Note: Descriptions are shown in the official language in which they were submitted.
2 0 ~ 7 ~ 8 ~ 48006CAN7A
-- 1 --
P~OTOT~ERMOGRA~IC ~LEMENT8
BACKGROUND OF THE INVENTION
5 1. Field of the Invention
The present invention relates to materials which
produce an increase in infrared sensitivity when added
to infrared sensitized photothermographic imaging
elements. These ele~ents comprise a photosensitive
lo silver halide, silver ~alt oxidizing agent, infrared
sensitizing dye, and reducing agent for silver ion in a
binder. ~he infrared supersensitizers of the present
invention comprise mercapto substituted heteroaromatic
compounds.
2. Backaround of the Art
Silver halide photothermographic imaging
materials, often referred to as "dry silver"
compo6itions because no liquid development is necessary
20 to produce the final image, have been known in the art
for many years. These imaging materials basically
comprise a light insen~itive, reducible silver source,
a light sensitive material which generate6 silver when
irradiated, and a reducing agent for the silver source.
25 The light sensi'ive material is generally photographic
silver halide which must be in catalytic proximity to
the light insensitive silver ~ource. Catalytic
proximity iB an intimate physical association of these
two materials so that when silver specks or nuclei are
30 generated by the irradiation or light exposure of the
photographic silver halide, those nuclei are able to
catalyze the reduction of the ~ilver source by the
reducing agent. It has been long understood that
silver is a catalyst for the reduction of silver ions
35 and the silver-generating light sensitive silver halide
catalyst progenitor may be placed into catalytic
proximity with the silver source in a number of
. ~ .............................. .
:
2~8748~
-- 2 --
different fashions, such as partial metathesis of the
silver source with a halogen-containing source (e.g.,
U.S. Pat. No. 3,457,075), coprecipitation of the silver
halide and silver source material (e.g., U.S. Pat. No.
5 3,839,049), and any other method which intimately
associate the silver halide and the silver source.
Silver halide photothermographic imaging materials
can undergo spectral 6ensitization which enables the
silver halide grains to benefit from radiation in
10 regions of the electromagnetic spectrum where the
silver halide would ordinarily not absorb. Dyes which
absorb radiation and can transfer energy to the grains
to help in the photoreduction of silver ions to
clusters of silver metal are conventionally used to
15 effect spectral sensitization. Infrared absorbing dyes
are required to sensitize silver halide into the
infrared region (750 nm to 1300 nm) and are described
by Mees in The Theory of the Photoaraphic Process,
third edition (MacMillan, 1966), pages 198-201.
20 Problems arise since 5 or more commonly 7 carbon atoms
in conjugated methine chains are necessary to sensitize
to the infrared versus 6horter methine chains for
vi6ible dyes. The longer methine chain of the IR dyes
lead to poor sensitizing efficiency and poor 6tability
25 on shelf aging. Therefore, IR sensitization i8 very
different and often more difficult than visible
sen6itization.
Supersensitization has developed as a method to
improve the efficiency and often the stability of
30 infrared sensitization. The 6upersensitizers are used
in combination with the infrared sensitizing dye. The
addition of the super6ensitizer, frequently in
quantities ranging from an equivalent molar rate to a
100 fold molar excess of supersensitizer to dye, can
35 increase the spectrally sen6itized speed of the
emul6ion by more than an order of magnitude. Some
super6en6itizer6 are dyes themselves, but many others
%~7~8~
-- 3 --
do not absorb radiation in signi~icant amounts in the
visible portion of the electromagnetic spectrum.
Therefore, the effect of the supersen~itizer~ on
spectral sensitization is not clearly dependent on the
5 ability of compounds to absorb radiation in the visible
or infrared portion of the spectrum. Certain
supersensitizers are sometimes more effective with one
sensitizing dye class versus a second dye class. Due
to supersensitizer-dye specificity and the large
10 sensitivity increases generated by supersensitizers, an
expanded selection of supersensitizers is desired.
Supersensitization has been used effectively in
silver halide photographic systems to minimize the
inefficiency of infrared sensitizing dyes. The
15 supersensitizers have included diazenyl and triazenyl
stilbenes as described in U.S. Pat. No. 2,875,058 and
Great Britain Patent No. 2,140,928, benzotriazoles as
described in U.S. Pat. No. 4,030,927 and 4,105,454,
thioureas as described in U.S. Pat. No. 4,607,006, U.S.
20 Pat. No. 3,458,318 and U.S. Pat. No. 3,954,481,
thiatriazoles as described in U.S. Pat No. 4,780,404
and 4,914,015, tetraazaindenes as described in U.S.
Pat. No. 3,695,888 and certain heterocyclic salts as
described in U.S. Pat. No. 4,596,767.
Mercapto aromatic compounds have also been used in
silver halide photographic elements as infrared
supersensitizers and include mercapto-substituted
oxazine, oxazole, thiazole, thiadiazole, imidazole or
tetrazole as described in U.S. Pat. No. 3,457,078 and
30 mercapto substituted triazoles as described in U.S.
Pat. No. 4,910,129.
Infrared supersensitization in photothermographic
systems has been previously demonstrated with metal
chelating agents in U.S. Pat. No. 4,873,184 and with
35 pyridine, pyrimidine and triazine derivatives in
J6 3,023,145A. However, due to dye specificity and the
dramatic benefits created by supersensitization, more
8~
- 4 -
chemical classes of super6ensitizer6 are desirable.
The photothermographic, infrared super6en6itizers
of the present invention are aromatic, heterocyclic
mercapto or disulphide compounds. These compounds have
5 been used extensively in photothermographic elements.
Mercapto heterocycles have appeared as antifoggants and
development restrainers in U.S. Pat. Nos. 4,639,408;
4,451,561; 3,961,963; 4,678,735 and 4,837,141 as post
print stabilizers in U.S. Pat. Nos. 3,617,289 and
10 3,997,346 in the preparation of silver soaps as in U.S.
Pat. Nos. 4,138,265; 4,728,600 and 4,859,580 as toners
in U.S. Pat. No. 4,201,582 and as speed enhancers in
U.S. Pat. No. 3,359,105 for an N-vinyl carbazole and an
organic halogen dye-forming, thermal imaging system.
U.S. Patent No. 4,968,597 describes the use of
mercapto substituted heteroaromatic compounds in a blue
sensitive silver halide layer of a color, heat-
developable material. No 6upersensitization was
observed in systems similar to those of the present
20 invention which had been spectrally sensitized to the
blue, green, or red. Only in infrared sensitive
sy6tem6 wa6 supersen6itization noted.
U.S. Patent No. 4,245,033 describe6 the use of a
number of classe6 of sulfur compounds in heat
25 developable photo6ensitive composition6. That system
varies from the present invention in that thioether6
and nonaromatic thiols work as well as aromatic thiols.
In addition, there are no infrared sensitized examples.
U.S. Patent No. 4,105,451, describes the use of
30 mercapto-aromatic compounds in combination with a
silver salt of a heterocyclic thione in a
photothermographic material incorporating very high
levels of ~ilver iodide. No infrared sen6itizing dyes
are shown.
2~7~80
-- 5 --
~RIEF DESCRIPTION OF ~HE INVENTION
Photothermographic emulsions which have been
spectrally sensitized to the infrared and near infrared
regions of the electromagnetic spectrum are
5 supersensitized by the addition of mercapto substituted
heteroaromatic compounds.
DETAILED DESCRIPTION OF THE INVEN~ION
Silver halide crystals have an inherent
10 photosensitivity only in the ultraviolet and blue
regions of the electromagnetic spectrum. In order to
provide the crystals with sensitivity to other portions
of the electromagnetic spectrum, dyes are used. These
dyes which extend the range of sensitivity of the
15 silver halide are generally referred to as spectral
sensitizing dyes. As noted above, supersensitizers
increase the efficiency of these spectral sensitizing
dyes.
Traditionally, emulsions which have been
20 spectrally sen6itized to the infrared regions of the
spectrum have been 6ensitized inefficiently. The
relative 6ensitivities of infrared sensitized emulsions
tend to be lower than the relative ~en6itivities of
emulsion6 spectrally sen6itized to the visible regions
25 of the 6pectrum. The need for 6upersen6itizers in the
infrared i5 therefore considered to be generally very
important.
It ha6 been found in the present invention that
heteroaromatic mercapto compounds (I) or heteroaromatic
30 disulfide compounds (II) are effective super3ensitizers
for photothermographic emulsions spectrally sensitized
to wavelengths longer than 750 nm (e.g. 750-1300 nm,
preferably 750 to 950 nm).
Ar-SM (I)
Ar-S-S-Ar (II)
wherein M repre6ents a hydrogen atom or an alkali metal
atom,
.
.
2~7~0
- 6 -
Ar represents an aromatic ring or fused aromatic
ring containing one or more of nitrogen, sulfur,
oxygen, selenium or tellurium atoms. Preferably the
heteroaromatic ring is benzimidazole, naphthimidazole,
5 benzothiazole, naphthothiazole, benzoxazole,
naphthoxazole, benzoselenazole, benzotellurazole,
imidazole, oxazole, pyrazole, triazole, thiadiazole,
tetrazole, triazine, pyrimidine, pyridazine, pyrazine,
pyridine, purine, quinoline or quinazolinone. However,
10 other heteroaromatic rings are envisioned under the
breadth of this invention.
The heteroaromatic ring may also carry
~ubstituents with examples of preferred 6ubstituents
being selected from the class consisting of halogen
(e.g. Br and Cl), hydroxy, amino, carboxy, alkyl (e.g.
of 1 or more carbon atoms, preferably 1 to 4 carbon
atoms) and alkoxy (e.g. of 1 or more carbon atoms,
preferably of 1 to 4 carbon atoms).
Specific examples of mercapto substituted
20 heteroaromatic compounds are set forth below, but the
present invention should not be construed as being
limited thereto.
M-l 2-mercaptobenzimidazole
M-2 2-mercaptobenzoxazole
M-3 2-mercaptobenzothiazole
M-4 2-mercapto-5-methylbenzimidazole
M-5 6-ethoxy-2-mercaptobenzothiazole
M-6 2,2'-Dithiobis-(benzothiazole)
M-7 3-mercapto-1,2,4-triazole
M-8 4,5-diphenyl-2-imidazolethiol
M-9 2-mercaptoimidazole
M-10 1-ethyl-2-mercaptobenzimidazole
M-11 2-mercaptoquinoline
M-12 8-mercaptopurine
M-13 2-mercapto-4(3H)-quinazolinone
M-14 7-trifluoromethyl-4-quinolinethiol
M-15 2,3,5,6-tetrachloro-4-pyridinethiol
,i , .
2~7 ~
- 7 -
M-16 4-amino-6-hydroxy-2-mercaptopyrimidine
monohydrate
N-17 2-amino-5-mercapto-1,3,4-thiadiazole
M-18 3-amino-5-mercapto-1,2,4-triazole
M-19 4-hydroxy-2-mercaptopyrimidine
M-20 2-mercaptopyrimidine
M-21 4,6-diamino-2-mercaptopyrimidine
M 22 2-mercapto-4-methylpyrimidine
hydrochloride
M-23 3-mercapto-5-phenyl-1,2,4-triazole
M-24 2-mercapto-4-phenyloxazole
The supersensitizers are used in general amount of
at least 0.001 moles/mole of silver in the emulsion
layer. Usually the range is between 0.001 and 1.0
15 moles of the compound per mole of silver and preferably
between 0.01 and 0.3 moles of compound per mole of
silver.
Supersensitization of infrared sensitized
photothermographic elements by mercapto substituted
20 heteroaromatic compounds has been shown to be effective
with a broad range of infrared 6ensitizin~ dyes. The
preferred infrared dyes are tricarbocyanine dyes
described in U.S. Pat. No. 4,536,473 and rigidized
tricarbocyanine dyes described in U.S. Pat. No.
25 4,515,888 and 4,959,294. Other effective classes of
infrared dyes are 4-quinoline pentamethine dyes
described in U.S. Pat. No. 4,536,473, merocyanine
infrared dyes and trinuclear dyes.
The infrared sensitizing dye used in the present
30 invention i8 incorporated in the silver
photothermographic layer in a content of 1 x 1o-5 mole
to 1 x 102 mole preferably 5 x 105 to 5 x 1o-3 mole, per
mole of total silver.
Specific examples of the infrared ~ensitizing dyes
35 used in the pre6ent invention are listed below, but the
,~.. ,
- -
- '
, '-
2~7~8~
- 8 -
present invention should not be construed as being
limited thereto.
D 1
~2) 2C}~ ( CE~2) 2coo-
~N~ D - 2
C2H5 C2~H5
C1130 ~ ~1 D-3
C2~5 C2H5
D ---
I
CZH5 C2E~I5
I
2 ~
Cl O
C2H5 C2H5
Cl
D - 6
-- ~ CH= CH--CH= Cl~--CH=~N 2 5
~+
~ C2HS
~3 ~
C2H5 N } ~;_N C2~5
Conventional silver halide photothermographic
chemi~try is used as the photothermographic chemistry
in the system of the present invention. Such chemistry
5 is well described in U.S. Patents 3,457,075; 3,839,049;
3,985,565; 4,022,617 and 4,460,681. These can be
either black-and-white or color chemistries. Either n
~ halidization (e.g., 3,457,075) or preformed silver
halide source6 (e.g., 3,839,049) may be used. Any of
10 the various photothermographic media, such as full
soaps, partial soaps, full salts, and the like may be
used in the photothermographic chemistry.
Conventional photothermographic chemistry
comprises a photosensitive silver halide catalyst, an
15 essentially light-insensitive silver compound capable
of being reduced to form a metallic silver image (e.g.,
2~$7~8~
-- 10 --
silver salts, both organic or inorganic, and ~ilver
complexes, usually light sensitive ~ilver materials), a
developing agent for silver ion (a mild reducing agent
for silver ion), and a binder. Color
5 photothermographic systems additionally have a leuco
dye or dye forming developer (alone or in combination
with a developer for silver ion), or a color
photographic coupler which would require a color
photographic developer to be used as the developing
10 agent for silver ion. Thus both negative and positive
systems can be used.
In particular, the dyes listed in Japanese Kohyo
National Publication No. 500352/82, published February
25, 1982 are preferred. Naphthols and arylmethyl-1-
15 naphthols are generally preferred.
Conventional photothermographic chemistry isusually constructed as one or two layers on a
substrate. Single layer constructions must contain the
cilver source material, the silver halide, the
20 developer and binder as well as optional additional
material6 such as toners, coating aids and other
ad~uvant6. Two-layer construction6 must contain silver
source and silver halide in one emulsion layer (usually
the layer adjacent to the 6ubstrate) and the other
25 ingredients in the 6econd layer or both layers. In the
pre6ent invention it is preferred to use two layer
chemi6try.
The 6ilver source material, as mentioned above,
ordinarily may be any material which contains a
30 reducible source of silver ions. Silver salts or
organic acids, particularly long chain ~lO to 30,
preferably 15 to 28 carbon atoms) fatty carboxylic
acids are preferred in the practice of the present
invention. Complexe6 of organic or inorganic silver
35 salt6 wherein the ligand has a gross stability constant
between 4.0 and 10.0 are also useful in the present
invention. The silver 60urce material should
2 ~
- 11
constitute from about 20 to 70 percent by weight of the
imaging layer. Preferably it i8 pre6ent as 30 to 55
percent by weight.
Suitable organic silver salts include silver salts
5 of organic compounds having a carboxy group. Preferred
examples thereof include a silver salt of an aliphatic
carboxylic acid and a 6ilver salt of an aromatic
carboxylic acid. Preferred examples of the silver
salts of aliphatic carboxylic acids include silver
10 behenate, silver stearate, silver oleate, silver
laurate, silver caprate, silver myristate, silver
palmitate, silver maleate, silver fumarate, silver
tartarate, silver furoate, silver linoleate, silver
butyrate and silver camphorate, mixtures thereof, etc.
15 Silver salts which are substituted with a halogen atom
of a hydroxyl group can also be effectively used.
Preferred examples of the silver salts of aromatic
carboxylic acid and other carboxyl group-containing
compounds include silver benzoate, a silver substituted
20 benzoate such as silver 3,5-dihydroxybenzoate, silver
o-methylbenzoate, silver m-methylbenzoate, silver
p-methylbenzoate, silver 2,4-dichlorobenzoate, silver
acetamidobenzoate, silver p-phenylbenzoate, etc.,
silver gallate, silver tannate, silver phthalate,
25 silver terephthalate, silver salicylate, silver
phenylacetate, silver pyromellitate, a silver salt of
3-carboxymethyl-4-methyl-4-thiazoline-2-thione or the
like as described in U.S. Pat. No. 3,785,830, and
silver salt of an aliphatic carboxylic acid containing
30 a thioether group as described in U.S. Pat. No.
3,330,633, etc.
Silver 6alts of compounds containing mercapto or
thione groups and derivatives thereof can be used.
Preferred examples of these compounds include a silver
35 salt of 3-mercapto-4-phenyl-1,2,4-triazole, a silver
salt of 2-mercaptobenzimidazole, a silver salt of 2-
mercapto-5-aminothiadiazole, a silver salt of 2-(S-
~ .. ~ ,,
2~1~7~8~
- 12 -
ethylglycolamido) benzothiazole, a 6ilver salt of
thioglycolic acid such as a silver salt of a S-alkyl
thioglycolic acid (wherein the alkyl group has from 12
to 22 carbon atoms) as described in Japanese patent
5 application No. 28221/73, a silver salt of a
dithiocarboxylic acid such as a silver salt of
dithioacetic acid, a silver salt of thioamide, a silver
salt of 5-carboxylic-1-methyl-2-phenyl-4-thiopyridine,
a silver salt of mercaptotriazine, a silver salt of
10 2-mercaptobenzoxazole, a silver æalt as described in
U.S. Pat. No. 4,123,274, for example, a silver salt of
a 1,2,4-mercaptothiazole derivative such as a silver
salt of 3-amino-5-benzylthio-1,2,4-thiazole, a silver
salt of a thione compound such as a silver salt of
15 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione as
disclosed in U.S. Pat. No. 3,301,678.
Furthermore, a silver salt of a compound
containing an imino group can be used. Preferred
examples of these compounds include a 6ilver salt of
20 benzotriazole and a derivative thereof as described in
Japanese Patent Publication Nos. 30270/69 and 18146/70,
for example, a silver salt of benzotriazole such as
silver ~alt of methylbenzotriazole, such as a silver
6alt of a halogen substituted benzotriazole, such as a
25 silver salt of 5-chlorobenzotriazole, etc., a silver
~alt of carboimidobenzotriazole, etc., a silver 6alt of
1,2,4-triazole, of 1-H-tetrazole as described in U.S.
Pat. No. 4,220,709, a silver 6alt of imidazole and an
imidazole derivative, and the like.
The light sensitive silver halide used in the
pre6ent invention can be employed in a ranqe of 0.0005
mole to 5 mole and, preferably, from 0.005 mole to 1.0
mole per mole of organic ~ilver 6alt.
The silver halide may be any photosensitive silver
35 halide such as silver bromide, silver iodide, silver
chloride, silver bromoiodide, silver chlorobromoiodide,
6ilver chlorobromide, etc.
2 ~ 8 ~
- 13 -
The silver halide may be added to the emulsion
layer in any fashion which places it in catalytia
proximity to the silver source.
The silver halide and the organic silver salt
5 which are separately formed in a binder can be mixed
prior to use to prepare a coating 601ution, but it is
also effective to blend both of them in a ball mill for
a long period of time. Further, it i8 effective to use
a process which comprises adding a halogen-containing
lo compound in the organic silver salts prepared to
partially convert the silver of the organic silver salt
to silver halide.
Methods of preparing these silver halide and
organic silver salts and manners of blending them are
15 described in Research Disclosures, No. 170-29, Japanese
Patent Application Nos. 32928/75 and 42529/76, U.S.
Pat. No. 3,700,458, and Japanese Patent Application
Nos. 13224/74 and 17216/75.
The use of preformed silver halide emulsions of
20 this invention can be unwa6hed or washed to remove
soluble salts. In the latter case the soluble salts
can be removed by chill-setting and leaching or the
emulsion can be coagulation washed, e.g., by the
procedures described in Hewitson, et al., U.S. Pat. No.
25 2,618,556; Yutzy et al., U.S. Pat. No. 2,614,928;
Yackel, U.S. Pat. No. 2,565,418; Hart et al., U.S. Pat.
No. 3,241,969; and Waller et al., U.S. Pat. No.
2,489,341. The silver halide grains may have any
crystalline habit including, but not limited to cubic,
30 tetrahedral, orthorhombic, tabular, laminar, platelet,
etc.
Photothermographic emulsions containing preformed
silver halide in accordance with this invention can be
sen6i~ized with chemical 6ensitizers, such as with
35 reduction agents; sulfur, selenium or tellurium
compound~; gold, platinum or palladium compounds, or
combinations of these. Suitable chemical sen6itation
. ~ . .,, i, , ,
2 ~
- 14 -
procedures are described in Shepard, U.S. Pat. No.
1,623,499; Waller, U.S. Pat. No. 2,399,083; McVeigh,
U.S. Pat. No. 3,297,447; and Dunn, U.S. Pat. No.
3,297,446.
~he reducing agent for silver ion may be any
material, preferably organic material, which will
reduce silver ion to metallic silver. Conventional
photographic developers such as phenidone,
hydroquinones, and catechol are useful but hindered
10 phenol reducing agents are preferred. The reducing
agent should be present as 1 to 20 percent by weight of
the imaging layer. In a two-layer construction, if the
reducing agent is in the second layer, slightly higher
proportions, of from about 2 to 20 percent tend to be
15 more desirable.
A wide range of reducing agents have been
disclosed in dry silver sy6tems including amidoximes
such as phenylamidoxime, 2-thienylamidoxime and
p-phenoxy-phenylamidoxime, azines, e.g., 4-hydroxy-
20 3,5-dimethoxybenzaldehyde azine; a combination of
aliphatic carboxylic acid aryl hydrazides and ascorbic
acid, such a6 2,2'-bis(hydroxymethyl)propionyl-beta-
phenyl hydrazide in combination with ascorbic acid; a
combination of polyhydroxybenzene and hydroxylamine, a
25 reductone and/or a hydrazine, e.g., a combination of
hydroquinone and bis~ethoxyethyl)hydroxylamine,
piperidinohexose reductone or formyl-4-methylphenyl
hydrazine, hydroxamic acids such as phenylhydroxamic
acid, p-hydroxyphenylhydroxamic acid, and beta-alanine
30 hydroxamic acid; a combination of azines and
sulphonamidophenols, e.g., phenothiazine and 2,6-
dichloro-4-benzene6ulphonamidophenol; alpha-
cyanophenylacetic acid derivatives euch a6 ethyl-alpha-
cyano-2-methylphenylacetate, ethyl-alpha-
35 cyanophenylacetate; bis-beta-naphthols as illustrated
by 2,2'-dihydroxy-1,1'-binaphthyl, 6,6'-dibromo-2,2'-
dihydroxy-1,1'-binaphthyl, and bi6(2-hydroxy-l-
'
- 15 - ~ ~ $ ~8Q
naphthyl)methane; a combination of bi~-beta-naphthol
and a 1,3-dihydroxybenzene derivative, e.g., 2,4-
dihydroxy-benzophenone or 2'4'-dihydroxyacetophenone;
5-pyrazolones such as 3-methyl-1-phenyl-5-pyrazolone;
5 reductones as illustrated by dimethylamino hexose
reductone, anhydro dihydro amino hexose reductone, and
anhydro dihydro piperidone hexose reductone;
sulphonamido-phenol reducing agents such as
2,6-dichloro-4-benzenesulphonamidophenol, and
10 p-benzenesulphonamidophenol; 2-phenylindane-1,3-dione
and the like; chromans such as 2,2-dimethyl-7-t-butyl-
6-hydroxychroman; 1,4-dihydro-pyridines such as
2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine;
bisphenols e.g., bis(2-hydroxy-3-t-butyl-5-
15 methylphenyl)methane, 2,2-bis(4-hydroxy-3-
methylphenyl)propane, 4,4-ethylidene-bis(2-tert-butyl-
6-methylphenol), and 2,2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane; ascorbic acid derivatives, e.g.,
l-ascorbylpalmitate, ascorbylstearate and unsaturated
20 aldehydes and ketones, such as benzyl and diacetyl;
3-pyrazolidones and certain indane-1,3-diones.
The literature disclo6es additives or "toners",
which improve the ima~e. Toner materials may be
present, for example, in amounts from 0.1 to 10 percent
25 by weight of all silver bearing components. Toners are
well known materials in the photothermographic art as
shown in U.S. Pat. Nos. 3,080,254, 3,847,612 and
4,123,282.
Examples of toners include phthalimide and
30 N-hydroxyphthalimide; cyclic imides such as
succinimide, pyrazoline-5-ones, and a quinazolinone, 3-
phenyl-2-pyrazoline-5-one, l-phenylurazole,
quinazoline, and 2,4-thiazolidinedione; naphthalimides,
e.g., N-hydroxy-1,8-naphthalimide; cobalt complexes,
35 e.g., cobaltic hexamine trifluoroacetate; mercaptans as
illustrated by 3-mercapto-1,2,4-triazole, 2,4-
dimercaptopyrimidine, 3-mercapto-4,5-diphenyl-1,2,4-
.
2~37l~8~
- 16 -
triazole and 2,5-dimercapto-1,3,4-thiadiazole; N-
(aminomethyl)aryl dicarboximides, e.g. (N-
dimethylaminomethyl)phthalimide, and
N-(dimethylaminomethyl)naphthalene-2,3-dicarboximide;
5 and a combination of blocked pyrazoles, isothiuronium
derivatives and certian photobleach agents, e.g., a
combination of N,N'-hexamethylene bis(l-carbamoyl-3,5-
dimethylpyrazole), 1,8-(3,6-
diazaoctane)bis(isothiuronium trifluoracetate) and 2-
(tribromomethylsulphonyl)-(benzothiazole); and
merocyanine dyes such as 3-ethyl-St(3-ethyl-2-
benzothiazolinylidene)-l-methylethylidene]-2-thio-2,4-
oxazolidinedione; phthalazinone, phthalazinone
derivatives or metal salts or these derivatives such as
15 4-(1-naphthyl)phthalazinone, 6-chlorophthalazinone,
5,7-dimethoxyphthalazinone, and 2,3-dihydro-1,4-
phthalazinedione; a combination of phthalazinone plus
6ulphinic acid derivatives, e.g., phthalic acid, 4-
methylphthalic acid, 4-nitrophthalic acid, and
20 tetrachlorophthalic anhydride; quinazolinediones,
benzoxazine or naphthoxazine derivatives; rhodium
complexes functioning not only as tone modifiers but
al60 a6 sources of halide ion for silver halide
formation in situ, such as ammonium hexachlororhodate
(III), rhodium bromide, rhodium nitrate and potassium
hexachlororhodate (III); inorganic peroxides and
persulphates, e.g., ammonium peroxydisulphate and
hydrogen peroxide; benzoxazine-2,4-diones such as 1,3-
benzoxazine-2,4-dione, 8-methyl-1,3-benzoxazine-2,4-
30 dione, and 6-nitro-1,3-benzoxazine-2,4-dione;
pyrimidines and asym-triazines, e.g., 2,4-
dihydroxypyrimidine, 2-hydroxy-4-aminopyrimidine, and
azauracil, and tetrazapentalene derivatives, e.g., 3,6-
dimercapto-1,4-diphenyl-lH,4H-2,3a,5,6a-
35 tetrazapentalene, and 1,4-di(o-chlorophenyl)-3,6-
dimercapto-lH,4H-2,3a,5,6a-tetrazapentalene.
2 ~ 8 ~
- 17 -
A number of methods have been proposed for
obtaining color images with dry silver systems. Such
methods include incorporated coupler materials, e.g., a
combination of silver benzotriazole, well known
5 magenta, yellow and cyan dye-forming couplers,
aminophenol developing agents, a base release agent
such as guanidinium trichloroacetate and 6ilver bromide
in poly(vinyl butyral); a combination of silver
bromoidodide, sulphonamidophenol reducing agent, silver
10 behenate, poly(vinyl butyral)~ an amine such as n-
octadecylamine and 2-equivalent or 4-equivalent cyan,
magenta or yellow dye-forming coupler~; incorporating
leuco dye bases which oxidize to form a dye image,
e.g./ Malachite Green, Crystal Violet and
15 pararo6aniline; a combination of in situ silver halide,
silver behenate, 3-methyl-1-phenylpyrazolone, and N,N'-
dimethyl-p-phenylenediamine hydrochloride;
incorporating phenolic leuco dye reducing agents such
as 2-(3,5-di-tert-butyl-4-hydroxyphenyl)-4,5-
20 diphenylimidazole, and bis(3,5-di-tert-butyl-4-
hydroxyphenyl)phenylmethane, incorporating azomethine
dyes or azo dye reducing agents; silver dye bleach
process, e.g., an element comprising silver behenate,
behenic acid, poly(vinyl butyral), poly(vinyl-
25 butyral)peptized silver bromoidodide emulsion, 2,6-
dichloro-4-benzenesulphonamidophenol, 1,8-(3,6-
diazaoctane)bis-isothiuronium-p-toluene sulphonate and
an 8ZO dye was exposed and heat processed to obtain a
negative silver image with a uniform distribution of
30 dye which was laminated to an acid activator sheet
comprising polyacrylic acid, thiourea and p-toluene
sulphonic acid and heated to obtain well defined
positive dye images; and incorporating amines such as
aminoacetanilide (yellow dye-forming), 3,3'-
35 dimethoxybenzidine (blue dye-forming) or
sulphanilanilide (magenta dye-forming) which react with
the oxidized form of incorporated reducing agents such
2 ~ 8 ~
- 18 -
as 2,6-dichloro-4-benzenesulphonamidophenol to form dye
images. Neutral dye images can be obtained by the
addition of amines such as behenylamine and p-
anisidine.
Leuco dye oxidation in such silver halide systems
are disclosed in U.S. Pat. Nos. 4,021,240; 4,374,821;
4,460,681 and 4,883,747.
Silver halide emulsions containing the
supersensitizers of this invention can be protected
10 further against the additional production of fog and
can be stabilized against loss of sensitivity during
keeping. Suitable antifoggants and 6tabilizers which
can be used alone or in combination, include tne
thiazolium salts described in Staud, U.S. Pat. N~.
15 2,131,038 and Allen U.S. Pat. No. 2,694,716; the
azaindenes described in Piper, U.S. Pat. No. 2,886,437
and Heimbach, U.S. Pat. No. 2,444,605; the mercury
salts de~cribed in Allen, U.S. Pat. No. 2,728,663; the
urazoles described in Anderson, U.S. Pat. No.
20 3,287,135; the sulfocatechols described in Kennard,
U.S. Pat. No. 3,235,652; the oximes described in Carrol
et al., British Patent No. 623,448; nitron;
nitroindazoles; the polyvalent metal salts described in
Jones, U.S. Pat. No. 2,839,405; the thiuronium salts
25 described by Herz, U.S. Pat. No. 3,220,839; and
palladium, platinum and gold salts described in
Trivelli, U.S. Pat. No. 2,566,263 and Damschroder, U.S.
Pat. No. 2,597,915.
Supersensitized emulsions of the invention can
30 contain plasticizers and lubricants such as
polyalcohols, e.g., glycerin and diols of the type
described in Milton, U.S. Pat. No. 2,960,404; fatty
acids or e6ters ~uch as those described in Robins, U.S.
Pat. No. 2,588,765 and Duane, U.S. Pat. No. 3,121,060;
35 and silicone resins such as those described in DuPont
British Patent No. 955,061.
2~7~
-- 19 --
The photothermographic elements can include image
dye stabilizers. Such image dye stabilizers are
illustrated by U.K. Patent No. 1,326,889; Lestina et
al. U.S. Pat. Nos. 3,432,300 and 3,698,909; Stern et
5 al. U.S. Pat~ No. 3,573,050; Arai et al. U.S. Pat. No.
3,764,337 and Smith et al. U.S. Pat. No. 4,042,394.
Photothermographic elements containing emulsion
layers supersensitized according to the present
invention can be used in photographic elements which
10 contain light absorbing materials and filter dyes such
as those described in Sawdey, U.S. Pat. No. 3,253,921;
Gaspar U.S. Pat. No. 2,274,782; Carroll et al., U.S.
Pat. No. 2,527j583 and Van Campen, U.S. Pat. No.
2,956,879. If desired, the dyes can be mordanted, for
15 example, as described in Milton and Jones, U.S. Pat.
No. 3,282,699.
Photothermographic elements containing emulsion
layers supersensitized as described herein can contain
matting agents such as starch, titanium dioxide, zinc
20 oxide, silica, polymeric beads including beads of the
type described in Jelley et al., U.S. Pat. No.
2,992,101 and Lynn, U.S. Pat. No. 2,701,245.
Emulsions supersenitized in accordance with this
invention can be used in photothermographic elements
25 which contain antistatic or conducting layers, such as
layers that comprise soluble salts, e.g., chlorides,
nitrates, etc., evaporated metal layers, ionic polymers
such as those described in Minsk, U.S. Pat. Nos.
2,861,056, and 3,206,312 or insoluble inorganic salts
30 such as those described in Trevoy, U.S. Pat. No.
3,428,451.
The binder may be selected from any of the well-
known natural or synthetic resins such as gelatin,
polyvinyl acetals, polyvinyl chloride, polyvinyl
35 acetate, cellulose acetate, polyolefins, polyesters,
polystyrene, polyacrylonitrile, polycarbonates, and the
like. Copolymers and terpolymers are of course
2~7~
- 20 -
included in these definitions. The preferred
photothermographic silver containing polymer is
polyvinyl butyral, but ethyl cellulose, methacrylate
copolymers, maleic anhydride ester copolymers,
5 polystyrene, and butadiene-styrene copolymers are also
useful.
Optionally these polymers may be used in
combination of two or more thereof. Such a polymer is
used in an amount sufficient to carry the components
10 dispersed therein, that is, within the effective range
of the action as the binder. The effective range can
be appropriately determined by one skilled in the art.
As a guide in the case of carrying at least an organic
silver salt, it can be said that a preferred ratio of
15 the binder to the organic silver salt ranges from 15:1
to 1:2, and particularly from 8:1 to 1:1.
Photothermographic emul6ions containing the
supersensitizer of the invention can be coated on a
wide variety of supports. Typical supports include
ZO polyester fllm, subbed polyester film, poly(ethylene
terephthalate)film, cellulose nitrate film, cellulose
ester film, poly(vinyl acetal) film, polycarbonate ~ilm
and related or re6inous materials, as well a~ glass,
paper metal and the like. Typically, a flexible
25 support is employed, especially a paper support, which
can be partially acetylated or coated with baryta
and/or an alphaolefin polymer, particularly a polymer
of an alpha-olefin containing 2 to 10 carbon atoms such
as polyethylene, polypropylene, ethylenebutene
30 copolymers and the like.
The sub6trate with a backside re~istive heating
layer may also be used in photothermographic imaging
systems such as shown in U.S. Pat. No. 4,460,681 and
4,374,921.
Photothermographic emulsions of this invention can
be coated by various coating procedures including dip
coating, air knife coating, curtain coating, or
2~
- 21 -
extrusion coating using hoppers of the type described
in Benguin, U.S. Pat. No. 2,681,294. If desired, two
or more layers may be coated simultaneously by the
procedures described in Russell, U.S. Pat. No.
5 2,761,791 and Wynn, British Patent No. 837,095.
The present invention will be illustrated in
detail in reference to the following examples, but the
embodiment of the present invention i5 not limited
thereto.
EXAMPLES 1-13
A silver halide-silver behenate dry soap was
prepared by the procedures described in U.S. Pat. No.
3,839,049. The silver halide totalled 9% of the total
15 silver while silver behenate comprised 91% of the total
silver. The silver halide was a 50/50 mixture of
preformed silver halide grains. Both had a composition
of 2% iodide and 98% bromide and were monodispersed.
The two ~ilver bromoiodide emulsions had grain sizes of
20 0.055 and 0.07 microns.
A photothermographic emulsion was prepared by
homogenizing 300 g of the silver halide-silver behenate
dry soap described above with 525 q toluene, 1675 g 2-
butanone and 50 g poly(vinylbutyral) (B-76, Monsanto).
The homogenized photothermographic emulsion (500
g) and 100 g 2-butanone were cooled to 55F with
stirring. Additional poly(vinylbutyral) (75.7 g B-76)
wa6 added and stirred for 20 minutes. Pyridinium
hydrobromide perbromide (0.45 g) was added and stirred
30 for 2 hours. The addition of 3.25 ml of a calcium
bromide solution (1 g of CaBr2 and 10 ml of methanol)
was followed by 30 minutes of stirring. The
temperature was rai~ed to 70F and the following were
added in 15 minute increments with stirring: 3 g 2-(4-
35 chlorobenzoyl)benzoic acid, IR dye solution (D-1 dye;
8.8 mg D-1 in 7.1 g DMF) and 16.6 g 1,1-bis(2-hydroxy-
3,5-dimethylphenyl)-3,5,5-trimethylhexane.
.~ .
2~$7480
- 22 -
The photothermographic emulsion was divided into
40 g portions. The control was coated at this stage
without additional additives. The remaining aliquots
were treated with 3 levels of heteroaromatic mercapto
S compounds added as 1% solutions in methanol (w/v). The
results are reported in Table 1 for the levels of
heteroaromatic mercapto compound listed as dry wei~ht
per 40 g aliquots giving the best balance of low fog
and high speed.
The silver photothermographic emulsions were
coated and clear 3 mil (0.76 x lO~m~ polyester by means
of a knife coater and dried at 175F for four minutes.
The dry coating weight was 23 g/m2.
An active, protective topcoat solution was
15 prepared with the following ingredients:
256 g acetone
123 g 2-butanone
50 g methanol
20.2 g cellulose acetate
2.89 g phthalazine
2.02 g 4-methylphthalic acid
0.69 g tetrachlorophthalic acid
0.90 g tetrabromophthalic anbydride
1.50 g tetrachlorophthalic anhydride
0.45 g 4-tribromomethylpyrimidine
The topcoat solution was coated over the silver layer
at a dry weight of 3.0 g/m2. The layer was dried at
165F for four minutes.
The coated materials were then exposed with a
30 continuous wedge and an EK 101 sensitometer through a
780 nm narrow band filter for 30.2 seconds. After
exposure, the film strips were processed at 260F for
ten seconds. The images obtained were evaluated by a
densitometer. Sensitometric results include Dmin,
35 speed (Spd: measured at O.D ~ 1.0), ergs (power to
reach optical density of 1.0), change in ~peed from
2 ~ 8 D
- 23 -
emulsion without heteroaromatic mercapto compound
(dSpd) and the percent that speed change (dSpd)
represented (%Spd). In all coatings, the maximum
density ranged from only 3.2 to 3.5 and wa not
S tabulated.
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- 25 -
A set of experiments were run to determine the
scope of the present invention. Table 2 contains a
list of sulfur compounds and silver halide, infrared
supersensitizers tested in the formula described for
Examples 1-13. The compounds were tested at the three
levels described in Examples 1-13 with the best level
listed in Table 2. The results show that thioethers,
thioureas and thiones do not supersensitize the
infrared photothermographic system. The thioureas and
also benzotriazole and Leucophor BCF (Sandoz,
sulfonated triazenyl stilbene) did not supersensitize
the photothermographic system although they are used
extensively as silver halide, infrared
supersensitizers.
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- 27 -
EXAMPLES 14-26
The same silver and topcoat formulas were used in
these examples as those given in Examples 1-13 except
that a pure silver bromide grain of 0.055 microns was
used instead of the 50/50 mixture of preformed, 0.055
and 0.07 micron silver bromoiodine grains used in
Examples 1-13.
These examples were again run as 40 g aliquots
with a control coated without addition of
heteroaromatic mercapto compound. The heteroaromatic
mercapto co~pounds used in Examples 14-17 were
evaluated at 3 levels while Examples 18-26 were
examined at 2 levels. The coated film strips were
exposed with a laser sensitometer incorporating a 780
nm laser diode. After exposure, the film strips were
processed at 260F for ~en seconds. The results are
compiled in Table 3.
TABLE 3
Merca~to ComDound
mg/40g
Ex. Number ~plit Emin ~E~ Eras dSDd %Spd
A None ---- 0.11 1.25 565 ---- 100
14 M-1 3.6 0.11 1.93 117 0.68 479
M-13 10.8 0.11 1.79 162 0.54 347
16 M-14 3.6 0.11 1.54 289 0.29 195
17 M-15 1.2 0.11 1.64 230 0.39 245
18 M-16 7.2 0.11 1.59 258 0.34 219
19 M-17 1.2 0.11 1.42 381 0.17 148
M-18 7.2 0.11 1.41 390 0.16 144
21 M-19 7.2 0.11 1.39 409 0.14 138
22 M-20 1.2 0.11 1.49 324 0.24 174
23 M-21 1.2 0.11 1.39 409 0.14 138
24 M-22 1.2 0.11 1.63 235 0.38 240
M-23 7.2 0.11 1.56 276 0.31 204
26 M-24 1.2 0.11 1.47 340 0.22 166
~ " i ,
~37~
- 28 -
Experiments were run to determine the necessity of
having a heteroaromatic system for the mercapto
supersensitizers. The silver and topcoat formulas were
the same as in Examples 14-26. The results are listed
in Table 4 and show the importance of having a
heteroaromatic system attached to the mercapto group in
order to supersensitize the infrared,
photothermographic film.
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- 30 -
EX~MPLES 27-33
The supersensitization effects of mercapto
heteroaromatic compounds on infrared sensitized
photothermographic systems were evaluated for other
infrared sensitizing dyes. The formula was the same as
in Examples 14-26. The infrared dyes were examined
with and without M-1 (2-mercaptobenzimidazole). The
sensitivity maximum of the infrared dyed
photothermographic film was found by exposing with a
series of narrow band filters and an EK 101
sensitometer. The speed and supersensitization effect
was evaluated on a laser sensitometer incorporating a
780 nm laser diode. The Dmin values were unaffected by
the addition of N-l. The results are listed in Table 5
and show clearly that mercapto heteroaromatic compounds
supersensitize all infrared dye classes in
photothermographic compositions.
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- 32 -
~XAMPLE 34
An in ~itu halidized photothermographic system was
examined for infrared supersensitization with mercapto
heteroarmatic compounds. A photothermograhpic emulsion
was prepared by combining 206 g of a 6ilver behenate
full soap di6persion (converted to 26% 6ilver by
weight) with the following ingredient6, each added in
its listed order with mixing:
40 g 2-butanone
0.54 g N-methylpyrrolidone
5.4 ml of ZnBr2 solution (10 g ZnBr2 and 100 ml of
methanol)
The mixture was held for 4 hours before adding the
following:
3.6 g poly(vinylbutyral) B-76
2.6 ml of pyridine solution (3.6 g pyridine and
71 g 2-butansne)
27.5 g poly(vinylbutyral) B-76
4.6 ml NBS solution (0.67 g N-bromosuccinimide
and 40 g 2-butanone)
The mixture was held overnight before adding the
following:
6.3 g 2,2'-methylenebis(4-ethyl-6-
tertiarybutylphenol)
IR dye solution (6 mg D-l and 4.0 g DMF)
The resulting composition wa~ divided into 40 g
portions. The control was coated without additional
additive~ while M-1(2-mercaptobenzimidazole) was added
to a second aliquot. The results are compiled in Table
6. The silver photothermographic emulsions were coated
on clear 3 mil (0.76 x lOJm) polyester by mean6 of a
knife coater and dried at 185F for three minutes. The
dry coating weight was 17 g/m2.
An active, protective topcoat solution was
prepared with the following ingredients:
224 g 2-butanone
~.,,., - .
2~37~0
- 33 -
33.3 g acetone
13.8 g methanol
20.7 g cellulose acetate
2.64 g phthalazine
1.86 g 4-methylphthalic acid
1.23 g tetrachlorophthalic anhydride
0.57 g tetrachlorophthalic acid
1.80 g 2-(tribromomethylsulfone)benzothiazole
The topcoat solution was coated at 2.7 g/nY over the
silver coating and dried at 185F for three minutes.
The coated material was exposed on a laser sensitometer
with a 780 nm laser diode and then processed at 260F
for ten seconds. The results listed in Table 6 show
that mercapto heteroaromatic compounds supersensitize
in situ halidized photothermographic systems sensitized
to the infrared.
TABLE 6
mg M-1 per
Ex. 40 q S~lit Dmin ~ Eras dS~d %S~d
P None 0.23 0.57 2717 --- 100
36 0.8 0.26 1.89 128 1.32 2090
EXAMPLES 35-40
The following coatings show that a combination of
mercapto heteroaromatic compounds may give improved
results as infrared supersensitizers for
photothermographic systems. The same silver and
topcoat formulas were used in these examples as those
given in Examples 14-26 except that a higher infrared
dye level was used (S0% more IR dye, D-l) and a change
was made in the tribromo antifoggant. Examples 14-26
had 0.45 g of 4-tribromomethylpyrimidine in the topcoat
solution whereas Examples 35-40 contained 2.25 g of
2-(tribromomethylsulfone)benzothiazole in the same
quantity of topcoat solution.
2~37~8~
- 34 -
The examples were again run as 40 g aliquots. The
coated film strips were exposed with a laser
sensitometer incorporating a 780 nm laser diode. After
exposure, the film 6trips were proces~ed at 260F for
ten seconds. The results are compiled in Table 7.
Example 35 was the optimized level for ~-1
(2-mercaptobenzimidazole) in terms of speed or
sensitivity. Examples 36-38 show the optimized level
of M-3 (2-mercaptobenzothiazole) to be slightly slower
in speed than M-l but higher in contrast
(cont = contra6t measured from a density of 0.25 to 2.0
above fog). The two mercapto heteroaromatic compounds
were combined in Examples 39 and 40 to produce higher
speed and contrast than when tested separately. The
difference between Examples 39 and 40 was that in
Example 39, N-l was added first and M-3 was added 15
minutes later whereas in Example 40, M-3 was added
first and M-1 was added 15 minutes later. Table 7
show6 that the combination of mercapto heteroaromatic
compounds produced higher speed and high contrast which
would be useful for graphic arts applications.
TABLE 7
Mercapto Com~ound~
mg M-l mg M-3
Per Per
$~ 40 q S~lit 40 a slit ~min ~ Cont
4.2 ---- 0.14 1.91123 2.92
36 ---- 1.4 0.16 1.72191 3.78
37 ---- 2.8 0.20 1.83148 3.84
38 ---- 4.2 0.16 1.77170 4.64
39 4.2 4.2 0.14 2.0197 4.42
4.2 4.2 0.14 2.0589 4.94
