U.S. patent number 3,630,732 [Application Number 04/648,881] was granted by the patent office on 1971-12-28 for thermographic recording material.
This patent grant is currently assigned to Gevaert-AGFA N.V.. Invention is credited to Eric Maria Brinckman, Gerard Albert Delzenne.
United States Patent |
3,630,732 |
Delzenne , et al. |
December 28, 1971 |
THERMOGRAPHIC RECORDING MATERIAL
Abstract
A photothermographic method of reproducing an original bearing
an image of material absorbing visible or infrared radiation and
converting the same into heat in which the original is arranged
with its image material in heat conductive relation with a
recording layer containing a normally solvent soluble material
adapted to react with a cross-linking agent and would be thereby
rendered less soluble, a compound decomposing when heated to yield
a cross-linking agent for said cross-linkable material and
uniformly distributed therethrough a finely divided substance
absorbing visible or infrared radiation and converting the same to
heat, and while the original and layer are thus arranged one of
them is uniformly exposed for a time not in excess of 10.sup.-.sup.
2 seconds to light or infrared radiation sufficiently intense to
decompose the compound in the areas of the layer corresponding to
the nonimage areas of the original whereby such nonimage areas
undergo a loss in solubility whereas the image areas remain
relatively soluble. Reflectographic exposure with the radiation
impinged upon the recording layer is preferred, with the layer
containing a sufficient amount of the finely divided material to
impart thereto an optical density of 0.2-0.8.
Inventors: |
Delzenne; Gerard Albert
(Gravenwezel, BE), Brinckman; Eric Maria (Mortsel,
BE) |
Assignee: |
Gevaert-AGFA N.V. (Mortsel,
BE)
|
Family
ID: |
10277479 |
Appl.
No.: |
04/648,881 |
Filed: |
June 26, 1967 |
Foreign Application Priority Data
|
|
|
|
|
Jun 24, 1966 [GB] |
|
|
28.555/66 |
|
Current U.S.
Class: |
430/200; 430/326;
250/318; 430/348 |
Current CPC
Class: |
G01D
15/14 (20130101); B41M 5/368 (20130101) |
Current International
Class: |
B41M
5/36 (20060101); G01D 15/14 (20060101); G03c
005/04 () |
Field of
Search: |
;250/65.1 ;96/28,27 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
650,367 |
|
Jul 1963 |
|
BE |
|
665,427 |
|
Jun 1964 |
|
BE |
|
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Hightower; Judson R.
Claims
We claim:
1. A photothermographic method of reproducing an original carrying
on at least one side thereof an image formed of material absorbing
radiation in the visible to infrared region of the spectrum and
converting such absorbed radiation into heat, which comprises the
steps of arranging said original with the image material in direct
face-to-face contacting heat-conductive relation with a recording
layer consisting essentially of the combination of a polymer which
is normally soluble in a solvent and is adapted to be rendered
insoluble in said solvent by reaction with a cross-linking agent
with a compound decomposing when heated to release a cross-linking
agent reactive with said polymer and uniformly distributed through
said layer finely divided particles of a substance absorbing
radiation in said region of the spectrum and converting the same to
heat, said combination being selected from a polymer containing
active hydrogen groups with a monomeric aromatic polyazide, a
monomeric polycarboxylic acid azide, or a monomeric polysulfonic
acid azide, a polymer containing hydroxyl groups with a
heat-sensitive latent polyisocyanate, a poly (diallyl-phthalate)
with a peroxide catalyst, and polymers containing aromatic azide,
carboxylic acid azide and sulfonic acid azide groups that on
heating decompose into intermediates that are self-cross-linking,
and said particles being present in sufficient amount to impart to
the layer an optical density of about 0.20-0.80; and uniformly
exposing the thus arranged original and said recording layer
through said layer for a time not in excess of 10.sup.-.sup.2
seconds to radiation within said region of an intensity sufficient
to initiate said cross-linking reaction in the areas of said
recording layer corresponding to the nonimage areas of said
original, whereby the nonimage areas of said layer become insoluble
as a consequence of the cross-linking reaction occurring therein
whereas the image areas of said layer remain soluble in said
solvent.
2. A method according to claim 1, wherein the said substances
absorbing visible light are finely divided black or dark colored
substances.
3. A method according to claim 2, wherein the said substances are
carbon particles.
4. A method according to claim 1, wherein the said layer is exposed
with a flash lamp.
5. A method according to claim 1, wherein the said layer previously
to the exposure is soluble in at least one organic solvent and
after the exposure is contacted with said solvent.
6. A method according to claim 5, wherein the said layer after the
said treatment is pressed against a receiving material, in order to
transfer thereon by separation a stratum from the image areas
thereof.
Description
This invention relates to a thermographic recording process based
on insolubilization under the influence of heat, and to the
production of resist images thereby.
A method has now been found for recording or reproducing
information, which method comprises recordwise or informationwise
exposing to electromagnetic radiation a recording material, which
comprises at least one recording layer (which may be carried by a
support or may be a self-supporting layer or sheet) incorporating a
composition which under the influence of heat can be completely or
relatively insolubilized with respect to a solvent or solvents
wherein it was previously soluble, and which composition contains
at least one compound that on heating yields an intermediate
reactive for cross-linking, and wherein said compound stands in
heat-conducting relationship with one or more substances, which
absorb electromagnetic radiation in at least a part of the
wavelength range of said radiation and convert at least a part of
the thus-absorbed radiation into heat, the exposure being of such
duration and intensity that an image or record is formed in or on
said layer in terms of differential solubility.
It is preferred that the total amount of electromagnetic energy
used in the method of the invention is provided by an exposure of
10.sup.-.sup.4 to 10.sup.-.sup.2 sec., preferably with an energy
intensity at the recording material of at least 0.1 watt. sec./ sq.
cm. In practice a maximum intensity of 1.5 watt. sec./sq. cm. at
the recording material will suffice.
By recordwise or informationwise exposure to electromagnetic
radiation is meant that the exposure may be progressive (in the
sense that relative movement takes place between the source of the
image or information and the recording material) or simultaneous,
e.g. as is the case of reflectographic or transmission exposure
respectively to or through an original, e.g. a printed text or
silver image transparency, When assuming for example, that the
information to be recorded is in the form of written or printed
matter, the record is in terms of a differentiation in solubility
in a solvent or mixture of solvents.
The exposure is applied and is preferably carried out by means of
electromagnetic radiation mainly within a wavelength range above
390 nm.
The heat applied by irradiation of said substances and the
concentration thereof in the recording member are chosen in a
sufficient degree to produce a useful differentiation in
insolubilization.
Having stated in general the concept of this invention, reference
will now be made in more detail to the composition and structure of
preferred heat-sensitive materials, and to suitable methods of
carrying out imagewise or recordwise exposure.
Preferably, the heat-sensitive material used in the performance of
the invention comprises at least one recording layer (which may be
carried by a support or may be a self-supporting layer or sheet)
preferably consisting for at least 80 percent by weight of a
compound e.g. a polymer that on heating yields an intermediate
reactive for cross-linking when heated between 50.degree. to
250.degree. C. The applied electromagnetic radiation is preferably
mainly visible light (e.g. at least 70 percent. The exposure time
influences image quality and for obtaining sharp images, e.g., of
printed texts, it is preferable for the exposure time to be no
longer than 10.sup.-.sup.1 second, and more preferably for a time
not exceeding 10.sup.-.sup.2 second. Such a brief exposure is
preferably achieved by the use of a flash lamp as the radiation
source.
Polymers that on heating yield an intermediate reactive for
cross-linking are, e.g., polymers containing aromatic azide groups
and/or carboxylic acid and/or sulfonic acid azide groups. The azide
system is already known in photoresist formation. Particulars about
such a cross-linking system which is suited for use according to
the present invention can be found in J. Appl. Polymer Sci., 7,
273-279 (1963), and in the Belgian Pat. specifications Nos.
650,367, 656,511, 665,427, 665,428 and 665,429.
As heat-sensitive monomeric cross-linking agents for a polymer or
polymer composition containing either active hydrogen atoms such as
present in a hydroxyl group, a thiol group, an amino group, or a
phenyl or pyridine group are mentioned monomeric polyazide
compounds, e.g. aromatic bisazides such as
p,p'-diazido-o,o'-disulfonic acid stilbene, bis-carboxylic acid
azides and bis-sulphonic acid azides. Further are mentioned
heat-sensitive latent polyisocyanates, e.g. those described in the
Belgian Pat. specification No. 612,896, which polyisocyanates are
also reactive for polymers containing active hydrogen atoms.
Further are mentioned polyamine compounds which can be used as
cross-linking agents for a polymer containing isocyanate groups.
Compounds, which on heating split off a polyamine, are described in
the Belgian Pat. specification No. 612,963.
Another polymer system wherein on heating reactive groups for
cross-linking are formed but in the presence of a peroxide catalyst
are polyallyl resins e.g. o-diallyl phthalate and
m-diallylphthalate resins.
Allylic homopolymerization is extremely slow at room temperature
and catalyzed compositions may be stored for a year or more at
ambient temperatures without substantial curing. The curing rate
increases rapidly with temperature, however, and fast curing is
obtained at temperatures of about 150.degree. C. and above.
Allylic polymerization and curing occur by intermolecular and
intramolecular additions. Unlike the condensation polymerization
reactions of azide polymers no gases are evolved, which results in
a low shrinkage of the cured composition. As suitable peroxide
catalysts are mentioned t-butyl perbenzoate, dicumylperoxide,
cumene hydroperoxide either alone or in combination with more
reactive peroxides such as benzoylperoxide. As very effective
catalysts are further mentioned bifunctional peroxide compounds
such as 2,5-dimethyl-2,5-di(tert.-butylperoxy)-hexyne-3. Their
effectiveness is explained by the fact that they decompose rapidly
at temperatures at which the unsaturation in the resins becomes
highly reactive (above 150.degree. C.). Furthermore, since they
decompose into biradicals, they also may act as cross-linking
agents.
If a catalyst is used for the cross-linking reaction it is
preferably formed in the recording member itself during recording
by the action of the imagewise applied heat.
According to a preferred embodiment of the present invention it is
possible to use a recording material wherein the compound producing
on heating the cross-linking agent, or catalyst and the
cross-linkable polymer or composition are applied in separate
layers. Such a composition then has the advantage of being more
stable under storage conditions, particularly if both layers are
separated by an interlayer, which, however, should not prevent
mixing by diffusion of the cross-linking agent and/or catalyst with
the cross-linkable polymer on heating.
The exposure of the heat-sensitive member containing said
light-absorbing substance(s) converting that light into heat is
preferably carried out with a radiation source producing to a major
extent visible light of a high intensity during a very short
exposure time, i.e. in a time not longer than 10.sup.-.sup.1
seconds. The intensity of the light incident upon the recording
member is preferably at least 0.1 watt. sec./sq. cm. So-called
flashlamps, which produce also infrared radiation and ultraviolet
radiation but only to a minor extent i.e. normally less than 30
percent of the total irradiation energy are preferred.
According to the present invention good results can be obtained
with a xenon gas discharge lamp, which can supply an energy of
200-2,000 watt. sec. in a period of 10.sup.-.sup.4 to
10.sup.-.sup.2 seconds.
According to a preferred arrangement the discharge lamp is in the
form of a thin tube fitted in a hollow glass cylinder in order to
make possible a uniform exposure of the recording material the
latter being applied to the periphery of the cylinder. More details
about such a gas discharge lamp can be found in Belgian Pat.
specification No. 664,868 and published Dutch Pat. application No.
6606719. The intensity of the light emitted by such a gas discharge
lamp is particularly high in the region of the visible
spectrum.
It is possible to employ a number of flash tubes operating
simultaneously, or to obtain a suitable image differentiation by
flashing a single tube at suitable intervals. Reflectors and other
optical components may be included to provide irradiation of
maximum uniformity.
Evidently radiation sources with a much lower energy than those
mentioned can be used if the light energy is focused onto a
relatively small heat-sensitive area e.g. by using a laser beam or
by carrying out the exposure progressively and/or intermittently.
Thus, the heat-sensitive material containing the light-absorbing
substance(s), which convert(s) incident electromagnetic energy into
heat, may be scanningwise exposed, e.g. by means of an imagewise
modulated high-intensity light spot, or may be progressively
exposed through a slot wherein light, e.g. of a tubelike radiation
source, is focused.
It is evident that the heat-sensitive material, before or during
the imagewise heating, can be integrally heated to a certain
temperature below the temperature at which the heat-sensitive
recording element is substantially insolubilized.
The substance(s) for absorbing radiation and converting it into
heat may be (a) finely divided solid substance(s), distributed
nondifferentially in the heat-sensitive layer of the recording
material. Finely divided substances suited for use in the recording
member and which convert visible light and infrared light into heat
are, e.g., carbon black, graphite, oxides or sulfides of heavy
metals, particularly of those heavy metals themselves in finely
divided state, such as silver, bismuth, lead, iron, cobalt, or
nickel. Preference is given to carbon black as light-absorbing
material in heat-conductive relationship with the insolubilizable
composition.
The heat-sensitive layer may comprise from 0.01 to 1, preferably
from 0.1 to 0.5 percent by weight of such finely divided substances
or pigments calculated on the weight of the recording layer. Black
or deep-black colored pigments are preferred. Particularly in the
case of reflex exposure, the optical density of the light-absorbing
recording layer should preferably be between 0.20 and 0.80 and may
be above 1 for direct exposure.
The heat-sensitive layer may further comprise plasticizers for the
applied polymers, such as glycerol, sorbitol, polyglycols,
polyethylene glycols and esters thereof such as glyceryl
monolaurate, polyethyleneglycol distearate and others.
The thickness of the recording layer depends on the use for which
the recording material is intended. If a relief image is to be
produced the thickness depends on the particular kind of master to
be manufactured, e.g. a printing master, such as a planographic,
intaglio or letterpress printing master. In general, the thickness
of the layer will vary from about 0.001 mm. to about 7 mm. Layers
ranging from about 0.001 mm. to about 0.70 mm. thickness will be
used for halftone plates (screen images). Layers ranging from about
0.25 to 1.50 mm. thickness will be used for the majority of
letterpress printing plates.
If the surface of the recording layer is somewhat sticky e.g. in
the case the recording layer is formed by means of a cross-linkable
high-viscous composition, the exposed recording layer can be
developed by means of a powder adhering to the areas of the
recording layer that have not been exposed to heat. If a sticky
character of the recording layer is not desired the latter may
contain an amount of filler or pigment, e.g. zinc oxide, which
reduces the adhesive character.
The base or support material for the cross-linkable layer can be of
any natural or synthetic product capable to be worked up in
fabrics, film or sheet form. It can be flexible or rigid,
reflective or nonreflective for the copying light. For the
manufacture of printing materials metals are normally preferred as
the base materials. However, e.g. where weight is critical,
synthetic resin or polymer sheets are desirable base materials.
Rotary pressplates can be prepared by using cylindrically shaped
base plates carrying the curable composition and by exposing them
directly through a concentrically disposed image-bearing
transparency to electromagnetic radiation e.g. infrared radiation,
which radiation is converted into heat in the recording element.
The support can also be a screening material, which is coated with
a heat-sensitive cross-linkable composition. As screening material
Japan paper (Yoshino paper), nylon fabrics with a size of mesh of
0.2 to 0.08 mm. and woven bronze wire are particularly suited. The
screening material impregnated or coated with the cross-linkable
composition forms a screen- or stencil-printing master blank. By
washing away the portions of the coated composition, which were not
cross linked, a printing master ready for screen printing is
obtained.
The recording member containing the cross-linkable substance or
substances used in the present invention can be applied to a
support or base from a solution or dispersion by coating techniques
known in the art.
If the composition is sufficiently film forming, it can also be
cast or extruded on a casting wheel or belt in the form of a
self-supporting sheet. Later on the sheet can be affixed to the
surface of a permanent support if necessary.
Exposure can be a direct exposure or a reflectographic exposure.
During reflectographic exposure the recording material which for
the purpose is sufficiently radiation transparent is placed between
the radiation source and the original. The original may be a
transparency or an opaque element, having an image formed by
surface areas only some of which absorb the radiation to be
employed, or which reflect such radiation but to different
extents.
In order to obtain very sharp images preference is given to that
type of exposure wherein the heat-sensitive recording layer stands
in contact with the image areas or portions of the original. Even
if image markings of an original are in heat-conductive
relationship with the recording layer during the exposure, any
radiation absorbed by such markings will not affect the recording
member, providing the exposure is sufficiently short (preferably
lower than 10.sup.-.sup.2 second) to prevent heat accumulating in
such portions to such an extent that an effective amount of heat
transfers by conduction from said portions to the recording member
in the areas corresponding with these portions.
The effectiveness of the recording with electromagnetic radiation
depends on the type of radiant energy, in other words the said
energy has to be emitted in a wavelength range wherein the
substances converting electromagnetic radiation into heat
absorb.
The applied radiation energy incident upon the recording material
is preferably not lower than 0.2 watt. sec./sq. cm. It is not
necessary for the recording material to be in heat-conductive
relationship with an original during an exposure. The recording
material may comprise, for instance, a heat-insulating or poorly
heat-conducting support sheet (such a resin sheet) for the
recording layer, the recording material being located with the
support sheet in contact with the original. Alternatively for
excluding such a heat-conductive contact an auxiliary thin
nonheat-conductive sheet e.g. resin sheet may be placed between the
original and the recording layer.
The recording material containing after the exposure an imagewise
differentiation in solubility can be used in various kinds of
techniques wherein relief or resist images have to be produced. In
these techniques the soluble portions of the imagewise exposed
recording element are removed e.g. dissolved in an appropriate
solvent, which should be selected with care, since it should have
good solvent action on the unexposed areas, yet have little action
on the exposed areas and also on the base material whereto the
thermoinsolubilizable composition has been applied. In view of the
uses aimed at, the solvent-treated material may serve as a resist
image for the etching of a relief printing plate or for the
formation of a printing plate carrying hydrophilic and hydrophobic
portions and which is suitable for lithographic printing. More
particularly are mentioned applications directed to the production
of ornamental plaques, patterns for automatic engraving machines,
cutting and stamping dies, relief maps for braille and as resists
in the preparation of printed or etched circuits.
After washing away the portions that have not been exposed to heat,
the polymer parts made insoluble by the imagewise heating may be
supplementarily more thoroughly hardened by any known hardening
technique applicable thereto. The purpose of this additional
hardening is to strengthen the insolubilized polymer parts as much
as possible. If, e.g., the remaining insolubilized polymer surface
is to be used as a printing plate, such subsequent hardening is
often desirable.
A differentiation in cohesion power of the recording element, more
particularly in wet state, can be used in a transfer process
wherein the uncross-linked parts of the recording layer are
transferred to a receiving material forming thereon a print or
relief image in correspondence with the areas which have not been
exposed to heat.
A differentiation in liquid permeability, which is practically
always the result of the created difference in solubility, can be
used in techniques wherein substances, e.g. substances which can
color or bleach the recording material, are selectively absorbed
into the recording material. For such techniques reference is made,
e.g., to out Belgian Pat. specification No. 656,713.
FIGS. 1 and 2 represent two possible methods of reflectographic
exposure.
As schematically illustrated in FIG. 1, the element 22 represents a
xenon gas discharge lamp, while 24 represents a line original
carrying light-absorbing characters 27, on the two sides of a
light-reflecting support 25. The heat-sensitive material 28
consists of a transparent support 29 and of a heat-sensitive layer
31 containing light-absorbing particles 32.
FIG. 2 represents another method of reflectographic exposure. Here
the support 29 of the heat-sensitive material 28 is in direct
contact with the characters 27 of the original 24.
Direct exposure through the original is illustrated in FIGS. 3 and
4. In FIG. 3 the light from the gas discharge lamp 22 passes first
through the transparent support 26 of the original 23, before it
strikes the heat-sensitive layer 31 of the heat-sensitive material
29. In this case the support 30 of this material can be opaque or
transparent. The light cannot pass through the parts of the
original 23 which bear the light-absorbing characters 27.
In FIG. 4, the original 23 has its side bearing the light-absorbing
characters 27 turned towards the gas discharge lamp 22.
In addition to the exposure methods illustrated by these figures,
several other exposure methods are possible. For a man skilled in
the art, these methods are not difficult to find out.
The following examples illustrate the present invention.
EXAMPLE 1
The following ingredients are thoroughly mixed in a ball-mill for 6
h.:
reaction product of 1 mole of p-azido- benzoic acid chloride with
the poly- ether, prepared by making to react 1 mole of
2,2-bis(4-hydroxyphenyl)- propane with 1.05 mole of epichloro-
hydrin 10 g. carbon black 0.3 g. methylene chloride 100 cc.
The suspension obtained is applied to a support of polyethylene
terephthalate in such a way, that the layer after being dried
possesses a density of 0.2 measured by transmitted light.
As illustrated by FIG. 3, this heat-sensitive material obtained is
irradiated for 8/1,000 sec. through a negative transparency by
means of an electronic flash lamp with an energy output of 1.03
watt. sec./sq. cm. Then the exposed material is dipped into
methylene chloride for some 30 sec. so that the exposed areas of
the heat-sensitive layer are removed. A black positive image is
obtained.
If the carbon black is omitted from the recording layer, the latter
is completely dissolved by methylene chloride after an imagewise
exposure.
EXAMPLE 2
A heat-sensitive recording material is prepared as in example 1,
with the difference, however, that the reaction product mentioned
therein is replaced by the same amount of the reaction product of
the polyether, prepared by making to react 1 mole of
m-azidosulphonylbenzoic acid chloride with the polyether prepared
by reacting 1 mole of 2,2-bis-(4-hydroxyphenyl)-propane with 1.05
mole epichlorohydrin. Coating is executed in such a way that an
optical density of 0.5 is obtained measured by transmitted
light.
As illustrated in FIG. 2, the rear side of the heat-sensitive
recording material is laid on an original to be copied, and the
whole is irradiated reflectographically by means of an electronic
flash lamp having an energy output of 0.90 watt. sec./sq. cm.
After soaking the exposed material in methylene chloride, a black
negative image of the original is obtained.
EXAMPLE 3
The following coating suspension is ground for 6 h. in a ball
mill:
poly(vinyl-n-butyral) containing 76.6 percent of acetal groups 3 g.
carbon black 0.2 g. isophthalic acid diazide 0.4 g. methylene
chloride 100 cc.
This suspension is coated on polyethylene terephthalate film in
such a way that after drying this layer possesses a density of 0.28
measured by transmitted light. Exposure and rinsing are done as
described in example 1. A sharp, black, positive image is
obtained.
When the isophthalic acid diazide is omitted from the layer, an
uncompletely washed and vague image is obtained.
EXAMPLE 4
A mixture of the following products is mixed in a ball mill for 3
h.:
40 percent solution in acetone of a branched polyester of adipic
acid, phthalic acid, and glycerol, having still 8.5 to 9 percent of
free hydroxyl groups 50 cc. zinc oxide 40 g. addition product of
2,4-toluene-diiso- cyanate and diethyl malonate 4 g. carbon black
0.2 g. acetone 50 cc.
This dispersion is applied to a support of polyethylene
terephthalate in such a way that the dried layer has a thickness of
10 .mu.. The material obtained is exposed as described in example 1
and rinsed with acetone. A dark grey positive image is
obtained.
EXAMPLE 5
The following ingredients are thoroughly mixed in a ball mill for 6
h.:
ethylcellulose 4 g. acetone 96 cc. carbon black 0.4 g. addition
product of toluene diiso- cyanate and diethyl malonate 1 g.
The fine suspension obtained is coated onto a subbed polyethylene
terephthalate film in such a way that after drying the applied
layer possesses a density of 0.32 measured by transmittance. This
heat-sensitive material with its sensitive side is laid onto an
original to be copied and the whole is exposed reflectographically
by means of an electronic flash lamp having an intensity of 1.03
watt. sec./sq. cm. Then the exposed material is pressed against a
paper sheet, moistened with methanol. After peeling apart both
materials, a greyish black print of the original is obtained on the
latter. By pressing the same master again and again onto other
paper sheets moistened with methanol, some 5 of such prints are
obtained.
EXAMPLE 6
The following ingredients are mixed for 4 h. in a ball mill:
poly(diallyl o-phthalate) 25 g. methyl isobutyl ketone 175 cc.
cumene hydroperoxide 7 g. carbon black 0.6 g.
The resulting fine suspension is coated onto a subbed polyethylene
terephthalate support in such a way that after drying, the layer
possesses a density of 0.26 measured by transmittance.
After exposure as in example 1, the material is rinsed with methyl
isobutyl ketone for a short while. A black positive image is left
on the film.
* * * * *