U.S. patent number 3,719,490 [Application Number 04/653,025] was granted by the patent office on 1973-03-06 for photosensitive element containing a photoreducible palladium compound and the use thereof in physical development.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to Henry J. Gysling, Joseph S. Yudelson.
United States Patent |
3,719,490 |
Yudelson , et al. |
March 6, 1973 |
PHOTOSENSITIVE ELEMENT CONTAINING A PHOTOREDUCIBLE PALLADIUM
COMPOUND AND THE USE THEREOF IN PHYSICAL DEVELOPMENT
Abstract
Light-sensitive palladium compounds are reduced on exposure to
actinic light to nuclei which are catalytic centers for the
deposition of metal from a physical developer. The palladium nuclei
are catalysts for deposition of metal from stable physical
developers, which developers do not respond to catalysts used in
the physical development of silver latent images.
Inventors: |
Yudelson; Joseph S. (Rochester,
NY), Gysling; Henry J. (Bronx, NY) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
24619184 |
Appl.
No.: |
04/653,025 |
Filed: |
July 13, 1967 |
Current U.S.
Class: |
430/202; 430/417;
430/495.1 |
Current CPC
Class: |
G03C
8/04 (20130101); G03C 1/04 (20130101); C08F
8/14 (20130101); G03C 1/50 (20130101) |
Current International
Class: |
C08F
8/14 (20060101); C08F 8/00 (20060101); G03C
1/04 (20060101); G03C 1/50 (20060101); G03C
8/04 (20060101); G03C 8/02 (20060101); G03c
005/24 (); G03c 001/00 () |
Field of
Search: |
;96/88,48,48PD,90
;117/34 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Brown; J. Travis
Assistant Examiner: Louis, Jr.; Won H.
Claims
We claim:
1. A photosensitive element comprising a support and a
light-sensitive compound which on exposure to actinic light forms
catalytic centers for the deposition of metal from a physical
developer, said compound having the formula [Pd(L).sub.x ].sub.y
Mz, wherein
L is a ligand, selected from the group consisting of
halogen ligands,
carboxylic acid ligands,
aromatic ligands,
nitrogen ligands,
phosphorous ligands,
arsenic ligands, and
antimony ligands;
M is selected from the group consisting of ions selected from the
group consisting of
hydrogen ions,
inorganic acid ions,
organic acid ions,
metal ions selected from the group consisting of sodium ions,
potassium ions, calcium ions, strontium ions, and aluminum ions,
and
onium ions, and [Pd(L).sub.x ] groups;
x is an integer from 0 through 4;
y is an integer from 1 through 4;
z is an integer from 0 through 2;
and x and z are not 0 at the same time.
2. A photosensitive element as defined in claim 1, wherein at least
a part of the support is porous and the light-sensitive palladium
compound is imbibed therein.
3. A photosensitive element as defined in claim 1, wherein the
light-sensitive palladium compound is coated on the support in a
hydrophilic binder.
4. A photosensitive element as defined in claim 1, wherein the
light-sensitive palladium compound is selected from the group
consisting of potassium palladium oxalate, palladium oxalate,
palladium tetrammine chloride, palladium tetrammine bromide, and
potassium palladous chloride.
5. A photosensitive element comprising a support and a
light-sensitive composition comprising potassium palladium
oxalate.
6. A method of producing photographic images comprising the steps
of
1. imagewise exposing to actinic light a photosensitive element
comprising a support and a light-sensitive palladium compound,
wherein the light-sensitive palladium compound has the formula
[Pd(L).sub.x ].sub.y Mz, wherein
L is a ligand, selected from the group consisting of
halogen ligands,
carboxylic acid ligands,
aromatic ligands,
nitrogen ligands,
phosphorous ligands,
arsenic ligands, and
antimony ligands;
M is selected from the group consisting of ions selected from the
group consisting of
hydrogen ions,
inorganic acid ions,
organic acid ions,
metal ions selected from the group consisting of sodium ions,
potassium ions, calcium ions, strontium ions, and aluminum ions,
and [Pd(L).sub.x ] groups;
x is an integer from 0 through 4;
y is an integer from 1 through 4;
z is an integer from 0 through 2;
and x and z are not 0 at the same time, and
2. developing the latent image thus formed with a physical
developer comprising a reducible heavy metal salt selected from the
group consisting of nicket salts, cobalt salts, iron salts,
chromium salts, copper salts, and mixtures thereof, a complexing
agent for heavy metal ions from said salt and a reducing agent for
heavy metal ions from said salt.
7. A method of producing photographic images as defined in claim 6,
further comprising the step of washing the element between exposure
and development to remove unexposed palladium compound.
8. A method of producing photographic images as defined in claim 6,
wherein development is accomplished by immersing the exposed
element in a bath of the physical developer.
9. A method of producing photographic images as defined in claim 6,
wherein development is accomplished by contacting the exposed
element with a receiving sheet containing the physical developer
and heating the element to cause migration of unexposed
light-sensitive palladium compound from the element to the
receiving sheet, where it is reduced and developed.
Description
This invention relates to photographic elements and processes. In a
particular aspect it relates to processes and elements for the
physical development of non-silver latent images.
Physical development of photographic images concerns the
amplification of a latent image by the deposition of metal from a
developer bath comprising a metal salt or complex and a reducing
agent. The bath is formulated so that it is stable under conditions
of storage, but in the presence of a catalyst, such as the latent
image, it decomposes and deposits reduced metal on catalytic sites.
Once a catalytic site is enveloped with metal deposited from the
bath it is essential that the reduced metal be autocatalytic, that
is, it too must catalyze the decomposition of the bath.
Physical development involving silver compounds is well known.
However, such processes have not had any substantial application
due to the fact that silver physical developer solutions are
extremely unstable. Thus, shortly after a physical developer bath
is prepared by mixing silver salts and reducing agents, reduced
silver begins to deposit rapidly, so that in a few hours the bath
is completely decomposed and is useless. This type of instability
is inherent in silver physical developer baths because of the
autocatalytic properties of silver metal.
Physical developer baths which are stable under storage conditions
can be formulated from salts or complexes of some metals other than
silver; however, these stable physical developer baths do not
respond to the catalysts which are commonly used in silver physical
development, such as colloidal silver, zinc sulfide, nickel
sulfide, etc.
Therefore, it is an object of this invention to provide new and
improved photographic elements and processes.
It is a further object of this invention to provide novel
photographic processes wherein photographic images are developed
with relatively stable physical developers.
It is a still further object of this invention to provide novel
processes where the only steps necessary to produce stable
photographic images are exposure and physical development.
It is another object of this invention to provide novel elements
which can be used in physical development processes.
The above and other objects of this invention will become apparent
to those skilled in the art from the further discussion of the
invention which follows.
In accordance with the present invention there is provided a
photographic element containing a light-sensitive palladium
compound which on exposure to actinic light forms catalytic centers
or sites for the deposition of metal from a physical developer.
Catalytic centers or sites are formed by photoreduction of the
palladium compound to elemental palladium, or to a compound which
is readily reduced to elemental palladium. After exposure the
element can be washed to remove unexposed palladium compound, or in
some embodiments this washing is not required. The element is then
contacted with a physical developer comprising a heavy metal salt,
a complexing agent for the metal salt and a reducing agent. In a
preferred embodiment the palladium nuclei formed by exposure act as
catalytic centers or sites for the deposition of metal from a bath
of the physical developer. They constitute a latent image which is
formed by exposure and which is developed and given density by
building up a deposit of metal thereon from the physical developer
bath. In another embodiment the element is contacted with a
receiving sheet containing the physical developer and the unexposed
palladium compound migrates to the receiving sheet where it is
reduced and developed.
A wide variety of light-sensitive palladium compounds such as salts
and complexes of palladium are useful in the elements of this
invention. Light-sensitive palladium compounds which are useful in
the practice of the present invention include those having the
general formula:
[Pd(L).sub.x ].sub.y M.sub.z (I)
where L is a ligand such as a halogen ligand such as bromine,
chlorine, or iodine, a carboxylic acid ligand such as a malonate
group, an oxalate group, etc., and aromatic ligand such as phenol,
styrene, naphthol, etc., a nitrogen ligand such as ammonia, an
amine such as methyl amine, ethyl amine, benzyl amine, propane
diamine, tetraethylene pentamine, aminoethanol, methylaminoethanol,
aminonaphthol, bipyridine, phenanthroline, ethylene
diaminetetraacetic acid, etc., a nitrile such as nitrilotriethanol,
benzonitrile, etc., an imine such as iminodiethanol, an oxime such
as salicylaldoxime or an azide such as benzhydrazide, a phosphorous
ligand such as triarylphosphine, trialkylphosphine, etc., an
arsenic ligand such as triarylarsine, trialkylarsine, etc., an
antimony ligand such as triarylantimony, trialkylantimony, etc.,
and the like; M is an ion such as a hydrogen ion, an inorganic acid
ion such as a chloride ion, a bromide ion, an iodide ion, a sulfate
ion, a nitrate ion, a phosphate ion, etc., an organic acid ion such
as an acetate ion, an acrylate ion, an ion, a malonate ion, etc., a
metal ion such as a sodium ion, a potassium ion, a calcium ion, a
strontium ion, an aluminum ion, etc., an onium ion such as those
containing nitrogen, phosphorus or sulfur like a quaternary
ammonium ion, a quaternary phosphonium ion, a tertiary sulfonium
ion, etc., and the like, or M can be a [Pd(L).sub.x ] group; x is
an integer from 0 through 4; y is an integer from 1 through 4; z is
an integer from 0 through 2, and x and z are not 0 at the same
time.
Light-sensitive compounds of Formula (I) which are useful in the
present invention include: palladium diammine dichloride, palladium
styrene dichloride, palladium di(tributylphosphine) dichloride,
palladium di(benzonitrile) dichloride, palladium
di(triphenylphosphine) dichloride, palladium di(triphenylarsine)
dichloride, palladium di(triphenylantimony) dichloride, palladium
di(1-naphthol) dichloride, palladium di( 2-naphthol) dichloride,
palladium di( 5-amino-1-naphthol) dichloride, palladium
di(benzylamine) dichloride, palladium o-phenylene-diamine
dichloride, palladium 1,10-phenanthroline dichloride, palladium
2,2'-bipyridine dichloride, palladium di(benzyhydrazide)
dichloride, palladium salicylaldoxime dichloride, palladium
di-(N-phenyl-2-naphthylamine) dichloride, and potassium palladous
chloride.
Certain palladium salts and complexes are preferred because they
are not readily reduced by the reducing agent in the physical
developer bath. Therefore, with these preferred compounds unexposed
palladium compound need not be removed from the element between
exposure and development. Use of these preferred compounds permit
reduction in the number of processing steps and greater efficiency
of operation since non-fogged images can be obtained without
washing between development and exposure.
Compounds of Formula I useful in the present invention which are
not readily reduced by the reducing agents of the present invention
include: palladium tetrammine di(tetraphenylboride), palladium
ethylenediamine dichloride, palladium di(1,3-propanediamine)
dichloride, palladium tetra(methylamine) dichloride, palladium
triethylenetetramine dichloride, palladium
tetra-(tetraethylenepentamine) dichloride, palladium
tetra(2-diethylaminoethanol) dichloride, palladium
tetra(2-aminoethanol) dichloride, palladium tetra(
2-methylaminoethanol) dichloride, palladium
tetra(nitrilotriethanol) dichloride, palladium tetra(
2,2'-iminodiethanol) dichloride, palladium
tetra(triphenylphosphine) dichloride, palladium tetrammine
dichloride, palladium tetrammine dibromide, palladium diammine
oxalate, palladium triphenylarsine oxalate, palladium
di(triphenylantimony) oxalate, palladium 2,2'-bipyridine oxalate,
palladium 1,10-phenanthroline oxalate, palladium oxalate, potassium
palladium oxalate, potassium palladium malonate, palladium
tetrammine palladium dioxalate and palladium tetrammine palladium
tetrachloride.
Light-sensitive palladium compounds useful in the practice of the
present invention can be prepared by techniques known to those
skilled in the art. Preparation of some of the palladium compounds
useful in the present invention are shown in Examples 1, 3 and 6.
Preparative methods for other palladium compounds can be found in
such works as Encyclopedia of Chemical Reactions, C.A. Jacobson;
Reinhold Publishing Corp. N.Y.; Vol. V, 1953, pp. 301-321; and
Tretise on Inorganic and Theoretical Chemistry, G.W. Mellor;
Longmans Green & Co., N.Y., Vol. XV, 1936, pp. 654-685.
The physical developer which is used to produce a visible image can
comprise an aqueous bath in which is dissolved a salt of a heavy
metal, a complexing agent for the metal ion, and reducing agent.
The physical developer bath is chosen so that deposition of the
heavy metal from the bath is catalyzed by palladium nuclei produced
on exposure. The heavy metal deposited from the bath must itself be
autocatalytic; that is, it must act as a catalyst for further
deposition of metal from the developer. This is necessary in order
that deposition and development will continue after palladium
nuclei are enveloped with heavy metal. With respect to the Periodic
Table, suitable heavy metals can be selected from Group VIII metals
such as nickel, cobalt, iron, palladium and platinum, Group VIB
metals such as chromium and Group IB metals such as copper, silver
and gold. Almost any heavy metal salt which is a source of the
desired heavy metal ions can be employed. Suitable heavy metal
salts useful in the invention include heavy metal halides such as
cobaltous bromide, cobaltous chloride, cobaltous iodide, ferrous
bromide, ferrous chloride, chromium bromide, chromium chloride,
chromium iodide, copper chloride, silver bromide, silver chloride,
silver iodide, gold chloride, palladium chloride and platinum
chloride, heavy metal sulfates such as nickel sulfate, ferrous
sulfate, cobaltous sulfate, chromium sulfate, copper sulfate,
palladium sulfate and platinum sulfate, heavy metal nitrates such
as nickel nitrate, ferrous nitrate, cobaltous nitrate, chromium
nitrate and copper nitrate, and heavy metal salts of organic acids
such as ferrous acetate, cobaltous acetate, chromium acetate and
copper formate. Baths can be formulated based on a single heavy
metal or based on mixtures of heavy metals. When more than one
heavy metal is employed in the bath, the image which is deposited
will generally be an alloy of the two metals. Physical developers
based on noble metals such as silver, gold and platinum are
relatively unstable and cannot be stored for long periods of time.
However, such physical developers are operative in the processes of
this invention and can be employed if the developer bath is
prepared shortly before use.
The complexing agent employed in the physical developer bath should
tie up the metal ions so that they show a lessened tendency to be
reduced spontaneously. However, the complexing agent should not
bind the metal ions so tightly that they will be unable to be
reduced and deposited on the latent image sites in the presence of
the catalyst. Suitable complexing agents include ammonium salts
such as ammonium chloride, organic acids such as aspartic acid,
malic acid, citric acid, glycolic acid, salts of organic acids such
as sodium citrate, potassium citrate, sodium glycolate, potassium
glycolate, sodium succinate, potassium succinate, potassium sodium
tartrate, etc. A single complexing agent can be used or a
combination of more than one complexing agent can be incorporated
in the physical developer bath.
The reducing agent can be any compound which provides a ready
source of electrons for the reduction of the metal ions and which
does not otherwise interfer with development. A general criteria
for a reducing agent useful in the physical developers of the
present invention is that the potential of the chemical couple of
the reducing agent, written as follows:
Reducing agent .revreaction. Products + electrons
must be more positive than that for the metal or metals which are
to be deposited from the bath. For example, the potential for the
nickel couple:
Ni.degree. .revreaction. Ni.sup.+.sup.+ + 2 electrons
is +0.277 volts for acidic solutions. It is necessary for the
reducing agent to possess a potential that is greater, i.e., more
positive, than +0.277 volts in order that it be capable of reducing
nickel ions in the bath. Suitable reducing agents include
hypophosphites such as sodium hypophosphite, manganous
hypophosphite, potassium hypophosphite, etc., hydrosulfites such as
sodium hydrosulfite, potassium hydrosulfite, calcium hydrosulfite,
etc., borohydrides such as sodium borohydride, potassium
borohydride, etc., hydrazines, and the like.
There can be added to the physical developer bath a variety of
other materials such as buffering agents, acid or base to adjust
the pH, preservatives, etc. in accordance with usual practices.
The proportions in which the various components of the physical
developer are present in the bath can vary over a wide range.
Suitable concentrations of metal salt in the developer bath are in
the range of from about 0.01 to about 0.5 moles of metal salt per
liter of bath. The upper limit of concentration is controlled by
the solubility of the particular metal salt employed. Preferably,
the bath is between about 0.05 molar and 0.25 molar with respect to
metal salt. The relative proportions of metal salt and complexing
agent are dependent upon the particular metal salt or salts and the
particular complexing agent or agents which are employed. As a
general rule sufficient complexing agent should be incorporated to
bind the metal ions and lessen the tendency of the metal ions to be
reduced prior to use of the developer. Depending upon the
particular metal salt and complexing agent employed, the amount of
complexing agent present can vary from about 4 mole to about 10
moles of complexing agent per mole of metal salt present. The
reducing agent can be present in amounts of from about 0.1 moles to
about 5 moles of reducing agent per mole of metal salt present.
In preparing photosensitive elements utilizing the palladium
compounds of this invention, the palladium compound can be imbibed
in or coated on a support, or it can be incorporated in a
self-supporting binder.
When the palladium compound is imbibed in a support, an aqueous
solution of the compound is prepared and a porous support is
immersed in the solution. After drying a photosensitive element is
obtained.
Suitable porous supports include paper, coated paper, porcelain,
polymeric films, such as are described hereinafter, on which is
coated such porous materials as gelatin, olefinic polymers such as
polyvinyl alcohols, polyvinyl phthalates, etc., carboxyl containing
polymers such as carboxymethyl cellulose, cellulose ether
phthalates, cellulose ether succinates, cellulose ether maleates,
copolymers of alkyl acrylates with acrylic acid, etc., and the
like.
The amount of palladium compound that is taken up in the support
generally varies from about 2 to about 25 mg. of
palladium/ft..sup.2 The amount which is absorbed by a polymer
coating on film base is dependent on the nature and coverage of the
polymer, the degree to which it has been crosslinked, the
temperature of the imbibing bath, and the pH of the bath. Coverages
as low as 2 mg. of palladium/ft.sup.2 are adequate when using
development conditions described herein. The photographic speed
will increase with increasing concentration of the light-sensitive
palladium compound. The preferred coverage is generally in the
range of 10 to 25 mg. of palladium/ft..sup.2
When the palladium compound is coated on a support, it is generally
coated with a hydrophilic binder. A solution or dispersion of the
palladium compound and binder is formulated, and after thorough
mixing it is coated on the support by any well-known coating
process such as hopper coating, doctor-blade coating, dip coating,
swirl coating, spray coating, etc.
Suitable binders in which the palladium compounds of the present
invention can be incorporated include gelatin such as bone gelatin,
pigskin gelatin, etc.; olefinic polymers such as polyvinyl alcohol,
polyvinyl phthalates, etc., carboxyl containing polymers such as
carboxymethyl cellulose, cellulose ether phthalates, cellulose
ether succinates, cellulose ether maleates, copolymers of alkyl
acrylates with acrylic acid, etc., and the like. Non-hydrophilic
polymers such as ethyl cellulose can be used in procedures which do
not involve imbibition and where the coating composition is a
stable dispersion which gives a porous coating upon drying. Such a
coating is described in Example 8.
The palladium compound-binder composition can be coated from
aqueous solution, or it can be coated from an organic solvent. In
some instances, where an organic solvent is employed, the palladium
compound-binder composition will form a water-in-oil type
dispersion with the organic solvent. Suitable solvents include
water immissible hydrocarbon solvents such as benzene, toluene,
etc.; halogenated hydrocarbons such as methylene chloride, ethylene
chloride, carbon tetrachloride, etc.; and the like. Mixtures of
such solvents can be employed advantageously in the practice of
this invention.
In preparing the coating compositions utilizing the palladium
compounds disclosed herein useful elements are obtained where
palladium is present in an amount equal to at least about 0.5
weight percent of the coating composition. The upper limit in the
amount of palladium present can be varied widely. When a binder is
employed, palladium is normally present in an amount from about 0.5
weight percent of the coating composition to about 20 weight
percent of the coating composition. A preferred weight range for
palladium in the coating composition is from about 1 weight percent
to about 10 weight percent.
Coating thicknesses of the palladium compound-binder compositions
on a support can vary widely. Normally, a wet coating thickness in
the range of about 0.001 inch to about 0.01 inch is useful in the
practice of the invention. A preferred range of coating thickness
is from about 0.002 inch to about 0.007 inch before drying,
although such thicknesses can vary depending upon the particular
application contemplated for the element.
Suitable supports for coating the palladium compound-binder
compositions of the present invention include paper,
polyethylene-coated paper, glassine, vegetable parchment, polymeric
films such as polystyrene film, cellulose nitrate film, cellulose
acetate film, cellulose acetate-butyrate film, cellulose
acetate-propionate film, polyethylene-terephthalate film,
polyethylene-sebacate film, polyethylene-adipate film, etc., and
the like. In some embodiments of this invention, a separate support
need not be utilized, the binder acting as the support
material.
Elements prepared according to the present invention can be exposed
by techniques well known to those skilled in the art of
photography. Since the compounds of this invention exhibit their
greatest sensitivity in the blue and near ultraviolet regions,
light sources rich in such radiation are preferably employed.
Exposure to actinic light causes the reduction of the palladium
compound to nuclei of elemental palladium which act as catalytic
centers or sites for the deposition of metal from the physical
developer. Depending upon the light source and the particular
palladium compounds, exposure times of from several seconds to
several minutes give satisfactory latent images.
Development of exposed elements can be effected by contacting the
element with a physical developer bath, for example by immersion,
for a period of time sufficient to produce an image of the desired
density. The time required to deposit a satisfactory heavy metal
image from the physical developer bath on the element can vary from
1 second to several hours depending upon the composition of the
particular bath being employed, the density of heavy metal image
desired, and the temperature of the bath. Satisfactory images can
be produced from baths at room temperature (20.degree. C.) or at
elevated temperatures. Bath temperature of from 20.degree. C. to
100.degree. C. are preferred.
Development can also be effected using a diffusion transfer
process. In such a process the photosensitive element is exposed in
the usual manner and is then contacted with a receiving sheet into
which has been imbibed one of the physical developer solutions
described above. When the element and the receiving sheet are in
contact, heat is applied to promote diffusion of unexposed
palladium compound from the element to the receiving sheet. Contact
temperatures of from 45.degree. C. to 100.degree. C. are suitable.
In the unexposed areas of the element the palladium compound
migrates from the element to the receiving sheet where it is
reduced and catalyzes the reduction of heavy metal salt in the
sheet to form a positive image on the receiving sheet. In the
exposed areas the palladium compound does not migrate as rapidly
because of the smaller differential in concentration of palladium
compound between the exposed areas of the element and the receiving
sheet which results from the formation of palladium nuclei on
exposure and the reduction of palladium compound in the vicinity of
these nuclei. Thus, the difference in concentration of the
palladium compound in exposed and unexposed areas of the element
permits the transfer of sufficient palladium compound to the
receiving sheet from unexposed areas of the element before a
significant amount of palladium compound has been transferred from
exposed areas of the element. Although the image formed on the
receiving sheet can be used as such, in some instances it is
preferred that the image be darkened further by immersing the
receiving sheet in one of the physical developer baths described
herein.
The physical developer solutions which are imbibed into the
receiving sheet differ somewhat from the physical developer baths
used for immersion development in that they contain a greater
proportion of heavy metal salt and reducing agent and a lesser
proportion of complexing agent. The additional reducing agent is
required to effect reduction of the unexposed palladium compound.
The ratio of reducing agent to metal salt can be the same as
described above, although ratios of from about 1 to about 5 moles
of reducing agent per mole of metal salt are preferred. The ratio
of complexing agent to metal salt is lower than the range indicated
above. Ratios of complexing agent to heavy metal salt of from about
0.5 moles to about 2.0 moles of complexing agent per mole of heavy
metal salt are preferred. As in the case of the baths discussed
above, these ratios will vary depending upon the particular metal
salt and complexing agent employed.
The photosensitive compositions and elements of this invention find
use in a wide variety of applications. Elements containing the
photosensitive palladium compounds of this invention can be exposed
to actinic radiation through a subject to be copied such as a
transparency, and can then be developed with an appropriate
physical developer bath. In this manner the processes and elements
of this invention can be used to produce positive or negative
copies from originals and continuous tone and line negatives for a
variety of use for which systems based on silver are employed.
Properties of certain of the heavy metal images can be utilized for
specialized applications. For example, ink receptive metals can be
used to produce lithographic printing masters, electrical
conducting metals can be used to prepare printed circuits, and
magnetic metals can be used to prepare magnetic images or
records.
The ink receptive properties of the heavy metal deposited from the
physical developer bath can be employed advantageously to make
lithographic plates. Elements used to prepare such lithographic
plates and masters require that the support and binder used be
hydrophilic. Thus, after exposure and development, the heavy metal
image areas will readily receive ink while in background areas,
where heavy metal has not been deposited, ink will be repelled by
the hydrophilic support or binder. These elements should be
developed for a period of time sufficient to deposit from the
developer bath enough heavy metal to mask the hydrophilic
properties of the substrate in image areas. While the density of
heavy metal required will vary depending upon the particular
substrate and heavy metal employed, and the conditions under which
it has been deposited, a heavy metal image density of about 1
gram/square foot or greater is generally sufficient to mask the
hydrophilic properties of the substrate.
The electrical conductive properties of images of such heavy metals
as copper, iron, nickel, etc., can be employed to produce printed
circuits using the elements and process of this invention. For such
applications, the supports and binders used should be
non-conductive.
The invention is further illustrated by the following examples
which include preferred embodiments thereof.
EXAMPLE 1
Four grams of potassium chloride were dissolved in 150 ml of water
and 2.5 gm. of palladium chloride (PdCl.sub.2) were added to this
solution. The mixture was stirred until all of the palladium
chloride was dissolved. The solution was evaporated on a steam bath
to a volume of 50 ml. and cooled in an ice bath. The resulting
crystals were washed twice with cold water, then washed with
ethanol and then ether. They were dried at room temperature. The
yield of potassium palladous chloride (K.sub.2 PdCl.sub.4) was
approximately 75 percent based on the palladium chloride. A strip
of water-leaf paper stock was impregnated with a dilute (one-half
percent) solution of potassium palladous chloride. After drying,
the impregnated strip was exposed to a 350 watt mercury arc at a
distance of 14-inches for one minute. The strip was then washed for
several minutes in running water to remove unexposed palladium
compound. It was then immersed in the following cobalt-type
physical developer at 80.degree. C.
cobaltous chloride -- CoCl.sub.2.sup.. 6H.sub.2 O 7.5 g. Aspartic
acid -- HOCOCHNH.sub.2 CH.sub.2 COOH 20.0 g. Sodium hypophosphite
-- NaH.sub.2 PO.sub.2.sup.. H.sub.2 O 7.5 g. Water to make 1
liter
After a one-minute immersion, the exposed areas of the strip had a
density of 0.8 and the unexposed areas remained essentially
unchanged.
EXAMPLE 2
A strip of paper stock was prepared, exposed and washed as in
Example 1. The strip was then immersed into a physical developer
containing nickel ions as the source of heavy metal ions and sodium
hypophosphite as the reducing agent (sold as "Enplate NI-410" by
Enthone, Inc., New Haven, Connecticut.). After three seconds'
immersion at 90.degree. C. the exposed portion of the strip
developed to a density of from 0.6 to 1.0 and the unexposed area
remained essentially unchanged.
EXAMPLE 3
Palladium tetrammine chloride (Pd(NH.sub.3).sub.4 Cl.sub.2) was
prepared by dissolving palladous chloride in concentrated ammonium
hydroxide, then lowering the pH of the solution to 6.0 with
hydrochloric acid. A paper strip was impregnated with a dilute
solution (0.5 percent) of this complex and dried. After drying, the
strip was exposed as described in Example 1. The strip was
developed by immersion for two seconds in the following nickel-type
physical developer at 90.degree. C.
nickel chloride -- NiCl.sub.2.sup.. 6H.sub.2 O 30 g. Sodium
hypophosphite -- NaH.sub.2 PO.sub.2.sup.. H.sub.2 O 10 g. Ammonium
chloride 50 g.
Water was added to make one liter of solution and the pH was
adjusted to 9.0 with ammonium hydroxide. The exposed areas of the
strip developed to a density of 1.5 whereas the unexposed area
remained unchanged.
EXAMPLE 4
A paper strip was impregnated with palladium tetrammine chloride as
in Example 3 and dried. The strip was exposed with a mercury arc as
described in Example 1, and was developed by immersion for five
seconds in the following iron-type physical developer at 75.degree.
C.
ferrous sulfate -- FeSO.sub.4.sup.. 7H.sub.2 O 30 g. Rochelle salt
(KNa Tartrate) 50 g. Sodium hypophosphite -- NaH.sub.2
PO.sub.2.sup.. H.sub.2 O 10 g.
Water was added to make one liter of solution and the pH was
adjusted to 9.1 with concentrated ammonium hydroxide. The exposed
areas of the strip developed to a density of 0.5 whereas the
unexposed area remained essentially unchanged.
EXAMPLE 5
A paper strip was impregnated with potassium palladous chloride as
in Example 1 and dried. The strip was exposed to a mercury arc as
described in Example 1. The exposed strip was then washed for
several minutes in running water to remove unreacted palladium
compound. It was then developed by immersion in the following
chromium-type physical developer for 20 seconds at 99.degree.
C.
chromium acetate -- CrAc.sub.3 30 g. Sodium acetate -- NaAc.sup..
3H.sub.2 O 20 g. Sodium glycolate 40 g. Sodium citrate .sup.. 5-1/2
H.sub.2 O 40 g. Sodium hypophosphite .sup.. H.sub.2 O 10 g.
Water was added to make one liter of solution. The pH of the
solution was 5.7. After development the exposed area of the strip
had a density of 0.8.
EXAMPLE 6
Potassium palladium oxalate (K.sub.2 PdOx.sub.2) was prepared as
follows. Two grams of potassium palladous chloride were dissolved
in 20 ml. of water. Another solution was prepared consisting of 10
grams of potassium oxalate (K.sub.2 Ox.sup.. H.sub.2 O) in 40 ml.
of water. The two solutions were mixed together and stirred for 10
minutes at room temperature. The precipitate which formed was
filtered and washed with ethanol until the filtrate was free of
chloride ion. It was then washed briefly with ethyl ether and dried
at room temperature. The yield of potassium palladium oxalate was
approximately 60 percent based on potassium palladous chloride. Two
paper strips were impregnated with a dilute solution (0.5 percent)
of this complex and dried. One of the strips was then exposed
behind a negative to a 350 watt mercury arc at 14-inches distance
for one minute. The second strip was exposed through a line copy
negative to a 250 watt photo-flood lamp (GE No. 2) at 12-inches
distance for one minute. Both samples were developed by immersion
for five minutes in the following nickel-type physical developer at
60.degree. C.
nickel sulfate -- NiSO.sub.4.sup.. 6H.sub.2 O 23.7 g. Sodium
hypophosphite -- NaH.sub.2 PO.sub.2.sup.. H.sub.2 O 23.9 g. Malic
acid (DL) -- HOCOCHOHCH.sub.2 COOH 48.2 g. Sodium succinate --
(CH.sub.2 COO).sub.2 Na.sub.2.sup.. 6H.sub.2 O 16.2 g.
Water was added to make one liter of solution. The pH of the
solution was 6.0. The exposed areas of both strips showed densities
above 1.0. The unexposed areas had densities less then 0.01.
EXAMPLE 7
The following solution was prepared:
Poly(vinyl alcohol) (sold as "71-30" by E.I. DuPont De Nemours
& Co.), 5 percent aqueous solution 10 g.
Palladium tetrammine chloride (0.5 percent solution) 10 ml.
Boric acid (1 percent solution) 1 ml.
The above solution was coated on a poly(vinyl alcohol) subbed
polyester film base using an 0.005 inch coating knife. After drying
it was exposed behind a negative to a 350 watt mercury arc at a
distance of 14 inches for one minute. It was developed by immersion
for 15 seconds in the cobalt-type physical developing bath
described in Example 1. The exposed area of the film strip had a
density of over 1.0 whereas the unexposed area remained
transparent.
EXAMPLE 8
Ten ml. of the coating solution described in Example 7 was
dispersed in 20 ml. of a 3.5 percent solution of ethyl cellulose
(sold as "T-10," by the Hercules Chemical Co.) in toluene by means
of a blender. A stable water-in-oil dispersion was obtained. A
coating of the dispersion was made on paper using a 0.005 inch
knife and dried. The coated element thus obtained was exposed and
developed as in Example 7. The exposed area of the strip had a
density exceeding 1.0 whereas the unexposed area had a density of
less than 0.01.
EXAMPLE 9
A strip of poly(ethylene terephthalate) support coated with gelatin
at a coverage of 350 mg. of gelatin/ft.sup.2 was immersed into a
0.5 percent solution of potassium palladium oxalate (K.sub.2
PdOx.sub.2) whose pH had been lowered to 2.0 by the addition of
p-toluenesulfonic acid. After 10 minutes immersion, the film was
wiped, dried, and exposed for 30 seconds through a line copy
negative to an exposure unit drawing 1000 watts distributed among a
small fan and 28 tungsten bulbs. The bulbs are 2-1/2 inches from
the negative during exposure. The film was then developed for 3
seconds in the nickel-type physical developer of Example 3. The
areas of film which had been exposed to light developed to a
density greater than 2, whereas the unexposed areas of the film
remained clear, thus resulting in a good quality positive copy of
the original negative. A sample of the film which had been imbibed
with a potassium palladium oxalate solution whose pH had not been
lowered required a 2-1/2 minute exposure in order to obtain a good
image using the same development procedure.
EXAMPLE 10
A strip of paper was immersed into a 0.5 percent solution of
potassium palladium oxalate whose pH had been lowered to 2.8 by the
addition of oxalic acid. After 10 minutes immersion, the paper was
dried and exposed for 7 seconds through a line copy negative to the
exposure unit described in Example 9. It was then developed for 3
seconds in the nickel physical developer of Example 3. A good
quality positive print was obtained. A sample of the film which had
been imbibed with a potassium palladium oxalate solution whose pH
had not been lowered from its original value (5.8) required an
exposure of 30 seconds in order to obtain a good image using the
development conditions described above.
EXAMPLE 11
A paper strip was impregnated with palladium tetrammine chloride
and dried. It was exposed as described in Example 7 and developed
for 1 minute at 25.degree. C. in a physical developer containing
copper ions and a reducing agent (sold as "Enplate CU-400" by
Enthone, Inc.) The exposed areas of the strip had a dark image
whereas the unexposed areas had a very faint image.
EXAMPLE 12
A strip of polyethylene terephthalate support coated with gelatin
at a coverage of 350 mg. of gelatin/ft.sup.2 was immersed into a
0.5 percent solution of potassium palladium oxalate whose pH had
been adjusted to 2.8 by means of oxalic acid. After 10 minutes
immersion the coating was wiped, dried, and exposed through a line
copy negative to a fluorescent light source [8-watt black light
tube (GE)] for 30 seconds at a distance of 2 inches. Next, a sheet
of baryta paper was impregnated with the following physical
developer to form a processing web and receiver.
Nickel chloride 0.6 molar Malic acid 0.6 molar Sodium hypophosphite
0.6 molar Water to make 1 liter Concentrated ammonium hydroxide
added to raise the pH to 7.0
The web was placed against the exposed film, and heated at
135.degree. F. for 3 seconds. A dark image appeared on the receiver
sheet in the areas which were in contact with the unexposed areas
of the gelatin film. After separating the negative and the receiver
sheet, the image on the latter could be darkened by immersing it in
a physical developer of the type used in Example 3.
EXAMPLE 13
A subbed polyethylene-coated paper support on which is coated a
heavy layer of a titanium dioxide-gelatin mixture was soaked in a
0.5 percent potassium palladium oxalate (K.sub.2 PdOx.sub.2)
solution at pH 2.8. The sheet was exposed through a negative line
image by means of a bank of eight 8-watt black-light tubes (GE
F8T5-BL) for 30 seconds at a distance of 2 inches. It was then
developed for approximately 2 minutes in the nickel physical
developer solution of Example 3 at 95.degree. C. A heavy metallic
nickel image appeared on the sheet in the exposed areas, whereas
the unexposed areas remained free of metal. The developed sheet was
put on an offset printing press, wet with fountain solution (a
dilute acid) and then inked with an oil-based ink. The plate took
up ink in the nickel image areas and the background remained ink
free. Several impressions were made using this printing master. The
adhesion of the metal image to the support was excellent.
EXAMPLE 14
A sheet of baryta coated paper was soaked in a 0.5 percent solution
of potassium palladium oxalate adjusted to pH 2.8. The treated
sheet was exposed through a negative line image as in Example 13.
It was then developed for approximately 2 hours in the nickel
physical developer of Example 6 at room temperature. A heavy
metallic nickel image appeared on the sheet in the exposed areas
whereas the unexposed areas remained free of metal. The developed
sheet was soaked in water and inked with lithographers' ink. The
sheet was then pressed against a sheet of bond paper and gave an
excellent ink transfer. The sheet was re-inked and the procedure
carried out for several impressions. There was no change in the
wettability characteristics of the master with extended use.
EXAMPLE 15
A sheet of polyethylene-coated paper on which had been coated a
mixture of titanium dioxide and polyvinyl alcohol was soaked in a
0.5 percent solution of potassium palladium oxalate adjusted to pH
2.8. The sheet was exposed through a negative line image by means
of a bank of eight 8-watt black-light tubes for 30 seconds at a
distance of 2 inches. It was then developed for approximately 1
minute in a copper physical developer solution at room temperature.
The physical developer was prepared by mixing five parts of the
following solution with one part of a 37 percent formaldehyde
solution.
Copper sulfate (CuSO.sub.4.sup.. 5H.sub.2 O) 35 gm. Rochelle salt
(KNaC.sub.4 H.sub.4 O.sub.6.sup.. 4H.sub.2 O) 170 gm.
Triethanolamine (HOC.sub.2 H.sub.4).sub.3 N 13 gm. Disodium
ethylene diaminetetraacetic acid 6.5 gm. Sodium hydroxide 50 gm.
Sodium carbonate 17 gm. Water to make 1 liter
The developed sheet showed an excellent copper image in the exposed
areas. It was put on an offset printing press, wet with fountain
solution, and inked with an oil-based ink. The plate showed good
inking differentiation and several prints were made with this
printing master.
EXAMPLE 16
A sheet of light weight water-leaf paper was impregnated with a 0.5
percent solution of palladium tetrammine chloride and dried. It was
then exposed to a 350 watt mercury arc at a distance of 14 inches
for one minute behind a negative which contained a line pattern.
The exposed sheet was then immersed for five seconds at 90.degree.
C. in the following nickel type physical developer:
Nickel chloride (NiCl.sub.2.sup.. 6H.sub.2 O) 30 gms. Sodium
hypophosphite (NaH.sub.2 PO.sub.2.sup.. H.sub.2 O) 10 gms. Ammonium
chloride (NH.sub.4 Cl) 50 gms.
Water was added to make one liter and the solution was adjusted to
pH 9 with ammonium hydroxide. An excellent image appeared which
showed a resistance of 50 ohms/square.
EXAMPLE 17
An absorbent porcelain plate ("Streak Plate" sold by the Will
Corporation) was dipped briefly in a 0.5 percent solution of
potassium palladium oxalate and dried. It was exposed as in Example
16 behind a negative which contained a line pattern. The plate was
then immersed for three minutes at 95.degree. C. in the following
nickel physical developer:
Nickel chloride (NiCl.sub.2.sup.. 6H.sub.2 O) 30 gms. Sodium
hypophosphite (NaH.sub.2 PO.sub.2.sup.. H.sub.2 O) 10 gms. Sodium
citrate (Na.sub.3 C.sub.6 H.sub.5 O.sub.7.sup.. 5-1/2H.sub.2 O) 100
gms. Ammonium chloride (NH.sub.4 Cl) 50 gms.
Water was added to make one liter of solution and it was adjusted
to pH 9 with ammonium hydroxide. An excellent image was formed
which showed a resistance of 40 ohms/square.
EXAMPLE 18
A sheet of poly(ethylene terephthalate) film base coated with
gelatin at a coverage of 350 mg. of gelatin/ft.sup.2 was imbibed
with a 0.5 percent solution of potassium palladium oxalate for ten
minutes and dried. It was exposed behind a line negative to a bank
of eight 8-watt fluorescent tubes (BL type, GE) for thirty seconds
and immersed in the physical developer solution used in Example 16
for 5 minutes. An excellent image was formed which had a resistance
of approximately 500 ohms/square.
Although this invention has been described in considerable detail
with particular reference to preferred embodiments thereof,
modifications and variations can be effected within the spirit and
scope of the invention as described above and as defined in the
following claims.
* * * * *