U.S. patent number 3,924,041 [Application Number 05/454,534] was granted by the patent office on 1975-12-02 for heat-sensitive recording material and process for producing same.
This patent grant is currently assigned to Kohjin Co., Ltd.. Invention is credited to Masuo Miyayama, Mineyuki Murase, Harumi Shiraiwa.
United States Patent |
3,924,041 |
Miyayama , et al. |
December 2, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Heat-sensitive recording material and process for producing
same
Abstract
A heat-sensitive recording material comprising support (A)
having provided thereon transfer layer (B) and support (C) in
order, these supports having the property that before heating the
adhesion strength between transfer layer (B) and support (C) is
smaller than the adhesion strength between transfer layer (B) and
support (A) and larger than 0.1 g/cm but, after heating to a
temperature higher than the heat sensitive temperature of transfer
layer (B), the adhesion strength between transfer layer (B) and
support (C) becomes greater than the adhesion strength between
support (A) and transfer layer (B), and the transfer layer (B)
comprising, at least on the side to be in contact with support (C),
a heat-sensitive composition containing as a major component a
mixture of a heat-sensitive substance which is fluidized at the
heat sensitive temperature of the heat-sensitive substance and an
adhesiveness-imparting agent which can adhere to support (C) at a
temperature not higher than the heat sensitive temperature of the
heat-sensitive agent; and a process for producing same. An
embodiment includes the transfer layer (B) comprising two layers:
one being a colored layer adhering to support (A); and the other
being a heat-sensitive layer adhering to support (C).
Inventors: |
Miyayama; Masuo (Shizuoka,
JA), Murase; Mineyuki (Shizuoka, JA),
Shiraiwa; Harumi (Shizuoka, JA) |
Assignee: |
Kohjin Co., Ltd. (Tokyo,
JA)
|
Family
ID: |
12366220 |
Appl.
No.: |
05/454,534 |
Filed: |
March 25, 1974 |
Foreign Application Priority Data
|
|
|
|
|
Mar 23, 1973 [JA] |
|
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48-32704 |
|
Current U.S.
Class: |
428/212; 427/152;
428/216; 427/208; 428/913; 427/148 |
Current CPC
Class: |
B41M
5/38207 (20130101); Y10S 428/913 (20130101); Y10T
428/24975 (20150115); Y10T 428/24942 (20150115) |
Current International
Class: |
B41M
5/26 (20060101); B41M 005/26 () |
Field of
Search: |
;117/36.7,36.8,36.9
;101/471 ;428/212,913,40,216,914 ;427/148,152,208 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Herbert, Jr.; Thomas J.
Attorney, Agent or Firm: Sughrue, Rothwell, Mion, Zinn &
Macpeak
Claims
What is claimed is:
1. A heat-sensitive recording material comprising a support (A)
having thereon a transfer layer (B) and a support (C) in turn, said
supports having the property that before heating the adhesion
strength between the transfer layer (B) and the support (C) is
smaller than the adhesion strength between the transfer layer (B)
and support (A) and larger than 0.1 g/cm but, after heating to a
temperature higher than the heat-sensitive temperature of the
transfer layer (B), the adhesion strength between the transfer
layer (B) and support (C) becomes greater than the adhesion
strength between support (A) and transfer layer (B), and said
transfer layer (B) comprising, at least on the side thereof in
contact with support (C), a heat-sensitive composition containing
as a major component a mixture of a heat-sensitive substance which
becomes fluid at the heat-sensitive temperature of the
heat-sensitive substance and an adhesiveness-imparting agent which
can adhere to support (C) at a temperature not higher than the
heat-sensitive temperature of said heat-sensitive substance.
2. The heat-sensitive recording material as described in claim 1,
wherein said transfer layer (B) comprises a colored layer in
adhesive contact with support (A) and a heat-sensitive layer in
adhesive contact with support (C).
3. The heat-sensitive recording material as described in claim 1,
wherein said transfer layer (B) comprises an ink-receptive layer in
contact with support (A) and a heat-sensitive layer in contact with
support (C).
4. The heat-sensitive recording material as described in claim 1,
wherein the proportion of said adhesiveness-imparting agent in said
heat-sensitive layer (B) is about 1 to 90 percent by weight of the
weight of said heat-sensitive layer (B).
5. The heat-sensitive recording material as described in claim 1,
wherein said transfer layer (B) has a thickness ranging from about
0.3 to 18 .mu..
6. The heat-sensitive recording material as described in claim 1,
wherein the peel strength between support (A) and layer (B) is
about 1 to 150 g/cm and the peel strength between layer (B) and
support (C) is about 0.1 to 50 g/cm before heating and not less
than 2 g/cm after heating.
7. The heat-sensitive recording material as described in claim 1,
wherein said heat-sensitive substance is a wax and said
adhesiveness-imparting agent is an ethylene-vinyl acetate
copolymer.
8. The heat-sensitive recording material as described in claim 7,
wherein said wax is candelilla wax, bees wax, montan wax, ceresine
wax, carnauba wax or a mixture thereof.
9. The heat-sensitive recording material as described in claim 8,
wherein said wax is montan wax or a mixture of montan wax and
carnauba wax.
10. A process for producing a heat-sensitive recording material,
which comprises applying support (A) and support (C) onto opposite
sides of transfer layer (B) at a temperature, for support (C), not
higher than the heat-sensitive temperature of said heat-sensitive
composition of layer (B) and not lower than the
adhesiveness-generating temperature of layer (B), said support (A),
transfer layer (B) and support (C) having the property that before
heating the adhesion strength between layer (B) and support (C) is
less than the adhesion strength between support (A) and layer (B)
and greater than 0.1 g/cm but, after heating to a temperature
higher than the heat-sensitive temperature of the transfer layer
(B), the adhesion strength between layer (B) and support (C)
becomes greater than the adhesion strength between support (A) and
layer (B), and said transfer layer (B) comprising at least at the
side thereof in contact with support (C) a heat-sensitive
composition containing as a major component a mixture of a
heat-sensitive substance which becomes fluid at the heat-sensitive
temperature of the heat-sensitive sheet and an
adhesiveness-imparting agent which can impart sufficient
adhesiveness to adhere to support (C) at a temperature lower than
the heat-sensitive temperature of said heat-sensitive
substance.
11. The process for producing a heat-sensitive recording material
as described in claim 10, including press-contacting support (C)
onto the heat-sensitive layer of transfer layer (B) after forming
transfer layer (B) on support (A).
12. The process for producing a heat-sensitive recording material
as described in claim 10, including adhering support (A) to
transfer layer (B) after forming transfer layer (B) on support
(C).
13. The process as described in claim 11, including forming
transfer layer (B) by first forming a colored layer on support (A)
and then forming a heat-sensitive layer thereon, and
press-contacting support (C) onto the heat-sensitive layer of
transfer layer (B).
14. The process as described in claim 11, including forming
transfer layer (B) by first forming an ink-receptive layer on
support (A) and then forming a heat-sensitive layer on said
ink-receptive layer and press-contacting support (C) onto the
heat-sensitive layer of transfer layer (B).
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a heat-sensitive recording
material and a process for producing the same.
2. Description of the Prior Art
Heretofore, a so-called transfer-type heat-sensitive copying method
is known in which a transfer sheet having a heat-sensitive transfer
layer and a receiving sheet are superposed on each other and heat
is imagewise applied to the heat-sensitive layer of the
heat-sensitive transfer sheet to imagewise soften and melt this
layer, thus imagewise transferring the transfer layer onto the
receiving layer to obtain a copy, as disclosed, for example, in
U.S. Pat. No. 2,769,391. The heat-sensitive copying material to be
used therefor comprises two independent sheets, i.e., a receiving
sheet and a transfer sheet. These two sheets are superposed over
each other for use in duplication.
Therefore, in the conventional method, insufficient contact between
the receiving sheet and the transfer sheet results in an
insufficient and non-uniform transfer of the transfer layer to the
receiving sheet upon application of heat. If the transfer layer is
increased in thickness than is necessary to achieve duplication so
as to improve the above defect, the transfer layer spreads too
widely in lateral direction upon transfer, which results in
obtaining discontinuous, broad or distorted images only.
Also, in the conventional method using two separate sheets, a
slight deviation can occur between the two sheets or one of the
sheets can wrinkle upon duplication. Therefore, it has the defect
in that transfer is not achieved at all in some areas, in that
seriously distorted copied images result, and in that the material
transfer is so difficult to handle that copying cannot be conducted
with stability.
Furthermore, in the conventional method, the transfer layer must
possess additional properties such as coloring properties when used
for copying documents, or an affinity for an ink when used for
producing a master for offset printing, as well as the
heat-sensitive property, depending upon the end use to which the
assembly is put. Since a conventional transfer layer has had to
possess a plurality of properties as described above, it has been
difficult to obtain a transfer layer capable of satisfying all of
these requirements.
SUMMARY OF THE INVENTION
An object of the present invention is to obtain a novel
heat-sensitive recording material without the defects which have
been encountered with the above-described conventional heat
recording materials.
Another object of the present invention is to provide a
heat-sensitive recording material which can be handled with ease
and stably provide a sharp and distinct copied image with no
distortion, no broadened areas and discontinuous areas, and to
provide a process for producing the same. The material of the
present invention can be applied to various heat-sensitive copying
or recording methods.
The above-described objects of the invention can be attained by
using the heat-sensitive recording material of the present
invention.
The heat-sensitive recording material of the present invention
comprises support A having thereon transfer layer B and support C
in order, these sheets having the property that before heating the
adhesion strength between transfer layer B and support C is less
than the adhesion strength between transfer layer B and support A
and is larger than 0.1 g/cm but, after heating to a temperature
higher than the heat sensitive temperature of transfer layer B, the
adhesion strength between transfer layer B and support C becomes
greater than the adhesion strength between support A and transfer
layer B, with the transfer B comprising, at least at the side
thereof in contact with support C, a heat-sensitive composition
containing as a major component a mixture of a heat-sensitive
substance which becomes fluid at the heat-sensitive temperature of
the heat-sensitive substance and an adhesiveness-imparting agent
which can adhere to support C at a temperature not higher than the
heat-sensitive temperature of the heat-sensitive substance. In this
invention, the recording material can be handled integrally as one
sheet by adhering the transfer layer B on support A to the
receiving support C with an appropriate degree of strength.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
FIG. 1 is a cross-sectional view showing one embodiment of the
heat-sensitive recording material of the present invention.
FIG. 2 is a cross-sectional view showing another embodiment of the
heat-sensitive recording material of the present invention in which
transfer layer B comprises a colored layer or an ink-receptive
layer B-1 and a heat-sensitive layer B-2.
FIF. 3 shows the condition of duplication using reflection exposure
method with the heat-sensitive recording material 1 of the present
invention, in which numeral 2 denotes an original and 3 an image
area.
FIG. 4 shows the condition of the material after copying, in which
delamination occurs between transfer layer B and support C at the
non-image area B and, at image area B', delamination occurs between
support A and transfer layer B'.
FIG. 5 shows the relationship between the press-contacting
temperature and the peel strength required between the transfer
layer B and support C, in one example of the heat-sensitive
recording material of the present invention, in the case of
press-contacting support C onto transfer B formed on support A.
DETAILED DESCRIPTION OF THE INVENTION
The transfer layer B of the present invention must comprise, at
least at one side thereof which is in contact with support C, a
heat-sensitive composition containing as a major component a
mixture of a heat-sensitive substance and an adhesiveness-imparting
agent. As long as this condition is satisfied, the number of layers
forming the transfer layer B is not particularly limited.
The transfer layer B can be formed as one layer comprising a
composition containing as a major component a mixture of a
heat-sensitive substance and an adhesiveness-imparting agent. It
can further contain a coloring agent such as an oil-soluble dye, a
water-soluble dye, an alcohol-soluble dye or a disperse dye, or an
organic or inorganic pigment if it is to have end-use applications
for copying documents, a spirit dye if it is to have end-use
applications for preparing a spirit master, or an ink-receptive
agent if it is to have end-use applications for producing a master
for general printing and, if desired, various polymers, low
molecular weight compounds, fillers and the like for the purpose of
adjusting the cohesive force of the transfer layer. A suitable
amount of these addenda can range from about 2 to 80, preferably 5
to 60, percent by weight of the layer.
Also, as a preferred improved embodiment, the transfer layer can
comprise two layers: one layer being a colored or ink-receptive
layer B-1 in contact with support A; and the other layer being a
heat-sensitive layer B-2 in contact with support C, containing as a
major component a mixture of a heat-sensitive substance and an
adhesiveness-imparting agent.
Where, for example, a reflection exposure method is used, the
transfer layer B must substantially transmit the ligth used for
exposure, while where a stencil transmission method is used, the
transfer layer B must possess a component which absorbs the light
used for exposure to generate heat.
The heat-sensitive substance must become fluid at the
heat-sensitive temperature employed upon heat-sensitive
duplication. Usually, the heat-sensitive temperature is preferably
not less than about 40.degree.C and not higher than about
200.degree.C, most preferably 50.degree. to 150.degree.C. As the
heat-sensitive substance, those which exhibit almost no fluidity at
a temperature lower than the heat-sensitive temperature but become
fluid very quickly at the heat-sensitive temperature, that is,
those substances which exhibit the characteristics as graphically
shown, e.g., by XY'Z, in FIG. 5 are preferable.
Suitable examples of such heat-sensitive substances are paraffins
having a variety of melting points, e.g. (50.degree. to
75.degree.C); waxes such as candelilla wax (m.p. 60.degree. -
80.degree.C), bees wax (m.p. 60.degree. - 66.degree.C), montan wax
(m.p. 65.degree. - 105.degree.C), ceresine wax (m.p. 65.degree. -
85.degree.C), carnauba wax (m.p. 75.degree. - 86.degree.C), etc.;
wax analogs such as stearic acid, stearyl alcohol, etc.; synthetic
resins such as coumarone-indene resins, phenolic resins, e.g.,
novalac (m.p. 50.degree. - 150.degree.C), alkylphenolic resins
(m.p. 70.degree. - 150.degree.C), petroleum resins, comparatively
low molecular weight polystyrene (e.g., having a number mean
molecular weight about 300 to 200,000, having a melting point of
about 50.degree. to 150.degree.C), aliphatic hydrocarbon polymers
(e.g., having an number mean molecular weight of about 500 to 2,000
and a melting point of about 50.degree. to 130.degree.C), etc.;
natural resins and modified ones thereof such as rosin, ester gum,
hydrogenated rosin, etc., these materials can be used either alone
or in combination.
The adhesiveness-imparting agent must impart adhesivity to the
mixture of the adhesiveness-imparting agent and the heat-sensitive
substance upon mixing such that the mixture can adhere to support C
at a temperature less than the heat-sensitive temperature of the
heat-sensitive substance.
Suitable examples of adhesiviness-imparting agent which can be used
and which satisfy the above-described requirement are a variety of
rubbers and resins having a glass transition point or a softening
point less than the heat-sensitive temperature of the
heat-sensitive substance, preferably a softening point or glass
transition point of more than 5.degree. less than the
heat-sensitive temperature from a practical standpoint. To
illustrate some specific examples, there are rubbers such as
natural rubber, polyisobutylene, butadiene rubber,
styrene-butadiene rubber, nitrile rubber, etc.; polyvinyl chloride
and the copolymers thereof (e.g., vinyl chloride-vinyl acetate,
vinyl chloride-vinyl propionate, vinyl chloride-vinylidene
chloride, vinyl chloride-vinyl acetate-maleic anhydride, etc.);
polyvinylidene chloride and copolymers thereof (e.g., vinylidene
chloride-methyl acetate, vinylidene chloride-ethyl acetate,
vinylidene chloride-acrylonitrile, vinylidene chloride-vinyl
chloride, etc.); polyvinyl acetate and the copolymers thereof
(e.g., vinyl acetate-methyl acrylate, vinyl acetate-ethyl acrylate,
etc.); polymethacrylates and the copolymers thereof (e.g., methyl
methacrylate-methyl acrylate, methyl methacrylate-ethyl acrylate,
methyl methacrylate-2-ethyl hexyl acrylate, etc.); polyacrylates
and the copolymers thereof; polystyrene and the copolymers thereof
(e.g., styrene-butadiene, etc.); ethylene copolymers such as
ethylene-vinyl acetate, ethylene-acrylate, etc.; other polyolefins;
polyvinyl ethers; polyvinyl butyral; polyesters; nylon, a variety
of plasticizers (e.g., dicyclohexyl phthalate, di(2-ethyl
hexyl)phthalate, etc.) or low molecular weight compounds capable of
exhibiting analogous effects; and the like. These materials have a
glass transition points or softening point up to 180.degree.C,
preferably up to 140.degree.C and can be suitably selected so as to
have the appropriate relationship to the heat-sensitive temperature
of the heat-sensitive substance with which they are used.
The amount of the adhesiveness-imparting agent employed can be
appropriately selected depending upon the combination of the
heat-sensitive substance and the adhesiveness-imparting agent used
or the desired degree of adhesion strength between, e.g., the
transfer layer B and support C. Generally, the proportion of the
adhesiveness-imparting agent in the heat-sensitive layer is about 1
to 90 percent by weight, preferably 5 to 70 percent by weight and,
more preferably, 20 to 50 percent by weight.
Transfer layer B can comprise two layers, i.e., a colored or
ink-receptive layer B-1 in contact with support A and a
heat-sensitive layer B-2 in contact with support C. In this case,
as such a colored layer B-1, those layers which are prepared by
incorporating in the heat-sensitive composition a variety of dyes
such as oil-soluble dyes (e.g., Oil Black, Oil Blue, Oil Red, Oil
Yellow, etc.), water-soluble dyes (e.g., Methylene Blue, Congo Red,
etc.), alcohol-soluble dyes (e.g., Rhodamine, Safranine, Victoria
Green, Crystal Violet, etc.) and disperse dyes; various organic or
inorganic pigments such as carbon black, titanium oxide, zinc
oxide, red iron oxide, Phthalocyanide Blue and Phthalocyanine Green
in a suitable amount, or those which are prepared by incorporating
the coloring agent in thermoplastic resins such as polyvinyl
chloride or a copolymer thereof, polyvinylidene chloride or a
copolymer thereof, polyvinyl acetate or a copolymer thereof,
polymethacrylate or a copolymer thereof, polyacrylate or a
copolymer thereof, polystyrene or a copolymer thereof, polyethylene
or a copolymer thereof, polyvinyl acetal, polyvinyl alcohol, an
alkylphenol resin, a polyamide, a polyester, a petroleum resin, a
coumarone-indene resin, etc., or in thermosetting resins such as a
melamine resin, a urea resin, a polyurethane, a reactive acrylic
resin, an epoxy resin, etc., a natural resin or a modified natural
resin such as rosin, ester gum, hydrogenated rosin, etc., various
waxes, paraffins, or the mixture thereof, can be used.
As the ink-receptive layer B-1, those ink-receptive layers prepared
by appropriately selecting ink-receptive materials from among
various waxes, the above described thermoplastic resins,
thermosetting resins, natural resins and the modified natural
resins and, if desired, incorporating a coloring agent and a filler
therein can be used. For example, for preparing a master for use in
offset printing using an oily ink, oleophilic substances such as
waxes, polystyrene, polyethylene, etc. are used, while for
preparing a master for printing using a water-color ink,
hydrophilic substances such as water-insolubilized polyvinyl
alcohol are used. Thus, the material is selected depending upon the
end use purpose.
The use of a colored or ink-receptive layer B-1 which is
heat-insensitive at a heat-sensitive temperature of the
heat-sensitive layer B-2 has the advantage of providing better
copied images, because an excessive fluidity of the transfer layer
upon heat sensitization can be controlled and the adhesion strength
between the support A and transfer layer B is made constant
regardless of the temperature.
As the heat-sensitive substance which forms the conventional
heat-sensitive transfer stratum comprising a transfer sheet and a
receiving sheet, those heat-sensitive substances which do not
exhibit any fluidity when the temperature is increased to a certain
point but become fluid very quickly at the heat-sensitive
temperature, such as carnauba wax, are preferable. However, if
adherence of transfer layer B comprising such a substance to
support C is attempted at a temperature less than the
heat-sensitive temperature of the transfer layer B by heat-pressing
support C onto the surface of transfer layer B, formed on support
A, using the above-described heat-sensitive substance alone, layer
B will not adhere to support C at all, while when the temperature
is increased to or higher than the heat-sensitive temperature,
layer B adheres to support C so strongly, due to the fluidity of
the heat-sensitive layer B, that the relative relationship in
adhesion strength between these sheets is not satisfactory. This
results in completely destroying the duplication ability thereof.
That is, it is extremely difficult to control the adhesion strength
between transfer layer B and receiving support C.
On the other hand, when those heat-sensitive substances whose
viscosity decreases and fluidity increases gradually with an
increase in temperature, such as a high molecular weight polymer,
are used, it becomes possible to control the adhesion strength
between transfer layer B and receiving support C to some extent,
even though not to a completely sufficient extent. However, the
change in fluidity versus the change in temperature is so slow that
it has the defects that the boundary of the copied image are
blurred, resulting in a copied image which is not sharp, and that
the adhesion strength between transfer layer B and receiving
support C tends to undergo changes with the lapse of time.
As is described above, when those substances which are preferred as
a heat-sensitive substance for transfer-type heat-sensitive
recording material are used per se as a heat-sensitive substance,
technical difficulties have occurred in that the adhesion strength
between the transfer layer B and the support C becomes impossible
to control, whereas when those substances in which the adhesion
strength between the transfer layer B and the support C can be
controlled to some extent are used as a heat-sensitive substance,
the heat-sensitive copying property is degraded.
However, it is now extremely easy to control the adhesion strength
between the transfer layer B and the receiving support C by adding
an adhesiveness-imparting agent to the heat-sensitive substance as
described in the present invention.
As support A, those supports which are not melted by the heat
applied upon heat-sensitive duplication, such as paper, plastic
films, and the like, can be used. The support A can be
appropriately selected depending upon the end-use application and
the copying method employed. For example, in using the reflection
exposure method as the copying method, support A must substantially
transmit the light used. An appropriate thickness of support A is a
thickness of about 5 to 500 .mu., preferably 5 to 100 .mu..
Suitable examples of plastic films are plastic films of
polypropylene, polyethylene, polyvinyl chloride; polyvinylidene
chloride, polymethyl methacrylate, polyvinyl alcohol, polystyrene,
polycarbonate, polyester, nylon, polyurethane, cellulose
derivatives, and the like. The choice of such a film will be
dependent upon the purpose for use. If desired, these sheets can be
subjected to a surface treatment such as corona discharge, flame
treatment, chemical treatment, etc. or a coating treatment to
appropriately adjust the adhesivity of the support.
As support C, those examples suitable for support A, such as paper
and plastic films can be selected depending upon the end use. In
order to adjust the adhesion between support C and transfer layer B
or to impart ink-repellent properties, hydrophilic properties or
marking properties, support C can be also subjected to, if desired,
a surface treatment or a coating treatment as described previously
for support A to appropriately adjust the adhesivity to the support
C.
The absolute values of the adhesion strength between these supports
are not particularly limited so long as the above-described
relative and the condition in which the adhesion strength between
layer B and support C before heating is greater than zero are
satisfied. However, in practice, the peel strength between support
A and transfer layer B is about 1 to 150 g/cm, preferably 2 to 50
g/cm, and the peel strength between layer B and support C is about
0.1 to 50 g/cm before heating and, after heating, is not less than
about 2 g/cm, preferably not less than 20 g/cm as measured as
described hereinafter.
As was described above, in the heat-sensitive recording material of
the present invention, the adhesion strength between layer B and
support C is greater than zero. That is, transfer layer B adheres
to support C with a certain degree of strength. Therefore, even
when the thickness of the transfer layer is reduced, transfer can
be effected in high yield and the material can be handled as one
sheet. In addition, good copied images with no distortion and image
broadening, which have been defects in conventional materials, can
be obtained with stability.
In order to obtain good copied images, it is necessary that the
cohesive strength of transfer layer (B) itself or the adhesion
strength between the colored or ink-receptive layer B-1 and the
heat-sensitive layer B-2 must be greater than both the adhesion
strength between transfer layer B and support C before heat
sensitizing and the adhesion strength between transfer layer B and
support A after heat sensitizing, whereas the cohesion strength
must be of such degree that, upon separating support A from support
C after copying, transfer layer B can be severed in an imagewise
manner. In order to adjust the cohesive force, means can be taken
in which various polymer a or low molecular weight compounds as
previously described, or fillers such as titanium oxide or silica
are incorporated or the transfer layer B can be formed as a
discontinuous layer comprising fine particles, e.g., having a
particle size ranging from about 0.1 to 100 .mu..
The process for producing the heat-sensitive recording material of
the present invention which comprises support A, transfer layer B
and support C comprises press-contacting support C onto the surface
of transfer layer B formed on support A, each support having the
property such that 1 before heating, the adhesion strength between
support A and layer B is greater than the adhesion strength between
transfer layer B and support C is greater than 0, and 2 this
relation is changed by heating to a temperature not less than the
heat sensitive temperature of the transfer layer B so that the
adhesion strength between transfer layer B and support C becomes
greater than the adhesion strength between support A and transfer
layer B.
The transfer layer B comprises, at least at one one side in contact
with support C, a heat-sensitive composition containing a major
component a mixture of a heat-sensitive substance and an
adhesiveness-imparting agent, this heat-sensitive substance
exhibiting fluidity at a heat-sensitive temperature upon
duplication and this adhesiveness-imparting agent imparting
sufficient adhesiveness so that adherence to support C at a
temperature less than the heat-sensitive temperature of the
heat-sensitive substance occurs. Support C is press-contacted onto
the surface of heat-sensitive composition of the transfer layer B
comprising the heat-sensitive composition at a temperature not
higher than the heat-sensitive temperature of the heat-sensitive
composition and at a temperature not lower than the
adhesiveness-generating temperature thereof.
Various methods for forming transfer layer B on support A can be
employed, e.g., a method of applying a solution in water or an
organic solvent, a dispersion in water or an organic solvent or a
melt of the heat-sensitive composition to support A, followed by
drying, or a method of forming a heat-sensitive composition layer
on a separate temporary support, bringing this heat-sensitive
composition layer into contact with support A and then removing the
temporary support. Suitable examples of organic solvents which can
be used as described hereinbefore are alcohols such as methanol,
ethanol, butanol and isopropyl alcohol, aromatic hydrocarbons such
as toluene, benzene and xylene, esters such as ethyl acetate and
butyl acetate, ketones such as methyl ethyl ketone, etc. These
solvents or water can be used alone or as a mixture using a
concentration in the solvent of 2 to 60 percent by weight.
Also, as a method for forming transfer layer (B) comprising a
colored or ink-receptive layer B-1 and a heat-sensitive layer B-2,
various methods can be employed, for example, a method of forming
on support A a colored or ink-receptive layer B-1 and a
heat-sensitive layer B-2 in turn, a method of forming a
heat-sensitive layer B-2 on a separate temporary support, bringing
this layer into contact with a colored or ink-receptive layer B-1
on support A previously formed, and then removing the temporary
support, or a method of forming on a separate temporary support a
heat-sensitive layer B-2 and a colored or ink-receptive layer B-1
in turn, bringing it into contact with support A, and then removing
the temporary support.
The thickness of transfer layer B can be appropriately selected
depending upon the end use purpose. However, generally the
thickness ranges from about 0.3 to 18 .mu., more preferably 0.5 to
5.mu.. In order to obtain good copied images, the transfer layer
should be as thin as possible. Where the layer B comprises two
layers, a suitable thickness for transfer layer B-1 ranges from
about 0.5 to 17 .mu. and for B-2 ranges from about 0.5 to 15 .mu.,
preferably 0.5 to 5 .mu..
Where transfer layer B comprises two layers, i.e., a colored or
ink-receptive layer B-1 and a heat-sensitive layer, it is easy to
make the thickness of the heat-sensitive layer B-2 as thin as about
0.5 to 5 .mu.. With such a structure, there is the advantage that
good copied images can be obtained even when the colored or
ink-receptive layer B-1 is quite thick.
After forming transfer layer B on support A as described above,
support C is press-contacted onto the surface of the transfer layer
B comprising the heat-sensitive composition. The press-contacting
temperature should not be higher than the heat-sensitive
temperature of the heat-sensitive composition and should not be
lower than the adhesiveness-generating temperature. A suitable
press-contacting temperature can range from room temperature (about
20.degree. - 30.degree.C) to about 180.degree.C, preferably
50.degree.C to 140.degree.C.
If the press-contacting temperature is not higher than the
adhesiveness-generating temperature, adherence of transfer layer B
to support C is impossible, while if the press-contacting
temperature is not lower than the heat-sensitive temperature, the
heat-sensitive substance is converted to a heat-sensitized state
and the adhesion strength between the transfer layer B and support
C becomes so great that relative relationship in the adhesion
strength between the supports is not satisfied, resulting in a
destruction of copying ability.
As has already been described, the adhesion strength between
transfer layer B and support C can usually be about 0.1 to 50 g/cm,
which can be highly controlled by selecting the press-contacting
temperature, the application pressure, the time, the kind of
adhesiveness-imparting agent, the compounds amount, and the
like.
Various press-contacting method can be employed, e.g., a method of
passing two superposed supports through two press rollers
maintained at an appropriate temperature, or a method of
press-contacting the two supports to each other using parallel
heating plates.
In addition, the order of press-contacting support A, transfer
layer B and support C can be different from that described above.
For example, formation of transfer layer B on a separate temporary
support, press-contacting support C onto transfer layer B at a
temperature higher than the heat sensitive temperature of the
transfer layer and not lower than the adhesiveness-generating
temperature, removal of the temporary support to prepare a
configuration comprising support C/transfer layer B, bringing the
transfer layer of this configuration into contact with the adhesive
agent-coated surface of support A coated with the adhesive agent
capable of adhering to the transfer layer at a temperature not
higher than the heat-sensitive temperature of the transfer layer,
and application of a pressure to the assembly at a temperature not
higher than the heat-sensitive temperature of transfer layer B is
within the scope of this invention.
The combination of support A, transfer layer B and support C in the
present invention includes, for example, polyester-(montan wax
(this first listed component in the parentheses here and in the
examples hereinafter being a heat sensitive substance),
polyisoprene (this second listed component in the parentheses here
and in the examples hereinafter being an adhesiveness-imparting
agent))-cellulose acetate, polypropylene-(carnauba wax,
styrene-butadiene copolymer rubber)-polyvinyl chloride, nylon-
(montan wax-polybutadiene)polypropylene, nylon-(montan wax, low
molecular weight polyethylene + a non-crystalline
polyester)-polystyrene, polypropylene-(montan wax, ethylene-vinyl
acetate copolymer)-cellulose acetate, polyethylene
terephthalate-(montan wax, polyvinyl butyral, ethylene-vinyl
acetate copolymer)-cellulose acetate, polyethylene
terephthalate-(carnauba wax, ethylene-vinyl acetate
copolymer)-internally plasticized polyvinyl chloride film,
nylon-(carnauba wax, + montan wax, ethylenevinyl acetate
copolymer)-internally plasticized polyvinyl chloride film,
polyethylene terephthalate-(montan wax, ethylene vinyl acetate
copolymer)-cellulose acetate, polyethylene terephthalate-(montan
wax + carnauba wax, ethylene vinyl acetate copolymer)-cellulose
acetate, and the like.
FIG. 1 is an enlarged cross-sectional view showing configuration 1
of the heat-sensitive copying material in accordance with the
present invention, wherein A, B and C represent support A, transfer
layer B and support C, respectively.
FIG. 2 is an enlarged cross-sectional view showing another
configuration 1' of the heat-sensitive copying material in
accordance with the present invention, wherein B-1 represents a
colored or ink-receptive layer B-1, and B-2 a heat-sensitive layer
B-2.
FIG. 3 shows the condition of copying employing a reflection
exposure method using the heat-sensitive copying material 1 of the
present invention, wherein numeral 2 denotes an original and 3
denotes an image area. Upon irradiation with infrared rays, heat is
generated in image area 3, which travels in the order of support A
and transfer layer B, and thus the temperature of transfer layer B
corresponding to the image area reaches the heat-sensitive
temperature. Thus, in the B'-portion, as a result of increase in
adhesion strength between portion B' and support C, the adhesion
strength between portion B' and support C becomes greater than the
adhesion strength between support A and portion B' after heating,
the former having been less than the latter before heating.
In this case, since the adhesion strength between layer B and
support C is greater than zero before copying, that is, transfer
layer B adheres to support C with a certain degree of adhesion
strength, layer B is in uniform contact with support C over the
entire surface with substantially no inclusions such as air bubbles
therebetween and the above-described change in the relative
relationship of the adhesion strength takes place uniformly and
completely over the entire heated portion B'.
Upon delaminating support C from support A as shown in FIG. 4, a
positive copied image B' corresponding to the image area is formed
on support C while a negative copied image is formed on support A.
Because no heating occurred in the non-image area, delamination
occurs between transfer layer B and support C since the adhesion
strength between support A and the transfer layer B is greater than
the adhesion strength between transfer layer B and support C,
whereas in the image area B', delamination occurs between support A
and transfer layer B' since the adhesion strength between transfer
layer B' and support C is greater than the adhesion strength
between support A and transfer layer B'.
FIG. 5 shows the relationship between the press-contacting
temperature and the adhesion strength between transfer layer B and
support C in conducting the press-contacting at a pressure of 3
kg/cm.sup.2 for 2 seconds, in which a heat-sensitive composition
provided on a polyethylene terephthalate film [support A ] is
brought into contact with a cellulose acetate film [support C ],
with this composition containing montan wax as a heat-sensitive
substance and ethylene-vinyl acetate copolymer (vinyl acetate
content: 40 percent by weight) as an adhesiveness-imparting agent
in a weight proportion of 70 : 30.
X represents the point at which adhesiveness appears, transfer
layer B being capable of adhering to support C at a temperature
higher than this temperature. Y represents the heat sensitive
temperature, the adhesion strength of transfer layer B to support C
sharply increasing at a temperature higher than this
temperature.
When a heat-sensitive substance, montan wax, alone is used as the
heat-sensitive composition, the adhesion strength between layer B
and support C increases along the curve XY'Z (represented by a
dotted line). From this, it is apparent that it is difficult to
adhere transfer layer B to support C at a temperature less than the
heat-sensitive temperature of the transfer layer (66.degree.C).
However, when a composition prepared by compounding the
heat-sensitive substance (montan wax) with an
adhesiveness-imparting agent (ethylene-vinyl acetate copolymer)
suitable adhesion property as shown by XYZ in FIG. 5 can
surprizingly be imparted to the transfer layer without destroying
the heat-sensitive property at all. This adhesion property is
characteristic of the heat-sensitive substance. The adhesion
strength between transfer layer B and support C can be closely
controlled by press-contacting support C onto transfer layer B at a
temperature between X and Y as shown in FIG. 5.
Additionally, although the adhesiveness-generating temperature of
the heat-sensitive composition can be room temperature (about
20.degree.- 30.degree.C) or less than that, it is preferably higher
than room temperature to stabilize the adhesion strength with the
lapse of time.
As the heat-sensitive substance, those with which the temperature
difference betweeen Y and Z in FIG. 5 is small are preferred,
because such substances provide sharp copied images. This
temperature difference is preferably less than about 20.degree.C,
e.g., a difference of 0.degree.C to 20.degree.C with a smaller
difference being preferred.
Additionally, the adhesion strength between support A and transfer
layer B can be varied somewhat depending upon the temperature as
long as the adhesion strength is intermediate in strength between
the adhesion strengths corresponding to Y and Z at least in the
heat-sensitive temperature range Y to Z.
The adhesion strength between support A and transfer layer B can be
adjusted by an appropriate selection of the material of support A
or transfer layer B, by using a support A which has been surface
treated and by a selection of laminating conditions of transfer
layer B onto support A.
The heat-sensitive recording material of the present invention can
be employed in various heat-sensitive copying or recording
methods.
That is, the heat-sensitive recording material of the present
invention can be used in a reflection or transmission exposure
method wherein an original having an image capable of absorbing
infrared rays or visible light and generating heat is superposed on
the heat-sensitive copying material and the assembly is irradiated
with infrared rays or visible light; a stencil transmission copying
method wherein a stencil bearing image areas capable of
transmitting infrared rays or visible light and nonimage areas
capable of reflecting infrared rays or visible light is superposed
on the copying material containing a substance capable of absorbing
infrared rays or visible light and generating heat, and infrared
rays or visible light are applied thereto from the stencil side; or
a heat-printing method using an imagewise heated plate or a heating
pen. A suitable exposure can be radiation of a wave length ranging
from about 400 to 10,000 m.mu., preferably 700 to 3,000 m.mu., for
an exposure time of less than 1 second, generally 0.5 to 0.001
second.
For example, the heat-sensitive recording material of the invention
can be used in the following applications.
1. It can be used for copying general documents or as a chart paper
for recording data of measuring devices, by using paper as support
C and incorporating a coloring agent in the transfer layer or
providing a colored layer.
2. It can be used as an intermediate original for use in diazo
copying, for photographing film, or as an intermediate original for
preparing an original printing plate, by using transparent plastic
films as support A and support C and incorporating a coloring agent
in the transfer layer or providing a colored layer.
3. It can be used as a stencil duplicating master using a porous
sheet as support A.
4. It is usable as a spirit master by incorporating a spirit dye in
the transfer layer or providing a colored layer containing a spirit
dye.
5. It is usable as a lithographic printing master by using an
ink-receptive or oleophilic light-sensitive substance such as wax
or providing an ink-receptive layer and using, as support C, a
support which, on at least the surface, is inkrepellent or can be
rendered hydrophilic.
6. It is usable as a printing master by providing a comparatively
thick, ink-receptive layer in the transfer layer and producing a
relief plate.
Of course various additional modifications of the present invention
can be made in view of the disclosure herein.
The present invention will now be illustrated in greater detail by
reference to the following non-limiting examples of preferred
embodiments of the present invention. Unless otherwise indicated,
all parts, percents, ratios and the like are by weight.
EXAMPLE 1
Configuration: Support A/Colored layer B-1/Heat-sensitive layer
B-2/Support C
Support A: Surface-corona-treated, stretched polypropylene film (20
.mu. thick)
Support C: Cellulose acetate film (50 .mu. thick)
Composition of Colored Layer (B-1): Weight Parts of Solids
______________________________________ Oil Black 2HB (black,
oil-soluble dye 40 Beckamine P-138 (butylated urea 35 formaldehyde
resin, produced by Dai Nippon Ink & Chemicals, Inc.) Nissetsu
PE-900 (reactive (OH group- 25 containing) acrylic resin, produced
by Nissetsu Ltd.) Composition of Heat-sensitive Layer (B-2): Weight
Parts of Solids Montan Wax (heat-sensitive substance 80 m.p.
78.degree.C) Adhesiveness-imparting Agent (as 20 shown in Table 1)
______________________________________
Process for Production
A 15% toluene/ethyl acetate mixed solvent solution of the colored
layer composition was coated onto the corona-treated surface of
support A in an amount of 1.5 g/m.sup.2 on a solids basis, and
dried at 100.degree.C. Then, a 20% toluene solution (heated to
40.degree.C) of the heat-sensitive layer composition was coated
onto the colored layer surface in an amount of 1.5 g/m.sup.2 on a
solids basis, then dried at 100.degree.C.
The heat-sensitive layer-coated surface of the thus prepared
configuration of support A/colored layer B-1/heat-sensitive layer
B-2 was brought into contact with support C and passed through two
press rollers heated to 60.degree.C to obtain a heat-sensitive
copying material. Additionally, a comparative sample was prepared
for comparison using montan wax alone as a heat-sensitive
composition.
The peel strength between the layers as measured in a manner
similar to ASTM D 1876-61T are as shown in Table 1, but using 2 cm
wide test sample and a head speed of 100 mm/min.
TABLE 1
__________________________________________________________________________
Peel Between Layers Peel Strength Between Peel Strength Between
Adhesiveness-imparting Agent Support A/ Layer (B-2)/ Layer (B-1)
Support C
__________________________________________________________________________
(g/cm) (g/cm) Dicyclohexyl Phthalate (Plasti- 20 2.0 cizer) Evaflex
No. 150 (ethylene-vinyl 20 0.8 acetate copolymer; vinyl acetate 33
wt%; made by Mitsui Polychemicals Co., Ltd.) Vistanex MNL 80
(polyisobutylene, 20 1.2 made by Esso Standard Petroleum Co.) None
(Comparative sample) 20 0
__________________________________________________________________________
As is shown in Table 1, the effects of the present invention are
apparent.
These heat-sensitive copying materials obtained by the process of
the present invention can be handled as one sheet and, when copying
was conducted superposing the material on an original using a
reflection exposure method using a commercially available
heat-sensitive copying machine, black, negative and positive copied
sheets were obtained in a simple copying operation.
The resulting copied sheets were favorably used as transparencies
for an overhead projector, as an intermediate original for
preparing a printing original plate and as an intermediate original
for use in diazo copying.
EXAMPLE 2
In a manner analogous to Example 1 except for changing the
composition of the heat-sensitive layer B-2 in Example 1 to that
shown in Table 2, heat-sensitive copying materials were obtained.
The results thus obtained are shown in Table 2.
Table 2
__________________________________________________________________________
Peel Strength Between Layer (B-2) and Support (C) Composition of
Heat- Peel Strength Between Layer (B-2) sensitive Layer and Support
(C)
__________________________________________________________________________
(g/cm) Montan Wax/Evaflex No. 40=80/20 0.6 " =60/40 0.8 " =50/50
3.0
__________________________________________________________________________
These heat-sensitive copying materials were easy to handle and
showed good copying properties similar to those obtained in Example
1.
EXAMPLE 3
In a manner analogous to Example 1 except for changing the
composition of the heat-sensitive layer B-2 in Example 1 to (50
parts of carnauba wax + 50 parts of Evaflex No. 40) and changing
support C and the press roll temperature as shown in Table 3,
heat-sensitive copying materials were obtained. The results thus
obtained are shown in Table 3.
Table 3
__________________________________________________________________________
Peel Strength Between Layer (B-2)/Support (C) Press Roll
Temperature Support (C) 50.degree.C 60.degree.C 65.degree.C
80.degree.C
__________________________________________________________________________
(g/cm) (g/cm) (g/cm) (g/cm) Cellulose Acetate Film 0 0.7*.sup.3
0.8*.sup.3 not less than 20 Corona-treated, Stretched 0 0.8*.sup.3
1.2*.sup.3 not less than Polypropylene Film 20 Vinylidene Chloride
Copoly- 0.2*.sup.3 1.2*.sup.3 1.5*.sup.3 not less than mer-coated
Paper*.sup. 1 20 Cellulose Acetate Film*.sup.2 0 0 0 not less than
20
__________________________________________________________________________
*.sup.1 :Saran F239, made by Asahi-Dow Ltd. *.sup.2 :Comparative
example using carnauba wax alone as the heat-sensitive layer
*.sup.3 :According to this invention.
The resulting heat-sensitive copying materials obtained in the
present invention were handled as one sheet and showed good copying
properties. The sample in which vinylidene chloride
copolymer-coated paper was used as support C was used as a document
copy by conducting duplication according to a transmission exposure
method.
EXAMPLE 4
Configuration: Support A/Spirit Dye Layer B-1/Heat-sensitive Layer
B-2/Support C
Support A : Polyethylene terephthalate film (12 .mu. thick)
Support C : Cellulose acetate film (50 .mu. thick)
Composition of Spirit Dye Layer (B-1):
______________________________________ Aizen Spilon Blue E-2B
(alcohol- 30 parts soluble dye, made by Hodogaya Chemical Co.,
Ltd.) Beckamine P-138 35 Nissetsu PE 900 25 Denka Butyral 3000-1
(polyvinyl 10 butyral, butyralation degree: 65 mol%, made by
Electro Chemical Industry, Co., Ltd.) Composition of Heat-sensitive
Layer (B-2): Montan Wax 70 parts Evaflex No. 40 30
______________________________________
In a manner analogous to Example 1 except for the press-contacting
temperature being 65.degree.C, a heat-sensitive copying material
was obtained. With this sample, the peel strength between support A
and layer B-1 was 5 g/cm and the peel strength layerB-2 and support
C was 0.5 g/cm.
When printing papers, wet with alcohol, were printed using a
commercially available spirit printing machine employing as a
master a positive copied sheet obtained from the above-described
heat-sensitive copying material by conducting duplication using a
heat-sensitive copying machine, printing was well effected to
obtain dark blue printed images.
EXAMPLE 5 ______________________________________ Configuration:
Support (A)/Transfer Layer (B)/Support (C) Support (A):
Polyethylene terephthalate film (12 .mu. thick) Support (C):
Internally plasticized polyvinyl chloride film (50 .mu. in
thickness) Composition of Transfer Layer (B): Carnauba Wax (m.p.
84.degree.C) 35 parts Evaflex No. 40 35 Oil Black 2HB 30
______________________________________
A toluene solution (heated to 60.degree.C) of the transfer layer
composition was coated onto support A in an amount of 2 g/m.sup.2
on a solid basis, and dried at 110.degree.C. Then, the transfer
layer-coated surface was brought into contact with support C and
pressure was applied thereto at 65.degree.C to obtain an integral
heat-sensitive copying material.
With this heat-sensitive copying material, the peel strength
between support A/layer B was 10 g/cm and the peel strength between
layer B/support C was 1 g/cm. This heat-sensitive copying material
was easy to handle, showed good copying properties and was
advantageously used for projection and as an intermediate
original.
EXAMPLE 6
Configuration: Support A/Transfer Layer B (ink-receptive
heat-sensitive layer)/Support C (paper having a hydrophilic layer
thereon)
In a manner analogous to Example 5 except for using as support C an
offset master for direct drawing (made by Fuji Photo Film Co.,
Ltd.), a heat-sensitive copying material was obtained for use as an
offset master. The peel strength between layer B and support C was
2 g/cm. After conducting heat-sensitizing copying using a
transmission exposure method, the surface of the resulting offset
master plate having an ink-receptive wax image was desensitized and
mounted on an offset printer. Upon conducting printing, good
impressions were obtained.
EXAMPLE 7
Configuration: Support A/Colored Layer B-1/Heat-sensitive Layer
B-2/Support C
Support (A) : Stretched nylon film (15 .mu. thick)
Support (C) : Internally plasticized polyvinyl chloride film (100
.mu. thick)
Composition of Colored Layer (B-1): Weight Parts of Solids
______________________________________ Montan Wax 35 Carnauba Wax
20 Evaflex No. 40 (ethylene-vinyl acetate 15 copolymer) Oil Black
HBB 30 Composition of Heat-sensitive Layer (B-2): Weight Parts of
Solids Montan Wax 35 Carnauba Wax 20 Evaflex No. 40 15
______________________________________
A toluene solution (heated to 60.degree.C) of the colored layer
composition was coated onto support A in an amount of 1.5 g/m.sup.2
on a solid basis, and dried at 110.degree.C. Then, a toluene
solution (heated to 60.degree.C) of the heat-sensitive layer
composition was coated on the colored layer-coated surface in an
amount of 2 g/m.sup.2 on a solid basis, and dried at 110.degree.C.
The heat-sensitive layer-coated surface of the thus prepared
constitution of support A/colored layer B-1/heat-sensitive layer
B-2 was brought into contact with support C, pressure being applied
thereto at 60.degree.C, to obtain an integral heat-sensitive
copying material.
With this heat-sensitive copying material, the peel strength
between support A and layer B-1 was 10 g/cm and the peel strength
between layer B-2 and support C was 0.2 g/cm.
The resulting heat-sensitive copying material was easy to handle,
showed good copying properties, and was advantageously used for
projection and as an intermediate original.
While the invention has been described in detail and with reference
to specific embodiments thereof, it will be apparent to one skilled
in the art that various changes and modifications can be made
therein without departing from the spirit and scope thereof.
* * * * *