forming layer:
The low temperature color forming layer as obtained in Example 1
was used. This was coated in 2-5 microns thick (when dried). As the
result of printing test by the method of Example 1, two colors,
green and violet, were obtained.
EXAMPLE 10
High temperature color forming layer:
The high temperature color forming layer as obtained in Example 6
was used.
Low temperature color forming layer:
The low temperature color forming composition was prepared by
following the procedure of Example 6 except that Malachite Green
Lactone was used in place of RL.
A printing sheet was prepared in a way similar to Example 1. The
resulting sheet was subjected to a printing test as in Example 1 to
produce blue and bluish green patterns.
EXAMPLE 11
20 parts of Leuco Auramine (LA) and 10 parts of a copolymer of
styrene and butadiene were ground for one hour until LA particles
became 0.5-2 microns in size. 60 parts of phenolic resin and 10
parts of a copolymer of styrene and butadiene were mixed and ground
for one hour until phenol resin particles became 1-2 microns in
particle. The two above obtained were mixed and coated in a paper
of 60 microns thick in 2-5 microns thick (when dried). Then the
high temperature color forming layer as obtained in Example 1 was
coated on the above color forming layer and further the low
temperature color forming layer as obtained in Example 1 was coated
thereon. Thickness of each layer was the same as that in Example
1.
The resulting heat sensitive multicolor recording member was
subjected to printing test at a low temperature ranging from
60.degree. to 80.degree.C, at a middle temperature ranging from
80.degree. to 110.degree.C, and at a high temperature ranging from
110.degree.C to 160.degree.C to produce clear patterns of red, blue
and black, respectively.
EXAMPLE 12
Procedure of Example 1 was repeated except that
N-(2,5-dichlorophenyl) leuco auramine was used in place of Crystal
Violet Lactone, and printing was effected as in Example 1. As the
result, there was obtained printings of black violet and bluish
black.
EXAMPLE 13
Following the procedure of Example 6 except that N-benzoyl auramine
was used in place of CVL, there were obtained printings of redish
orange and yellow.
EXAMPLE 14
Following the procedure of Example 9 except that
N(p-nitrophenyl)rhodamine B lactam was used in place of Malachite
Green Lactone, there were obtained printings of redish pink and
black green.
EXAMPLE 15
Following the procedure of Example 1 except that
8'-methoxybenzoindolinospiropyran was used in place of Crystal
Violet Lactone and .beta.-naphthol was used in place of phenolic
resin, there were obtained printings of red and brownish black.
* * * * *