U.S. patent application number 10/935384 was filed with the patent office on 2006-03-16 for silver salt-toner co-precipitates and imaging materials.
This patent application is currently assigned to Eastman Kodak Company. Invention is credited to Kui Chen-Ho, Dirk J. Hasberg, Doreen C. Lynch, Chaofeng Zou.
Application Number | 20060057510 10/935384 |
Document ID | / |
Family ID | 35457735 |
Filed Date | 2006-03-16 |
United States Patent
Application |
20060057510 |
Kind Code |
A1 |
Hasberg; Dirk J. ; et
al. |
March 16, 2006 |
SILVER SALT-TONER CO-PRECIPITATES AND IMAGING MATERIALS
Abstract
Thermally developable materials such as thermographic and
photo-thermographic materials include a co-precipitate comprising
first and second organic silver salts, the first organic silver
salt comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole. The first
organic silver salt can be used in the imaging process as a source
of reducible silver ions, and the second organic silver salt can be
a source of a toning agent. The co-precipitate can be prepared
using double-jet precipitation techniques to provide an aqueous
dispersion that can be used in imaging formulations.
Inventors: |
Hasberg; Dirk J.;
(Rochester, NY) ; Lynch; Doreen C.; (Afton,
MN) ; Chen-Ho; Kui; (Woodbury, MN) ; Zou;
Chaofeng; (Maplewood, MN) |
Correspondence
Address: |
Paul A. Leipold;Patent Legal Staff
Eastman Kodak Company
343 State Street
Rochester
NY
14650-2201
US
|
Assignee: |
Eastman Kodak Company
|
Family ID: |
35457735 |
Appl. No.: |
10/935384 |
Filed: |
September 7, 2004 |
Current U.S.
Class: |
430/619 |
Current CPC
Class: |
G03C 2001/03535
20130101; G03C 2200/40 20130101; Y10S 430/165 20130101; G03C
1/49809 20130101; G03C 1/34 20130101; G03C 1/0051 20130101; G03C
2200/33 20130101; Y10S 430/166 20130101 |
Class at
Publication: |
430/619 |
International
Class: |
G03C 1/00 20060101
G03C001/00 |
Claims
1. A co-precipitate particle comprising first and second organic
silver salts, said first organic silver salt comprising a silver
salt of a nitrogen-containing heterocyclic compound containing an
imino group, and said second organic silver salt being uniformly
distributed throughout the volume of said particle and comprising a
silver salt of a mercaptotriazole, wherein said second organic
silver salt comprises a silver salt of a mercaptotriazole having
the following Structure (I): ##STR23## wherein R.sub.1 and R.sub.2
independently represent hydrogen, an alkyl group, an alkenyl group,
a cycloalkyl group, an aromatic or non-aromatic heterocyclyl group,
an amino or amide group, an aryl group, or a
Y.sub.1--(CH.sub.2).sub.k-group wherein Y.sub.1 is an aryl group or
an aromatic or non-aromatic heterocyclyl group, and k is 1-3, or
R.sub.1 and R.sub.2 taken together can form a 5- to 7-membered
aromatic or non-aromatic nitrogen-containing heterocyclic ring, or
still again, R.sub.1 or R.sub.2 can represent a divalent linking
group linking two mercaptotriazole groups, and R.sub.2 may further
represent carboxy or its salts, provided that R.sub.1 and R.sub.2
are not simultaneously hydrogen, and when R.sub.1 is an
unsubstituted phenyl group, R.sub.2 is not hydrogen.
2. The co-precipitate particle of claim 1 having an aspect ratio of
at least 2 and said first organic silver salt comprises a silver
salt of a benzotriazole.
3. The co-precipitate particle of claim 1 wherein R.sub.1 is an
alkyl or phenyl group and R.sub.2 is hydrogen.
4.-7. (canceled)
8. The co-precipitate particle of claim 1 that has an aspect ragtio
of at least 3 and a width index for particle diameter of 1.25 or
less.
9. The co-precipitate particle of claim 1 wherein the molar ratio
of said first organic silver salt to said second organic silver
salt is from about 100:1 to about 15:1.
10. A co-precipitate particle comprising first and second organic
silver salts, said first organic silver salt comprising a silver
salt of a benzotriazole, and said second organic silver salt
comprising a silver salt of a mercaptotriazole represented by the
following Structure (T-1), wherein the molar ratio of said first
organic silver salt to said second organic silver salt is from
about 100:1 to about 15:1, and at least 95 mol % of said second
organic silver salt is present within a localized portion that is
from about 90 to 100 volume % of said co-precipitate particle
wherein 100 volume % represents the outer surface of said
co-precipitate particle: ##STR24##
11. (canceled)
12. A method of making a co-precipitate particle of first and
second organic silver salts, said first organic silver salt
comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and said second organic silver
salt uniformly distributed throughout the volume of said particle
and comprising a silver salt of a mercaptotriazole, said method
comprising: A) preparing aqueous solution A containing a
nitrogen-containing heterocyclic compound containing an imino
group, A') preparing aqueous solution A' containing a
mercaptotriazole, wherein solutions A and A' are the same solution,
B) preparing aqueous solution B of silver nitrate, and C)
simultaneously adding said aqueous solutions A and B to a reaction
vessel containing an aqueous dispersion of a hydrophilic polymer
binder or a water-dispersible polymer latex binder that has a pH of
from about 7.5 to about 10, via controlled double-jet
precipitation, while maintaining a constant temperature of from
about 30 to about 75.degree. C., a constant pH, and a constant vAg
equal to or greater than -50 mV in said reaction vessel, thereby
preparing in said reaction vessel a dispersion of said hydrophilic
polymer binder or said water-dispersible polymer latex binder and
co-precipitate particles of said first and second silver salts, and
said hydrophilic polymer binder or said water-dispersible polymer
latex binder being present in said dispersion in an amount of from
about 2 to about 10 weight %, wherein said second organic silver
salt comprises a silver salt of a mercaptotriazole having the
following Structure (I): ##STR25## wherein R.sub.1 and R.sub.2
independently represent hydrogen, an alkyl group, an alkenyl group,
a cycloalkyl group, an aromatic or non-aromatic heterocyclyl group,
an amino or amide group, an aryl group, or a
Y.sub.1--(CH.sub.2).sub.k-group wherein Y.sub.1 is an aryl group or
an aromatic or non-aromatic heterocyclyl group, and k is 1-3, or
R.sub.1 and R.sub.2 taken together can form a 5- to 7-membered
aromatic or non-aromatic nitrogen-containing heterocyclic ring, or
still again, R.sub.1 or R.sub.2 can represent a divalent linking
group linking two mercaptotriazole groups, and R.sub.2 may further
represent carboxy or its salts, provided that R.sub.1 and R.sub.2
are not simultaneously hydrogen, and when R.sub.1 is an
unsubstituted phenyl group, R.sub.2 is not hydrogen.
13. The method of claim 12 wherein the ratio of the molar flow rate
(A.sub.1) of the nitrogen-containing heterocyclic compound
containing an imino group in Solution A to the total Ag moles
precipitated is from about 0.004 to about 0.04 mol/min/mol Ag and
the ratio of the molar flow rate (B.sub.1) of Solution B to the
total Ag moles precipitated is from about 0.004 to about 0.04
mol/min/mol Ag.
14. The method of claim 12 wherein solutions A and A' are different
and solution A' is added to said reaction vessel such that the
ratio of molar flow rate (A'.sub.1) of the mercaptotriazole in
Solution A' to the total Ag moles precipitated is from about 0.004
to about 0.04 mol/min/mol Ag and the ratio of the molar flow rate
of Solution B to the total Ag moles precipitated is from about
0.004 to about 0.04 mol/min/mol Ag.
15. The method of claim 12 wherein said nitrogen-containing
heterocyclic compound containing an imino group is present in said
Solution A at a concentration of at least 0.1 mol/l and said
mercaptotriazole is present in said Solution A at a concentration
of at least 0.1 mol/l.
16. The method of claim 12 wherein the pH in said reaction vessel
is maintained at from about 7.5 to about 10, and said vAg is
maintained in said reaction vessel from about .+-.51 to about 0
mV.
17. (canceled)
18. The method of claim 12 wherein said co-precipitate particle has
an aspect ratio of at least 2, said first organic silver salt
comprises a silver salt of a benzotriazole, and said second organic
silver salt comprises a silver salt of a mercaptotriazole that is
the silver salt of Compound T-1, ##STR26##
19. A method of making a co-precipitate comprising: A) preparing
aqueous solution A containing a benzotriazole at a concentration of
from about 2 to about 4 mol/l, A') preparing aqueous solution A'
that is different from solution A and contains a mercaptotriazole
of Structure (T-1) at a concentration of from about 0.5 to about 3
mol/l, B) preparing aqueous solution B of silver nitrate, and C)
simultaneously adding said aqueous solutions A and B to a reaction
vessel containing an aqueous dispersion of a hydrophilic polymer
binder or a water-dispersible polymer latex binder that has a pH of
from about 7.5 to about 10, via controlled double-jet
precipitation, while maintaining a constant temperature of from
about 30 to about 75.degree. C., a constant pH, and a constant vAg
equal to or greater than -50 mV in said reaction vessel, E) adding
solution A' to said reaction vessel during step C but only after at
least 75 volume % of solution B has been added to said reaction
vessel, thereby preparing in said reaction vessel a dispersion of
said hydrophilic polymer binder or said water-dispersible polymer
latex binder and particles of the co-precipitate of said first and
second organic silver salts, and said hydrophilic polymer binder or
said water-dispersible polymer latex binder being present in said
dispersion in an amount of from about 2 to about 10 weight %,
##STR27##
20. A black-and-white, non-photosensitive thermographic material
comprising a support and having thereon at least one
non-photosensitive thermally developable imaging layer comprising a
hydrophilic polymer binder or a water-dispersible polymer latex
binder and in reactive association: a. a non-photosensitive source
of reducible silver ions, and b. a reducing agent for said
reducible silver ions, wherein said non-photosensitive source of
reducible silver ions predominantly comprises a co-precipitate
particle comprising first and second organic silver salts, said
first organic silver salt comprising a silver salt of a
nitrogen-containing heterocyclic compound containing an imino
group, and said second organic silver salt being uniformly
distributed throughout the volume of said particle and comprising a
silver salt of a mercaptotriazole.
21. A black-and-white photothermographic material comprising a
support and having thereon at least one thermally developable
imaging layer comprising a hydrophilic polymer binder or a
water-dispersible polymer latex binder and in reactive association:
a. a photosensitive silver halide that is spectrally sensitized to
a wavelength of from about 300 to about 450 nm, b. a
non-photosensitive source of reducible silver ions, and c. a
reducing agent for said reducible silver ions, wherein said
non-photosensitive source of reducible silver ions predominantly
comprises a co-precipitate particle comprising first and second
organic silver salts, said first organic silver salt comprising a
silver salt of a nitrogen-containing heterocyclic compound
containing an imino group, and said second organic silver salt
being uniformly distributed throughout the volume of said particle
and comprising a silver salt of a mercaptotriazole.
22. The material of claim 21 wherein first organic silver salt
comprises a silver salt of a benzotriazole and said second organic
silver salt comprises a silver salt of a mercaptotriazole having
the following Structure (I): ##STR28## wherein R.sub.1 and R.sub.2
independently represent hydrogen, an alkyl group, an alkenyl group,
a cycloalkyl group, an aromatic or non-aromatic heterocyclyl group,
an amino or amide group, an aryl group, or a
Y.sub.1--(CH.sub.2).sub.k-group wherein Y.sub.1 is an aryl group or
an aromatic or non-aromatic heterocyclyl group, and k is 1-3, or
R.sub.1 and R.sub.2 taken together can form a 5- to 7-membered
aromatic or non-aromatic nitrogen-containing heterocyclic ring, or
still again, R.sub.1 or R.sub.2 can represent a divalent linking
group linking two mercaptotriazole groups, and R.sub.2 may further
represent carboxy or its salts, provided that R.sub.1 and R.sub.2
are not simultaneously hydrogen, and when R.sub.1 is an
unsubstituted phenyl group, R.sub.2 is not hydrogen.
23. The material of claim 21 wherein said mercaptotriazole is a
silver salt of one or more of the following Compounds T-1 through
T-59: ##STR29## ##STR30## ##STR31## ##STR32## ##STR33## ##STR34##
##STR35## ##STR36## ##STR37##
24. A black-and-white photothermographic material comprising a
support and having thereon at least one thermally developable
imaging layer comprising a hydrophilic polymer binder or a
water-dispersible polymer latex binder and in reactive association:
a. a photosensitive silver halide, b. a non-photosensitive source
of reducible silver ions, and c. a reducing agent for said
reducible silver ions, wherein said non-photosensitive source of
reducible silver ions predominantly comprises a co-precipitate
particle comprising first and second organic silver salts, said
first organic silver salt comprising a silver salt of a
nitrogen-containing heterocyclic compound containing an imino
group, and said second organic silver salt comprising a silver salt
of a mercaptotriazole, wherein said first organic silver salt
comprising a silver salt of a benzotriazole and said second organic
silver salt is present within a localized portion that is from
about 75 to 100 volume % of said co-precipitate particle wherein
100 volume % represents its outer surface and comprises a silver
salt of a mercaptotriazole that is the silver salt of Compound
(T-1), ##STR38##
25. (canceled)
26. The material of claim 24 wherein said second organic silver
salt is present within a localized portion that is from about 90 to
100 volume % of said co-precipitate particle wherein 100 volume %
represents its outer surface, and said co-precipitate particle has
an aspect ratio of at least 3 and a width index for particle
diameter of 1.25 or less.
27. (canceled)
28. A black-and-white photothermographic material comprising a
support and having thereon at least one thermally developable
imaging layer comprising a hydrophilic polymer binder or a
water-dispersible polymer latex binder and in reactive association:
a. a photosensitive silver halide present as ultrathin tabular
grains, b. a non-photosensitive source of reducible silver ions,
and c. a reducing agent for said reducible silver ions, wherein
said non-photosensitive source of reducible silver ions comprises a
co-precipitate particle comprising first and second organic silver
salts, said first organic silver salt comprising a silver salt of a
nitrogen-containing heterocyclic compound containing an imino
group, and said second organic silver salt being uniformly
distributed throughout the volume of said particle and comprising a
silver salt of a mercaptotriazole.
29. The material of claim 28 wherein said first organic silver salt
comprises a silver salt of a benzotriazole and said second organic
silver salt comprises a silver salt of a mercaptotriazole having
the following Structure (I): ##STR39## wherein R.sub.1 and R.sub.2
independently represent hydrogen, an alkyl group, an alkenyl group,
a cycloalkyl group, an aromatic or non-aromatic heterocyclyl group,
an amino or amide group, an aryl group, or a
Y.sub.1--(CH.sub.2).sub.k-group wherein Y.sub.1 is an aryl group or
an aromatic or non-aromatic heterocyclyl group, and k is 1-3, or
R.sub.1 and R.sub.2 taken together can form a 5- to 7-membered
aromatic or non-aromatic nitrogen-containing heterocyclic ring, or
still again, R.sub.1 or R.sub.2 can represent a divalent linking
group linking two mercaptotriazole groups, and R.sub.2 may further
represent carboxy or its salts, provided that R.sub.1 and R.sub.2
are not simultaneously hydrogen, and when R.sub.1 is an
unsubstituted phenyl group, R.sub.2 is not hydrogen.
30. The material of claim 28 wherein said co-precipitate has an
aspect ratio of at least 3 and a width index for particle diameter
of 1.25 or less.
31. The material of claim 28 wherein said reducing agent is an
ascorbic acid or reductone.
32. The material of claim 31 wherein said reducing agent is a fatty
acid ester of ascorbic acid, and said hydrophilic binder is
gelatin, a gelatin derivative, or a cellulosic material, and said
one or more thermally developable imaging layers has a pH of less
than 7.
33.-34. (canceled)
35. A black-and-white photothermographic material comprising a
support having on a frontside thereof, a) one or more frontside
thermally developable imaging layers comprising a hydrophilic
polymer binder or a water-dispersible polymer latex binder, and in
reactive association, a photosensitive silver halide, a
non-photo-sensitive source of reducible silver ions, and a reducing
agent for said non-photosensitive source of reducible silver ions,
b) said material comprising on the backside of said support, one or
more backside thermally developable imaging layers having the same
or different composition as said frontside thermally developable
imaging layers, and c) optionally, an outermost protective layer
disposed over said one or more thermally developable imaging layers
on either or both sides of said support, wherein said
non-photosensitive source of reducible silver ions comprises a
co-precipitate particle comprising first and second organic silver
salts, said first organic silver salt comprising a silver salt of a
nitrogen-containing heterocyclic compound containing an imino
group, and said second organic silver salt comprising a silver salt
of a mercaptotriazole being uniformly distributed throughout the
volume of said particle.
36. The material of claim 35 wherein said co-precipitate comprises
rod-shaped particles that have a length of from about 0.1 to about
0.5 .mu.m, a diameter of from about 0.03 to about 0.07 .mu.m, an
aspect ratio of from about 3 to about 10, and a width index for
particle diameter of from about 1.1 to about 1.2.
37. The material of claim 35 wherein said photosensitive silver
halide is sensitive to electromagnetic radiation of from about 300
to about 450 nm.
38. The material of claim 35 wherein said first organic silver salt
is a silver benzotriazole and said silver salt of said
mercaptotriazole is represented by a silver salt of the following
Structure (I): ##STR40## wherein R.sub.1 and R.sub.2 independently
represent hydrogen, an alkyl group, an alkenyl group, a cycloalkyl
group, an aromatic or non-aromatic heterocyclyl group, an amino or
amide group, an aryl group, or a Y.sub.1--(CH.sub.2).sub.k-group
wherein Y.sub.1 is an aryl group or an aromatic or non-aromatic
heterocyclyl group, and k is 1-3, or R.sub.1 and R.sub.2 taken
together can form a 5- to 7-membered aromatic or non-aromatic
nitrogen-containing heterocyclic ring, or still again, R.sub.1 or
R.sub.2 can represent a divalent linking group linking two
mercaptotriazole groups, and R.sub.2 may further represent carboxy
or its salts, provided that R.sub.1 and R.sub.2 are not
simultaneously hydrogen.
39. A black-and-white photothermographic material comprising a
support having on a frontside thereof, a) one or more frontside
thermally developable imaging layers comprising a hydrophilic
polymer binder or a water-dispersible polymer latex binder, and in
reactive association, a photosensitive silver halide, a
non-photo-sensitive source of reducible silver ions, and a reducing
agent for said non-photosensitive source of reducible silver ions,
b) said material comprising on the backside of said support, one or
more backside thermally developable imaging layers having the same
or different composition as said frontside thermally developable
imaging layers, and c) optionally, an outermost protective layer
disposed over said one or more thermally developable imaging layers
on either or both sides of said support, wherein said
non-photosensitive source of reducible silver ions comprises a
co-precipitate particle comprising first and second organic silver
salts, said first organic silver salt comprising a silver salt of a
nitrogen-containing heterocyclic compound containing an imino
group, and said second organic silver salt being uniformly
distributed throughout the volume of said particle and comprising a
silver salt of a mercaptotriazole, wherein said thermally
developable imaging layers on both sides of said support are
essentially the same, said reducing agent is a fatty acid ester of
ascorbic acid, said photosensitive silver halide is present as
tabular grains of silver bromide or silver iodobromide, said first
organic silver salt is silver benzotriazole, and said silver salt
of said mercaptotriazole is the silver salt of Compound T-1,
##STR41##
40. The material of claim 35 wherein each of said thermally
developable imaging layers on both sides of said support has been
coated out of an aqueous formulation comprising an aqueous
solvent.
41. The black-and-white photothermographic material of claim 39
wherein at least 95 mol % of said second organic silver salt is
present within a localized portion that is from about 95 to 100
volume % of said co-precipitate particle wherein 100 volume %
represents its outer surface.
42. The black-and-white photothermographic material of claim 41
wherein at least part of the outer surface of said co-precipitate
particle is covered by said second organic silver salt.
43.-47. (canceled)
48. A method of forming a visible image comprising: A) imagewise
exposing the photothermographic material of claim 21 to form a
latent image, B) simultaneously or sequentially, heating said
exposed photothermographic material to develop said latent image
into a visible image.
49. A method of forming a visible image comprising: A) imagewise
exposing the photothermographic material of claim 24 to form a
latent image, B) simultaneously or sequentially, heating said
exposed photothermographic material to develop said latent image
into a visible image.
50. The method of claim 49 wherein said thermally developable
material comprises a transparent support, and said image-forming
method further comprises: C) positioning said exposed and
thermally-developed material with the visible image therein between
a source of imaging radiation and an imageable material that is
sensitive to said imaging radiation, and D) exposing said imageable
material to said imaging radiation through the visible image in
said exposed and thermally-developed material to provide an image
in said imageable material.
51. The method of claim 49 wherein said imagewise exposing is
carried out using visible or X-radiation.
52. The method of claim 49 wherein said photothermographic material
is arranged in association with one or more phosphor intensifying
screens during imaging.
53. The method of claim 49 further comprising using said exposed
photothermographic material for medical diagnosis.
54. An imaging assembly comprising the photothermographic material
of claim 24 that is arranged in association with one or more
phosphor intensifying screens.
55. An imaging assembly comprising the photothermographic material
of claim 35 that is arranged in association with a phosphor
intensifying screens on each side thereof.
56. The imaging assembly of claim 55 wherein said
photothermographic material comprises a photosensitive silver
halide that is spectrally sensitive to a wavelength of from about
360 to about 420 nm, and said phosphor intensifying screens are
capable of emitting radiation in the range of from about 360 to
about 420 nm.
57. A dispersion of a hydrophilic polymer binder or a
water-dispersible polymer latex binder and one or more
co-precipitate particles comprising first and second organic silver
salts, said first organic silver salt comprising a silver salt of a
nitrogen-containing heterocyclic compound containing an imino
group, and said second organic silver salt being uniformly
distributed throughout the volume of said particle and comprising a
silver salt of a mercaptotriazole, and said hydrophilic polymer
binder or said water-dispersible polymer latex binder being present
in said dispersion in an amount of from about 2 to about 10 weight
%, wherein said mercaptotriazole is represented by the following
Structure (I): ##STR42## wherein R.sub.1 and R.sub.2 independently
represent hydrogen, an alkyl group, an alkenyl group, a cycloalkyl
group, an aromatic or non-aromatic heterocyclyl group, an amino or
amide group, an aryl group, or a Y.sub.1--(CH.sub.2).sub.k-group
wherein Y.sub.1 is an aryl group or an aromatic or non-aromatic
heterocyclyl group, and k is 1-3, or R.sub.1 and R.sub.2 taken
together can form a 5- to 7-membered aromatic or non-aromatic
nitrogen-containing heterocyclic ring, or still again, R.sub.1 or
R.sub.2 can represent a divalent linking group linking two
mercaptotriazole groups, and R.sub.2 may further represent carboxy
or its salts, provided that R.sub.1 and R.sub.2 are not
simultaneously hydrogen, and when R.sub.1 is an unsubstituted
phenyl group, R.sub.2 is not hydrogen.
58. The dispersion of claim 57 wherein said first organic silver
salt is silver benzotriazole, said mercaptotriazole is the silver
salt of Compound T-1, and said hydrophilic binder is gelatin or a
gelatin derivative, ##STR43##
59. The material of claim 21 wherein at least 75 weight % of the
total binders in said at least one thermally developable imaging
layer is gelatin or a gelatin derivative, and said material further
comprises a protective topcoat layer in which at least 75 weight %
of the total binders is gelatin or a gelatin derivative.
60. The material of claim 35 comprising an outermost protective
layer disposed over said one or more thermally developable imaging
layers on both sides of said support, and at least 75 weight % of
the total binders in both said outermost protective layers and said
one or more thermally developable imaging layers on both sides of
said support is gelatin or a gelatin derivative.
61. The material of claim 21 further comprising a
2-alkylphthalazinium salt.
62. The material of claim 61 wherein said 2-alkylphthalazinium salt
is 2-butylphthalazinium chloride.
Description
FIELD OF THE INVENTION
[0001] This invention relates to co-precipitates in the form of
nano-crystals or particles containing two or more of specific
organic silver salts. This invention also relates to a method of
making these co-precipitates and to their use in thermally
developable materials such as thermographic and photothermographic
materials. It also relates to methods of forming images using the
thermally developable materials.
BACKGROUND OF THE INVENTION
[0002] Silver-containing photothermographic imaging materials (that
is, thermally developable photosensitive imaging materials) that
are imaged with actinic radiation and then developed using heat and
without liquid processing have been known in the art for many
years. Such materials are used in a recording process wherein an
image is formed by imagewise exposure of the photothermographic
material to specific electromagnetic radiation and developed by the
use of thermal energy. These materials, also known as "dry silver"
materials, generally comprise a support having coated thereon: (a)
a photocatalyst (that is, a photo-sensitive compound such as silver
halide) that upon such exposure provides a latent image in exposed
grains that are capable of acting as a catalyst for the subsequent
formation of a silver image in a development step, (b) a relatively
or completely non-photosensitive source of reducible silver ions,
(c) a reducing composition (usually including a developer) for the
reducible silver ions, and (d) a hydrophilic or hydrophobic binder.
The latent image is then developed by application of thermal
energy.
[0003] In photothermographic materials, exposure of the
photographic silver halide to light produces small clusters
containing silver atoms (Ag.sup.0).sub.n. The imagewise
distribution of these clusters, known in the art as a latent image,
is generally not visible by ordinary means. Thus, the
photosensitive material must be further developed to produce a
visible image by the reduction of silver ions that are in catalytic
proximity to silver halide grains bearing the silver-containing
clusters of the latent image. This produces a black-and-white
image. The non-photosensitive silver source is catalytically
reduced to form the visible black-and-white negative image while
much of the silver halide, generally, remains as silver halide and
is not reduced. In most instances, the source of reducible silver
ions is an organic silver salt in which silver ions are complexed
with organic silver coordinating ligands.
[0004] Thermographic materials are similar in nature except that
the photocatalyst is omitted and imaging and development are
carried out simultaneously using a thermal imaging means. Such
materials also include an organic silver salt that provides
reducible silver ions required for imaging.
Differences Between Photothermography and Photography
[0005] The imaging arts have long recognized that the field of
photothermography is clearly distinct from that of photography.
Photothermographic materials differ significantly from conventional
silver halide photographic materials that require processing with
aqueous processing solutions.
[0006] In photothermographic imaging materials, a visible image is
created by heat as a result of the reaction of a developer
incorporated within the material. Heating at 50.degree. C. or more
is essential for this dry development. In contrast, conventional
photographic imaging materials require processing in aqueous
processing baths at more moderate temperatures (from 30.degree. C.
to 50.degree. C.) to provide a visible image.
[0007] In photothermographic materials, only a small amount of
silver halide is used to capture light and a non-photosensitive
source of reducible silver ions (for example a silver carboxylate
or a silver benzotriazole) is used to generate the visible image
using thermal development. Thus, the imaged photosensitive silver
halide serves as a catalyst for the physical development process
involving the non-photosensitive source of reducible silver ions
and the incorporated reducing agent. In contrast, conventional
wet-processed, black-and-white photographic materials use only one
form of silver (that is, silver halide) that, upon chemical
development, is itself at least partially converted into the silver
image, or that upon physical development requires addition of an
external silver source (or other reducible metal ions that form
black images upon reduction to the corresponding metal). Thus,
photothermographic materials require an amount of silver halide per
unit area that is only a fraction of that used in conventional
wet-processed photographic materials.
[0008] In photothermographic materials, all of the "chemistry" for
imaging is incorporated within the material itself. For example,
such materials include a developer (that is, a reducing agent for
the reducible silver ions) while conventional photographic
materials usually do not. Even in so-called "instant photography,"
the developer chemistry is physically separated from the
photo-sensitive silver halide until development is desired. The
incorporation of the developer into photothermographic materials
can lead to increased formation of various types of "fog" or other
undesirable sensitometric side effects. Therefore, much effort has
gone into the preparation and manufacture of photothermographic
materials to minimize these problems.
[0009] Moreover, in photothermographic materials, the unexposed
silver halide generally remains intact after development and the
material must be stabilized against further imaging and
development. In contrast, silver halide is removed from
conventional photographic materials after solution development to
prevent further imaging (that is in the aqueous fixing step).
[0010] Because photothermographic materials require dry thermal
processing, they present distinctly different problems and require
different materials in manufacture and use, compared to
conventional, wet-processed silver halide photographic materials.
Additives that have one effect in conventional silver halide
photographic materials may behave quite differently when
incorporated in photothermographic materials where the chemistry is
significantly more complex. The incorporation of such additives as,
for example, stabilizers, antifoggants, speed enhancers,
supersensitizers, and spectral and chemical sensitizers in
conventional photographic materials is not predictive of whether
such additives will prove beneficial or detrimental in
photothermographic materials. For example, it is not uncommon for a
photographic antifoggant useful in conventional photographic
materials to cause various types of fog when incorporated into
photothermographic materials, or for supersensitizers that are
effective in photographic materials to be inactive in
photothermographic materials.
[0011] These and other distinctions between photothermographic and
photographic materials are described in Imaging Processes and
Materials (Neblette's Eighth Edition), noted above, Unconventional
Imaging Processes, E. Brinckman et al. (Eds.), The Focal Press,
London and New York, 1978, pp. 74-75, in Zou et al., J. Imaging
Sci. Technol. 1996, 40, pp. 94-103, and in M. R. V. Sahyun, J.
Imaging Sci. Technol. 1998, 42, 23.
Problem to be Solved
[0012] As noted above, non-photosensitive sources of reducible
silver ions are critical to the imaging mechanism of both
photothermographic and thermographic materials. Various organic
silver salts are useful for this purpose including silver
carboxylates (both aliphatic and aromatic), silver salts of
nitrogen-containing heterocyclic compounds, silver sulfonates, and
many others known in the art as described for example in U.S. Pat.
No. 6,576,410 (Zou et al.).
[0013] Aqueous-based photothermographic materials have been known
for many years in which the imaging components and binders are
formulated in and coated from solvents comprising primarily water.
It has been necessary in designing such materials that the various
imaging components be compatible with water and other water-soluble
or -dispersible components. Silver benzotriazole has been found
particularly useful in aqueous-based materials because of the
hydrophilic nature of silver benzotriazole crystal surfaces and its
compatability with most water-soluble binders.
[0014] One challenge in photothermographic materials is the need to
prevent image artifacts known as "black spots" after thermal
development. Black spots are believed to be caused by
crystallization of active toners or agglomeration of toner
particles during dispersion, melt preparation, coating, and drying
of thermographic and photothermographic materials. Upon thermal
development, the local concentration of active toner where these
toner particles reside is so high as to cause spontaneous
development in the non-imaged areas, resulting in high-density
black spots.
[0015] Another challenge in photothermographic materials is the
need to improve their stability after use. This is referred to as
"Archival Stability" or "Dark Stability." It is desirable that the
D.sub.min not increase, and that the D.sub.max, tint, and tone of
the image not change.
[0016] A further challenge in photothermographic materials is the
need to improve their stability at ambient temperature and relative
humidity during storage prior to use. This stability is referred to
as "Natural Age Keeping" (NAK) or as "Raw Stock Keeping" (RSK). It
is desirable that photothermographic materials be capable of
maintaining imaging properties, including photospeed and D.sub.max,
while minimizing any increase in D.sub.min during storage periods.
Natural Age Keeping is a problem especially for photothermographic
films compared to conventional silver halide photographic films
because, as noted above, all the components needed for development
and image formation in photothermographic systems are incorporated
into the imaging element, in intimate proximity, prior to
development. Thus, there are a greater number of potentially
reactive components that can prematurely react during storage.
[0017] Mercaptotriazoles have been described for use as toners in
photothermographic materials in U.S. Pat. No. 3,832,186 (Masuda et
al.), U.S. Pat. No. 4,201,582 (White), U.S. Pat. No. 4,105,451
(Smith et al.), and U.S. Pat. No. 6,713,240 (Lynch et al.). The
mercaptotriazoles described in U.S. Pat. No. 6,713,240 are
especially useful toners (or toning agents) and development
accelerators for photothermographic materials.
[0018] Mercaptotriazoles suitable for thermally developable imaging
materials often have poor water solubility and cause undesirable
precipitation when added to aqueous-based imaging formulations,
thereby adversely affecting coating quality and density
uniformity.
[0019] Moreover, the presence of such toners in photothermographic
materials during storage before use also may accelerate the
increase in D.sub.min. Thus, photothermographic materials that
include large quantities of mercaptotriazole toners to accelerate
the development reaction may be susceptible to keeping problems,
leading to reduced "NAK."
[0020] U.S. Pat. No. 6,576,414 (Irving et al.) and U.S. Pat. No.
6,548,236 (Irving et al.) describe both color and black-and-white
photothermographic materials containing core/shell particles having
two or more different organic silver salts. The particles function
as silver sources.
[0021] There remains a need to effectively incorporate specific
organic silver salts and mercaptotriazole toners into aqueous-based
photothermographic imaging formulations and materials so that
formation of black spots is reduced and sensitometric properties
are not changed during Natural Age Keeping, and so that Archival
Stability is improved, all without sacrifice of desired photospeed
and other sensitometric properties.
SUMMARY OF THE INVENTION
[0022] This invention provides a co-precipitate particle comprising
first and second organic silver salts, the first organic silver
salt comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole,
[0023] wherein the second organic silver salt comprises a silver
salt of a mercaptotriazole having the following Structure (I):
##STR1## wherein R.sub.1 and R.sub.2 independently represent
hydrogen, an alkyl group, an alkenyl group, a cycloalkyl group, an
aromatic or non-aromatic heterocyclyl group, an amino or amide
group, an aryl group, or a Y.sub.1--(CH.sub.2).sub.k-group wherein
Y.sub.1 is an aryl group or an aromatic or non-aromatic
heterocyclyl group, and k is 1-3,
[0024] or R.sub.1 and R.sub.2 taken together can form a 5- to
7-membered aromatic or non-aromatic nitrogen-containing
heterocyclic ring,
[0025] or still again, R.sub.1 or R.sub.2 can represent a divalent
linking group linking two mercaptotriazole groups, and.
[0026] R.sub.2 may further represent carboxy or its salts,
[0027] provided that R.sub.1 and R.sub.2 are not simultaneously
hydrogen, and when R.sub.1 is an unsubstituted phenyl group,
R.sub.2 is not hydrogen.
[0028] Preferred embodiments comprise a co-precipitate particle
comprising first and second organic silver salts, the first organic
silver salt comprising a silver salt of a benzotriazole, and the
second organic silver salt comprising a silver salt of a
mercaptotriazole represented by Structure (I) noted above, wherein
R.sub.1 is an alkyl or phenyl group and R.sub.2 is hydrogen,
provided that when R.sub.1 is an unsubstituted phenyl group,
R.sub.2 is not hydrogen, and wherein the molar ratio of the first
organic silver salt to the second organic silver salt is from about
100:1 to about 15:1, and at least 95 mol % ofthe second organic
silver salt is present within a localized portion that is from
about 90 to 100 volume % of the co-precipitate particle wherein 100
volume % represents the outer surface of the co-precipitate
particle.
[0029] This invention also provides a method of making a
co-precipitate particle of first and second organic silver salts,
the first organic silver salt comprising a silver salt of a
nitrogen-containing heterocyclic compound containing an imino
group, and the second organic silver salt comprising a silver salt
of a mercaptotriazole, the method comprising:
[0030] A) preparing aqueous solution A containing a
nitrogen-containing heterocyclic compound containing an imino
group,
[0031] A') preparing aqueous solution A' containing a
mercaptotriazole, wherein solutions A and A' are the same or
different solutions,
[0032] B) preparing aqueous solution B of silver nitrate, and
[0033] C) simultaneously adding the aqueous solutions A and B to a
reaction vessel containing an aqueous dispersion of a hydrophilic
polymer binder or a water-dispersible polymer latex binder that has
a pH of from about 7.5 to about 10, via controlled double-jet
precipitation, while maintaining a constant temperature of from
about 30 to about 75.degree. C., a constant pH, and a constant vAg
equal to or greater than -50 mV in the reaction vessel, and
[0034] E) adding solution A', if different from solution A, to the
reaction vessel during or after step C while maintaining a constant
temperature of from about 30 to about 75.degree. C., a constant pH,
and a constant vAg equal to or greater than -50 mV in the reaction
vessel,
[0035] thereby preparing in the reaction vessel a dispersion of the
hydrophilic polymer binder or the water-dispersible polymer latex
binder and particles of a co-precipitate particle of the first and
second silver salts, and the hydrophilic polymer binder or the
water-dispersible polymer latex binder being present in the
dispersion in an amount of from about 2 to about 10 weight %,
[0036] wherein the second organic silver salt comprises a silver
salt of a mercaptotriazole having Structure (I) noted above.
[0037] Preferred embodiments of this method of making the
co-precipitate comprise:
[0038] A) preparing aqueous solution A containing a
nitrogen-containing heterocyclic compound containing an imino group
at a concentration of from about 2 to about 4 mol/l,
[0039] A') preparing aqueous solution A' that is different from
solution A and contains a mercaptotriazole of Structure (I) at a
concentration of from about 0.5 to about 3 mol/l,
[0040] B) preparing aqueous solution B of silver nitrate, and
[0041] C) simultaneously adding aqueous solutions A and B to a
reaction vessel containing an aqueous dispersion of a hydrophilic
polymer binder or a water-dispersible polymer latex binder that has
a pH of from about 7.5 to about 10, via controlled double-jet
precipitation, while maintaining a constant temperature of from
about 30 to about 75.degree. C., a constant pH, and a constant vAg
equal to or greater than -50 mV in the reaction vessel,
[0042] E) adding solution A' to the reaction vessel during step C
but only after at least 75 volume % of solution B has been added to
the reaction vessel,
[0043] thereby preparing in the reaction vessel a dispersion of the
hydrophilic polymer binder or the water-dispersible polymer latex
binder and particles of the co-precipitate of the first and second
organic silver salts, and the hydrophilic polymer binder or the
water-dispersible polymer latex binder being present in the
dispersion in an amount of from about 2 to about 10 weight %.
[0044] This invention also provides a black-and-white,
non-photosensitive thermographic material comprising a support and
having thereon at least one non-photosensitive thermally
developable imaging layer comprising a hydrophilic polymer binder
or a water-dispersible polymer latex binder and in reactive
association:
[0045] a. a non-photosensitive source of reducible silver ions,
and
[0046] b. a reducing agent for the reducible silver ions,
[0047] wherein the non-photosensitive source of reducible silver
ions predominantly comprises a co-precipitate particle comprising
first and second organic silver salts, the first organic silver
salt comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole.
[0048] In addition, a black-and-white photothermographic material
comprising a support and having thereon at least one thermally
developable imaging layer comprising a hydrophilic polymer binder
or a water-dispersible polymer latex binder and in reactive
association:
[0049] a. a photosensitive silver halide that is spectrally
sensitized to a wavelength of from about 300 to about 450 nm,
[0050] b. a non-photosensitive source of reducible silver ions,
and
[0051] c. a reducing agent for the reducible silver ions,
[0052] wherein the non-photosensitive source of reducible silver
ions predominantly comprises a co-precipitate particle comprising
first and second organic silver salts, the first organic silver
salt comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole.
[0053] In addition, a black-and-white photothermographic material
of this invention comprises a support and having thereon at least
one thermally developable imaging layer comprising a hydrophilic
polymer binder or a water-dispersible polymer latex binder and in
reactive association:
[0054] a. a photosensitive silver halide,
[0055] b. a non-photosensitive source of reducible silver ions,
and
[0056] c. a reducing agent for the reducible silver ions,
[0057] wherein the non-photosensitive source of reducible silver
ions predominantly comprises a co-precipitate particle comprising
first and second organic silver salts, the first organic silver
salt comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole,
[0058] wherein the second organic silver salt comprises a silver
salt of a mercaptotriazole having Structure (I) noted above.
[0059] Still again, a black-and-white photothermographic material
of this invention comprises a support and having thereon at least
one thermally developable imaging layer-comprising a hydrophilic
polymer binder or a water-dispersible polymer latex binder and in
reactive association:
[0060] a. a photosensitive silver halide present as ultrathin
tabular grains,
[0061] b. a non-photosensitive source of reducible silver ions,
and
[0062] c. a reducing agent for the reducible silver ions,
[0063] wherein the non-photosensitive source of reducible silver
ions comprises a co-precipitate particle comprising first and
second organic silver salts, the first organic silver salt
comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole.
[0064] In preferred embodiments, a black-and-white
photothermographic material comprises a support having on a
frontside thereof,
[0065] a) one or more frontside thermally developable imaging
layers comprising a hydrophilic polymer binder or a
water-dispersible polymer latex binder, and in reactive
association, a photosensitive silver halide, a non-photo-sensitive
source of reducible silver ions, and a reducing agent for the
non-photosensitive source reducible silver ions,
[0066] b) the material comprising on the backside of the support,
one or more backside thermally developable imaging layers having
the same or different composition as the frontside thermally
developable imaging layers, and
[0067] c) optionally, an outermost protective layer disposed over
the one or more thermally developable imaging layers on either or
both sides of the support,
[0068] wherein the non-photosensitive source of reducible silver
ions comprises a co-precipitate particle comprising first and
second organic silver salts, the first organic silver salt
comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole.
[0069] In still other embodiments of this invention a
black-and-white photothermographic material comprises a support and
has therein at least one thermally developable imaging layer
comprising a hydrophilic polymer binder or a water-dispersible
polymer latex binder and in reactive association:
[0070] a. a photosensitive silver halide present as ultrathin
tabular grains,
[0071] b. a non-photosensitive source of reducible silver ions,
and
[0072] c. a reducing agent for the reducible silver ions,
[0073] wherein the non-photosensitive source of reducible silver
ions comprises a co-precipitate particle comprising first and
second organic silver salts, the first organic silver salt
comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole, and
[0074] wherein at least part of the outer surface of the
co-precipitate particle is covered by the second organic silver
salt.
[0075] Yet again, other embodiments include a black-and-white
photo-thermographic material comprising a support having on a
frontside thereof,
[0076] a) one or more frontside thermally developable imaging
layers comprising a hydrophilic polymer binder or a
water-dispersible polymer latex binder, and in reactive
association, a photosensitive silver halide, a non-photo-sensitive
source of reducible silver ions, and a reducing agent for the
non-photosensitive source reducible silver ions,
[0077] b) the material comprising on the backside of the support,
one or more backside thermally developable imaging layers having
the same or different composition as the frontside thermally
developable imaging layers, and
[0078] c) optionally, an outermost protective layer disposed over
the one or more thermally developable imaging layers on either or
both sides of the support,
[0079] wherein the non-photosensitive source of reducible silver
ions comprises a co-precipitate particle comprising first and
second organic silver salts, the first organic silver salt
comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole, and
[0080] wherein at least part of the outer surface of the
co-precipitate particle is covered by the second organic silver
salt.
[0081] A black-and-white photothermographic material also comprises
a support and having thereon at least one thermally developable
imaging layer comprising a hydrophilic polymer binder or a
water-dispersible polymer latex binder and in reactive
association:
[0082] a. a photosensitive silver halide,
[0083] b. a non-photosensitive source of reducible silver ions,
and
[0084] c. a reducing agent for the reducible silver ions,
[0085] wherein the non-photosensitive source of reducible silver
ions predominantly comprises a co-precipitate particle comprising
first and second organic silver salts, the first organic silver
salt comprising a silver salt of a nitrogen-containing heterocyclic
compound containing an imino group, and the second organic silver
salt comprising a silver salt of a mercaptotriazole that is
represented by the following Structure (I): ##STR2## wherein
R.sub.1 is an alkyl or phenyl group and R.sub.2 is hydrogen,
[0086] provided that when R.sub.1 is an unsubstituted phenyl group,
R.sub.2 is not hydrogen.
[0087] This invention also provides a method of forming a visible
image comprising:
[0088] A) imagewise exposing a photothermographic material of this
invention to form a latent image,
[0089] B) simultaneously or sequentially, heating the exposed
photothermographic material to develop the latent image into a
visible image.
[0090] An imaging assembly of this invention comprises a
photothermographic material of this invention that is arranged in
association with one or more phosphor intensifying screens.
[0091] Still again, this invention provides a dispersion of a
hydrophilic polymer binder or a water-dispersible polymer latex
binder and co-precipitate particles comprising first and second
organic silver salts, the first organic silver salt comprising a
silver salt of a nitrogen-containing heterocyclic compound
containing an imino group, and the second organic silver salt
comprising a silver salt of a mercaptotriazole, and the hydrophilic
polymer binder or the water-dispersible polymer latex binder being
present in the dispersion in an amount of from about 2 to about 10
weight %,
[0092] wherein the mercaptotriazole is represented by Structure (I)
noted above.
[0093] We have found that certain organic silver salts (such as
silver benzotriazoles) and silver salts of toners (such as silver
salts of certain mercaptotriazoles) can be made and co-precipitated
as a mixture of two organic silver salts in the same particles. The
resulting mixed silver salts are stable amorphous particles or
crystals. Although not wishing to be bound by theory, we believe
that upon thermal development, the silver mercaptotriazole
decomposes, releasing the mercaptotriazole toner to help form a
dense black silver image, and also to accelerate thermal
development. Non-released mercaptotriazole remains immobilized as
its silver salt in the co-precipitate particles and cannot
contribute either to black spots or increased D.sub.min upon
storage. Natural Age Keeping and Archival Stability are improved
while photospeed and other sensitometric properties in the
thermally developable imaging materials are not affected.
DETAILED DESCRIPTION OF THE INVENTION
[0094] The thermally developable materials can be used in
black-and-white photothermography and in electronically generated
black-and-white hardcopy recording. They can be used in microfilm
applications, in radiographic imaging (for example digital medical
imaging), X-ray radiography, and in industrial radiography.
Furthermore, in some embodiments, the absorbance of these materials
between 350 and 450 nm is desirably low (less than 0.5), to permit
their use in the graphic arts area (for example, imagesetting and
phototypesetting), in the manufacture of printing plates, in
contact printing, in duplicating ("duping"), and in proofing.
[0095] The photothermographic materials are particularly useful for
medical imaging of human or animal subjects in response to visible
or X-radiation for use in medical diagnosis. Such applications
include, but are not limited to, thoracic imaging, mammography,
dental imaging, orthopedic imaging, general medical radiography,
therapeutic radiography, veterinary radiography, and
autoradiography. When used with X-radiation, the photothermographic
materials may be used in association with one or more phosphor
intensifying screens, with phosphors incorporated within the
photothermographic emulsion, or with a combination thereof.
[0096] The photothermographic materials can be made sensitive to
radiation of any suitable wavelength. Thus, in some embodiments,
the materials are sensitive at ultraviolet, visible, near infrared,
or infrared wavelengths, of the electromagnetic spectrum. In these
embodiments, the materials are preferably sensitive to radiation
greater than 300 nm (such as sensitivity to, from about 300 nm to
about 750 nm, preferably from about 300 to about 600 nm, and more
preferably from about 300 to about 450 nm). In other embodiments
they are sensitive to X-radiation. Increased sensitivity to
X-radiation can be imparted through the use of phosphors.
[0097] The photothermographic materials are also useful for
non-medical uses of visible or X-radiation (such as X-ray
lithography and industrial radiography). In these and other imaging
applications, it is particularly desirable that the
photothermographic materials be "double-sided."
[0098] In some embodiments of the thermally developable materials,
the components needed for imaging can be in one or more imaging or
emulsion layers on one side ("frontside") of the support. The
layer(s) that contain the photo-sensitive photocatalyst (such as a
photosensitive silver halide) for photothermographic materials or
the co-precipitate containing the non-photosensitive source of
reducible silver ions, or both, are referred to herein as the
emulsion layer(s). In photothermographic materials, the
photocatalyst and non-photosensitive source of reducible silver
ions are in catalytic proximity and preferably are in the same
emulsion layer.
[0099] Where the thermally developable materials contain imaging
layers on one side of the support only, various non-imaging layers
can also be disposed on the "backside" (non-emulsion or non-imaging
side) of the materials, including, conductive layers, antihalation
layer(s), protective layers, antistatic layers, and transport
enabling layers.
[0100] In such instances, Various non-imaging layers can also be
disposed on the "frontside" or imaging or emulsion side of the
support, including protective topcoat layers, primer layers,
interlayers, opacifying layers, antistatic layers, antihalation
layers, acutance layers, auxiliary layers, and other layers readily
apparent to one skilled in the art.
[0101] For preferred embodiments, the thermally developable
materials are "double-sided" or "duplitized" and have the same or
different emulsion coatings (or thermally developable imaging
layers) on both sides of the support. Such constructions can also
include one or more protective topcoat layers, primer layers,
interlayers, antistatic layers, acutance layers, antihalation
layers, auxiliary layers, conductive layers, and other layers
readily apparent to one skilled in the art on either or both sides
of support. Preferably, such thermally developable materials have
essentially the same layers on each side of the support.
[0102] When the thermally developable materials are heat-developed
as described below in a substantially water-free condition after,
or simultaneously with, imagewise exposure, a silver image
(preferably a black-and-white silver image) is obtained.
DEFINITIONS
[0103] As used herein:
[0104] In the descriptions of the thermally developable materials,
"a" or "an" component refers to "at least one" of that component
(for example, the first and second organic silver salts).
[0105] The "co-precipitate" particles of this invention can also be
referred to as "crystals", wherein each particle or crystal
comprises a mixture of silver salts as described herein.
[0106] Unless otherwise indicated, the terms "thermally developable
materials," "thermographic materials," "photothermographic
materials," and "imaging assemblies" are used herein in reference
to embodiments of the present invention:
[0107] Heating in a substantially water-free condition as used
herein, means heating at a temperature of from about 50.degree. C.
to about 250.degree. C. with little more than ambient water vapor
present. The term "substantially water-free condition" means that
the reaction system is approximately in equilibrium with water in
the air and water for inducing or promoting the reaction is not
particularly or positively supplied from the exterior to the
material. Such a condition is described in T. H. James, The Theory
of the Photographic Process, Fourth Edition, Eastman Kodak Company,
Rochester, N.Y., 1977, p. 374.
[0108] "Photothermographic material(s)" means a construction
comprising at least one photothermographic emulsion layer or a
photothermographic set of emulsion layers (wherein the
photosensitive silver halide and the source of reducible silver
ions, that is the co-precipitate, are in one layer and the other
essential components or desirable additives are distributed, as
desired, in the same layer or in an adjacent coated layer). These
materials also include multilayer constructions in which one or
more imaging components are in different layers, but are in
"reactive association." For example, one layer can include the
non-photosensitive source of reducible silver ions and another
layer can include the reducing agent and/or photosensitive silver
halide.
[0109] "Thermographic material(s)" can be similarly constructed but
are intentionally non-photosensitive (thus no photosensitive silver
halide is intentionally added).
[0110] When used in photothermography, the term, "imagewise
exposing" or "imagewise exposure" means that the material is imaged
using any exposure means that provides a latent image using
electromagnetic radiation. This includes, for example, by analog
exposure where an image is formed by projection onto the
photosensitive material as well as by digital exposure where the
image is formed one pixel at a time such as by modulation of
scanning laser radiation.
[0111] When used in thermography, the term, "imagewise exposing" or
"imagewise exposure" means that the material is imaged using any
means that provides an image using heat. This includes, for
example, analog exposure where an image is formed by differential
contact heating through a mask using a thermal blanket or infrared
heat source, as well as by digital exposure where the image is
formed one pixel at a time such as by modulation of a thin film
thermal printhead or by heating with a modulated scanning laser
beam.
[0112] The thermographic materials are "direct" thermographic
materials and thermal imaging is carried out in a single
thermographic material containing all of the necessary imaging
chemistry. Direct thermal imaging is distinguishable from what is
known in the art as thermal transfer imaging (such as dye transfer
imaging) in which the image is produced in one material ("donor")
and transferred to another material ("receiver") using thermal
means.
[0113] "Catalytic proximity" or "reactive association" means that
the materials are in the same layer or in adjacent layers so that
they readily come into contact with each other during thermal
imaging and development.
[0114] "Emulsion layer," "imaging layer," or "photothermographic
(or thermographic) emulsion layer," means a layer of a
photothermographic (or thermographic) material that contains the
photosensitive silver halide (not present in thermographic
materials) and/or non-photosensitive source of reducible silver
ions (contained in the co-precipitate). It can also mean a layer of
the material that contains, in addition to the photosensitive
silver halide and/or non-photosensitive source of reducible ions,
additional essential components and/or desirable additives such as
the reducing agent(s). These layers are usually on what is known as
the "frontside" of the support but they can be on both sides of the
support.
[0115] In addition, "frontside" also generally means the side of a
thermally developable material that is first exposed to imaging
radiation, and "backside" generally refers to the opposite side of
the thermally developable material.
[0116] "Photocatalyst" means a photosensitive compound such as
silver halide that, upon exposure to radiation, provides a compound
that is capable of acting as a catalyst for the subsequent
development of the thermally developable material.
[0117] Many of the materials used herein are provided as a
solution. The term "active ingredient" means the amount or the
percentage of the desired material contained in a sample. All
amounts listed herein are the amount of active ingredient
added.
[0118] "Ultraviolet region of the spectrum" refers to that region
of the spectrum less than or equal to 410 nm, and preferably from
about 100 nm to about 410 nm, although parts of these ranges may be
visible to the naked human eye. More preferably, the ultraviolet
region of the spectrum is the region of from about 190 nm to about
405 nm.
[0119] "Visible region of the spectrum" refers to that region of
the spectrum of from about 400 nm to about 700 nm.
[0120] "Short wavelength visible region of the spectrum" refers to
that region of the spectrum of from about 400 nm to about 450
nm.
[0121] "Blue region of the spectrum" refers to that region of the
spectrum of from about 400 nm to about 500 nm.
[0122] "Green region of the spectrum" refers to that region of the
spectrum of from about 500 nm to about 600 nm.
[0123] "Red region of the spectrum" refers to that region of the
spectrum of from about 600 nm to about 700 nm.
[0124] "Infrared region of the spectrum" refers to that region of
the spectrum of from about 700 nm to about 1400 nm.
[0125] "Non-photosensitive" means not intentionally light
sensitive.
[0126] "Transparent" means capable of transmitting visible light or
imaging radiation without appreciable scattering or absorption.
[0127] The sensitometric terms "photospeed,""speed," or
"photographic speed" (also known as sensitivity), absorbance,
contrast, D.sub.min, and D.sub.max have conventional definitions
known in the imaging arts. In photothermographic materials,
D.sub.min is considered herein as image density achieved when the
photothermographic material is thermally developed without prior
exposure to radiation. It is the average of eight lowest density
values on the exposed side of the fiducial mark. In thermographic
materials, D.sub.min is considered herein as the image density in
the areas with the minimum application of heat by the thermal
printhead.
[0128] In photothermographic materials, the term D.sub.max is the
maximum image density achieved when the photothermographic material
is exposed to a particular radiation source and a given amount of
radiation energy and then thermally developed. In thermographic
materials, the term D.sub.max is the maximum image density achieved
when the thermographic material is thermally imaged with a given
amount of thermal energy.
[0129] The terms "density," "optical density (OD)," and "image
density" refer to the sensitometric term absorbance.
[0130] "Spd-1" (Speed-1) is Log1/E+4 corresponding to the density
value of 0.25 above D.sub.min where E is the exposure in
ergs/cm.sup.2.
[0131] "Spd-2" (Speed-2) is Log1/E+4 corresponding to the density
value of 1.0 above D.sub.min where E is the exposure in
ergs/cm.sup.2.
[0132] Average Contrast-1 ("AC-1") is the absolute value of the
slope of the line joining the density points of 0.60 and 2.00 above
D.sub.min.
[0133] "Archival Stability" or "Dark stability" is the stability of
the imaged film when stored for a period of time under temperature
and relative humidity conditions defined in the Examples.
[0134] "Aspect ratio" refers to the ratio of particle or grain
"ECD" to particle or grain thickness wherein ECD (equivalent
circular diameter) refers to the diameter of a circle having the
same projected area as the particle or grain.
[0135] "Width index" is a measure of particle size distribution
within a defined range [See, T. Allen, Particle Size Measurement,
Vol I, Chapman & Hall, London, UK, 1997, p. 54]. As used
herein, the width index is determined from the 14.sup.th,
50.sup.th, and 86.sup.th percentile of the cumulative frequency
distribution for the characteristic particle dimension under
consideration, defined by the following formula: [ ( 50 .times.
.times. percentile / 14 .times. .times. percentile ) + ( 86 .times.
.times. percentile / 50 .times. .times. percentile ) ] 2
##EQU1##
[0136] Using this formula, a dispersion of completely monodisperse
particles would have a width index of one.
[0137] The phrase "organic silver coordinating ligand" refers to an
organic molecule capable of forming a bond with a silver atom.
Although the compounds so formed are technically silver
coordination complexes or silver compounds they are also often
referred to as silver salts.
[0138] In the compounds described herein, no particular double bond
geometry (for example, cis or trans) is intended by the structures
drawn unless otherwise specified. Similarly, in compounds having
alternating single and double bonds and localized charges their
structures are drawn as a formalism. In reality, both electron and
charge delocalization exists throughout the conjugated chain.
[0139] As is well understood in this art, for the chemical
compounds herein described, substitution is not only tolerated, but
is often advisable and various substituents are anticipated on the
compounds used in the present invention unless otherwise stated.
Thus, when a compound is referred to as "having the structure" of,
or as "a derivative" of, a given formula, any substitution that
does not alter the bond structure of the formula or the shown atoms
within that structure is included within the formula, unless such
substitution is specifically excluded by language.
[0140] As a means of simplifying the discussion and recitation of
certain substituent groups, the term "group" refers to chemical
species that may be substituted as well as those that are not so
substituted. Thus, the term "alkyl group" is intended to include
not only pure hydrocarbon alkyl chains, such as methyl, ethyl,
n-propyl, t-butyl, cyclohexyl, iso-octyl, and octadecyl, but also
alkyl chains bearing substituents known in the art, such as
hydroxyl, alkoxy, phenyl, halogen atoms (F, Cl, Br, and I), cyano,
nitro, amino, and carboxy. For example, alkyl group includes ether
and thioether groups (for example
CH.sub.3--CH.sub.2--CH.sub.2--O--CH.sub.2-- and
CH.sub.3--CH.sub.2--CH.sub.2--S--CH.sub.2--), hydroxyalkyl (such as
1,2-dihydroxyethyl), haloalkyl, nitroalkyl, alkylcarboxy,
carboxyalkyl, carboxamido, sulfoalkyl, and other groups readily
apparent to one skilled in the art. Substituents that adversely
react with other active ingredients, such as very strongly
electrophilic or oxidizing substituents, would, of course, be
excluded by the ordinarily skilled artisan as not being inert or
harmless.
[0141] Research Disclosure is a publication of Kenneth Mason
Publications Ltd., Dudley House, 12 North Street, Emsworth,
Hampshire PO10 7DQ England (also available from Emsworth Design
Inc., 147 West 24th Street, New York, N.Y. 10011).
[0142] Other aspects, advantages, and benefits of the present
invention are apparent from the detailed description, examples, and
claims provided in this application.
The Photocatalyst
[0143] The photothermographic materials include one or more
photocatalysts in the photothermographic emulsion layer(s). Useful
photocatalysts are typically photosensitive silver halides such as
silver bromide, silver iodide, silver chloride, silver bromoiodide,
silver chlorobromoiodide, silver chlorobromide, and others readily
apparent to one skilled in the art. Mixtures of silver halides can
also be used in any suitable proportion. Silver bromide and silver
bromoiodide are more preferred silver halides, with the latter
silver halide having up to 10 mol % silver iodide based on total
silver halide.
[0144] In some embodiments, higher amounts of iodide may be present
in the photosensitive silver halide grains up to the saturation
limit of iodide as described in U.S. patent application Publication
2004/0053173 (Maskasky et al.).
[0145] The shape (morphology) of the photosensitive silver halide
grains used in the present need not be limited. The silver halide
grains may have any crystalline habit including cubic, octahedral,
tetrahedral, orthorhombic, rhombic, dodecahedral, other polyhedral,
tabular, laminar, twinned, or platelet morphologies and may have
epitaxial growth of crystals thereon. If desired, a mixture of
these crystals can be employed. Silver halide grains having cubic
and tabular morphology (or both) are preferred. More preferably,
the silver halide grains are predominantly (at least 50% based on
total silver halide) present as tabular grains.
[0146] The silver halide grains may have a uniform ratio of halide
throughout. They may have a graded halide content, with a
continuously varying ratio of, for example, silver bromide and
silver iodide or they may be of the core-shell type, having a
discrete core of one or more silver halides, and a discrete shell
of one of more different silver halides. Core-shell silver halide
grains useful in photothermographic materials and methods of
preparing these materials are described for example in U.S. Pat.
No. 5,382,504 (Shor et al.), incorporated herein by reference.
Iridium and/or copper doped core-shell and non-core-shell grains
are described in U.S. Pat. No. 5,434,043 (Zou et al.) and U.S. Pat.
No. 5,939,249 (Zou), both incorporated herein by reference.
[0147] In some instances, it may be helpful to prepare the
photosensitive silver halide grains in the presence of a
hydroxytetraazaindene or an N-heterocyclic compound comprising at
least one mercapto group as described in U.S. Pat. No.
6,413,710(Shor et al.), that is incorporated herein by
reference.
[0148] The photosensitive silver halide can be added to (or formed
within) the emulsion layer(s) in any fashion as long as it is
placed in catalytic proximity to the non-photosensitive source of
reducible silver ions in the co-precipitate.
[0149] It is preferred that the silver halide grains be preformed
and prepared by an ex-situ process, chemically and spectrally
sensitized, and then be added to and physically mixed with the
non-photosensitive source of reducible silver ions.
[0150] It is also possible to form the source of reducible silver
ions in the presence of ex-situ-prepared silver halide grains. In
this process, the co-precipitated source of reducible silver ions
is formed in the presence of the preformed silver halide grains.
Co-precipitation of the reducible source of silver ions in the
presence of silver halide provides a more intimate mixture of the
two materials [see, for example U.S. Pat. No. 3,839,049 (Simons)]
to provide a "preformed emulsion." This method is useful when
non-tabular silver halide grains are used.
[0151] In general, the non-tabular silver halide grains used in
this invention can vary in average diameter of up to several
micrometers (.mu.m) and they usually have an average particle size
of from about 0.01 to about 1.5 .mu.m (preferably from about 0.03
to about 1.0 .mu.m, and more preferably from about 0.05 to about
0.8 .mu.m). The average size of the photosensitive silver halide
grains is expressed by the average diameter if the grains are
spherical, and by the average of the diameters of equivalent
circles for the projected images if the grains are cubic, tabular,
or other non-spherical shapes. Representative grain sizing methods
are described by in Particle Size Analysis, ASTM Symposium on Light
Microscopy, R. P. Loveland, 1955, pp. 94-122, and in C. E. K. Mees
and T. H. James, The Theory of the Photographic Process, Third
Edition, Macmillan, New York, 1966, Chapter 2.
[0152] In most preferred embodiments of this invention, the silver
halide grains are provided predominantly (based on at least 50 mol
% silver) as tabular silver halide grains that are considered
"ultrathin" and have an average thickness of at least 0.02 .mu.m
and up to and including 0.10 .mu.m (preferably an average thickness
of at least 0.03 .mu.m and more preferably of at least 0.04 .mu.m,
and up to and including 0.08 .mu.m and more preferably up to and
including 0.07 .mu.m).
[0153] In addition, these ultrathin tabular grains have an
equivalent circular diameter (ECD) of at least 0.5 .mu.m
(preferably at least 0.75 .mu.m, and more preferably at least 1
.mu.m). The ECD can be up to and including 8 .mu.m (preferably up
to and including 6 .mu.m, and more preferably up to and including 4
.mu.m).
[0154] The aspect ratio of the useful tabular grains is at least
5:1 (preferably at least 10:1, and more preferably at least 15:1)
and generally up to 50:1. The grain size of ultrathin tabular
grains may be determined by any of the methods commonly employed in
the art for particle size measurement, such as those described
above. Ultrathin tabular grains and their method of preparation and
use in photothermographic materials are described in U.S. Pat. No.
6,576,410 (Zou et al.) and U.S. Pat. No. 6,673,529 (Daubendiek et
al.) that are incorporated herein by reference.
[0155] The ultrathin tabular silver halide grains can also be doped
using one or more of the conventional metal dopants known for this
purpose including those described in Research Disclosure item
38957, September, 1996 and U.S. Pat. No. 5,503,970 (Olm et al.),
incorporated herein by reference. Preferred dopants include iridium
(III or IV) and ruthenium (II or III) salts. Particularly preferred
silver halide grains are ultrathin tabular grains containing
iridium-doped azole ligands. Such tabular grains and their method
of preparation are described in copending and commonly assigned
U.S. Ser. No. 10/826,708 (filed on Apr. 16, 2004 by Olm et al.)
that is incorporated herein by reference.
[0156] It is also possible to form some in-situ silver halide, by a
process in which an inorganic halide- or an organic
halogen-containing compound is added to an organic silver salt to
partially convert the silver of the organic silver salt to silver
halide as described in U.S. Pat. No. 3,457,075 (Morgan et al.).
[0157] The one or more light-sensitive silver halides used in the
photothermographic materials are preferably present in an amount of
from about 0.005 to about 0.5 mole (more preferably from about 0.01
to about 0.25 mole, and most preferably from about 0.03 to about
0.15 mole) per mole of non-photosensitive source of reducible
silver ions.
Chemical Sensitizers
[0158] If desired, the photosensitive silver halides used in the
photothermographic materials can be chemically sensitized using any
useful compound that contains sulfur, tellurium, or selenium, or
may comprise a compound containing gold, platinum, palladium,
ruthenium, rhodium, iridium, or combinations thereof, a reducing
agent such as a tin halide or a combination of any of these. The
details of these materials are provided for example, in T. H.
James, The Theory of the Photographic Process, Fourth Edition,
Eastman Kodak Company, Rochester, N.Y., 1977, Chapter 5, pp.
149-169. Suitable conventional chemical sensitization procedures
and compounds are also described in U.S. Pat. No. 1,623,499
(Sheppard et al.), U.S. Pat. No. 2,399,083 (Waller et al.), U.S.
Pat. No. 3,297,447 (McVeigh), U.S. Pat. No. 3,297,446 (Dunn), U.S.
Pat. No. 5,049,485 (Deaton), U.S. Pat. No. 5,252,455 (Deaton), U.S.
Pat. No. 5,391,727 (Deaton), U.S. Pat. No. 5,912,111 (Lok et al.),
U.S. Pat. No. 5,759,761 (Lushington et al.), U.S. Pat. No.
6,296,998 (Eikenberry et al), and U.S. Pat. No. 5,691,127
(Daubendiek et al.), and EP 0 915 371 A1 (Lok et al.), all
incorporated herein by reference.
[0159] Certain substituted or and unsubstituted thioureas can be
used as chemical sensitizers including those described in U.S. Pat.
No. 6,296,998 (Eikenberry et al.), U.S. Pat. No. 6,322,961 (Lam et
al.), U.S. Pat. No. 4,810,626 (Burgmaier et al.), and U.S. Pat. No.
6,368,779 (Lynch et al.), all of the which are incorporated herein
by reference.
[0160] Still other useful chemical sensitizers include tellurium-
and selenium-containing compounds that are described in and U.S.
Pat. No. 5,158,892 (Sasaki et al.), U.S. Pat. No. 5,238,807 (Sasaki
et al.), U.S. Pat. No. 5,942,384 (Arai et al.) U.S. Pat. No.
6,620,577 (Lynch et al.), and U.S. Pat. No. 6,699,647 (Lynch et
al.), all of which are incorporated herein by reference.
[0161] Noble metal sensitizers for use in the present invention
include gold, platinum, palladium and iridium. Gold (I or III)
sensitization is particularly preferred, and described in U.S. Pat.
No. 5,858,637 (Eshelman et al.) and U.S. Pat. No. 5,759,761
(Lushington et al.). Combinations of gold(III) compounds and either
sulfur- or tellurium-containing compounds are useful as chemical
sensitizers and are described in U.S. Pat. No. 6,423,481 (Simpson
et al.). All of the above references are incorporated herein by
reference.
[0162] In addition, sulfur-containing compounds can be decomposed
on silver halide grains in an oxidizing environment according to
the teaching in U.S. Pat. No. 5,891,615 (Winslow et al.). Examples
of sulfur-containing compounds that can be used in this fashion
include sulfur-containing spectral sensitizing dyes.
[0163] Other useful sulfur-containing chemical sensitizing
compounds that can be decomposed in an oxidized environment are the
diphenylphosphine sulfide compounds described in copending and
commonly assigned U.S. Ser. No. 10/731,251 (filed Dec. 9, 2003 by
Simpson, Burleva, and Sakizadeh), incorporated herein by
reference.
[0164] The chemical sensitizers can be used in making the silver
halide emulsions in conventional amounts that generally depend upon
the average size of silver halide grains. Generally, the total
amount is at least 10.sup.-10 mole per mole of total silver, and
preferably from about 10.sup.-8 to about 10.sup.-2 mole per mole of
total silver. The upper limit can vary depending upon the
compound(s) used, the level of silver halide, and the average grain
size and grain morphology.
Spectral Sensitizers
[0165] The photosensitive silver halides used in the
photothermographic materials may be spectrally sensitized with one
or more spectral sensitizing dyes that are known to enhance silver
halide sensitivity to ultraviolet, visible, and/or infrared
radiation of interest. Non-limiting examples of sensitizing dyes
that can be employed include cyanine dyes, merocyanine dyes,
complex cyanine dyes, complex merocyanine dyes, holopolar cyanine
dyes, hemicyanine dyes, styryl dyes, and hemioxanol dyes. They may
be added at any stage in chemical finishing. of the
photothermographic emulsion, but are generally added after chemical
sensitization. It is particularly useful that the photosensitive
silver halides be spectrally sensitized to a wavelength of from
about 300 to about 750 nm, preferably from about 300 to about 600
nm, more preferably to a wavelength of from about 300 to about 450
nm, even more preferably from a wavelength of from about 360 to 420
nm, and most preferably from a wavelength of from about 380 to
about 420 nm. A worker skilled in the art would know which dyes
would provide the desired spectral sensitivity.
[0166] Suitable sensitizing dyes such as those described in U.S.
Pat. No. 3,719,495 (Lea), U.S. Pat. No. 4,396,712 (Kinoshita et
al.), U.S. Pat. No. 4,439,520 (Kofron et al.), U.S. Pat. No.
4,690,883 (Kubodera et al.), U.S. Pat. No. 4,840,882 (Iwagaki et
al.), U.S. Pat. No. 5,064,753 (Kohno et al.), U.S. Pat. No.
5,281,515 (Delprato et al.), U.S. Pat. No. 5,393,654 (Burrows et
al), U.S. Pat. No. 5,441,866 (Miller et al.), U.S. Pat. No.
5,508,162 (Dankosh), U.S. Pat. No. 5,510,236 (Dankosh), and U.S.
Pat. No. 5,541,054 (Miller et al.), and Japanese Kokai 2000-063690
(Tanaka et al.), 2000-112054 (Fukusaka et al.), 2000-273329 (Tanaka
et al.), 2001-005145 (Arai), 2001-064527 (Oshiyama et al.), and
2001-154305 (Kita et al.), and Research Disclosure, item 308119,
Section IV, December, 1989. All of these publications are
incorporated herein by reference.
[0167] Teachings relating to specific combinations of spectral
sensitizing dyes also provided in U.S. Pat. No. 4,581,329 (Sugimoto
et al.), U.S. Pat. No. 4,582,786 (Ikeda et al.), U.S. Pat. No.
4,609,621 (Sugimoto et al.), U.S. Pat. No. 4,675,279 (Shuto et
al.), U.S. Pat. No. 4,678,741 (Yamada et al.), U.S. Pat. No.
4,720,451 (Shuto et al.), U.S. Pat. No. 4,818,675 (Miyasaka et
al.), U.S. Pat. No. 4,945,036 (Arai et al.), and U.S. Pat. No.
4,952,491 (Nishikawa et al.), all of which are incorporated herein
by reference.
[0168] Also useful are spectral sensitizing dyes that decolorize by
the action of light or heat as described in U.S. Pat. No. 4,524,128
(Edwards et al.), and Japanese Kokai 2001-109101 (Adachi),
2001-154305 (Kita et al.), and 2001-183770 (Hanyu et al.), all of
which are incorporated herein by reference.
[0169] Dyes may be selected for the purpose of supersensitization
to attain much higher sensitivity than the sum of sensitivities
that can be achieved by using each dye alone.
[0170] An appropriate amount of spectral sensitizing dye added is
generally about 10.sup.-10 to 10.sup.-1 mole, and preferably, from
about 10.sup.-7 to 10.sup.-2 mole per mole of silver halide.
Non-Photosensitive Source of Reducible Silver Ions
[0171] The non-photosensitive source of reducible silver ions used
in the thermally developable materials includes one or more organic
silver salts of nitrogen-containing heterocyclic compounds
containing an imino group. Such silver(I) salts are comparatively
stable to light and form a silver image when heated to 50.degree.
C. or higher in the presence of an exposed silver halide (for
photothermographic materials) and a reducing agent. These salts are
also used in thermographic materials where they directly
participate in thermal image formation.
[0172] Representative organic silver salts include, but are not
limited to, silver salts of benzotriazole and substituted
derivatives thereof (for example, silver methylbenzotriazole and
silver 5-chlorobenzotriazole), silver salts of nitrogen acids
selected from the group consisting of imidazole, pyrazole, urazole,
1,2,4-triazole and 1H-tetrazole nitrogen acids or combinations
thereof, as described in U.S. Pat. No. 4,220,709 (deMauriac). Also
included are the silver salts of imidazole and imidazole
derivatives as described in U.S. Pat. No. 4,260,677 (Winslow et
al.). Both of these patents are incorporated herein by reference. A
nitrogen acid as described herein is intended to include those
compounds which have the moiety --NH-- in the heterocyclic nucleus.
Particularly useful silver salts are the silver salts of
benzotriazole, substituted derivatives thereof, or mixtures of two
or more of these salts. A silver salt of benzotriazole is most
preferred.
[0173] While the noted organic silver salts are the predominant
silver salts in the materials, secondary organic silver salts can
be used if present in "minor" amounts (less than 40 mol % based on
the total moles of organic silver salts). However, these secondary
organic silver salts are not generally part of the
co-precipitate.
[0174] Such secondary organic silver salts include silver salts of
heterocyclic compounds containing mercapto or thione groups and
derivatives thereof such as silver triazoles, oxazoles, thiazoles,
thiazolines, imidazoles, diazoles, pyridines, and triazines as
described in U.S. Pat. No. 4,123,274 (Knight et al.) and U.S. Pat.
No. 3,785,830 (Sullivan et al.). Examples of other useful silver
salts of mercapto or thione substituted compounds that do not
contain a heterocyclic nucleus include silver salts of thioglycolic
acids, dithiocarboxylic acids, and thioamides. Silver salts of
organic acids including silver salts of long-chain aliphatic or
aromatic carboxylic acids may also be included as secondary silver
salts.
[0175] Secondary organic silver salts can also be core-shell silver
salts as described in U.S. Pat. No. 6,355,408 (Whitcomb et al.),
that is incorporated herein by reference wherein a core has one or
more silver salts and a shell has one or more different silver
salts. Other secondary organic silver salts can be silver dimer
compounds that comprise two different silver salts as described in
U.S. Pat. No. 6,566,045 (Whitcomb) that is incorporated herein by
reference.
[0176] Still other useful secondary silver salts are the silver
core-shell compounds comprising a primary core comprising one or
more photosensitive silver halides, or one or more
non-photosensitive inorganic metal salts or non-silver containing
organic salts, and a shell at least partially covering the primary
core, wherein the shell comprises one or more non-photosensitive
silver salts, each of which silver salts comprises a organic silver
coordinating ligand. Such compounds are described in U.S. patent
application Publication 2004/0023164 (Bokhonov et al.) that is
incorporated herein by reference.
[0177] The one or more non-photosensitive sources of reducible
silver ions (both primary and secondary organic silver salts) are
preferably present in a total amount of about 5% by weight to about
70% by weight, and more preferably, about 10% to about 50% by
weight, based on the total dry weight of the emulsion layers.
Alternatively, the total amount of reducible silver ions is
generally present in an amount of from about 0.001 to about 0.2
mol/m.sup.2 of the dry thermally developable material (preferably
from about 0.01 to about 0.05 mol/m.sup.2).
[0178] The total amount of silver (from all silver sources) in the
photothermographic materials is generally at least 0.002
mol/m.sup.2 and preferably from about 0.01 to about 0.05
mol/m.sup.2 for single-sided materials. For double-sided coated
materials, total amount of silver from all sources would be
doubled. The amount of silver in the thermographic materials is
generally from about 0.01 to about 0.05 mol/m.sup.2.
The Silver Salt of Mercaptotriazole Toners
[0179] Toners are compounds that when added to the
photothermographic imaging layer(s) shift the color of the
developed silver image from yellowish-orange to brown-black or
blue-black. Many toners also increase the rate of development of
the silver image. Compounds useful in this invention are silver
salts of mercaptotriazole toner compounds. Thus, the second organic
silver salts useful in the present invention include one or more
silver salts of mercaptotriazoles. Numerous mercaptotriazoles are
described in U.S. Pat. No. 3,832,186 (Masuda et al.), U.S. Pat. No.
4,451,561 (Hirabayshi et al.), U.S. Pat. No. 5,149,620 (Simpson et
al.), and U.S. Pat. No. 6,713,240 (Lynch et al.), all incorporated
herein by reference.
[0180] In preferred embodiments, the useful mercaptotriazoles can
be represented by the following Structure (I): ##STR3## wherein
R.sub.1 and R.sub.2 independently represent hydrogen, a substituted
or unsubstituted alkyl group of from 1 to 7 carbon atoms (such as
methyl, ethyl, isopropyl, t-butyl, n-hexyl, hydroxymethyl, and
benzyl), a substituted or unsubstituted alkenyl group having 2 to 5
carbon atoms in the hydrocarbon chain (such as ethenyl,
1,2-propenyl, methallyl, and 3-buten-1-yl), a substituted or
unsubstituted cycloalkyl group having 5 to 7 carbon atoms forming
the ring (such as cyclopenyl, cyclohexyl, and
2,3-dimethylcyclohexyl), a substituted or unsubstituted aromatic or
non-aromatic heterocyclyl group having 5 or 6 carbon, nitrogen,
oxygen, or sulfur atoms forming the aromatic or non-aromatic
heterocyclyl group (such as pyridyl, furanyl, thiazolyl, and
thienyl), an amino or amide group (such as amino or acetamido), and
a substituted or unsubstituted aryl group having 6 to 10 carbon
atoms forming the aromatic ring (such as phenyl, tolyl, naphthyl,
and 4-ethoxyphenyl).
[0181] In addition, R.sub.1 and R.sub.2 can be a substituted or
unsubstituted Y.sub.1-(CH.sub.2).sub.k-group wherein Y.sub.1 is a
substituted or unsubstituted aryl group having 6 to 10 carbon atoms
as defined above for R.sub.1 and R.sub.2, or a substituted or
unsubstituted aromatic or non-aromatic heterocyclyl group as
defined above for R.sub.1. Also, k is 1-3. In particular, R.sub.1
and R.sub.2 can represent a divalent linking group (such as a
1,4-phenylene, methylene, or ethylene group) that links two
mercaptotriazole groups (that is Y.sub.1 is another
mercaptotriazole group).
[0182] Alternatively, R.sub.1 and R.sub.2 taken together can form a
substituted or unsubstituted, saturated or unsaturated 5- to
7-membered aromatic or non-aromatic nitrogen-containing
heterocyclic ring comprising carbon, nitrogen, oxygen, or sulfur
atoms in the ring (such as pyridyl, diazinyl, triazinyl,
piperidine, morpholine, pyrrolidine, pyrazolidine, and
thiomorpholine).
[0183] Additionally, R.sub.2 may represent a carboxy group or its
salts.
[0184] The definition of mercaptotriazoles of Structure (I) also
includes the following provisos:
[0185] 1) R.sub.1 and R.sub.2 are not simultaneously hydrogen,
and
[0186] 2) When R.sub.1 is unsubstituted phenyl, R.sub.2 is not
hydrogen.
[0187] Preferably, R.sub.1 is a substituted or unsubstituted alkyl
group (such as methyl, t-butyl, and benzyl), or a substituted
phenyl group (such as, o-, m-, and p-tolyl or o-, m-, and
p-chloro). More preferably, R.sub.1 is benzyl.
[0188] Preferably, R.sub.2 is hydrogen, acetamido, or
hydroxymethyl. More preferably, R.sub.2 is hydrogen.
[0189] It is well known that heterocyclic compounds exist in
tautomeric forms. Both annular (ring) tautomerism and substituent
tautomerism are possible. In 1,2,4-mercaptotriazoles, at least
three tautomers (a 1H form, a 2H form, and a 4H form) are possible.
Thiol-thione substituent tautomerism is also possible.
Interconversion among these tautomers can occur rapidly and
individual tautomers are usually not isolatable, although one
tautomeric form may predominate. For the 1,2,4-mercaptotriazoles of
this invention, the 4H-thiol structural formalism is used with the
understanding that other tautomers do exist.
[0190] The exact crystal structure of the co-precipitate of the
first organic silver salt comprising a nitrogen-containing
heterocyclic compound containing an imino group, and the second
organic silver salt comprising a silver salt of a mercaptotriazole,
is not known. However, we believe that the following Structure (II)
is one fair representation of a silver salt of a mercaptotriazole
molecule. ##STR4## wherein R.sub.1 and R.sub.2 are as defined
above.
[0191] Representative mercaptotriazoles useful in the practice of
the present invention include the silver salts (that is, silver
coordination complexes or silver compounds) of the following
compounds T-1 through T-59: ##STR5## ##STR6## ##STR7## ##STR8##
##STR9## ##STR10## ##STR11## ##STR12## ##STR13## ##STR14##
[0192] Compounds T-1, T-2, T-11, T-12, T-16, T-37, T-41, and T-44
are more preferred in the practice of this invention, and Compound
T-1 is most preferred.
[0193] The mercaptotriazole compounds described herein can be
readily prepared using known synthetic methods. For example,
compound T-1 can be prepared as described in U.S. Pat. No.
4,628,059 (Finkelstein et al.). Additional preparations of various
mercaptotriazoles are described in U.S. Pat. No. 3,769,411
(Greenfield et al.), U.S. Pat. No. 4,183,925 (Baxter et al.), and
U.S. Pat. No. 6,074,813 (Asanuma et al.), DE 1 670 604 (Korosi),
and in Chem. Abstr. 1968, 69, 52114j. Some mercaptotriazole
compounds are commercially available.
Co-Precipitates
[0194] The non-photosensitive source of reducible silver ions and
the mercaptotriazole toner compound are incorporated into the
thermally developable materials as co-precipitated silver salts.
Thus, the co-precipitate is a mixture of "first" and "second"
organic silver salts in which the "first" organic silver salt
comprises one or more silver salts of nitrogen-containing
heterocyclic compounds containing an imino group (described above).
The "second" organic silver salt comprises one or more silver salts
of mercaptotriazoles (described above).
[0195] Preferably, the first organic silver salt is a silver salt
of a benzotriazole (described above) and the second organic silver
salt is a silver salt of a mercaptotriazole compound defined by
Structure (I) identified above.
[0196] The co-precipitate particles can have various shapes. For
example, they can be rod-shaped, cubic, tabular, or platelet in
form. Preferably, they are rod-shaped and have an aspect ratio of
at least 2, more preferably at least 3 and up to 20, and most
preferably of from about 3 to about 10. The particles (any shape)
generally have largest dimensions (length or diameter) ranging from
about 0.2 to about 0.8 .mu.m. The rod-shaped particles generally
have a diameter of less than or equal to 0.1 .mu.m and a length
that is less than 1 .mu.m. Preferably, the particles have a
diameter of from about 0.03 to about 0.07 .mu.m and a length of
from about 0.1 to about 0.5 .mu.m.
[0197] Where the co-precipitate particles are rod-shaped, the
distribution of co-precipitate crystals is relatively uniform in
size as defined by a width index for particle diameter of 1.25 or
less, and preferably from about 1.1 to about 1.2.
[0198] The most preferred co-precipitate particles are composed of
silver benzotriazole as the first organic silver salt and a silver
salt of the mercaptotriazole identified as Compound T-1 above as
the second organic silver salt. These particles have an aspect
ratio of from about 4 to about 7.5, a width index for grain
diameter of from about 1.1 to about 1.2, a length of from about 0.1
to about 0.3 .mu.m, and a diameter of from about 0.04 to about 0.06
.mu.m.
[0199] The distribution of the first and second organic silver
salts throughout the co-precipitate may take many forms so long as
at least some second organic silver salt is present within 25
volume % of the outer surface of the co -precipitate
[0200] Thus, in some embodiments, the first and second organic
silver salts are uniformly distributed throughout the
co-precipitate particle volume. These particles are substantially
homogenous in composition.
[0201] However, in other embodiments, there is a concentration
gradient of the second organic silver salt throughout the
co-precipitate particle. This concentration gradient can be
continuous and increase steadily in concentration from the center
of the particle to its outer surface. For example, the
concentration gradient can be defined using "volume % " of the
co-precipitate particle wherein 0 volume % represents the center of
the particle and 100 volume % represents the outer surface. Instead
of continuous concentration gradient, there can be discrete bands
of specific concentrations of the second organic silver salt at
specific volume regions of the particle, which bands are
interrupted by bands of the first organic silver salt. The
continuous gradients or discrete bands can be obtained by adding
the mercaptotriazole to the reaction mixture at particular times
using specific flow rates as one skilled in the art would
appreciate.
[0202] In preferred embodiments, there is more of the second
organic silver salt closer to the outer surface than towards the
center of the co-precipitate crystal. Thus, the second organic
silver salt is distributed predominantly near the co-precipitate
outer surface. For example, at least 95 mol % of the second organic
silver salt can be present within a localized portion that is from
about 75 to 100 volume % of the co-precipitate particle.
Preferably, at least 95 mol % of the second organic silver salt can
be present within a localized portion that is from about 90 to 100
volume % of the co-precipitate particle. More preferably, at least
95 mol % of the second organic silver salt can be present within a
localized portion that is from about 95 to 100 volume % of the
co-precipitate particle. Even more preferably, 100% of the second
organic silver salt is present within the defined localized
portions.
[0203] In still other preferred embodiments, the second organic
silver salt is at least partially covering the surface of the
co-precipitate, and more preferably, it completely covers the outer
particle surface.
[0204] The molar ratio of the first organic silver salt to the
second organic silver salt in the co-precipitate particle is
generally from about 100:1 to about 15:1 and preferably from about
60:1 to about 25:1. As noted above, these molar ratios can be
constant throughout the crystal (homogeneous), or vary within
regions and it is particularly different at the outer surface
compared to the particle center.
[0205] The co-precipitates of this invention are generally prepared
using certain conditions and procedure that will provide particles
with desired morphology and concentration gradients of the second
organic silver salt, depending upon amounts and times of addition
of various organic silver salts. Thus, the method of making the
co-precipitate is carried out by first preparing an aqueous
solution (solution A) of one or more suitable nitrogen-containing
heterocyclic compounds containing an imino group. These
heterocyclic compounds are generally present in solution A at a
concentration of at least 0.1 mol/l, and preferably from about 2 to
about 4 mol/l.
[0206] The one or more mercaptotriazoles are included within
Solution A or in a separate Solution A' at a concentration of at
least 0.1 mol/l, and preferably from about 0.5 to about 3
moles/liter. Solution A or A' can also contain one or more bases
(such as hydroxides) to adjust the pH. Preferably, solutions A and
A' are different so that upon addition the various organic silver
salts are formed at different rates and in different regions of the
co-precipitate particle.
[0207] An aqueous solution (Solution B) of one or more aqueous
soluble inorganic silver salts (such as silver nitrate) is also
prepared.
[0208] A suitable reaction vessel is used to make the primary
silver salts. In this vessel is an aqueous solution of from about 2
to about 10 weight % of one or more hydrophilic polymer binders
(see below) or water-dispersible hydrophobic polymer binders (in
latex form). Suitable bases (such as a hydroxide) may be included
to adjust the pH of this vessel solution to from about 7.5 to about
10 (preferably from about 8 to about 9.5).
[0209] Solutions A and B are then simultaneously added to the
reaction vessel at constant flow rates A.sub.1 and B.sub.1,
respectively, for up to 240 minutes while maintaining a constant pH
(generally from about 7.5 to about 10 and preferably from about 8
to about 9.5) and a constant vAg equal to or greater than -50 mV in
the reaction vessel. By greater than -50 mV is meant more positive
than -50 mV. The vAg is preferably maintained at greater than or
equal to 0 mV and more preferably greater than or equal to +50 mV.
The ratio of the molar flow rate Ato the total moles of silver
precipitated is generally from about 0.004 to about 0.04
mol/min/mol Ag of the imino-group-containing compound and the ratio
of the molar flow rate B.sub.1 to the total moles of silver
precipitated is generally from about 0.004 to about 0.04 mol
Ag/min/mol Ag. Optimum flow rates can be readily determined to
obtain particles of a desired aspect ratio and size with routine
experimentation. The contents of the reaction vessel are generally
kept at a constant temperature of from about 30 to about 75.degree.
C. and preferably from about 35 to about 55.degree. C.
[0210] Either or both of Solutions A and B can be introduced into
the reaction vessel at steady flow rates, or at variable flow
rates. For example, the flow rate of the addition of solution B can
be increased to flow rate B.sub.2 for up to 60 minutes while
maintaining constant temperature, pH, and vAg in the reaction
vessel. The ratio of flow rate B.sub.2 to flow rate B.sub.1 is from
about 1.4:1 to about 1.8:1. A further change in the flow rate of
Solution B can also be made by increasing it to flow rate B.sub.3
for up to 60 minutes while maintaining constant temperature, pH and
vAg in the reaction vessel. The ratio flow rate B.sub.3 to flow
rate B.sub.2 is from about 1.8:1 to about 2.2:1.
[0211] Solution A', if different from solution A, can be similarly
added to the reaction vessel at a steady or variable flow. For
example, the ratio of the molar flow rate A'.sub.1 to the total
moles of silver can be from about 0.004 to about 0.04 mol/min/mol
Ag. Solution A' may be added to the reaction vessel so that the
second organic silver salt is present within a localized portion of
the co-precipitate particle. For example, solution A' can be added
after at least 75 volume % of solution B has been added to the
reaction vessel. More preferably, solution A' is added to provide
at least 95 mol % of the second organic silver salt from within
about 90 to about 100 volume % of the particle.
[0212] The addition of solutions A (and A') and B to the reaction
vessel then produces a dispersion or a co-precipitate containing
two or more different organic silver salts within the hydrophilic
polymer binder or the water-dispersible polymer latex binder. The
one or more binders are generally present in the silver salt
dispersion in an amount preferably of from about 2 to about 10
weight %. Particularly useful hydrophilic polymer binders include
those hydrophilic binders described below in the "Binders" section,
and are preferably gelatin or a gelatin derivative.
[0213] In addition to the silver salts of one or more suitable
nitrogen-containing heterocyclic compounds containing an imino
group and the one or more silver salts of mercaptotriazoles,-the
co-precipitate can contain small amounts of other silver salts.
Thus, ternary and quaternary co-precipitates are envisioned.
[0214] Representative preparatory conditions and procedures are
illustrated in below in the Examples.
Reducing Agents
[0215] The thermally developable materials can include one or more
suitable reducing agents that would be apparent to one skilled in
the art to reduce silver(I) to metallic silver. Preferably, such
reducing agents are reductones or ascorbic acids.
[0216] A "reductone" reducing agent means a class of unsaturated,
di- or poly-enolic organic compounds which, by virtue of the
arrangement of the enolic hydroxyl groups with respect to the
unsaturated linkages, possess characteristic strong reducing power.
The parent compound, "reductone" is 3-hydroxy-2-oxo-propionaldehyde
(enol form) and has the structure HOCH.dbd.CH(OH)--CHO. In some
reductones, an amino group, a mono-substituted amino group or an
imino group may replace one or more of the enolic hydroxyl groups
without affecting the characteristic reducing behavior of the
compound. Examples of reductone reducing agents can be found in
U.S. Pat. No. 2,691,589 (Henn et al), U.S. Pat. No. 3,615,440
(Bloom), U.S. Pat. No. 3,664,835 (Youngquist et al.), U.S. Pat. No.
3,672,896 (Gabrielson et al.), U.S. Pat. No. 3,690,872 (Gabrielson
et al.), U.S. Pat. No. 3,816,137 (Gabrielson et al.), U.S. Pat. No.
4,371,603 (Bartels-Keith et al.), U.S. Pat. No. 5,712,081
(Andriesen et al.), and U.S. Pat. No. 5,427,905 (Freedman et al.),
all of which references are incorporated herein by reference.
[0217] An "ascorbic acid" reducing agent (also referred to as a
developer or developing agent) means ascorbic acid, complexes
thereof, and derivatives thereof. Ascorbic acid reducing agents are
described in a considerable number of publications in photographic
processes, including U.S. Pat. No. 5,236,816 (Purol et al.) and
references cited therein.
[0218] Useful ascorbic acid and reductone reducing agents include
ascorbic acid and the analogues, isomers, complexes, and
derivatives thereof. Such compounds include, but are not limited
to, D- or L-ascorbic acid, 2,3-dihydroxy-2-cyclohexen-1-one,
3,4-dihydroxy-5-phenyl-2(5H)-furanone, sugar-type derivatives
thereof (such as sorboascorbic acid, y-lactoascorbic acid,
6-desoxy-L-ascorbic acid, L-rhamnoascorbic acid,
imino-6-desoxy-L-ascorbic acid, glucoascorbic acid, fucoascorbic
acid, glucoheptoascorbic acid, maltoascorbic acid, L-arabosascorbic
acid), sodium ascorbate, niacinamide ascorbate, potassium
ascorbate, isoascorbic acid (or L-erythroascorbic acid), and salts
thereof (such as alkali metal, ammonium or others known in the
art), endiol type ascorbic acid, an enaminol type ascorbic acid, a
thioenol type ascorbic acid, and an enamin-thiol type ascorbic
acid, as described for example in EP 0 585 792 A1 (Passarella et
al.), EP 0 573 700 A1 (Lingier et al.), EP 0 588 408 A1 (Hieronymus
et al.), U.S. Pat. No. 5,498,511 (Yamashita et al.), U.S. Pat. No.
5,089,819 (Knapp), U.S. Pat. No. 5,278,035 (Knapp), U.S. Pat. No.
5,384,232 (Bishop et al.), U.S. Pat. No. 5,376,510 (Parker et al.),
and U.S. Pat. No. 2,688,549 (James et al.), Japanese Kokai 7-56286
(Toyoda), and Research Disclosure, publication 37152, March 1995.
Mixtures of these developing agents can be used if desired.
[0219] Particularly useful reducing agents are ascorbic acid mono-
or di-fatty acid esters such as the monolaurate, monomyristate,
monopalmitate, monostearate, monobehenate, diluarate, distearate,
dipalmitate, dibehenate, and dimyristate derivatives of ascorbic
acid as described in U.S. Pat. No. 3,832,186 (Masuda et al.) and
U.S. Pat. No. 6,309,814 (Ito). Preferred ascorbic acid reducing
agents and their methods of preparation are those described in
copending and commonly assigned U.S. Ser. No. 10/764,704 (filed on
Jan. 26, 2004 by Ramsden et al.) and those described in copending
and commonly assigned U.S. Ser. No. 10/_____ (filed on even date
herewith by Brick, Ramsden, and Lynch and entitled "Developer
Dispersions for Thermally Developable Materials") and having
Attorney Docket D-88215/JLT, both of which are incorporated herein
by reference. A preferred reducing agent is L-ascorbic acid
6-O-palmitate.
[0220] The reducing agent (or mixture thereof) described herein is
generally present as 1 to 10% (dry weight) of the emulsion layer.
In multilayer constructions, if the reducing agent is added to a
layer other than an emulsion layer, slightly higher proportions, of
from about 2 to 15 weight % may be more desirable. Co-developers
may be present generally in an amount of from about 0.001% to about
1.5% (dry weight) of the emulsion layer coating.
Other Addenda
[0221] The photothermographic materials can also contain other
additives such as shelf-life stabilizers, antifoggants, contrast
enhancing agents, development accelerators, acutance dyes,
post-processing stabilizers or stabilizer precursors, thermal
solvents (also known as melt formers), humectants, and other
image-modifying agents as would be readily apparent to one skilled
in the art.
[0222] To further control the properties of photothermographic
materials, (for example, contrast, D.sub.min, speed, or fog), it
may be preferable to add one or more heteroaromatic mercapto
compounds or heteroaromatic disulfide compounds of the formulae
Ar--S-M.sup.1 and Ar--S--S--Ar, wherein M.sup.1 represents a
hydrogen atom or an alkali metal atom and Ar represents a
heteroaromatic ring or fused hetero-aromatic ring containing one or
more of nitrogen, sulfur, oxygen, selenium, or tellurium atoms.
Preferably, the heteroaromatic ring comprises benzimidazole,
naphthimidazole, benzothiazole, naphthothiazole, benzoxazole,
naphthoxazole, benzoselenazole, benzotellurazole, imidazole,
okazole, pyrazole, triazole, thiazole, thiadiazole, tetrazole,
triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine,
quinoline, or quinazolinone. Useful heteroaromatic mercapto
compounds are described as supersensitizers in EP 0 559 228 B1
(Philip Jr. et al.).
[0223] The photothermographic materials can be further protected
against the production of fog and can be stabilized against loss of
sensitivity during storage. Suitable antifoggants and stabilizers
that can be used alone or in combination include thiazolium salts
as described in U.S. Pat. No. 2,131,038 (Brooker et al.) and U.S.
Pat. No. 2,694,716 (Allen), azaindenes as described in U.S. Pat.
No. 2,886,437 (Piper), triazaindolizines as described in U.S. Pat.
No. 2,444,605 (Heimbach), urazoles as described in U.S. Pat. No.
3,287,135 (Anderson), sulfocatechols as described in U.S. Pat. No.
3,235,652 (Kennard), oximes as described in GB 623,448 (Carrol et
al.), polyvalent metal salts as described in U.S. Pat. No.
2,839,405 (Jones), thiuronium salts as described in U.S. Pat. No.
3,220,839 (Herz), compounds having --SO.sub.2CBr.sub.3 groups as
described in U.S. Pat. No. 5,594,143 (Kirk et al.) and U.S. Pat.
No. 5,374,514 (Kirk et al.), and
2-(tribromomethyl-sulfonyl)quinoline compounds as described in U.S.
Pat. No. 5,460,938 (Kirk et al.).
[0224] The photothermographic materials may also include one or
more polyhalo antifoggants that include one or more polyhalo
substituents including but not limited to, dichloro, dibromo,
trichloro, and tribromo groups. The antifoggants can be aliphatic,
alicyclic or aromatic compounds, including aromatic heterocyclic
and carbocyclic compounds. Particularly useful antifoggants of this
type are polyhalo antifoggants, such as those having a
--SO.sub.2C(X').sub.3 group wherein X' represents the same or
different halogen atoms.
[0225] Another class of useful antifoggants includes those
compounds described in U.S. Pat. No. 6,514,678 (Burgmaier et al.),
incorporated herein by reference.
[0226] Advantageously, the photothermographic materials also
include one or more thermal solvents (also called "heat solvents,"
"thermosolvents," "melt formers," "melt modifiers," "eutectic
formers," "development modifiers," "waxes," or "plasticizers").
[0227] By the term "thermal solvent" is meant an organic material
that becomes a plasticizer or liquid solvent for at least one of
the imaging layers upon heating at a temperature above 60.degree.
C. Useful for that purpose are polyethylene glycols having a mean
molecular weight in the range of 1,500 to 20,000, urea, methyl
sulfonamide, ethylene carbonate, and compounds described as thermal
solvents in Research Disclosure, December 1976, item 15027, pp.
26-28. Other representative examples of such compounds include
niacinamide, hydantoin, 5,5-dimethylhydantoin, salicylanilide,
succinimide, phthalimide, N-potassium-phthalimide,
N-hydroxyphthalimide, N-hydroxy-1,8-naphthalimide, phthalazine,
1-(2H)-phthalazinone, 2-acetylphthalazinone, benzanilide,
1,3-dimethylurea, 1,3-diethylurea, 1,3-diallylurea,
meso-erythritol, D-sorbitol, tetrahydro-2-pyrimidone, glycouril,
2-imidazolidone, 2-imidazolidone-4-carboxylic acid, and
benzenesulfonamide. Combinations of these compounds can also be
used including, for example, a combination of succinimide and
1,3-dimethylurea.
[0228] It may be advantageous to include a base-release agent or
base precursor in the photothermographic materials. Representative
base-release agents or base precursors include guanidinium
compounds, such as guanidinium trichloroacetate, and other
compounds that are known to release a base but do not adversely
affect photographic silver halide materials, such as phenylsulfonyl
acetates as described in U.S. Pat. No. 4,123,274 (Knight et
al.).
Phosphors
[0229] In some embodiments, it is also effective to incorporate
X-radiation-sensitive phosphors in the photothermographic materials
as described in U.S. Pat. No. 6,573,033 (Simpson et al.) and U.S.
Pat. No. 6,440,649 (Simpson et al.), both of which are incorporated
herein by reference. Other useful phosphors are primarily
"activated" phosphors known as phosphate phosphors and borate
phosphors. Examples of these phosphors are rare earth phosphates,
yttrium phosphates, strontium phosphates, or strontium
fluoroborates (including cerium activated rare earth or yttrium
phosphates, or europium activated strontium fluoroborates) as
described in U.S. Ser. No. 10/826,500 (filed Apr. 16, 2004 by
Simpson, Sieber, and Hansen).
[0230] The one or more phosphors used in the practice of this
invention are present in the photothermographic materials in an
amount of at least 0.1 mole per mole, and preferably from about 0.5
to about 20 mole per mole, of total silver in the
photothermographic material.
Binders
[0231] The photosensitive silver halide (if present), the
co-precipitate of the first and second organic silver salts
described above, the reducing agent, antifoggant(s), and any other
additives used in the present invention are added to and coated in
one or more binders using a suitable aqueous solvent. Thus,
aqueous-based formulations are used to prepare the thermographic
and photothermographic materials. Mixtures of different types of
hydrophilic and/or hydrophobic binders can also be used.
Preferably, hydrophilic polymer binders and water-dispersible
polymeric latexes are used to provide aqueous-based formulations
and thermally developable materials.
[0232] Examples of useful hydrophilic polymer binders include, but
are not limited to, proteins and protein derivatives, gelatin and
gelatin derivatives (hardened or unhardened), cellulosic materials,
acrylamide/methacrylamide polymers, acrylic/methacrylic polymers,
polyvinyl pyrrolidones, polyvinyl alcohols, poly(vinyl lactams),
polymers of sulfoalkyl acrylate or methacrylates, hydrolyzed
polyvinyl acetates, polyamides, polysaccharides, and other
naturally occurring or synthetic vehicles commonly known for use in
aqueous-based photographic emulsions (see for example Research
Disclosure, item 38957, noted above).
[0233] Particularly useful hydrophilic polymer binders are gelatin,
gelatin derivatives, polyvinyl alcohols, and cellulosic materials.
Gelatin and its derivatives are most preferred, and comprise at
least 75 weight % of total binders when a mixture of binders is
used.
[0234] Aqueous dispersions of water-dispersible polymeric latexes
may also be used, alone or with hydrophilic or hydrophobic binders
described herein. Such dispersions are described in, for example,
U.S. Pat. No. 4,504,575 (Lee), U.S. Pat. No. 6,083,680 (Ito et al),
U.S. Pat. No. 6,100,022 (Inoue et al.), U.S. Pat. No. 6,132,949
(Fujita et al.), U.S. Pat. No. 6,132,950 (Ishigaki et al.), U.S.
Pat. No. 6,140,038 (Ishizuka et al.), U.S. Pat. No. 6,150,084 (Ito
et al.), U.S. Pat. No. 6,312,885 (Fujita et al.), and U.S. Pat. No.
6,423,487 (Naoi), all of which are incorporated herein by
reference.
[0235] Minor amounts (less than 50 weight % based on total binder
weight) of hydrophobic binders (not in latex form) may also be
used. Examples of typical hydrophobic binders include polyvinyl
acetals, polyvinyl chloride, polyvinyl acetate, cellulose acetate,
cellulose acetate butyrate, polyolefins, polyesters, polystyrenes,
polyacrylonitrile, polycarbonates, methacrylate copolymers, maleic
anhydride ester copolymers, butadiene-styrene copolymers, and other
materials readily apparent to one skilled in the art. The polyvinyl
acetals (such as polyvinyl butyral and polyvinyl formal), cellulose
ester polymers, and vinyl copolymers (such as polyvinyl acetate and
polyvinyl chloride) are preferred. Particularly suitable binders
are polyvinyl butyral resins that are available under the name
BUTVAR.RTM. from Solutia, Inc. (St. Louis, Mo.) and PIOLOFORM.RTM.
from Wacker Chemical Company (Adrian, Mich.) and cellulose ester
polymers.
[0236] Hardeners for various binders may be present if desired.
Useful hardeners are well known and include diisocyanates as
described for example, in EP 0 600 586B1 (Philip, Jr. et al.) and
vinyl sulfone compounds as described in U.S. Pat. No. 6,143,487
(Philip, Jr. et al.), and EP 0 640 589A1 (Gathmann et al.),
aldehydes and various other hardeners as described in U.S. Pat. No.
6,190,822 (Dickerson et al.).
[0237] Where the proportions and activities of the
photothermographic materials require a particular developing time
and temperature, the binder(s) should be able to withstand those
conditions. Generally, it is preferred that the binder does not
decompose or lose its structural integrity at 120.degree. C. for 60
seconds. It is more preferred that it does not decompose or lose
its structural integrity at 177.degree. C. for 60 seconds.
[0238] The binder(s) is used in an amount sufficient to carry the
components dispersed therein. Preferably, a binder is used at a
level of about 10% by weight to about 90% by weight, and more
preferably at a level of about 20% by weight to about 70% by
weight, based on the total dry weight of the layer in which it is
included. The amount of binders on opposing sides of the support in
double-sided materials may be the same or different.
Support Materials
[0239] The thermally developable materials comprise a polymeric
support that is preferably a flexible, transparent film that has
any desired thickness and is composed of one or more polymeric
materials. They are required to exhibit dimensional stability
during thermal development and to have suitable adhesive properties
with overlying layers. Useful polymeric materials for making such
supports include, but are not limited to, polyesters, cellulose
acetate and other cellulose esters, polyvinyl acetal, polyolefins,
polycarbonates, and polystyrenes. Preferred supports are composed
of polymers having good heat stability, such as polyesters and
polycarbonates. Polyethylene terephthalate film is a particularly
preferred support. Support materials may also be treated or
annealed to reduce shrinkage and promote dimensional stability.
[0240] It is also useful to use supports comprising dichroic mirror
layers as described in U.S. Pat. No. 5,795,708 (Boutet),
incorporated herein by reference.
[0241] Also useful are transparent, multilayer, polymeric supports
comprising numerous alternating layers of at least two different
polymeric materials that preferably reflect at least 50% of actinic
radiation in the range of wavelengths to which the
photothermographic material is sensitive. Such polymeric supports
are described in U.S. Pat. No. 6,630,283 (Simpson et al.) that is
incorporated herein by reference.
[0242] Support materials can contain various colorants, pigments,
antihalation or acutance dyes if desired. For example, blue-tinted
supports are particularly useful for providing images useful for
medical diagnosis. Support materials may be treated using
conventional procedures (such as corona discharge) to improve
adhesion of overlying layers, or subbing or other
adhesion-promoting layers can be used.
Thermographic and Photothermographic Formulations and
Constructions
[0243] The imaging components are prepared in a formulation
containing a hydrophilic polymer binder (such as gelatin, a
gelatin-derivative, or a cellulosic material) or a
water-dispersible polymer in latex form in an aqueous solvent such
as water or water-organic solvent mixtures to provide aqueous-based
coating formulations. Thus, the thermally developable imaging
layers on one or both sides of the support are prepared and coated
out of aqueous formulations. In preferred embodiments, each
thermally developable imaging layers has a pH less than 7. This pH
value can be determined using a surface pH electrode after placing
a drop of KNO.sub.3 solution on the sample surface. Such electrodes
are available from Corning (Corning, N.Y.).
[0244] The thermally developable materials can contain plasticizers
and lubricants such as poly(alcohols) and diols as described in
U.S. Pat. No. 2,960,404 (Milton et al.), fatty acids or esters as
described in U.S. Pat. No. 2,588,765 (Robijns) and U.S. Pat. No.
3,121,060 (Duane), and silicone resins as described in GB 955,061
(DuPont). The materials can also contain inorganic or organic
matting agents as described in U.S. Pat. No. 2,992,101 (Jelley et
al.) and U.S. Pat. No. 2,701,245 (Lynn). Polymeric fluorinated
surfactants may also be useful in one or more layers as described
in U.S. Pat. No. 5,468,603 (Kub).
[0245] U.S. Pat. No. 6,436,616 (Geisler et al.), incorporated
herein by reference, describes various means of modifying
photothermographic materials to reduce what is known as the
"woodgrain" effect, or uneven optical density.
[0246] The thermally developable materials can include one or more
antistatic agents in any of the layers on either or both sides of
the support. Conductive components include soluble salts,
evaporated metal layers, or ionic polymers as described in U.S.
Pat. No. 2,861,056 (Minsk) and U.S. Pat. No. 3,206,312 (Sterman et
al.), insoluble inorganic salts as described in U.S. Pat. No.
3,428,451 (Trevoy), electroconductive underlayers as described in
U.S. Pat. No. 5,310,640 (Markin et al.), electronically-conductive
metal antimonate particles as described in U.S. Pat. No. 5,368,995
(Christian et al.), and electrically-conductive metal-containing
particles dispersed in a polymeric binder as described in EP 0 678
776 A1 (Melpolder et al.). Particularly useful conductive particles
are the non-acicular metal antimonate particles described in U.S.
Pat. No. 6,689,546 (LaBelle et al.). All of the above patents and
patent applications are incorporated herein by reference.
[0247] Still other conductive compositions include one or more
fluoro-chemicals each of which is a reaction product of
R.sub.f--CH.sub.2CH.sub.2--SO.sub.3H with an amine wherein R.sub.f
comprises 4 or more fully fluorinated carbon atoms as described in
U.S. Pat. No. 6,699,648 (Sakizadeh et al.) that is incorporated
herein by reference.
[0248] Additional conductive compositions include one or more
fluoro-chemicals described in more detail in U.S. Pat. No.
6,762,013 (Sakizadeh et al.) that is incorporated herein by
reference.
[0249] For duplitized thermally developable materials, each side of
the support can include one or more of the same or different
imaging layers, interlayers, and protective topcoat layers. In such
materials preferably a topcoat is present as the outermost layer on
both sides of the support. The thermally developable layers on
opposite sides can have the same or different construction and can
be overcoated with the same or different protective layers. The
co-precipitates can be the same or different on opposite sides of
the support.
[0250] Layers to promote adhesion of one layer to another are also
known, as described in U.S. Pat. No. 5,891,610 (Bauer et al.), U.S.
Pat. No. 5,804,365 (Bauer et al.), and U.S. Pat. No. 4,741,992
(Przezdziecki). Adhesion can also be promoted using specific
polymeric adhesive materials as described for example in U.S. Pat.
No. 5,928,857 (Geisler et al.).
[0251] Layers to reduce emissions from the film may also be
present, including the polymeric barrier layers described in U.S.
Pat. No. 6,352,819 (Kenney et al.), U.S. Pat. No. 6,352,820 (Bauer
et al.), U.S. Pat. No. 6,420,102 (Bauer et al.), U.S. Pat. No.
6,667,148 (Rao et al.), and U.S. Pat. No. 6,746,831 (Hunt), all
incorporated herein by reference.
[0252] The formulations described herein (including the thermally
developable formulations) can be coated by various coating
procedures including wire wound rod coating, dip coating, air knife
coating, curtain coating, slide coating, or extrusion coating using
hoppers of the type described in U.S. Pat. No. 2,681,294 (Beguin).
Layers can be coated one at a time, or two or more layers can be
coated simultaneously by the procedures described in U.S. Pat. No.
2,761,791 (Russell), U.S. Pat. No. 4,001,024 (Dittman et al.), U.S.
Pat. No. 4,569,863 (Keopke et al.), U.S. Pat. No. 5,340,613
(Hanzalik et al.), U.S. Pat. No. 5,405,740 (LaBelle), U.S. Pat. No.
5,415,993 (Hanzalik et al.), U.S. Pat. No. 5,525,376 (Leonard),
U.S. Pat. No. 5,733,608 (Kessel et al.), U.S. Pat. No. 5,849,363
(Yapel et al.), U.S. Pat. No. 5,843,530 (Jerry et al.), and U.S.
Pat. No. 5,861,195 (Bhave et al.), and GB 837,095 (Ilford).
Atypical coating gap for the emulsion layer can be from about 10 to
about 750 .mu.m, and the layer can be dried in forced air at a
temperature of from about 20.degree. C. to about 100.degree. C. It
is preferred that the thickness of the layer be selected to provide
maximum image densities greater than about 0.2, and more
preferably, from about 0.5 to 5.0 or more, as measured by a MacBeth
Color Densitometer Model TD 504.
[0253] Simultaneously with or subsequently to application of an
emulsion formulation to the support, a protective overcoat
formulation can be applied over the emulsion formulation.
[0254] Preferably, two or more layer formulations are applied
simultaneously to a film support using slide coating techniques,
the first layer being coated on top of the second layer while the
second layer is still wet.
[0255] In other embodiments, a "carrier" layer formulation
comprising a single-phase mixture of the two or more polymers may
be applied directly onto the support and thereby located underneath
the emulsion layer(s) as described in U.S. Pat. No. 6,355,405
(Ludemann et al.), incorporated herein by reference. The carrier
layer formulation can be applied simultaneously with application of
the emulsion layer formulation.
[0256] Mottle and other surface anomalies can be reduced in the
materials by incorporation of a fluorinated polymer as described in
U.S. Pat. No. 5,532,121 (Yonkoski et al.) or by using particular
drying techniques as described in U.S. Pat. No. 5,621,983 (Ludemann
et al.).
[0257] While the first and second layers can be coated on one side
of the film support, manufacturing methods can also include forming
on the opposing or backside of the polymeric support, one or more
additional layers, including a conductive layer, antihalation
layer, or a layer containing a matting agent (such as silica), or a
combination of such layers. Alternatively, one backside layer can
perform all of the desired functions.
[0258] To promote image sharpness, photothermographic materials can
contain one or more layers containing acutance and/or antihalation
dyes that are chosen to have absorption close to the exposure
wavelength and are designed to absorb scattered light. One or more
antihalation compositions may be incorporated into one or more
antihalation backing layers, antihalation underlayers, or as
antihalation overcoats.
[0259] Dyes useful as antihalation and acutance dyes include
squaraine dyes described in U.S. Pat. No. 5,380,635 (Gomez et al.)
and U.S. Pat. No. 6,063,560 (Suzuki et al.), and EP 1 083 459A1
(Kimura), indolenine dyes described in EP 0 342 810A1 (Leichter),
and cyanine dyes described in U.S. patent application Publication
2003/0162134 (Hunt et al.), all incorporated herein by
reference.
[0260] It may also be useful to employ compositions including
acutance or antihalation dyes that will decolorize or bleach with
heat during processing, as described in U.S. Pat. No. 5,135,842
(Kitchin et al.), U.S. Pat. No. 5,266,452 (Kitchin et al.), U.S.
Pat. No. 5,314,795 (Helland et al.), and U.S. Pat. No. 6,306,566,
(Sakurada et al.), and Japenese Kokai 2001-142175 (Hanyu et al.)
and 2001-183770 (Hanye et al.). Useful bleaching compositions are
also described in Japanese Kokai 11-302550 (Fujiwara), 2001-109101
(Adachi), 2001-51371 (Yabuki et al.), and 2000-029168 (Noro). All
of the noted publications are incorporated herein by reference.
[0261] Other useful heat-bleachable backside antihalation
compositions can include an infrared radiation absorbing compound
such as an oxonol dye or other compounds used in combination with a
hexaarylbiimidazole (also known as a "HABI" ), or mixtures thereof.
HABI compounds are described in U.S. Pat. No. 4,196,002 (Levinson
et al.), U.S. Pat. No. 5,652,091 (Perry et al.), and U.S. Pat. No.
5,672,562 (Perry et al.), all incorporated herein by reference.
Examples of such heat-bleachable compositions are described for
example in U.S. Pat. No. 6,455,210 (Irving et al.), U.S. Pat. No.
6,514,677 (Ramsden et al.), and U.S. Pat. No. 6,558,880 (Goswami et
al.), all incorporated herein by reference.
[0262] Under practical conditions of use, these compositions are
heated to provide bleaching at a temperature of at least 90.degree.
C. for at least 0.5 seconds (preferably, at a temperature of from
about 100.degree. C. to about 200.degree. C. for from about 5 to
about 20 seconds).
Imaging/Development
[0263] The photothermographic materials can be imaged in any
suitable manner consistent with the type of material, using any
suitable imaging source (typically some type of radiation or
electronic signal). In some embodiments, the materials are
sensitive to radiation in the range of from about at least 100 nm
to about 1400 nm, and normally from about 300 nm to about 750 nm
(preferably from about 300 to about 600 nm, more preferably from
about 300 to about 450 nm, even more preferably from a wavelength
of from about 360 to 420 nm, and most preferably from about 380 to
about 420 nm), using appropriate spectral sensitizing dyes.
[0264] Imaging can be achieved by exposing the photothermographic
materials to a suitable source of radiation to which they are
sensitive, including ultraviolet radiation, visible light, near
infrared radiation, and infrared radiation to provide a latent
image. Suitable exposure means are well known and include
incandescent or fluorescent lamps, xenon flash lamps, lasers, laser
diodes, light emitting diodes, infrared lasers, infrared laser
diodes, infrared light-emitting diodes, infrared lamps, or any
other ultraviolet, visible, or infrared radiation source readily
apparent to one skilled in the art such as described in Research
Disclosure, item 38957 (noted above).
[0265] In preferred embodiments, the photothermographic materials
can be indirectly imaged using an X-radiation imaging source and
one or more prompt-emitting or storage X-ray sensitive phosphor
screens adjacent to the photothermographic material. The phosphors
emit suitable radiation to expose the photothermographic material.
Preferred X-ray screens are those having phosphors emitting in the
blue region of the spectrum (from 400 to 500 nm) and those emitting
in the green region of the spectrum (from 500 to 600 nm).
[0266] In other embodiments, the photothermographic materials can
be imaged directly using an X-radiation imaging source to provide a
latent image.
[0267] Thermal development conditions will vary, depending on the
construction used but will typically involve heating the
photothermographic material at a suitably elevated temperature, for
example, at from about 50.degree. C. to about 250.degree. C.
(preferably from about 80.degree. C. to about 200.degree. C. and
more preferably from about 100.degree. C. to about 200.degree. C.)
for a sufficient period of time, generally from about 1 to about
120 seconds. Heating can be accomplished using any suitable heating
means. A preferred heat development procedure for
photothermographic materials includes heating at from 130.degree.
C. to about 165.degree. C. for from about 3 to about 25
seconds.
[0268] Imaging of the thermographic materials is carried out using
a suitable imaging source of thermal energy such as a thermal print
head or a modulated scanning laser beam.
Use as a Photomask
[0269] In some embodiments, the photothermographic and
thermographic materials are sufficiently transmissive in the range
of from about 350 to about 450 nm in non-imaged areas to allow
their use in a method where there is a subsequent exposure of an
ultraviolet or short wavelength visible radiation sensitive
imageable medium. The heat-developed materials absorb ultraviolet
or short wavelength visible radiation in the areas where there is a
visible image and transmit ultraviolet or short wavelength visible
radiation where there is no visible image. The materials may then
be used as a mask and positioned between a source of imaging
radiation (such as an ultraviolet or short wavelength visible
radiation energy source) and an imageable material that is
sensitive to such imaging radiation, such as a photopolymer, diazo
material, photoresist, or photosensitive printing plate.
[0270] These embodiments of the imaging method of this invention
are carried out using the following Steps A through D:
[0271] A) imagewise exposing a photothermographic material having a
transparent support to form a latent image,
[0272] B) simultaneously or sequentially, heating the exposed
photothermographic material to develop the latent image into a
visible image,
[0273] C) positioning the exposed and photothermographic material
with the visible image therein between a source of imaging
radiation and an imageable material that is sensitive to the
imaging radiation, and
[0274] D) exposing the imageable material to the imaging radiation
through the visible image in the exposed and photothermographic
material to provide an image in the imageable material.
Imaging Assemblies
[0275] In some embodiments, the photothermographic materials are
used or arranged in association with one or more phosphor
intensifying screens and/or metal screens in what is known as
"imaging assemblies." Duplitized visible light sensitive
photothermographic materials are preferably used in combination
with two adjacent intensifying screens, one screen in the "front"
and one screen in the "back" of the material. The front and back
screens can be appropriately chosen depending upon the type of
emissions desired, the desired photicity, and emulsion speeds. The
imaging assemblies can be prepared by arranging the
photothermographic material and one or more phosphor intensifying
screens in a suitable holder (often known as a cassette), and
appropriately packaging them for transport and imaging uses.
[0276] There are a wide variety of phosphors known in the art that
can be formulated into phosphor intensifying screens as described
in hundreds of publications. U.S. Pat. No. 6,573,033 (noted above)
describes phosphors that can be used in this manner. Particularly
useful phosphors are those that emit radiation having a wavelength
of from about 300 to about 450 nm and preferably radiation having a
wavelength of from about 360 to about 420 nm.
[0277] Preferred phosphors useful in the phosphor intensifying
screens include one or more alkaline earth fluorohalide phosphors
and especially the rare earth activated (doped) alkaline earth
fluorohalide phosphors. Particularly useful phosphor intensifying
screens include a europium-doped barium fluorobromide
(BaFBr.sub.2:Eu) phosphor. Other useful phosphors are described in
U.S. Pat. No. 6,682,868 (Dickerson et al.) and references cited
therein, all incorporated herein by reference.
[0278] The following examples are provided to illustrate the
practice of the present invention and the invention is not meant to
be limited thereby.
Materials and Methods for the Examples:
[0279] All materials used in the following examples can be prepared
using known synthetic procedures or are readily available from
standard commercial sources, such as Aldrich Chemical Co.
(Milwaukee, Wis.) unless otherwise specified. All percentages are
by weight unless otherwise indicated.
[0280] BZT is benzotriazole. AGBZT is silver benzotriazole.
[0281] BYK-022 is a defoamer and is available from Byk-Chemie Corp.
(Wallingford, Conn.).
[0282] CELVOL.RTM. V203S is a polyvinyl alcohol and is available
from Celanese Corp. (Dallas, Tex.).
[0283] L-Ascorbic acid 6-O-palmitate is available from Alfa Aesar
Corp., (Ward Hill, Mass.).
[0284] TRITON.RTM. X-114 is a surfactant and is available from Dow
Chemical Corp. (Midland Mich.).
[0285] Densitometry measurements were carried out on an X-Rite.RTM.
Model 301 densitometer that is available from X-Rite Inc.
(Grandville, Mich.).
[0286] Compounds A-1 and A-2 are described in U.S. Pat. No.
6,605,418 (noted above) and are believed to have the following
structures: ##STR15##
[0287] Compound SS-1a is described in U.S. Pat. No. 6,296,998
(Eikenberry et al.) and is believed to have the following
structure: ##STR16##
[0288] Bisvinyl sulfonyl methane (VS-1) is
1,1'(methylenebis(sulfonyl))-bis-ethene and is described in EP 0
640 589 A1 (Gathmann et al.). It is believed to have the following
structure: ##STR17##
[0289] Compound T-1 is
2,4-dihydro-4-(phenylmethyl)-3H-1,2,4-triazole-3-thione. It is
believed to have the structure shown above. It may also exist as
the thione tautomer. The silver salt of this compound is referred
to as AgT-1. The sodium salt of this compound is referred to as
NaT-1.
[0290] Gold sensitizer Compound GS-1 is believed to have the
following structure. ##STR18##
[0291] Blue sensitizing dye SSD-1 is believed to have the following
structure. ##STR19## Densitometry
[0292] Densitometry measurements were made on a custom built
computerized scanning-densitometer that meets ISO Standards 5-2 and
5-3 and takes an optical density reading every 0.33 mm. The results
are believed to be comparable to measurements from commercially
available densitometers.
[0293] Density of the wedges was measured using a filter
appropriate to the sensitivity of the photothermographic material
to obtain graphs of density versus log exposure (that is, D log E
curves). D.sub.min is the density of the non-exposed areas after
development and it is the average of the eight lowest density
values.
Preparation of Silver Benzotriazole Emulsions
Preparation of Pure AGBZT Emulsions:
[0294] Comparative gelatin emulsions C-1 and C-4 of silver
benzotriazole (AgBZT) were prepared as described below. Amounts
listed as g/kg refer to grams of material per kilogram of solution
of that material.
[0295] A stirred reaction vessel was charged with 900 g of
lime-processed gelatin, and 6 kg of deionized water.
[0296] Solution A: A solution containing 216 g/kg of benzotriazole,
710 g/kg of deionized water, and 74 g/kg of sodium hydroxide was
prepared.
[0297] The mixture in the reaction vessel was adjusted to a pH of
8.9 with 2.5N sodium hydroxide solution. The small amount of
Solution A shown in TABLE II was added to adjust the solution vAg.
The temperature of the reaction vessel was maintained at
approximately 50.degree. C.
[0298] Solution B: A second solution containing 362 g/kg of silver
nitrate and 638 g/kg of deionized water was prepared.
[0299] Solutions A and B were then added to the reaction vessel by
conventional controlled double-jet addition at the Solution B flow
rates given in TABLE III. The rate of addition of Solution A was
controlled to maintain constant vAg and pH in the reaction
vessel.
[0300] For example, in the preparation of comparative emulsion C-1,
Solution B was initially added at a flow rate of about 25 ml/min
for 20 minutes, the flow rate of Solution B was then accelerated
over 41 minutes to about 40 ml/min, and finally the flow rate of
Solution B was further accelerated over 30 minutes to about 80
ml/min.
[0301] The AgBZT emulsions were washed by conventional
ultrafiltration process as described in Research Disclosure, Vol.
131, March 1975, Item 13122. The pH of AgBZT emulsions was adjusted
to 6.0 using 2.0N sulfuric acid.
Preparation of AgBZT/AgT-1 Co-Precipitated Emulsions:
[0302] Co-precipitated AgBZT/AgT-1 comparative emulsions C-2 and
C-3, and inventive emulsion samples I-1 through I-9 were prepared
as described below.
[0303] A stirred reaction vessel was charged with 900 g of
lime-processed gelatin, and 6 kg of deionized water.
[0304] Solution A: A solution containing 216 g/kg of benzotriazole,
710 g/kg of deionized water, and 74 g/kg of sodium hydroxide was
prepared
[0305] The mixture in the reaction vessel was adjusted to a pH of
8.9 with 2.5N sodium hydroxide solution. The small amount of
Solution A shown in TABLE II, was added to adjust the solution vAg.
The temperature of the reaction vessel was maintained at
approximately 50.degree. C.
[0306] Solution B: A second solution containing 362 g/kg of silver
nitrate and 638 g/kg of deionized water was prepared.
[0307] Solution A': A third series of solutions containing
benzotriazole, compound T-1, sodium hydroxide and de-ionized water
was prepared having the compositions shown in TABLE IV.
[0308] Solutions A and B were then added to the reaction vessel by
conventional controlled double-jet addition at the Solution B flow
rates given in TABLE III. The rate of addition of Solution A was
controlled to maintain constant vAg and pH in the reaction vessel.
For the proportion of the silver nitrate (Solution B) addition,
indicated in TABLE IV, Solution A was replaced with Solution A'.
Solutions B and A' were then added to the reaction vessel by
conventional controlled double-jet addition, while maintaining
constant vAg and pH in the reaction vessel.
[0309] For example, in the preparation of comparative emulsion C-2,
Solution B was added at a flow rate of about 50 ml/min for 22
minutes, along with Solution A, by conventional controlled
double-jet addition. At this point, about 30% of the total amount
of Solution B had been added during the precipitation. Solution A
was then replaced with Solution A'. Solutions B and A' were then
added at a flow rate of about 50 ml/min for 7.5 minutes by
conventional controlled double-jet addition, while maintaining
constant vAg and pH in the reaction vessel. At this point, the
about 40% of the total amount of Solution B had been added during
the precipitation. Solution A' was then replaced with Solution A.
Solutions A and B were then added at a flow rate of about 50 ml/min
for 7.5 minutes by conventional controlled double-jet addition,
while maintaining constant vAg and pH in the reaction vessel. The
flow rate of Solution B was then accelerated over 27 minutes to
about 85 ml/min, while maintaining constant vAg and pH in the
reaction vessel.
[0310] The AgBZT/AgT-1 co-precipitated emulsions were washed by
conventional ultrafiltration process as described in Research
Disclosure, Vol. 131, March 1975, Item 13122. The pH of AgBZT/AgT-1
emulsions was adjusted to 6.0 using 2.0N sulfuric acid.
[0311] Emulsion C-1 contained no AgT-1.
[0312] Emulsions C-2 and C-3 had a core-shell construction with a
core of AgBZT surrounded by a shell of AgBZT/AgT-1, further
surrounded by a surface shell of AgBZT. The AgT-1 was not within 75
volume % of the surface of the particle.
[0313] Emulsion C-4 contained no AgT-1.
[0314] Emulsions I-1 through I-7 and I-9 had core-shell structures
with a core of AgBZT surrounded by a shell containing a various
quantities of silver AgBZT/AgT-1. The AgT-1 was in the surface
layer.
[0315] Emulsion I-8 had 95 mol % of AgT-1 within 75 to 85 volume %
of the surface. TABLE-US-00001 TABLE II Amount of Solution A
Measured vAg Emulsion Added [g] [mV] pAg C-1 0.8 80 8.26 C-2 38.5 0
9.50 C-3 38.5 0 9.50 C-4 5.0 60 8.58 I-1 0.8 80 8.26 I-2 0.8 80
8.26 I-3 0.8 80 8.26 I-4 38.5 0 9.50 I-5 38.5 0 9.50 I-6 38.5 0
9.50 I-7 5.0 60 8.58 I-8 38.5 0 9.50 I-9 5.0 60 8.58
[0316] TABLE-US-00002 TABLE III Growth Solution B flow rate Time
[mV] [ml/min] [min] Emulsions C-1, I-1, I-2, I-3 80 Addition 1 25
20 80 Addition 2 25-40 41 80 Addition 3 40-80 30 Emulsions C-4,
I-7, I-9 60 Addition 1 40 12 60 Addition 2 40-50 30 60 Addition 3
50-85 27 Emulsions C-2, C-3, I-4, I-5, I-6, I-8 0 Addition 1 50 37
0 Addition 2 50-85 27
[0317] TABLE-US-00003 TABLE IV Percent of Silver Percent of Silver
Solution A': Solution A': Solution A': Solution A': Added at Start
of Added at End of Amount of Amount of Amount of Amount of Addition
of Addition of Emulsion BZT [g/kg] T-1 [g/kg] NaOH [g/kg] H.sub.2O
[g/kg] Solution A' Solution A' C-2 195 79 83 643 30 40 C-3 195 79
83 643 50 60 I-1 0 336 70 594 97.7 100 I-2 0 336 70 594 97.4 100
I-3 0 336 70 594 96.9 100 I-4 0 336 70 594 96.9 100 I-5 190 99 85
626 90 100 I-6 185 119 87 609 90 100 I-7 0 336 70 594 96.9 100 I-8
195 79 83 643 75 85 I-9 0 336 70 594 97.9 100
[0318] TABLE-US-00004 TABLE V Diameter Emulsion Length [.mu.m]
Diameter [.mu.m] Aspect Ratio Width Index C-1 0.153 0.049 3.15 1.17
C-2 0.153 0.085 1.82 1.17 C-3 0.171 0.073 2.34 1.15 C-4 0.254 0.046
5.59 1.17 I-1 0.392 0.058 6.78 1.15 I-2 0.364 0.051 7.14 1.14 I-3
0.363 0.054 6.77 1.17 I-4 0.232 0.059 3.95 1.13 I-5 0.230 0.057
4.02 1.13 I-6 0.232 0.058 4.02 1.13 I-7 0.235 0.048 4.92 1.12 I-8
0.194 0.063 3.11 1.12 I-9 0.259 0.047 5.58 1.14
EXAMPLE 1
Preparation of Photothermographic Materials
[0319] Photothermographic materials of this invention and
comparative materials were prepared and evaluated as follows:
Preparation of Ultra-Thin Tabular Grain Silver Halide Emulsions
[0320] An ultrathin tabular grain silver halide emulsion was
prepared as described in copending and commonly assigned U.S. Ser.
No. 10/826,708 (filed on Apr. 16, 2004 by Olm et al.) and
incorporated herein by reference.
[0321] A vessel equipped with a stirrer was charged with 6 liters
of water containing 4.21 g of lime-processed bone gelatin, 4.63 g
of sodium bromide, 75.6 mg of potassium iodide, a known
antifoamant, and 1.25 ml of 0.1 molar sulfuric acid. It was then
held at 39.degree. C. for 5 minutes. Simultaneous additions were
then made of 25.187 ml of 0.6 molar silver nitrate and 19.86 ml of
0.75 molar sodium bromide over 30 seconds. Following nucleation, 50
ml of a 0.58% solution of the oxidant Oxone was added. Next, a
mixture of 0.749 g of sodium thiocyanate and 30.22 g of sodium
chloride dissolved in 136.4 g of water were added and the
temperature was increased to 54.degree. C. over 9 minutes. After a
5-minute hold, 100 g of oxidized methionine lime-processed bone
gelatin in 1.412 liters of water containing additional antifoamant
at 54.degree. C. were then added to the vessel. During the next 38
minutes, the first growth stage took place wherein solutions of 0.6
molar silver nitrate, 0.75 molar sodium bromide, and a 0.29 molar
suspension of silver iodide (Lippmann) were added to maintain a
nominal uniform iodide level of 4.2 mole %. The flow rates during
this growth segment were linearly increased from 9 to 42 ml/min
(silver nitrate), from 11.4 to 48.17 ml/min (sodium bromide) and
from 0.8 to 3.7 ml/min (silver iodide). The flow rates of the
sodium bromide were unbalanced from the silver nitrate in order to
increase the pBr during the segment. During the next 64 minutes,
the second growth stage took place wherein solutions of 3.5 molar
silver nitrate and 4.5 molar sodium bromide and a 0.29 molar
suspension of silver iodide (Lippmann) were added to maintain a
nominal iodide level of 4.2 mole %. The flow rates during this
segment were increased from 8.6 to 38 ml/min (silver nitrate) and
from 5.2 to 22.0 ml/min (silver iodide). The flow rates of the
sodium bromide were allowed to fluctuate as needed to maintain a
constant pBr.
[0322] During the next 38 minutes, the third growth stage took
place wherein solutions of 3.5 molar silver nitrate, 4.5 molar
sodium bromide, and a 0.29 molar suspension of silver iodide
(Lippmann) were added to maintain a nominal iodide level of 4.2
mole %. The flow rates during this segment were 42 ml/min (silver
nitrate), nominally 32 ml/min (sodium bromide)-pBr control, and 22
ml/min (silver iodide). The temperature was decreased from
54.degree. C. to 35.degree. C. during this segment. At a point
approximately 13.5 minutes after the start of this segment, 1 ml of
a 2.06 millimolar aqueous solution of K.sub.2
[IrCl.sub.5(5-bromo-thiazole)] was added. This corresponds to a
concentration of 0.164 ppm to silver halide. ##STR20##
K.sub.2 [IrCl.sub.5(5-bromo-thiazole)]
[0323] A total of 12.6 moles of silver iodobromide (4.2% bulk
iodide) were formed. The resulting emulsion was washed via
ultrafiltration. Lime-processed bone gelatin (269.3 g) was added
along with a biocide and pH and pBr were adjusted to 6 and 2.5,
respectively.
[0324] The resulting emulsion was examined by Transmission Electron
Microscopy. Tabular grains accounted for greater than 99% of the
total projected area. The mean ECD of the grains was 2.6 .mu.m. The
mean tabular thickness was 0.063 .mu.m.
[0325] This emulsion was spectrally sensitized with 1.0 mmol of
blue sensitizing dye SSD-1 per mole of silver halide. Chemical
sensitization was carried out using 0.0055 mmol of sulfur
sensitizer (compound SS-1a) per mole of silver halide at 60.degree.
C. for 10 minutes.
Preparation of Photothermographic Emulsion Formulations:
[0326] Component A (Comparative Samples 1-CS-1 and 1-CS-2): A
portion of the AgBZT emulsion prepared above and hydrated gelatin
(35% gelatin/65% water) were placed in a beaker and heated to
50.degree. C. for 15 minutes to form a homogeneous dispersion. A 5%
aqueous solution of 3-methyl-benzothiazolium iodide was added and
heated for 15 minutes at 50.degree. C. The sodium salt of
benzotriazole was added and stirring was continued for 15 minutes
at 50.degree. C. At this point, for Comparative Sample 1-CS-1
solution of Compound NaT-1 was added. For Comparative Sample
1-CS-2, no compound T-1 was added. 2.5 N sulfuric acid was added to
the resulting melt at 40.degree. C. to adjust the dispersion pH to
5.5.
[0327] Component B (Inventive Samples 1-IN-6 through 1-IN-12): A
portion of AgBZT/AgT-1 mixed crystal emulsion prepared above and
hydrated gelatin (35% gelatin/65% water) were used to prepare a
dispersion similar to that of Component A except the addition of
Compound T-1 was omitted.
[0328] Component C: A portion of the tabular-grain silver halide
emulsion prepared above was placed in a beaker and melted by
heating at 40.degree. C.
[0329] Component D: The materials listed in TABLE VI below were
added to water and heated to 50.degree. C.
[0330] Coating of Samples:
[0331] Components A, C, and D (Comparative) or Components B, C and
D (Inventive) were mixed immediately before coating to form a
photothermographic emulsion formulation. Each formulation was
coated as a single layer on a 7 mil (178 .mu.m) transparent,
blue-tinted poly(ethylene terephthalate) film support using a knife
coater to form an imaging layer having the dry composition shown
below in TABLE VI. Samples were dried at 116.degree. F. (47.degree.
C.) for 7 minutes. TABLE-US-00005 TABLE VI Dry Coating Component
Compound Weight [g/m.sup.2] A AgBZT 3.21 A Lime processed gelatin
1.28 A Sodium benzotriazole 0.10 A 3-Methyl-benzothiazolium 0.08
iodide A Compound NaT-1 0.08 B AgBZT/AgT-1 mixed crystals 3.21 B
Lime processed gelatin 1.28 B Sodium benzotriazole 0.10 B
3-Methyl-benzothiazolium 0.08 iodide C Silver (from silver halide
0.27 emulsion) D Succinimide 0.14 D 1,3-Dimethylurea 0.17 D A-1
0.07 D VS-1 0.07 D meso-Erythritol 0.42 D L-ascorbic acid
6-O-pivalate 2.90
Evaluation of Samples:
[0332] Samples of each of the resulting photothermographic
materials were imagewise exposed for 10.sup.-2 seconds using an
EG&G flash sensitometer equipped with a P-16 filter and a 0.7
neutral density filter. Following exposure, the samples were
thermally developed using a heated flatbed processor for 18 seconds
at 150.degree. C. to generate continuous tone wedges. These samples
provided initial D.sub.min, D.sub.max, and photospeed values.
[0333] TABLES VII and VIII summarize the initial sensitometry and
keeping stability for AgBZT/AgT-1 co-precipitated emulsions.
[0334] Comparative sample 1-CS-1 has toner compound T-1 physically
mixed with the AgBZT coating melt as would be done in conventional
procedures where toners and developer are added into emulsion layer
in solution or as solid particle dispersions. The coatings of
Comparative Sample 1-CS-1 show a large number of black spots after
thermal development, indicating agglomeration of T-1 particles in
the coating layer.
[0335] Comparative Sample 1-CS-2 contained no toner compound T-1.
This sample gave a faint image.
[0336] Comparative samples 1-CS-3 and 1-CS-4 contained AgT-1 buried
within the particle as an inner layer not within 75 volume % of the
surface of the particle.
[0337] Inventive samples 1-IN-6 through 1-IN-11 all had at least
some portion of AgT-1 on the surface of AgBZT/AgT-1 particle.
[0338] Inventive sample 1-IN-12 had 95 mol % of AgT-1 within 75 to
85 volume % of the surface.
[0339] The results, shown below in TABLES VII and VIII, demonstrate
that AgBZT/AgT-1 co-precipitated emulsions gave excellent
sensitometry under various preparative conditions. In addition,
samples having AgT-1 on the surface of the co-precipitate provided
higher photospeed and density than samples having AgT-1 located
within 75 to 85 volume % of the outer surface, while maintaining
low D.sub.min. No black spots were found after thermal development.
TABLE-US-00006 TABLE VII Amount Amount of of NaT-1 T-1 in Co-
Invention/ in AgBZT precipitated AgBZT Sample Emulsion Comparative
[g/mol Ag] [g/mol Ag] 1-CS-1 C-1 Comparative 5.0 0.0 1-CS-2 C-1
Comparative 0.0 0.0 1-CS-3 C-2 Comparative 0.0 4.0 1-CS-4 C-3
Comparative 0.0 4.0 1-IN-6 I-1 Invention 0.0 4.4 1-IN-7 I-2
Invention 0.0 5.0 1-IN-8 I-3 Invention 0.0 6.0 1-IN-9 I-4 Invention
0.0 6.0 1-IN-10 I-5 Invention 0.0 5.0 1-IN-11 I-6 Invention 0.0 6.0
1-IN-12 I-8 Invention 0.0 4.0
[0340] TABLE-US-00007 TABLE VIII Invention/ Sample Emulsion
Comparative Dmin Dmax Spd-1 Spd-2 Image Quality 1-CS-1 C-1
Comparative 0.257 2.857 5.243 4.851 black spots 1-CS-2 C-1
Comparative 0.301 0.434 **** **** Faint Image 1-CS-3 C-2
Comparative 0.237 0.529 4.176 **** no black spots 1-CS-4 C-3
Comparative 0.244 0.854 4.539 **** no black spots 1-IN-6 I-1
Invention 0.254 2.683 5.144 4.663 no black spots 1-IN-7 I-2
Invention 0.250 2.835 5.227 4.900 no black spots 1-IN-8 I-3
Invention 0.265 2.756 5.275 4.911 no black spots 1-IN-9 I-4
Invention 0.261 2.447 5.194 4.846 no black spots 1-IN-10 I-5
Invention 0.248 2.489 5.114 4.634 no black spots 1-IN-11 I-6
Invention 0.252 2.208 5.047 4.462 no black spots 1-IN-12 I-8
Invention 0.248 1.305 4.754 4.085 no black spots **** - Could not
be measured
Natural Age Keeping:
[0341] Non-imaged samples were stored in a black polyethylene bag
for 6 weeks at ambient room temperature and relative humidity to
determine their Natural Age Keeping properties. The samples were
then imaged and compared with the freshly imaged samples.
[0342] The results, shown below in TABLES IX and X demonstrate that
photothermographic materials incorporating a physical mixture of
silver benzotriazole (AgBZT) with a 1,2,4-triazine compound
(compound T-1) exhibit a greater increase in D.sub.min, and a
greater decrease in D.sub.max and Speed-2 upon Natural Age Keeping
than photothermographic materials incorporating co-precipitated
particles of AgBZT/AgT-1. TABLE-US-00008 TABLE IX NAK NAK
Invention/ Initial 6 Week 6 Week Initial 6 Week 6 Week Sample
Emulsion Comparative Dmin Dmin .DELTA. Dmin Dmax Dmax .DELTA. Dmax
1-CS-1 C-1 Comparative 0.257 0.386 +0.229 2.857 1.573 -1.284 1-IN-6
I-1 Invention 0.254 0.280 +0.026 2.683 2.142 -0.541 1-IN-7 I-2
Invention 0.250 0.282 +0.032 2.835 1.609 -1.226 1-IN-8 I-3
Invention 0.265 0.329 +0.064 2.756 1.848 -0.908 1-IN-9 I-4
Invention 0.261 0.279 +0.018 2.447 1.105 -1.342
[0343] TABLE-US-00009 TABLE X NAK NAK Invention/ Initial 6 Week 6
Week Initial 6 Week 6 Week Sample Emulsion Comparative Spd-1 Spd-1
.DELTA. Spd-1 Spd-2 Spd-2 .DELTA. Spd-2 1-CS-1 C-1 Comparative
5.243 5.220 -0.023 4.851 3.848 -1.003 1-IN-6 I-1 Invention 5.144
5.318 +0.174 4.663 4.726 +0.099 1-IN-7 I-2 Invention 5.227 5.151
-0.086 4.900 4.130 -0.770 1-IN-8 I-3 Invention 5.275 5.372 +0.097
4.911 4.517 -0.394 1-IN9 I-4 Inventive 5.194 5.076 -0.118 4.846
**** **** **** - Could not be measured
EXAMPLE 2
Preparation of Photothermographic Materials
[0344] Photothermographic materials of this invention and
comparative materials were prepared and evaluated as follows.
Preparation of Ultra-Thin Tabular Grain Silver Halide Emulsion:
[0345] A reaction vessel equipped with a stirrer was charged with 6
liters of water containing 2.1 g of deionized oxidized-methionine
lime-processed bone gelatin, 3.49 g of sodium bromide, and an
antifoamant (at pH=5.8). The solution was held at 39.degree. C. for
5 minutes. Simultaneous additions were then made of 50.6 ml of 0.3
molar silver nitrate and 33.2 ml of 0.448 molar sodium bromide over
1 minute. Following nucleation, 3.0 ml of a 0.1 M solution of
sulfuric acid was added. After 1 minute 15.62 g sodium chloride
plus 375 mg of sodium thiocyanate were added and the temperature
was increased to 54.degree. C. over 9 minutes. After a 5-minute
hold, 79.6 g of deionized oxidized-methionine lime-processed bone
gelatin in 1.52 liters of water containing additional antifoamant
at 54.degree. C. were then added to the reactor. The reactor
temperature was held for 7 minutes (pH=5.6).
[0346] During the next 36.8 minutes, the first growth stage took
place (at 54.degree. C.), in three segments, wherein solutions of
0.3 molar AgNO.sub.3, 0.448 molar sodium bromide, and a 0.16 molar
suspension of silver iodide (Lippmann) were added to maintain a
nominal uniform iodide level of 3.2 mole %. The flow rates during
this growth stage were increased from 9 to 42 ml/min (silver
nitrate) and from 0.73 to 3.3 ml/min (silver iodide). The flow
rates of the sodium bromide were allowed to fluctuate as needed to
affect a monotonic pBr shift of 2.45 to 2.12 over the first 12
minutes, of 2.12 to 1.90 over the second 12 minutes, and of 1.90 to
1.67 over the last 12.8 minutes. This was followed by a 1.5 minute
hold.
[0347] During the next 59 minutes the second growth stage took
place (at 54.degree. C.) during which solutions of 2.8 molar silver
nitrate, and 3.0 molar sodium bromide, and a 0.16 molar suspension
of silver iodide (Lippmann) were added to maintain a nominal iodide
level of 3.2 mole %. The flow rates during this segment were
increased from 10 to 39.6 ml/min (silver nitrate) and from 5.3 to
22.6 ml/min (silver iodide). The flow rates of the sodium bromide
were allowed to fluctuate as needed to affect a monotonic pBr shift
of 1.67 to 1.50. This was followed by a 1.5 minute hold.
[0348] During the next 34.95 minutes, the third growth stage took
place during which solutions of 2.8 molar silver nitrate, 3.0 molar
sodium bromide, and a 0.16 molar suspension of silver iodide
(Lippmann) were added to maintain a nominal iodide level of 3.2
mole %. The flow rates during this segment were 39.6 ml/min (silver
nitrate) and 22.6 ml/min (silver iodide). The temperature was
linearly decreased to 35.degree. C. during this segment. At the
23.sup.rd minute of this segment a 50 ml aqueous solution
containing 0.85mg of an Iridium dopant
(K.sub.2[Ir(5-Br-thiazole)Cl.sub.5]) was added. The flow rate of
the sodium bromide was allowed to fluctuate to maintain a constant
pBr of 1.50. ##STR21##
K.sub.2 [IrCl.sub.5(5-bromo-thiazole)]
[0349] A total of 8.5 moles of silver iodobromide (3.2% bulk
iodide) were formed. The resulting emulsion was washed using
ultrafiltration. Deionized lime-processed bone gelatin (326.9 g)
was added along with a biocide and pH and pBr were adjusted to 6
and 2.5 respectively.
[0350] The resulting emulsion was examined by Scanning Electron
Microscopy. Tabular grains accounted for greater than 99% of the
total projected area. The mean ECD of the grains was 2.522 .mu.m.
The mean tabular thickness was 0.049 .mu.m.
[0351] This emulsion was spectrally sensitized with 3.31 mmol of
blue sensitizing dye SSD-1 per mole of silver halide. This dye
quantity was split 80%/20% with the majority being added before
chemical sensitization and the remainder afterwards. Chemical
sensitization was carried out using 0.0085 mmol of sulfur
sensitizer (compound SS-1a) and 0.00079 mmol per mole of silver
halide of gold sensitizer (compound GS-1) at 60.degree. C. for 6.3
minutes.
Preparation of Photothermographic Emulsion Formulations:
[0352] Component E (Samples 2-CS-1 and 2-CS-2): A portion of AgBZT
emulsion C-4 prepared above and hydrated gelatin (35% gelatin/65%
water) were placed in a beaker and heated to 50.degree. C. for 15
minutes to form a homogeneous dispersion. A 5% aqueous solution of
3-methylbenzothiazolium iodide was added and heated for 15 minutes
at 50.degree. C. The sodium salt of benzotriazole was added and the
dispersions were stirred again for 15 minutes at 50.degree. C.
Comparative samples 2-CS-1A and 2-CS-1B contained no compound T-1.
Comparative samples 2-CS-2A and 2-CS-2B contained compound T-1
physically mixed with AgBZT as would be done in conventional
procedures where toner and developer are added into the emulsion
layer in solution or as a solid particle dispersion. For this
sample a solution of Compound NaT-1 was added with stirring. 2.5 N
sulfuric acid was added to all of the resulting melts at 40.degree.
C. to adjust the dispersion pH to 5.0. Addition of a solution of
compound A-2 was followed by addition of a solution of ZONYL FS300
surfactant.
[0353] Component F (Inventive Sample 2-IN-3 and 2-IN-4): A portion
of AgBZT/AgT-1 mixed crystal emulsions I-7 and I-9 prepared above
and hydrated gelatin (35% gelatin/65% water) were used to prepare a
dispersion similar to that of Component E except the addition of
Compound T-1 was omitted.
[0354] Component G: A portion of the tabular-grain silver halide
emulsion, prepared as described above, was placed in a beaker and
melted by heating at 40.degree. C.
[0355] Component H: Succinimide, 1,3-dimethylurea, and
pentaerythritol listed in TABLE XI below were added to water and
dissolved by sonication at 50.degree. C. To this was added an
aqueous dispersion of 29.2% L-ascorbic acid-6-O-palmitate, 2.92%
polyvinyl alcohol (CELVOL.RTM. V 203S), 0.87% TRITON.RTM. X-114,
and 0.03% BYK-022. The dispersion was prepared by circulating the
materials in a Netzsch mill until the average particle size was
0.46 .mu.m.
Topcoat Formulation:
[0356] An aqueous gelatin topcoat formulation was prepared.
Coating and Evaluation of Samples:
[0357] Components E, G, and H (Comparative) or Components F, G and
H (Inventive) were mixed immediately before coating to form a
photothermographic emulsion formulation. Each photothermographic
emulsion and the topcoat formulation was dual knife coated onto a
7-mil (178 .mu.m) transparent, blue-tinted poly(ethylene
terephthalate) film support. The coating gap for the
photothermographic layer was adjusted to achieve the dry coating
weights shown below in TABLE XI. The dry coating weight of the
gelatin topcoat layer was approximately 0.81 g/m.sup.2. Samples
were dried at 116.degree. F. (47.degree. C.) for 10 minutes.
TABLE-US-00010 TABLE XI Dry Coating Component Compound Weight
[g/m.sup.2] E AgBZT 2.98 E Lime processed gelatin 2.24 E Sodium
benzotriazole 0.09 E 3-Methyl-benzothiazolium 0.07 iodide E
Compound A-2 0.07 E Compound T-1 0.08 F AgBZT/AgT-1 mixed crystals
3.06 F Lime processed gelatin 2.24 F Sodium benzotriazole 0.09 F
3-Methyl-benzothiazolium 0.07 iodide F Compound A-2 0.07 G Silver
(from silver halide 0.26 emulsion) H Succinimide 0.15 H
1,3-Dimethylurea 0.33 H Pentaerythritol 0.47 H L-ascorbic acid
6-O-palmitate 3.79
[0358] The resulting photothermographic films were imagewise
exposed for 10.sup.-2 seconds using an EG&G flash sensitometer
equipped with a P-16 filter and a 0.7 neutral density filter.
Following exposure, samples of each film were thermally developed
using a heated flatbed processor for both 18 and 23 seconds at
150.degree. C.
[0359] Sensitometry results, shown below in TABLE XII and TABLE
XIII, demonstrate that photothermographic materials containing a
co-precipitate of AgBZT/AgT-1 show high D.sub.max, low D.sub.min,
and excellent photospeed.
[0360] As noted above, samples of each photothermographic material
were also developed at 150.degree. C. for 23 seconds rather than 18
seconds. This determines the process latitude of the
photothermographic material. The results, shown below in TABLE
XIII, demonstrate that materials incorporating the co-precipitate
of AgBZT/AgT-1 exhibit less increase in D.sub.min than materials
incorporating the AgBZT emulsion with AgT-1 physically added, when
subjected to more severe development conditions.
[0361] Archival Stability: Imaged samples of each film were
illuminated with 100 foot-candles (1076 lux) at 70.degree. F.
(21.2.degree. C.) and 50% relative humidity for 2 hours. The
samples were then sealed in a light and humidity tight aluminum bag
and stored for 48 hours at 120.degree. F. (48.9.degree. C.) and 50%
relative humidity. The D.sub.min of the samples was measured before
and after storage. Two measurements were made on each sample. For
the first measurement, the densitometer was equipped with a visible
filter with a transmittance peak at about 530 nm. In the second
measurement, the densitometer was fitted with a blue filter with a
transmission peak at about 440 nm. The difference in density before
and after storage using these filters is reported below in TABLE
XIII as "Archival Stability" (.DELTA. Blue and .DELTA. Visible) and
demonstrates that inventive samples containing a co-precipitate of
AgBZT/AgT-1 showed less increase in D.sub.min (increased background
density or "print-out") when subjected to accelerated aging
conditions when compared to control samples not incorporating a
co-precipitate of AgBZT/AgT-1. TABLE-US-00011 TABLE XII Amount
Amount of of NaT-1 T-1 in Co- Invention/ in AgBZT precipitated
AgBZT Sample Emulsion Comparative [g/mol Ag] [g/mol Ag] 2-CS-1A C-4
Comparative 0.0 0.0 2-CS-1B C-4 Comparative 0.0 0.0 2-CS-2A C-4
Comparative 6.0 0.0 2-CS-2B C-4 Comparative 6.0 0.0 2-IN-3A I-9
Inventive 0.0 4.0 2-IN-3B I-9 Inventive 0.0 4.0 2-IN-4A I-7
Invention 0.0 6.0 2-IN-4B I-7 Invention 0.0 6.0
[0362] TABLE-US-00012 TABLE XIII Devel- opment Archival Stability
Time .DELTA. Vis- Sample [seconds] Dmin Dmax Spd-1 Spd-2 .DELTA.
Blue ible 2-CS-1A 18 0.27 0.51 **** **** +3.41 +2.08 2-CS-1B 23
0.28 0.56 **** **** NM NM 2-CS-2A 18 0.33 3.18 4.96 4.65 +0.65
+0.56 2-CS-2B 23 0.41 3.38 5.06 4.79 NM NM 2-IN-3A 18 0.27 2.48
4.92 4.43 +1.48 +1.29 2-IN-3B 23 0.27 3.13 5.07 4.75 NM NM 2-IN-4A
18 0.30 3.08 5.11 4.78 +0.55 +0.47 2-IN-4B 23 0.32 3.31 5.22 4.96
NM NM **** - Could not be measured. NM - Was not measured.
EXAMPLE 3
Preparation of Photothermographic Materials Containing
Phenylmercaptotetrazole (PMT Compounds)
[0363] The following example demonstrates that
phenylmercaptotetrazole (PMT) and
1-(3-acetamidophenyl)-5-mercaptotetrazole (Ac-PMT), two compounds
taught to be useful as co-precipitated silver sources in U.S. Pat.
No. 6,576,414 (Irving et al.) and U.S. Pat. No. 6,548,236 (Irving
et al.), but whose non-silver parent compounds are not toners in
photothermographic materials, do not function as toner-release
agents in photothermographic materials.
[0364] Co-precipitated crystals of silver benzotriazole and silver
phenylmercaptotriazole (AgBZT/AgPMT) or silver benzotriazole and
1-(3-acetamido-phenyl)5-mercaptotetrazole (AgBZT/AgAc-PMT) were
prepared in a manner similar to that described for emulsion I-2 in
Example 1 above, except that a portion of the BZT was replaced with
PMT. Three samples were prepared for each PMT compound using PMT
levels of 0%, 1%, and 2% of total silver.
[0365] The AgBZT/AgPMT/AgT-1 emulsions were prepared as core/shell
crystals, as taught in U.S. Pat. Nos. 6,576,414 and 6,548,236 (both
noted above) with an inner core of AgBZT, followed by a shell of
AgPMT, followed by a surface shell of AgT-1, spanning the last 2.6%
of Ag.
[0366] The AgBZT/AgAc-PMT+AgT-1 emulsions were prepared as
core/shell crystals, also as taught in U.S. Pat. Nos. 6,576,414 and
6,548,236 (both noted above), with an inner core of AgBZT, followed
by a mixed shell containing both AgAc-PMT and AgT-1, where the
amount of AgT-1 corresponds to 2.6% of the total Ag.
[0367] Photothermographic formulations were prepared, coated,
dried, and imaged in a manner also similar to that described in
Example 2. No topcoat was used. Samples containing 0% of PMT
derivatives contained only co-precipitated AgBZT/AgT-1 and were
essentially similar to Inventive Sample 2-IN-4 of Example 2.
[0368] The results, shown below in TABLES XIV, XV, and XVI
demonstrate that the presence of a phenylmercaptotetrazole (PMT) in
the crystal actually provides materials with higher D.sub.min and
lower D.sub.max, Speed-1, Speed-2, and Average Contrast (AC-1) than
materials containing only AgBZT/AgT-1.
[0369] Non-imaged samples of each material were stored in a black
polyethylene bag for 2 months at ambient room temperature and
relative humidity to determine their Natural Age Keeping
properties. The samples were then imaged and compared with the
freshly imaged samples.
[0370] The results, shown below in TABLES XIV, XV, and XVI
demonstrate that photothermographic materials incorporating mixed
crystals of AgBZT/AgPMT/AgT-1 or AgBZT/AgAc-PMT+AgT-1, have poorer
Natural Age Keeping and exhibit a greater increase in D.sub.min,
and a greater decrease in D.sub.max, Speed-2, and Average
Contrast-1 upon Natural Age Keeping than photothermographic
materials incorporating co-precipitated particles of AgBZT/AgT-1.
##STR22## TABLE-US-00013 TABLE XIV NAK NAK Invention/ Initial 2
Month 2 Month Initial 2 Month 2 Month Sample Comparative Dmin Dmin
.DELTA. Dmin Dmax Dmax .DELTA. Dmax Amount of PMT (%) 3-IN-1 0
Invention 0.283 0.298 +0.015 3.119 2.834 -0.285 3-CS-2 1
Comparative 0.294 0.305 +0.011 2.820 2.314 -0.505 3-CS-3 2
Comparative 0.290 0.326 +0.036 2.101 1.715 -0.386 Amount of Ac-PMT
(%) 3-IN-4 0 Invention 0.278 0.300 +0.022 3.243 2.688 -0.554 3-CS-5
1 Comparative 0.288 0.296 +0.007 2.399 1.201 -1.198 3-CS-6 2
Comparative 0.294 0.296 +0.003 1.423 1.149 -0.275
[0371] TABLE-US-00014 TABLE XV NAK NAK Invention/ Initial 2 Month 2
Month Initial 2 Month 2 Month Sample Comparative Spd-1 Spd-1
.DELTA. Spd-1 Spd-2 Spd-2 .DELTA. Spd-2 Amount of PMT (%) 3-IN-1 0
Invention 5.006 5.210 +0.204 4.709 4.774 +0.065 3-CS-2 1
Comparative 5.048 5.202 +0.154 4.688 4.628 -0.060 3-CS-3 2
Comparative 4.792 4.956 +0.164 4.097 3.767 -0.330 Amount of Ac-PMT
(%) 3-IN-4 0 Invention 5.157 5.127 +0.022 4.891 4.632 -0.259 3-CS-5
1 Comparative 5.010 4.582 -0.428 4.482 **** **** 3-CS-6 2
Comparative 4.558 3.614 -0.944 3.332 **** ****
[0372] TABLE-US-00015 TABLE XVI NAK Invention/ Initial 2 Month 2
Month Sample Comparative AC-1 AC-1 .DELTA. AC-1 Amount of PMT (%)
3-IN-1 0 Invention 3.507 1.869 -1.638 3-CS-2 1 Comparative 1.978
0.934 -1.044 3-CS-3 2 Comparative *** *** *** Amount of Ac-PMT (%)
3-IN-3 0 Invention 3.918 1.400 -1.638 3-CS-4 1 Comparative 1.354
**** **** 3-CS-5 2 Comparative **** **** **** **** - Could not be
measured.
[0373] The invention has been described in detail with particular
reference to certain preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *