U.S. patent number 3,615,443 [Application Number 04/635,757] was granted by the patent office on 1971-10-26 for presensitized planographic printing plate.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to James G. Smith.
United States Patent |
3,615,443 |
Smith |
October 26, 1971 |
**Please see images for:
( Certificate of Correction ) ** |
PRESENSITIZED PLANOGRAPHIC PRINTING PLATE
Abstract
A presensitized printing plate comprising a support, a hardened
gelatin photographic silver halide emulsion layer, a
developer-containing layer and a reflecting layer between the
emulsion and the support which contains a metal oxide and has
certain Reflectance characteristics. The emulsion can be a
direct-positive one and can optionally contain a halogen-accepting
compound and a sulfonated compound to increase sensitivity.
Inventors: |
Smith; James G. (N/A, NY) |
Assignee: |
Company; Eastman Kodak
(NY)
|
Family
ID: |
24548997 |
Appl.
No.: |
04/635,757 |
Filed: |
May 3, 1967 |
Current U.S.
Class: |
430/264; 430/204;
430/523; 430/302 |
Current CPC
Class: |
G03F
7/06 (20130101) |
Current International
Class: |
G03F
7/06 (20060101); G03F 007/02 () |
Field of
Search: |
;96/33,84 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Winkelman; John
Claims
I claim:
1. In a presensitized printing plate comprising a support, a
hardened gelatin photographic silver halide emulsion layer, a layer
no farther from said support than said emulsion layer and
containing a polyhydroxybenzene developing agent which is a halogen
substituted, phenyl substituted, or two-six carbon atoms containing
alkyl substituted polyhydroxybenzene developing agent and which
oxidizes upon development to render gelatin oleophilic in developed
areas; the improvement comprising a layer between said emulsion
layer and said support containing an oxide of titanium or zinc and
having an average Reflectance of at least 60 percent over
wavelengths in the visible region of the spectrum in the range of
about 420 to about 500 millimicrons.
2. The presensitized printing plate of claim 1 in which the layer
containing a metal oxide has an average Reflectance of at least 80
percent over wavelengths in the visible region of the spectrum in
the range of about 420 to about 500 millimicrons.
3. The presensitized printing plate of claim 1 in which said oxide
is titanium dioxide.
4. The presensitized printing plate of claim 1 in which said
developing agent is 4-phenyl catechol and said oxide is zinc
oxide.
5. The presensitized printing plate of claim 4 in which said silver
halide is silver chloride and said 4-phenyl catechol is in said
emulsion layer.
6. The presensitized printing plate of claim 1 in which said silver
halide is silver chloride and said developing agent is 4-phenyl
catechol which is contained in said layer between said emulsion
layer and said support.
7. The presensitized printing plate of claim 1 in which said layer
between said emulsion layer and said support contains an
antihalation dye.
8. The presensitized printing plate of claim 1 in which said
emulsion is a direct-positive emulsion.
9. The presensitized printing plate of claim 8 in which said
emulsion layer contains grains comprising a central core of silver
halide containing centers which promote deposition of photolytic
silver and an outer shell covering said core comprising a fogged
silver halide that develops to silver without exposure.
10. The presensitized printing plate of claim 9 in which said
developing agent is 4-phenyl catechol and said oxide is titanium
dioxide.
11. The presensitized printing plate of claim 9 in which said
developing agent is 4-phenyl catechol and said oxide is zinc
oxide.
12. The presensitized printing plate of claim 10 in which said
emulsion layer is a hardened gelatin photographic silver chloride
emulsion layer containing grains comprising a central core of
silver chloride containing centers which promote deposition of
photolytic silver and an outer shell covering said core comprising
a fogged silver chloride that develops to silver without exposure
and said 4-phenyl catechol is in said emulsion layer.
13. The presensitized printing plate of claim 9 in which said
emulsion has adsorbed to the fogged grains a halogen-accepting
compound having an anodic polarographic halfwave potential less
than 0.85 and a cathodic polarographic halfwave potential which is
more negative than -1.0.
14. The presensitized printing plate of claim 13 in which said
halogen-accepting compound is a merocyanine dye.
15. The presensitized printing plate of claim 13 in which said
emulsion also contains a sulfonated compound having the
formula:
R-so.sub.3 m wherein R represents a polynuclear aromatic group and
M represents a hydrogen atom or a water-soluble cation salt
group.
16. A process which comprises (a) exposing to a subject a
presensitized printing plate comprising a support, a hardened
gelatin photographic silver halide emulsion layer, and between said
emulsion layer and said support, a layer containing an oxide of
titanium or zinc and having an average Reflectance of at least 60
percent over wavelengths in the visible region of the spectrum in
the range of about 420 to about 500 millimicrons and (b) developing
the emulsion layer with a polyhydroxybenzene developing agent which
is a halogen substituted, phenyl substituted or two-six carbon
atoms containing alkyl substituted polyhydroxybenzene developing
agent and which renders gelatin oleophilic in developed areas.
17. The process of claim 16 wherein said silver halide is silver
chloride, said developing agent is 4-phenyl catechol which is
contained in said layer between said emulsion layer and said
support, and said developing step (b) is accomplished by contacting
said exposed emulsion layer with an alkaline solution.
18. The process of claim 16 wherein said printing plate is a
positive-working presensitized printing plate comprising a support,
a hardened gelatin photographic emulsion layer containing grains
comprising a central core of photographic silver halide containing
centers which promote deposition of photolytic silver and an outer
shell covering said core comprising a fogged photographic silver
halide that develops to silver without exposure.
19. The process of claim 18 which includes step (c) inking the
developed areas with greasy printing ink and printing therefrom in
a lithographic printing press.
20. The process of claim 18 wherein said emulsion has adsorbed to
the fogged grains a halogen-accepting compound having an anodic
polarographic halfwave potential which is more negative than
-1.0.
21. The process of claim 20 wherein said halogen-accepting compound
is a merocyanine dye.
22. The process of claim 20 wherein said emulsion also contains a
sulfonated compound having the formula:
R-so.sub.3 m wherein R represents a polynuclear aromatic group and
M represents a hydrogen atom or a water-soluble cation salt group.
Description
Background of the Invention
1. Field of the Invention
This invention relates to novel photographic materials, their
preparation and use. In one of its aspects, this invention relates
to novel presensitized printing plates and their use in
lithography. In another of its aspects, this invention relates to
novel presensitized printing plates, particularly positive-working
plates, which contain a metal oxide in a layer between the support
and the photographic silver halide emulsion layer.
2. Description of the Prior Art
Lithographic printing plates are well known and have been prepared,
for example, from metal, cellulose ester or paper supports carrying
light-sensitive layers. An outstanding lithographic printing plate
which does not depend upon the printing character being
substantially above or below the hydrophilic nonprinting surface,
as opposed to other plates such as relief or intaglio, is described
in U.S. Pat. No. 3,146,104 of Yackel et al. issued Aug. 25, 1964.
In this lithographic printing plate, a gelatin photographic silver
halide emulsion layer either contains or is coated effectively
adjacent to a layer containing a developing agent which oxidizes
upon development to render gelatin oleophilic in developed areas.
Upon thinking the exposed and developed plate and printing on a
lithographic press, the desired lithographic reproduction, which
can be positive or negative with respect to the original subject is
obtained. To avoid halation effects and achieved good resolution
with the lithographic printing plates described in the Yackel et
al. patent, antihalation materials such as carbon black have been
employed in a layer between the photographic silver halide layer
and the support. The use of such materials as carbon black for this
purpose has resulted in a significant loss in photographic speed.
However, omitting the carbon black results in poor exposure
latitude and resolution. It would be very desirable to have a
printing plate which combines good photographic speed, exposure
latitude and resolution.
Summary of the Invention
According to one embodiment of this invention, there is provided a
presensitized printing plate comprising a support, a hardened
gelatin photographic silver halide emulsion layer, a layer no
farther from said support than said emulsion layer containing a
polyhydroxybenzene developing agent which oxidizes upon development
to render gelatin oleophilic in developed areas, and between said
emulsion layer and said support, a reflecting layer containing a
metal oxide and having the Reflectance characteristics described
hereinafter.
According to another embodiment of this invention, there is
provided a process employing a presensitized printing plate
comprising a hardened gelatin photographic silver halide emulsion
layer and a reflecting layer containing a metal oxide, as described
hereinafter, and processing this plate after exposure with a
polyhydroxybenzene developing agent which oxidizes in the presence
of the gelatin in the silver halide emulsion layer to render
gelatin oleophilic in developed areas.
The reflecting layer present in the presensitized plate of this
invention requires a certain opacity, as defined by its average
Reflectance described herein, and must contain a metal oxide.
Pigments which have been used in the past to impart opacity to
reflecting layers but which are not metal oxides do not give the
desired results in the practice of this invention. Thus, as shown
in example 2 which follows, pigments such as barium sulfate impart
the desired Reflectance characteristics to the reflecting layer but
the presensitized plates have poor resolution. Furthermore, it
could not have been expected that a carbon black containing layer
which absorbs light could be replaced by a metal oxide reflecting
layer in a printing plate to obtain good exposure latitude without
losing photographic speed or resolution.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The gelatin photographic silver halide emulsion layer used in the
presensitized printing plate described herein can be any negative
or direct-positive silver halide emulsion. These emulsions can
contain silver halide grains which form latent images predominantly
on the surface of the grains or those which form latent images
predominantly inside the silver halide crystal, as exemplified by
those described in Davey and Knott U.S. Pat No. 2,592,250 issued
Apr. 8, 1952, direct-positive emulsions such as those described in
Kendall and Hill U.S. Pat No. 2,541,472 issued Feb. 13, 1951, or
Fallesen U.S. Pat. No. 2,497,875 issued Feb. 21, 1950. If desired,
a positive-working plate can be obtained by employing a
photographic emulsion layer which comprises separate layers of
fogged photographic silver halide coated over unfogged silver
halide as described in Yackel and Abbott U.S. Pat. No. 3,146,104
issued Aug. 25, 1964. A negative-working plate is obtained when the
unfogged silver halide emulsion is used alone, as described in U.S.
Pat. No. 3,146,104.
In practicing this invention, it has been found that particularly
good results are obtained with positive-working plates in which the
photographic silver halide emulsion layers are layers of
photographic reversal or direct-positive emulsions containing
grains comprising a central core of a silver halide containing
centers which promote the deposition of photolytic silver and an
outer shell or covering for said core of a fogged or spontaneously
developable silver halide. Such emulsions can be called "covered
grain emulsions." The fogged shell of such grains develops to
silver without exposure. In preparing this type of reversal
emulsion, before a shell of silver halide is added to the silver
halide core, the core emulsion is first chemically or physically
treated by methods previously described in the prior art to produce
centers which promote deposition of photolytic silver, i.e., latent
image nucleating centers. Such centers can be obtained by various
techniques such as chemical sensitization, particularly good
results being obtained with techniques of the type described by
Antoine Hautot and Henri Saubenier in Science et Industries
Photographiques, Volume XXVIII, Jan. 1957, pages 57 to 65. Chemical
sensitization techniques which can be employed include three major
classes, namely, gold or noble metal sensitization, sulfur
sensitization, such as by a labile sulfur compound, and reduction
sensitization, i.e., treatment of the silver halide with a strong
reducing agent which introduces small specks of metallic silver
into the silver salt crystal or grain. The shell of the grains
comprising the reversal emulsions is prepared by precipitating over
the core grains a light-sensitive silver halide salt that can be
fogged and which fog is removable by bleaching. The shell is of
sufficient thickness to prevent access to the core by the developer
used in processing. The silver halide shell is surface fogged to
make it developable to metallic silver with conventional surface
image developing compositions. Substantially all of the silver
halide grains in an emulsion are fogged prior to exposure and/or
processing, i.e., such emulsions are uniformly fogged. Such fogging
can be effected by chemical sensitization to fog using the
sensitizing agents described for chemically sensitizing the core
emulsion, high intensity light and like fogging means well known to
those skilled in the art. While the core need not be sensitized to
fog, the shell is fogged, for example, reduction fogged with a
reducing agent such as stannous chloride. Fogging by means of a
reduction sensitizer, high pH and low pAg silver halide
precipitating conditions and the like can be suitably utilized.
In one embodiment of the invention, the direct-positive emulsion
has adsorbed to the fogged grains a halogen-accepting compound
having an anodic polarographic halfwave potential less than 0.85
and a cathodic polarographic halfwave potential which is more
negative than -1.0. These emulsions have an unusually high
sensitivity or photographic speed. If the halogen-accepting
compound does not have the polarographic halfwave potential set
forth above, the emulsions containing the compound will not have an
unusually high sensitivity.
In another embodiment of the invention, certain high molecular
weight organic compounds, particularly sulfonated compounds as
described hereinafter, can be used in combination with
halogen-accepting compounds to effect an even greater increase in
photographic speed or sensitivity.
The halogen-accepting compounds employed in practicing the one
embodiment of this invention referred to above are absorbed to the
fogged silver halide grains. The halogen acceptors which give
particularly good results in the practice of this invention can be
characterized in terms of their polarographic halfwave potentials,
i.e., their oxidation reduction potentials determined by
polarography. Cathodic measurements can be made with a b 1
.times.10.sup.-4 molar solution of the halogen acceptor in a
solvent, for example, methanol which is 0.05 molar in lithium
chloride using a dropping mercury electrode with the polarographic
halfwave potential of the most positive cathodic wave being
designated E.sub.(C). Anodic measurements can be made with 1
.times.10 .sup.-4 molar aqueous solvent solution, for example,
methanolic solutions of the halogen acceptor which are 0.05 molar
in sodium acetate and 0.005 molar in acetic acid using a carbon
paste or pyrolytic graphite electrode, with the voltametric half
peak potential for the most negative anodic response being
designated E.sub.(a). In each measurement, the reference electrode
can be aqueous silver -silver chloride (saturated potassium
chloride) electrode at 20.degree. C. Electrochemical measurements
of this type are known in the art and are described in New
Instrumental Methods in Electrochemistry, by Delahay, Interscience
Publishers, New York, N.Y. 1954; Polarography, by Kolthoff and
Lingane, 2nd Edition, Interscience Publishers, New York, N.Y.,
1952; Analytical Chemistry, 36,2426 (1964) by Elving; and
Analytical Chemistry, 30, 1576 (1958) by Adams.
Compounds which can be employed as halogen acceptors in the
practice of this invention include organic or inorganic compounds
having an anodic polarographic halfwave potential E.sub.(a) less
than 0.85 and a cathodic polarographic potential E.sub.(c) which is
more negative than -1.0. A preferred class of halogen-accepting
compounds is characterized by an anodic halfwave potential which is
less than 0.62 and a cathode halfwave potential which is more
negative than -1.3. A preferred class of halogen acceptors that can
be used in the practice of this invention comprises the spectral
sensitizing merocyanine dyes having the formula: ##SPC1## where A
represents the atoms necessary to complete an acid heterocyclic
nucleus, e.g., rhodanine, 2-thiohydantoin and the like, B
represents the atoms necessary to complete a basic
nitrogen-containing heterocyclic nucleus, e.g., benzothiazole,
naphthothiazole, benzoxazole and the like, each L represents a
methine linkage, e.g., and n is an integer from 0 to 2 , i.e., 0.
1or 2. Specific examples of merocyanine dyes falling within the
above formula include:
3-carboxymethyl-5-[(3-ethyl-2-benzothiazolinylidene)-ethylidene]-rhodanine;
3-ethyl-5-]1-(4-sulfobutyl)-4(1H)-pyridylidene]-rhodanine, sodium
salt;
3-carboxymethyl-5-[(3-ethyl-2-benzoxazolinylidene)-ethylidene]-2-thio-2,4-o
xazolidinedione;
1-carboxymethyl-5-[(3-ethyl-2-benzothiazolinylidene)-ethylidene]-3-phenyl-3
-thiohydantoin;
4- (1-ethylnaphtho[1,2-d]thiazolin-2-ylidene)-1-methylethylidene
-3-methyl-1-(4-sulfophenyl)-2-pyrazolin-5-one;
4-[(3-ethyl-6-nitro-2-benzothiazolinylidene)ethylidene]-3-phenyl-2-isoxazol
in-5-one; etc.
For a further description of suitable halogen acceptors see Wise
U.S. application Ser. No. 615,360 filed Feb. 13, 1967. Suitable
procedures for preparing merocyanine dyes are described in Brooker
et al. U.S. Pat. Nos. 2,493,747 and 2,493,748 issued Jan. 10,
1950.
The halogen accepting compounds employed in practicing the one
embodiment of this invention referred to above can be used in
widely varying concentrations. However, the halogen-accepting
compounds are generally employed at concentrations in the range of
about 100 milligrams to about 1.0 gram, preferably about 150 to
about 600 milligrams per mole of silver halide.
As already indicated, the halogen-accepting compounds described
herein can be employed in combination with certain types of high
molecular weight organic compounds to achieve an even greater
increase in the photographic speed of direct-positive emulsions.
These compounds are sulfonated and comprise polynuclear aromatic
compounds containing at least one sulfo group. The term
"polynuclear aromatic" as used herein is intended to mean 2 or more
benzene rings fused together (for example, as in naphthalene,
pyrene, etc. or at least 2 benzene rings or aromatic rings directly
joined together (for example, as in diphenyl, terphenyl,
quaterphenyl, etc.), or through an aliphatic linkage. Such
sulfonated derivatives can conveniently be represented by the
following general formula:
R-so.sub.3 m wherein R represents a polynuclear aromatic group as
defined above and M represents a cation such as a hydrogen atom or
a water-soluble cation salt group (e.g., sodium, potassium,
ammonium, triethylammonium, triethanolammonium, pyridinium,
etc.),
Included among the sulfonated derivatives of the above formula are
the following typical examples:
Calcofluor White-MR. This is the trade name for a
bis(s-triazin-2-ylamino)stilbene-2,2'-disulfonic acid, sodium
salt.
Leucophor B. This is the trade name for a
bis(s-triazin-2-ylamino)stilbene-2,2'-disulfonic acid, sodium
salt.
Sodium 6-(4-methoxy-3-sulfo-w-phenylacrylol)-pyrene.
3,4-Bis(4-methoxy-3-sulfobenzamido)-dibenzothiophene dioxide,
sodium salt.
4',4"-Bis(2,4-dimethoxy-5-sulfobenzamido)-p-terphenyl, disodium
salt.
Chyrsene-6-sulfonic acid, sodium salt.
4,4'-Bis[2-phenoxy-4-(2-hydroxyethylamino)-1,3,5-triazin-6-ylamino]stilbene
-2,2'-disulfonic acid, disodium salt.
These sulfonated derivatives may be used in any concentration
effective for the intended purpose. Good results are generally
obtained by employing the compounds in concentrations in the range
of about 0.02 to about 10 grams per mole of silver halide.
The silver halide employed in the preparation of the photographic
emulsion layers of the printing plates described herein include any
of the photographic silver halides, as exemplified by silver
bromide, silver iodide, silver chloride, silver chlorobromide,
silver bromiodide, silver chlorobromiodide and the like, These
photographic silver halides can be coated at silver coverages of
about 10 to about 400, preferably about 20 to about 100 milligrams
per square foot.
The developing agents employed in the practice of this invention
include the developing agents which are capable of oxidation in the
presence of the hardened gelatin present in the photographic
emulsion layer to produce an image receptive to greasy printing
ink, i.e., upon development, they render the gelatin in the
developed areas oleophilic. They can be incorporated into one or
more layers of the photographic element of this invention or they
can be supplied from outside of the element, e.g., from solution or
from a layer on a separate support. The polyhydroxybenzene
developing agents substituted with halogen, monocyclic aryl groups
of the benzene series and alkyl groups of at least two and
preferably from two to six carbon atoms have the property of making
gelatin oleophilic in developed areas. The 1,2-dihydroxybenzene
developing agents substituted by halogen, monocyclic aryl of the
benzene series and alkyl groups of at least two carbon atoms and
preferably two to six carbon atoms are particularly useful in the
process. Developing agents possessing the necessary properties thus
include certain polyhydroxybenzene developing agents such as
pyrogallol and substituted polyhydroxybenzene developing agents,
particularly dihydroxybenzene substituted with, for example,
halogen, alkyl groups of at least two and preferably from two to
six carbon atoms and a monocycylic aryl group of the benzene
series, e.g., o-chlorohydroquinone, o-bromohydroquinone, 4-phenyl
catechol, 4-phenethyl catechol, 4-phenpropyl catechol, 4-t-butyl
catechol, 4-n-butylpyrogallol, nordihydroguiauretic acid,
4,5-dibromocatechol, 3,3,6-tribromo-4 -phenylcatechol and 1-phenyl
3-(N-n-hexylcarboxamide)
-4[p-(.beta.-hydroquinolylethyl)-phenylazo]-5-pyrazolone. Esters of
such developing agents, e.g., formates and acetates of pyrogallol
hydrolyze in alkaline solutions and can be used in the processes of
the incorporated Such esters are intended to be included in the
specification and claims where reference is made to
polyhydroxybenzene developing agents. In certain cases it has been
found to be advantageous to include with the polyhydroxybenzene
developing agent such as pyrogallol, an auxiliary developing agent
such as pyrogallol, an auxiliary developing agent such as
monoethyl-p-aminophenol or a 3-pyrazolidone, which latter
developing agents by themselves do not yield oleophilic images in
the processes described, but which do appear to act synergistically
with the polyhydroxybenzenes to yield oleophilic images. The
developing agents are generally employed in the photographic
elements at coverages of about 5 to about 200, preferably about 10
to about 50 milligrams per square foot of support and are
incorporated in a layer which is no farther from the support than
the photographic emulsion layer, i.e., they are incorporated into
the photographic emulsion layer or a layer between the emulsion
layer and the support, e.g., an adjacent or contiguous layer.
However, these developing agents can be incorporated in a layer,
e.g., a gelatin layer, on a separate support which is wetted with
activator and brought into contact with the photographic emulsion
layer during processing.
In the photosensitive elements of this invention, the silver salt
emulsion layer should be substantially hardened in order to prevent
the processed plate from adhering to printing blankets, papers,
etc. For this purpose, the emulsion should be as hard as a gelatin
layer containing at least about 0.2 gram and preferably about 0.5
to about 10 grams of dry formaldehyde per pound of gelatin, i.e.,
it should have a melting point in water greater than 150.degree. F.
and preferably greater than 200.degree. F.
The reflecting layers included in the presensitized printing plates
of this invention provide good antihalation qualities without the
significant photographic speed loss generally associated with the
use of carbon black in antihalation layers. These good antihalation
qualities are shown by resolution characteristics which are
comparable to those of plates containing carbon black containing
antihalation layers.
The reflecting layers, which are between the photographic silver
halide emulsion layer and the support in the presensitized printing
plates of this invention, contain a metal oxide, generally in a
gelatin binder, and have an average Reflectance of at least
60percent, often at least 80 percent, over wavelengths in the
visible region of the spectrum in the range of about 420 to about
500 millimicrons. Reflectance is that fraction of light which is
reflected from the surface of the metal oxide containing layer
coated on the support which Reflectance is measured at the defined
wavelengths of the spectrum. This Reflectance can be determined
using any method suitable for this purpose, including for example,
the use of a standard recording spectrophotometer which will
measure Reflectance at different wavelengths over the range of abut
420 to about 500 millimicrons. When averaged, the Reflectance at
the wavelengths over this range must be at least 60 percent,
generally in the range of about 60 to about 95 percent, and
preferably in the range of about 80 to about 95 percent. The metal
oxides employed in these layers can be any photographically inert
metal oxide which will impart the desired average Reflectance such
as aluminum or magnesium oxide, although oxides of metals from
Group IIB and IVB of the Periodic Table, such as zinc oxide and
titanium dioxide, are preferred. The metal oxides employed have an
average particle size up to about 10 microns, although the particle
size is generally less than about 5 microns and can be 0.1 micron
or less. The metal oxide is generally coated at a coverage in the
range of about 0.1 to about 10, preferably about 0.5 to about 5
grams per square foot of support. The metal oxides are in a layer
between the emulsion layer and the support which layer can also
contain the polyhydroxybenzene developing agent when developing
agent is coated in the layer beneath the photographic emulsion
layer. Where the support employed is paper or some other support
coated with an alphaolefin polymer, it is convenient to incorporate
the metal oxide into the resin coating on the photographic emulsion
side surface of the support.
As already indicated, the presensitized printing plates of this
invention give prints having good resolution even without the usual
antihalation pigments such as carbon black or antihalation dyes.
However, the metal oxide containing layers in the presensitized
plates of this invention can contain antihalation dyes,
particularly merocyanine dyes, if desired. These layers can also
contain other addenda, for example, organic or inorganic pigments
and brightening agents, as long as the metal oxide is present and
the layer has the required Reflectance characteristics.
Although gelatin can be the sole binding agent, various colloids
can be used with gelatin as vehicles or binding agents in the
photographic emulsion layers employed in the practice of this
invention. However, gelatin or a gelatin derivative which is
primarily gelatin, is used for at least a part, for example, at
least 10 percent, by weight, of the binder in the photographic
emulsion layer. Other binding agents can be used with the gelatin
in the emulsion layer or in other layers alone or with gelatin
include any of the hydrophilic colloids generally employed in the
photographic field such as colloidal albumin, polysaccharides,
cellulose derivatives, synthetic resins such as polyvinyl
compounds, including polyvinyl alcohol derivatives, acrylamide
polymers, and the like. In addition to the hydrophilic colloids,
the vehicle or binding agent can contain dispersed polymerized
vinyl compounds, particularly those which increase the dimensional
stability of photographic materials. Suitable compounds of this
type include water-insoluble polymers of alkyl acrylates or
methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates,
and the like. The binding agent is generally coated at a coverage
in the range of about 50 to about 2000, preferably about 100
milligrams to about 1000 milligrams per square foot of support.
The photographic layers described herein can be superimposed upon a
wide variety of supports. Typical are the flexible supports which
are generally employed in printing plates, as exemplified by
supports of metals such as aluminum, paper, cellulose nitrate film,
cellulose acetate film, polyvinyl acetal film, polystyrene film,
polyethylene terephthalate film and related films or resinous
materials and other related materials. Supports such as paper which
are partially acetylated or coated with an alpha-olefin polymer,
particularly a polymer of an alpha-olefin containing two to 10
carbon atoms, as exemplified by polyethylene, polypropylene,
ethylene-butene copolymers and the like, give good results.
In practicing this invention, the ink-receptive areas of the
printing plates on a background of hydrophilic material are
obtained by alkaline activation of a silver halide developing agent
in the presence of a gelatin photographic silver halide emulsion
layer. The result is to form a silver image and oxidized developing
agent in the region of development. The element can then be inked
in the developed areas with greasy printing ink and a print made
therefrom in a lithographic press. The gelatin in the emulsion
layer can undergo additional hardening at the same time as
development. However, the hardening of the gelatin layer in the
region of development is incidental to successful operation of the
invention since some developing agents, such as catechol,
hydroquinone and toluthydroquinone, which are known to be strong
gelatin-tanning silver halide developing agents, are not useful in
the sensitive elements of this invention because the oxidation
products formed in the presence of the gelatin silver halide
emulsion layer do not form oleophilic images, whereas other closely
related silver halide developing agents such as chlorohydroquinone,
are quite useful in the process of the invention.
The photographic silver halide emulsions employed in the printing
plates of this invention can be chemically sensitized by any method
suitable for this purpose. For example, the emulsions can be
digested with naturally active gelatin or they can contain such
addenda as chemical sensitizers, for example, sulfur sensitizers
(for example, allyl thiocarbamide, thiourea, allyl isothiocyanate,
cystine, etc.), they can be treated during or after the formation
of the silver salts with salts of polyvalent metals such as
bismuth, the noble metals and/or the metals of Group VIIIB of the
Periodic Table such as ruthenium, rhodium, palladium, iridium,
osmium, platinum and the like, and can contain various gold
compounds (e.g., potassium chloroaurate, auric trichloride, etc.)
(see Baldsiefen U.S. Pat. No. 2,540,085 issued Feb. 6, 1951;
Damschroder U.S. Pat. No. 2,597,856 issued May 27, 1952; and yutzy
and leermakers u.s. Pat. No. 2,597,915 issued may 27, 1952),
various palladium compounds such as potassium chloropalladate
(Stauffer and Smith U.S. Pat. No. 2,598,079 issued May 27, 1952)
etc., reduction sensitizers such as stannous salts (Carrol U.S.
Pat. No. 2,478,850 issued Nov. 15, 1949), polyamines, such as
diethyl triamine (Lowe and Jones U.S. Pat. No. 2,518,698 issued
Aug. 15, 1950), polyamines, such as spermine (Lowe and Allen U.S.
Pat. No. 2,521,925 issued Sept. 12, 1950), or
bis(.beta.-aminoethyl)sulfide and its water-soluble salts (Lowe and
Jones U.S. Pat. No. 2,521,926 issued Sept. 12, 1950) or mixtures of
such sensitizers, antifoggants, such as ammonium chloroplatinate
(Trivelli and Smith U.S. Pat. No. 2,566,245 issued Aug. 28, 1951),
benzotriazole, nitrobenzimidazole, 5-nitroindazole, benzidine,
mercaptans, etc. (see Mees, "The Theory of the Photographic
Process," Mac Millian Publishing Company, 1942, page 460) or
mixtures thereof, hardeners such as aldehyde hardeners, aziridine
hardeners, hardeners which are derivatives of dioxane,
oxypolysaccharides such as oxystarch or oxy plant gums and other
types of hardeners for gelatin and hydrophilic colloids. These
photographic emulsions can also contain spectral sensitizers such
as the cyanines, merocyanines, complex (trinuclear) cyanines,
complex (trinuclear) merocyanines, styryls and hemicyanines.
Particularly good spectral sensitizers which can be used are the
merocyanines disclosed in Brooker et al. U.S. Pat. Nos. 2,493,747
and 2,493,748 issued Jan. 10, 1950.
The invention can be further illustrated by reference to the
accompanying drawing in which:
FIGS. 1, 2 and 3 are each diagrammatical cross-sectional views of
printing plates representing separate embodiments of this
invention.
FIG. 4 is a set of Reflectance curves for three supports coated
with a gelatin layer containing titanium dioxide, barium sulfate or
zinc oxide.
In FIG. 1 there is shown a cross-sectional view of a presensitized
printing plate of the type which can be advantageously employed in
the practice of this invention. The plate comprises a support 1
such as paper, layer 2 is a hydrophilic organic colloid layer, for
example, gelatin containing polyhydroxybenzene developing agent and
metal oxide, as described herein and layer 3 is a hardened gelatine
photographic silver halide emulsion layer (negative or positive).
The element illustrated, if desired, can also contain additional
layers (not shown) such as gelatin layers, subbing layers and the
like.
FIGS. 2 and 3 are variations of FIG. 1 in which, in FIG. 2, the
polyhydroxybenzene developing agent is in the photographic silver
halide emulsion layer 4 and, in FIG. 3, the emulsion layer 5
comprises a fogged gelatin photographic silver halide layer coated
over an unfogged gelatin photographic silver halide layer to give a
positive-working plate.
FIG. 4 is gives the Reflectance curves for three paper supports
coated with gelatin layers containing (A) titanium dioxide having
an average particle size of 2 microns, (B) barium sulfate having an
average particle size of 2 microns and (C) zinc oxide having an
average particle size of 2 microns, all as in example 2.
This invention can be further illustrated by the following examples
of preferred embodiments thereof although it will be understood
that these examples are included merely for purposes of
illustration and are not intended to limit the scope of the
invention unless otherwise specifically indicated.
EXAMPLE 1
A positive-working presensitized plate having good exposure
latitude is obtained when the covered grain photographic emulsions
described herein are coated over metal oxide containing layers
which may also contain a dye such as merocyanine dyes, e.g.,
thiazoline-rhodanine merocyanines. To illustrate, the following
gelatin dispersions are coated over a polyethylene coated paper
support: ##SPC2##
Coatings 2 and 3 have an average Reflectance over the 420-500
millimicron of the spectrum over 60 percent.
Each of the resulting coatings 1-3 is overcoated with a fogged
covered grain photographic emulsion prepared as follows:
A gelatin silver chloride photographic emulsion is prepared by
simultaneously adding at 70.degree. C. over a period of about 20
minutes, 1000 milliliters of a 4 molar silver nitrate aqueous
solution and 1000 milliliters of a 4 molar sodium chloride aqueous
solution to a well-stirred aqueous solution of 1000 milliliters of
0.01 molar sodium chloride containing 40 grams of gelatin. 5000
Milliliters of water containing 280 grams of gelatin is added and
the emulsion is cooled. One-quarter of the resulting gelatin silver
chloride emulsion (containing 1.0 mole percent silver chloride) is
melted at 40.degree. C., 100 milligrams of potassium chloroiridite
(dissolved in water) is added and the emulsion heated to 70.degree.
c. This prepared emulsion constitutes the silver chloride core
containing physical discontinuities that trap electrons over which
is formed a shell of silver chloride.
The shell of silver chloride is formed by adding to the core
emulsion 500 milliliters of 4 molar silver nitrate aqueous solution
and 500 milliliters of 4 molar sodium chloride aqueous solution
simultaneously over a period of 20 minutes. 160 Grams of gelatin,
previously soaked in 340 milliliters of water, is stirred in and
the emulsion cooled. During both additions of the silver nitrate
and sodium chloride (i.e., to form both the core and the shell),
the two solutions are added at approximately constant rates.
Sufficient silver chloride is formed in the shell to give a ratio
of 4 moles of shell silver chloride to 1 mole of core silver
chloride. The resulting covered grain emulsion is melted, the
gelatin content increased to 160 grams per mole of silver chloride
and water added to 4000 grams per mole of silver chloride.
Two milligrams of thiourea dioxide per mole of silver chloride are
added to the emulsion at 40.degree. C. The emulsion is fogged by
heating it to 55.degree. C. and holding it for 40 minutes at this
temperature. It is cooled immediately to 40.degree. C. The
following additional additives are incorporated into one mole of
the fogged emulsion: i240 grams gelatin, 200 milligrams of a
thiazoline-rhodanine merocyanine green sensitizer of the type
described in Brooker et al. U.S. Pat. No. 2,493,748 issued Jan. 10,
1950, 1 gram of a sulfonated triazinyl-stilbene of the type
described in Formula II of McFall U.S. Pat. No. 2,933,390 issued
Apr. 19, 1960, and 25 milliliters of a 10 percent formaldehyde
solution.
The emulsion is coated at a coverage of 72 milligrams silver per
square foot and 215 milligrams of gelatin per square foot. The
resulting coatings are deliberately overexposed by exposing for 8
seconds to a 40-watt bulb at 27 inches through a parallel test line
object covered with a step tablet, processed for 20 seconds at
85.degree. F. in an 8 percent potassium phosphate solution
containing 0.1 gram potassium bromide per liter and stopped for 20
seconds in a phosphoric acid bath.
The plate is then placed in a lithographic printing press, inked in
the conventional manner and printed to give a positive lithographic
print.
Plates with coatings 2 and 3 exhibit very little or no loss in
image quality with overexposure as compared to those containing
coating 1. This illustrated the good exposure latitude of the
former in comparison to the latter. Furthermore, sensitometric
tests show that the use of the metal oxide interlayer of coating 2
does not decrease the photographic speed, although with the dye of
coating 3 there is a slight speed loss of 0.15 log E.
Similar results are obtained when the 4-phenyl catechol developing
agent is replaced in the above procedure with 4-t-butyl catechol,
pyrogallol or
1-phenyl-3-(N-n-hexylcarboxamide)-4-[p-(.beta.-hydroquinolylethyl)-phenyla
zo]-5-pyrazolone.
EXAMPLE 2
As already indicated, replacing a carbon black containing
antihalation layer of the presensitized plates described herein
with the metal oxide reflecting layer results in improved
photographic speed while maintaining good resolution. Furthermore,
such pigments as barium sulfate cannot be substituted for the metal
oxide disclosed herein. To illustrate these features, a silver
chloride direct-positive emulsion is prepared as described in
example 1. The emulsion is coated on a series of gelatin layers as
described in the following table, which gelatin layers are coated
on polyethylene coated paper supports. The emulsion is coated at a
coverage of 72 milligrams of silver and 215 milligrams of gelatin
per square foot of polyethylene coated support. In each case, the
gelatin emulsion and the gelatin developer layers are hardened
using about 1 gram of formaldehyde per 100 grams of gelatin. The
emulsion is green sensitized by the addition of a merocyanine dye.
##SPC3##
Each of the above elements is exposed to a revolving power chart,
processed for 20 seconds at 85.degree. F. in an 8 percent potassium
phosphate solution containing 0.1 gram potassium bromide per liter
(pH 12), and stopped for 20 seconds in a 2 percent phosphoric acid
bath. The plate is put on a conventional lithographic printing
press, inked and several lithographic prints are made. The
following characteristics are noted.
Coating Relative Resolution No. Speed (Lines/mm.) Addenda
__________________________________________________________________________
1 33 7 Carbon 2 100 5 Zinc oxide 3 100 3 Barium sulfate 4 100 7
Titanium dioxide 5 100 3 None
In the above table, as well as in the following tables, the
relative speed indicated is a function of the exposure necessary to
give a density of 0.2 above background fog.
Resolution, as reported in the above and following tables is
measured in lines per millimeter (mm.) printed at the optimum
exposure level.
It is obvious from an inspection of the above table that the
presensitized printing plates of this invention exhibit excellent
resolution without the substantial loss in photographic speed which
results from the use of carbon black. Furthermore, the use of
pigments such as barium sulfate gives a plate having good speed but
very poor resolution.
EXAMPLE 3
As previously pointed out, the polyhydroxybenzene developing agents
can be included in the photographic emulsion layer of the printing
plates described herein and the metal oxide can be dispersed in
polyethylene coated over a support such as paper. To illustrate, a
direct-positive emulsion is prepared as described in example 1. A
dispersion of 4-phenyl catechol in tri-o-cresyl phosphate is added
directly to the emulsion which is coated on a paper fiber sheet
coated with polyethylene containing titanium dioxide having an
average particle size of about 2 microns. The metal oxide layer has
an average Reflectance at 420-500 millimicrons of about 85 percent,
and is coated at a coverage of about 3.4 grams of polyethylene and
0.34 gram of titanium dioxide per square foot of support. Two paper
supports have the polyethylene surfaces electron bombarded, as
described in British Pat. No. 975,108 to improve adhesion, and the
reversal emulsion is coated on the supports at the coverages
indicated in the following table. About 1 gram of formaldehyde per
100 grams of gelatin is added to the emulsion as a hardener just
prior to coating and the emulsion is green sensitized by the
addition of a merocyanine dye. A sample of each coating is
processed and used as a lithographic plate as described in example
2 to give the results indicated below. ##SPC4##
EXAMPLE 4
A positive-working presensitized plate using a photographic silver
halide emulsion layer which comprises a fogged emulsion coated over
an unfogged emulsion, as described in Yackel et al. U.S. Pat. No.
3,146,104 issued Aug. 25, 1964, together with the metal oxide
layers described herein has good photographic speed and resolution.
To illustrate, a direct-positive printing plate is prepared as
described in example 3 of the Yackel et al. patent. The layers are
coated on a support comprising a paper fiber sheet having a
polyethylene coated surface. The top layer comprises fogged
gelatino-silver chloride emulsion. The middle layer comprises an
unfogged gelatino-silver chloride emulsion green sensitized with a
merocyanine dye. The bottom layer comprises a gelatin layer
containing 4-phenyl catechol dispersed in tri-o-cresyl phosphate,
and titanium dioxide. In each case the gelatin layers are hardened
by the addition of approximately 1 gram of formaldehyde per 100
grams of gelatin. The layers are coated at the coverages indicated
in the following table. ##SPC5##
The elements are exposed, processed, inked and printed on a
lithographic press, as described in example 2, to give an image
resolution of 7 lines per millimeter. In contrast, similar coatings
in which the titanium dioxide is omitted have a resolution of only
3 lines per millimeter.
EXAMPLE 5
A negative-working presensitized plate which comprises a hardened
silver halide gelatin emulsion layer, as described in the Yackel et
al. patent together with the metal oxide layers described herein
has good photographic speed and resolution. To illustrate, a
negative-working printing plate is prepared as described in example
2 of the Yackel et al. patent. The layers are coated on a support
comprising a paper fiber sheet having a polyethylene coated
surface. The top layer comprises a gelatin silver chloride emulsion
green sensitized with a merocyanine dye. The bottom layer comprises
a gelatin layer containing 4-phenyl catechol dispersed in
tri-o-cresyl phosphate, and titanium dioxide. In each case the
gelatin layers are hardened by the addition of approximately 1 gram
of formaldehyde per 100 grams of gelatin. The layers are coated at
the coverages indicated in the following table. ##SPC6##
The elements are exposed, processed, inked and printed in a
lithographic press, as described in example 2, to give an image
resolution of 7 lines per millimeter. In contrast, similar coatings
in which the titanium dioxide is omitted have a resolution of only
3 lines per millimeter.
Image resolution and exposure latitude of the presensitized
printing plates of this invention are improved by the elimination
of excess developing agent. This is accomplished by developing the
printing plate in face-to-face contact with a web such as a
hardened gelatin pad, a fogged silver halide emulsion layer or
polyethylene-coated paper. The following example will illustrate
this feature.
EXAMPLE 6
A. A photographic element of the type described in example 4 above
is exposed in a process camera to a line and halftone original,
processed in an 8 percent K.sub.3 PO.sub.4 activator at 85.degree.
F. with agitation for 20 seconds followed by a 20-second immersion
in a 2 percent phosphoric acid stop bath and then squeegeed.
B. A photographic element of the type described in example 4 above
is exposed in a process camera to a line and halftone original,
processed in an 8 percent K.sub.3 PO.sub.4 activator at 85.degree.
F. for 5 seconds and then brought into face-to-face contact with a
hardened gelatin layer coated on a paper support. The two sheets
are held into contact for 30 seconds and then separated. The
processed element is then immersed for 20 seconds in a 2 percent
phosphoric acid stop bath and squeegeed.
C. A photographic element of the type described in example 4 above
is processed in the same manner as in B. with the exception of
bringing the element into face-to-face contact with a hardened
fogged silver halide gelatin emulsion layer coated on a paper
support.
The above plates are inked and printed on a lithographic press. The
prints made from plates B and C produce a much better reproduction
of the halftone picture and the fine line subject matter than the
prints made from plate A.
When the photographic elements of example 6 are exposed in a
process camera, the image formed is wrong-reading, which
necessitates the use of a prism or mirror system in order to give
right-reading prints. Such prisms or mirror systems, however,
affect the optical properties of the camera and lower the image
quality. A way to achieve right-reading lithographic prints using a
process camera without an image-reversing device is to use the
gelatin-coated support from part B. above as a lithographic plate.
When the photographic element of part B. above is brought into
face-to-face contact with the hardened gelatin layer coated on a
paper support, oxidized developing agent is transferred imagewise
to the gelatin-coated layer and forms a hydrophobic image which is
a mirror image of the photographic element. When the gelatin-coated
sheet is immersed in a phosphoric acid stop bath, squeegeed, inked
and printed on a lithographic press, right-reading prints are
obtained which are similar in quality to the prints obtained from
the photographic element.
Thus, by the practice of this invention there is provided a means
for obtaining a presensitized printing plate having good exposure
latitude, photographic speed and resolution characteristics.
Furthermore, the use of metal oxides rather than carbon black in
antihalation layers of the presensitized printing plates of this
invention gives comparable exposure latitude and resolution without
the speed loss encountered when carbon black is used. In addition,
the use of a metal oxide such as titanium dioxide or zinc oxide in
the antihalation layer rather than carbon black gives a
presensitized plate having a white background which makes it easy
to inspect the dark image after processing. In contrast, the use of
carbon black in an antihalation layer gives a dark background which
makes it difficult to inspect the dark image.
Although the invention has been described in considerable detail
with reference to certain preferred embodiments thereof, it will be
understood that variations and modifications can be effected
without departing from the spirit and scope of the invention as
described hereinabove and as defined in the appended claims.
* * * * *