U.S. patent number 3,647,503 [Application Number 04/848,703] was granted by the patent office on 1972-03-07 for multicolored heat-transfer sheet and processes for heat transfer of multicolored ink impressions.
This patent grant is currently assigned to Toppan Printing Company, Limited. Invention is credited to Masao Anzai, Akio Ebihara, Takashi Mizutani.
United States Patent |
3,647,503 |
Mizutani , et al. |
March 7, 1972 |
MULTICOLORED HEAT-TRANSFER SHEET AND PROCESSES FOR HEAT TRANSFER OF
MULTICOLORED INK IMPRESSIONS
Abstract
Processes for the transfer of multicolored ink impressions by
the application of heat and the multicolored heat-transfer sheets
which enable these processes to be carried out. A sheet is printed
on with a plurality of layers having ink impressions, each layer
comprising one of a number of color agents which are respectively
distributed in a dry solid resinous binder. The color agents are
selected for their sublimation characteristics and said binder
includes a quantity of a filler to cause each of said printed
layers of inks to be porous to be able to pass the vaporized color
agents. The layers are printed in successive order such that the
binders have progressively different porosities and/or the color
agents possess progressively different sublimation
characteristics.
Inventors: |
Mizutani; Takashi (Tokyo,
JA), Anzai; Masao (Tokyo, JA), Ebihara;
Akio (Tokyo, JA) |
Assignee: |
Toppan Printing Company,
Limited (Tokyo, JA)
|
Family
ID: |
27285778 |
Appl.
No.: |
04/848,703 |
Filed: |
August 8, 1969 |
Foreign Application Priority Data
|
|
|
|
|
Dec 18, 1968 [JA] |
|
|
43/84387 |
Apr 9, 1969 [JA] |
|
|
44/27397 |
Apr 9, 1969 [JA] |
|
|
44/27398 |
|
Current U.S.
Class: |
428/316.6; 8/453;
427/148; 427/243; 428/914; 503/227; 427/152; 428/310.5 |
Current CPC
Class: |
D06P
5/004 (20130101); B41M 5/0356 (20130101); Y10S
428/914 (20130101); Y10T 428/249961 (20150401); Y10T
428/249981 (20150401) |
Current International
Class: |
B41M
5/035 (20060101); D06P 5/24 (20060101); D06P
5/28 (20060101); B41c 001/06 (); B44d 001/14 () |
Field of
Search: |
;117/36.1,36.2,36.4,76P,76T,38 ;101/470,473 ;161/46T |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Van Balen; William J.
Claims
What is claimed is:
1. A sheet adapted for transferring a multicolored image to a
receiving surface on the subjecting of said sheet to a transfer
temperature, said sheet including a support and a plurality of
layers superposed successively on said support, each layer
including a respective one of a plurality of coloring agents
collectively capable of producing said multicolored image and
characterized by respective sublimation characteristics, said
layers each having a porosity characteristic whereby said agents
when sublimated can pass through to said receiving surface, at
least one of the characteristics of the respective layers varying
progressively from layer to layer at or below said transfer
temperature.
2. A sheet as claimed in claim 1 wherein the color agents have
respective and progressively decreasing sublimation characteristics
from the layer adjacent the support to the layer furthest from said
support.
3. A sheet as claimed in claim 1 wherein the layers have respective
and progressively increasing porosity characteristics from the
layer adjacent the support to the layer furthest from said
support.
4. A sheet as claimed in claim 1 wherein the layers are of a
composition adapted to assume the respective porosity
characteristics on application of said transfer temperature.
5. A sheet as claimed in claim 3 wherein said layers include a
resinous binder in which said coloring agents are distributed and
respectively different amounts of filler in the binder, said filler
being adapted to make the layers porous.
6. A sheet as claimed in claim 5 wherein the filler is of a
material which will not soften or melt at said transfer temperature
and wherein there are 50-150 parts by weight of said filler to 100
parts of said binder.
7. A sheet as claimed in claim 4 wherein the filler includes a
foaming agent which is activated at approximately said transfer
temperature.
8. A sheet as claimed in claim 7 wherein there is 2-30 percent by
weight of filler in the resinous binder.
9. A process comprising depositing on a support a succession of
layers each including a binder with a respective sublimable
coloring agent therein, applying the support with the layers
thereon against a receiving surface, and subjecting the support and
layers to a temperature at which the coloring agents pass through
the layers and deposit on the receiving surface, the coloring
agents and binders being made of materials and being so arranged as
to have their respective sublimation and porosity characteristics
compensate for the different number of layers through which the
different coloring agents must pass.
10. A process as claimed in claim 9 wherein the layers are arranged
in increasing order of porosity in progression away from said
support.
11. A process as claimed in claim 10 wherein the coloring agents in
the respective layers are arranged in decreasing order of
sublimation characteristics in progression away from said
support.
12. A process as claimed in claim 10 wherein the layers are
rendered porous on application of said temperature.
Description
BACKGROUND OF THE INVENTION
The present invention relates to processes for the heat transfer
(i.e., transfer caused by the application of heat) of multicolored
ink impressions onto various surfaces, and to the multicolored
heat-transfer sheets which enable these processes to be carried
out, the inks for said ink impressions comprising sublimable
coloring agents and binders which contain fillers.
Some processes for the heat transfer of ink impressions onto
various surfaces are known, these using transfer paper having
impressions of desired pattern. These known processes are limited
to the heat transfer of single-colored patterns such as monochromes
or line drawings and are inadequate for transfer of a multicolored
ink impressions. The reason for this is that, when a heat-transfer
process is carried out using transfer sheet for a three-colored
pattern printed, for example, in layers of yellow, magenta and
cyanine, according to the prior art process, the obtained image
transferred onto a receiving surface is quite different from that
of the original ink impression. This is due to the fact that, in
this heat-transfer process, the cyanine coloring agent, which is
printed last and in the upper layer, is transferred without any
interruption, whereas the magenta coloring agent in the middle
layer is, during transfer, intercepted by the film of the binder
for the upper cyanine layer. Further, the yellow coloring agent in
the lower layer is interrupted by the two layers of the binders for
the cyanine and magenta colors. As a result, an image which is
colored differently from the original is obtained.
SUMMARY OF THE INVENTION
It is a general object of the invention to provide improved
processes for the heat-transfer of ink impressions of multicolored
patterns onto various surfaces as well as the multicolored
heat-transfer sheets which enable these process to be carried out,
these improved processes and sheets eliminating prior
inadequacies.
To achieve the above and other objects of the invention, there are
provided processes and sheets to produce a multicolored heat
transfer by the printing on a sheet or support of several layers of
ink impressions including fillers and sublimable coloring agents of
different colors, wherein each layer of ink impressions has a
porosity at the time of heat transfer. According to the respective
porosity of each printed layer, the sublimed or gaseous coloring
agents can penetrate from the lower layer adjacent the support to
the receiving surface to transfer. There are two preferred methods
to make the printed layer porous. One method is to use a binder
including an inactive filler of fine grains, said filler being
insoluble in the solute and solvent of the binder and, moreover,
incapable of being softened or melted by the transfer heating. The
other method is to use a binder including a filler which produces
vapor to make the layer porous by heating before the sublimation of
the coloring agents, said vapor being inert with respect to the
coloring agents.
Another object of the invention is to provide processes and sheets
for the heat transfer of ink impressions to effect a transfer the
coloring agents of each layer in a uniform manner, and in such a
way that the amount of filler contained in the upper layer furthest
from the support is richer than that in the lower layer, and/or,
the sublimation tendency of the coloring agent in the lower layer
is higher than that in the upper layer.
Generally, a multicolored ink impression is provided with color
tone by means of a combination and gradation of the three primary
colors, that is, yellow, magenta and cyanine. These colors usually
printed in the order of yellow, magenta and cyanine, but this
printing order is not mandatory. The ink impressions of the layers
of yellow, magenta and cyanine are printed with respective plates
made by a conventional photographic methods for offset, gravure,
relief, or silk-screen printing.
Multicolored ink impressions of this invention are usually printed
with three colored layers similarly to a conventional process. A
process to produce multicolored heat-transfer sheet by triple
printing will next be explained and it will be understood that
processes involving more than three printing steps will be
accomplished similarly.
In accordance with the present invention, to produce multicolored
heat transfer onto a sheet of a material such as, for example,
paper, the ink impressions are respectively printed in three layers
in the order of yellow, magenta and cyanine. The ink of each layer
respectively consists of a coloring agent and a binder including a
filler which makes the layer porous. More particularly, the amount
of fillers mixed in the binders is larger for subsequently printed
layers and/or the coloring agent of ink is more sublimable for each
layer which is to be printed earlier (that is, if a layer is to be
a lower layer). In other words, yellow ink is to be printed on a
support or sheet, this ink consists of a sublimable yellow coloring
agent and a binder containing A percent by weight of filler which
makes the layer porous. If next a magenta ink is to be printed over
the already printed layer of yellow, said magenta ink consists of a
sublimable magenta coloring agent and a binder containing B percent
by weight of the same filler. If then a cyanine ink is to be
printed over the already printed layer of magenta, said cyanine ink
consists of a sublimable cyanine coloring agent and a binder
containing C percent by weight of the same filler. With respect to
the filler percentages, A < B < C.
In another type of multicolored heat transfer a yellow ink is
printed on paper, said yellow ink consisting of a yellow coloring
agent which is highly sublimable and a binder-containing filler
which is capable of making the ink layer porous. Next, a magenta
ink is printed over the yellow, said magenta ink consisting of a
sublimable magenta coloring agent which is moderately sublimable
and the same binder. Lastly, a cyanine ink is printed over the
magenta, said cyanine ink consisting of a sublimable cyanine
coloring agent which is slowly sublimable and the same binder.
Paper with desired multicolored pattern of ink impression is
attainable.
Suitable coloring agents for an ink according to the present
invention are basic triphenylmethane colors, dispersed dyes,
mordant dyes, azo-anthraquinone-triphenyl-methane colors, oxidizing
colors and so forth. The chemical constitutions of the coloring
agents do not have to be limited precisely. Coloring agents of the
proper sublimation characteristics are readily selected.
Serviceable binders are carboxymethylcelluloses, alginic acids and
their derivatives, and polymers containing vinyl alcohol, vinyl
acetate, vinyl chloride, acrylic acid, meta acrylic acid, maleic
acid and so forth.
Fillers of the inactive type are simple inorganic substances and
compounds containing at least one atom of silicon, barium, calcium,
potassium, magnesium, zinc, iron, aluminum, tin, lead, cadmium,
sulfur and carbon, such as sulfates (barium sulfate, calcium
sulfate), carbonates (calcium carbonate, magnesium carbonate),
silicates (aluminum silicate, magnesium silicate), sulfides (zinc
sulfide), and oxides (aluminum oxide, silicon oxide). Also, there
can be used organic substances such as synthetic resins
(thermosetting resins are preferable), natural resins (such as
reclaimed rubber), and natural substances (such as powdered
charcoal, powdered cellulose). It is necessary to define the grain
size of the filler according to the desired cleanness of the ink
impression and; normally, the preferable grain size is less than
5.mu. in diameter.
Preferably, the filler is included in 100 parts of the binder an
amount in the range of 50-150 parts by weight. If the binder
includes too much filler, the adhesiveness of the ink impression
becomes weak, whereas if the binder includes too small an amount of
filler, the porosity in the ink impression is too little so that
the sublimed vapor of the coloring agent can not pass through from
the lower layer to be transferred.
To enable carrying out the transfer of each colored layer equally
by varying the content of filler for the respective colored inks,
the amount of filler in the upper layer is greater than that in the
lower layer. That is, when the multicolored pattern on the
heat-transfer paper is printed in the order of yellow, magenta and
cyanine, the amount of filler increases for yellow, magenta and
cyanine, respectively.
The filler causes the printed layer to be porous so as to enable
the same to be penetrated by a sublimed coloring agent. The
porosity of a layer furthest from the base surface of the heat
transfer paper must be larger to pass the sublimed vapor of the
coloring agents of the lower layers. Therefore, the amount of
filler in each layer is larger in the layer furthest from the base
surface of the heat-transfer paper.
The heat-transfer paper, constituted as described above, is placed
on a receiving surface which it contacts with its pattern surface
and is heated by pressing the same with, for example, an electric
iron set at a definite temperature. The coloring agents printed in
each layer sublime and the respective sublimed vapors pass through
the porous upper layers over them to transfer to and condense on
the receiving surface equally. Thus the same colored image as that
of the heat transfer paper is obtained. The transfer is possible
for several tens of times, although the transferred image may
become gradually inferior.
If the filler is of the type including a foaming agent and the
printed layer is made to be porous by heating, the following
materials that generally produce nitrogen gas may be used: azo
compounds such as azo azodicarbonamide, azobisisobutyronitrile,
azocyclohexylnitrile, diazoaminobenzene, barium azodicarboxylate;
sulfonyl hydrazide such as benzene sulfonyl hydrazide, benzene
sulfonyl hydrazine, toluene sulfonyl hydrazide, diphenyl
sulfon-3,3'-disulfonyl hydrazide; nitroso compounds such as
N,N-dinitroso pentamethylene tetrazene,
N,N'-dimethyl-N,N'-dinitroso terephthalic acid, and inorganic
substances such as sodium bicarbonate, ammonium bicarbonate and
ammonium nitrite.
In case a filler of this kind is used to equalize the heat transfer
of each coloring agent and if the impression of the pattern is
printed in the order of yellow, magenta and cyanine and the
included amounts of the filler are respectively A, B and C weight
percents to the respective binder, then it must be that A < B
< C, and A, B and C are preferably from 2 to 30 percent.
The heat-transfer paper, constituted as described above, is placed
on a receiving surface which is contacted with its pattern surface
and heated by pressing, for example, by means of an electric iron
set at a definite temperature. The included foaming agent is thus
gasified and the respective printed layers are made porous. Almost
simultaneously the coloring agents sublime and transfer or pass
through the porous layers of the ink impressions to the receiving
surface. In this case, the amount of the included filler in the ink
in the upper layer is larger than that in the lower layer and the
porosity of the upper layer is larger than that of the lower layer.
The sublimed coloring agent in the lower layer can thus transfer
through the porous upper layer equally to that in the lower layer
and deposit on the receiving surface to form a multicolored image
of nearly the same color and shape as that of the colored pattern
of the heat transfer paper. Moreover, when the sublimation
characteristic of the coloring agent in each layer of the ink
impression is different, the coloring agent in the lower layer
should be more sublimable than that in the upper layer, so as to
equalize the velocity of the transfer onto the receiving
surface.
EXAMPLE 1
On printing paper suited for gravure, using gravure plates with
three inks of the following composition in the order of yellow,
magenta and cyanine, a heat-transfer paper having a multicolored
pattern is obtained.
1. Yellow Ink Water-soluble Acrylic Resin 8 parts Water 92 parts
Silica (mean particle size: 1-2 .mu.) 5 parts Diacelliton Fast
Yellow G (Trademark: Mitsubishi Kasei Kabushiki Kaisha, Ja.) 15
parts 2. Magenta Ink Water-Soluble Acrylic Resin 8 parts Water 92
parts Silica 7 parts Kayalon Fast Rubine B (Trademark: Nihon Kayaku
Kabushiki Kaisha, Ja.) 15 parts 3. Cyanine Ink Water-Soluble
Acrylic Resin 8 parts Water 92 parts Silica 9 parts Sumikalon Blue
FB (Trademark: Sumitomo Kagaku Kabushiki Kaisha, Ja.) 15 parts
Placing the heat-transfer paper printed with the above-described
ink over clean white polyester fabric which is closely contacted,
and heating the same at 180.degree. C. for 30 seconds, will produce
polyester fabric having the same colored image as the ink
impression printed on the transfer paper.
EXAMPLE II
On printing paper suited for gravure, using gravure plates with
three inks of the following composition in the order of yellow,
magenta and cyanine including azodicarbonamide as the filler,
wherein the azodecarbonamide is of particles under 300 mesh, which
decomposes producing gas at temperatures 190.degree.-200.degree.
C., a heat-transfer paper having a multicolored pattern for ink
impression is obtained.
1. Yellow Ink Water-soluble Acrylic Resin 7 parts Water 93 parts
Azodicarbonamide (foaming agent) 0.7 parts(10%) Diacelliton Fast
Yellow G (Trademark: Mitsubishi Kasei Kabushiki Kaisha, Ja.) 15
parts 2. Magenta Ink Water-Soluble Acrylic Resin 7 parts Water 93
parts Azodicarbonamide (foaming agent) 1.05 parts(15%) Kayalon Fast
Rubine B (Trademark: Nihon Kayaku Kabushiki Kaisha, Ja.)15 parts 3.
Cyanine Ink Water-Soluble Acrylic Resin 7 7 parts Water 93 parts
Azodicarbonamide (foaming agent) 1.4 parts(20%) Sumikalon Blue FB
(Trademark: Sumitomo Kagaku Kabushiki Kaisha, Ja.) 15 parts
This heat-transfer paper, when placed over clean white polyester
fabric and heated at 195.degree. C. for 60 seconds, will produce
the same multicolored image on the polyester fabric as that of the
original.
EXAMPLE III
Using three inks of the following composition instead of the inks
in Example II, a heat-transfer paper is obtained.
1. Yellow Ink Water Soluble Acrylic Resin 8 parts Water 92 parts
Dinitrosopentamethylene tetramine 1.6 parts (foaming agent)
Diacelliton Fast Yellow G (Trademark: Mitsubishi Kasei Kabushiki
Kaisha, Ja.) 10 parts 2. Magenta Ink Water Soluble Acrylic Resin 8
parts Water 92 parts Dinitrosopentamethylene tetramine 1.6 parts
(foaming agent) Kayalon Fast Rubine B (Trademark: Nihon Kayaku
Kabushiki Kaisha, Ja.) 12.5 parts 3. Cyanine Ink Water Soluble
Acrylic Resin 8 parts Water 92 parts Dinitrosopentamethylene
tetramine 1.6 parts (foaming agent) Sumikalon Blue FB (Trademark:
Sumitomo Kagaku Kabushiki Kaisha, Ja.) 15 parts
By the same condition of the process as in Example II, the same
result is obtainable.
EXAMPLE IV
On printing paper suited for printing with inks of the following
composition, gravure prints may be printed.
1. Yellow Ink Water-Soluble Acrylic Resin 12 parts Water 98 parts
Silica 10 parts p-amino-acetanilide 10 parts 2. Magenta Ink
Water-Soluble Acrylic Resin 12 parts Water 98 parts Silica 10 parts
2-Chloro-4-nitro-aniline 10 parts 3. Cyanine Ink Water-Soluble
Acrylic Resin 12 parts Water 98 parts Silica 10 parts
1-4-Dimethyl-amino-anthraquinone 10 parts
In the same printing order as indicated above, each ink of
above-described composition is charged into respective units of a
gravure printing machine and rolled multicolored heat-transfer
paper is attained by the known process of gravure printing.
Sublimation velocity of the coloring agent used in this printing is
measured to show that p-amino-acetanilide sublimes most highly,
2-chloro-4-nitro-aniline sublimes moderately and
1-4-dimethyl-amino-anthyraquinone sublimes most slowly. When said
heat-transfer paper is placed over a receiving sheet and pressed
with heating, the same colored image as that of the heat-transfer
paper is obtained.
EXAMPLE V
Using inks as described in the following table, a multicolored
heat-transfer paper is obtained in the same process as described in
Example IV.
1.yellow Ink Polyvinylalcohol 20 parts Water 150 parts Soft Clay 15
parts Diacelliton Fast Yellow G (Trademark: Mitsubishi Kasei
Kabushiki Kaisha, Ja. 10 parts 2.Magenta Ink Polyvinylalcohol 20
parts Water 150 parts Soft Clay 15 parts Cibacet Brilliant Pink 4BN
(Trademark: Ciba, Ltd., Switz.) 12 parts. 3.Cyanine Ink
Polyvinylalcohol 20 parts Water 150 parts Soft Clay 15 parts
Cibacet Brilliant Blue 3RL (Trademark: Ciba, Ltd., Switz. 12
parts
Sublimation velocities of the above-mentioned coloring agents are
measured to indicate that:
Diacelliton Fast Yellow G sublimes most quickly,
Cibacet Brilliant Pink 4BN sublimes moderately,
Cibacet Brilliant Blue 3RL sublimes most slowly. The heat-transfer
paper printed with the above-mentioned inks by layers in the
above-mentioned order, when placed over a receiving material, and
heated with pressing at 180.degree. C. for 60 seconds, will produce
the same multicolored image on the receiving surface as the
multicolored ink impression of the heat-transfer paper.
As described above, the image on the surface of the receiving
material obtained with the process and the multicolored
heat-transfer sheet according to the present invention, is very
superior in its colors as compared with that attained in the prior
art. That is, by heat transfer, quite the same colored image as the
original is obtained most clearly and cleanly.
As the heat-transfer process of the invention is a process for
producing an image by the sublimation of a plurality of coloring
agents, the receiving material may be ordinary paper, artificial
resin, fiber material or metal on which not only a single colored
but also a multicolored image can be obtained.
* * * * *