U.S. patent number 3,819,382 [Application Number 05/156,047] was granted by the patent office on 1974-06-25 for light-sensitive material having developers embedded therein.
This patent grant is currently assigned to Agfa-Gevaert Aktiengesellschaft. Invention is credited to Helmut Kampfer, Kurt Ley, Ernst Roos, Anita Von Konig.
United States Patent |
3,819,382 |
Von Konig , et al. |
June 25, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
LIGHT-SENSITIVE MATERIAL HAVING DEVELOPERS EMBEDDED THEREIN
Abstract
Light-sensitive photographic material having reducible metal
compound that forms metal nuclei when exposed to light, and also
has reducing agent incorporated in it to form an image when
processed without an external developer, shows greater storage
stability when the reducing agent is selected from certain hydroxy
chromans and coumaranes. The reducible metal compound can be a
compound of silver or other Group Ib metal, and can be formed in
situ from a non-light sensitive silver salt.
Inventors: |
Von Konig; Anita (Leverkusen,
DT), Kampfer; Helmut (Cologne, DT), Roos;
Ernst (Cologne, DT), Ley; Kurt (Leverkusen,
DT) |
Assignee: |
Agfa-Gevaert Aktiengesellschaft
(Leverkusen, DT)
|
Family
ID: |
5775095 |
Appl.
No.: |
05/156,047 |
Filed: |
June 23, 1971 |
Foreign Application Priority Data
|
|
|
|
|
Jun 26, 1970 [DT] |
|
|
2031748 |
|
Current U.S.
Class: |
430/619;
430/617 |
Current CPC
Class: |
G03C
1/49827 (20130101); G03C 1/42 (20130101); G03C
8/06 (20130101) |
Current International
Class: |
G03C
1/42 (20060101); G03C 1/498 (20060101); G03C
8/02 (20060101); G03C 8/06 (20060101); G03c
001/02 () |
Field of
Search: |
;96/114.1
;117/36.8,36.2,36.9 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Smith; Ronald H.
Assistant Examiner: Kelly; M. F.
Attorney, Agent or Firm: Connolly and Hutz
Claims
We claim:
1. A light-sensitive photographic sheet material containing a
silver salt composition which comprises a light-insensitive silver
salt, a catalytic amount of silver halide, and containing a
reducing agent that causes development of a visible image by
reducing the silver salt composition when processed with heat,
wherein the improvement comprises the reducing agent has the
following formula: ##SPC5##
wherein
n is 0 or 1;
R.sub.1, r.sub.2, r.sub.3, r.sub.4, r.sub.5 and R.sub.6 are
hydrogen or alkyl groups having up to 9 carbon atoms, but
R.sub.3 and R.sub.4 or R.sub.4 and R.sub.5 may be joined together
to complete a carbocyclic ring system having 5, 6 or 7 carbon
atoms, and
R.sub.6 may further represent an alkoxy group having up to 6 carbon
atoms or a tertiary amino group of the formula: ##SPC6##
wherein
R.sub.7 and R.sub.8 represent alkyl having up to 6 carbon atoms or
are together the ring members required for completing a 5-, 6- or
7-membered ring;
R.sub.9, r.sub.10 are hydrogen, alkyl or alkoxy having up to 6
carbon atoms, and at least one of them represents a hydroxyl
group;
R.sub.11, r.sub.12 are hydrogen, alkyl or alkoxy having up to 9
carbon atoms, cycloalkyl, aralkyl, aryl or a group of the formula:
##SPC7##
wherein
R.sup.7 and R.sup.8 have the meanings indicated above.
2. A light-sensitive photographic sheet material containing a
silver salt composition which comprises silver behenate reducible
in the proximity of a catalytic amount of silver nuclei by weak
reducing agents, and containing a reducing agent that causes
development of a visible image by reducing the silver salt
composition when processed with heat, wherein the improvement
comprises the reducing agent has the following formula:
##SPC8##
wherein
n is 0 or 1;
R.sub.1, r.sub.2, r.sub.3, r.sub.4, r.sub.5 and R.sub.6 are
hydrogen or alkyl groups having up to 9 carbon atoms, but
R.sub.3 and R.sub.4 or R.sub.4 and R.sub.5 may be joined together
to complete a carbocyclic ring system having 5, 6 or 7 carbon
atoms, and
R.sub.6 may further represent an alkoxy group having up to 6 carbon
atoms or a tertiary amino group of the formula: ##SPC9##
wherein
R.sub.7 and R.sub.8 represent alkyl having up to 6 carbon atoms or
are together the ring members required for completing a 5-, 6- or
7-membered ring;
R.sub.9, r.sub.10 are hydrogen, alkyl or alkoxy having up to 6
carbon atoms, and at least one of them represents a hydroxyl
group;
R.sub.11, r.sub.12 are hydrogen, alkyl or alkoxy having up to 9
carbon atoms, cycloalkyl, aralkyl, aryl or a group of the formula:
##SPC10##
wherein
R.sup.7 and R.sup.8 have the meanings indicated above.
3. A light-sensitive photographic sheet material containing a
silver salt composition which comprises a light-insensitive silver
salt of a fatty acid, a catalytic amount of silver nuclei, and
containing a reducing agent that causes development of a visible
image by reducing the silver salt composition when processed with
heat, wherein the improvement comprises the reducing agent has the
following formula: ##SPC11##
wherein
n is 0 or 1;
R.sub.1, r.sub.2, r.sub.3, r.sub.4, r.sub.5 and R.sub.6 are
hydrogen or alkyl groups having up to 9 carbon atoms, but
R.sub.3 and R.sub.4 or R.sub.4 and R.sub.5 may be joined together
to complete a carbocyclic ring system having 5, 6 or 7 carbon
atoms, and
R.sub.6 may further represent an alkoxy group having up to 6 carbon
atoms or a tertiary amino group of the formula: ##SPC12##
wherein
R.sub.7 and R.sub.8 represent alkyl having up to 6 carbon atoms or
are together the ring members required for completing a 5-, 6- or
7-membered ring;
R.sub.9, r.sub.10 are hydrogen, alkyl or alkoxy having up to 6
carbon atoms, and at least one of them represents a hydroxyl
group;
R.sub.11, r.sub.12 are hydrogen, alkyl or alkoxy having up to 9
carbon atoms, cycloalkyl, aralkyl, aryl or a group of the formula:
##SPC13##
wherein
R.sup.7 and R.sup.8 have the meanings indicated above.
Description
The invention relates to a light-sensitive photographic material
which contains developer substances in particular in those layers
which contain silver salts.
The principle of embedding developer substances in photographic
emulsion layers has been known for a long time but the substances
conventionally used for this purpose, which are based on aromatic
compounds substituted with hydroxyl or amino groups, do not satisfy
all the requirements in practice. Some of these compounds do not
have a sufficiently powerful development action, whereas those
which are sufficiently powerful developers diminish the stability
in storage of the light-sensitive layers. The reason for this is
the sensitivity of the developers to oxidation with atmospheric
oxygen.
The photographic processes for processing exposed, light-sensitive
materials which contain embedded developer substances may be
subdivided into two main groups, one group comprising those
processes in which aqueous treatment baths are used, whereas the
other group comprises processes in which the exposed photographic
materials are processed at elevated temperature without the use of
development baths.
In the first group of processes, the materials are developed simply
by the action of an alkaline solution and are stabilized against
further changes by light by means of stabilizer baths or by fixing
and washing with water. The heat copying processes belong to the
second group.
The principle of heat copying processes has been described in
German Patent Specification No. 880,045 and involves developing the
material by simply heating it after exposure. The process described
in German Patent Specification No. 1,300,014 also belongs to the
heat copying type of process. In the process described in the
last-mentioned patent specification, photographic recording
materials are used which contain an oxidizing agent, a reducing
agent and a minor quantity of a light-sensitive substance whose
photolytic products initiate the redox reaction which is
accompanied by production of color. The oxidizing agents used in
this process are organic silver salts and the reducing agents are
aminophenols, hydroxylamines, pyrazolidones or phenols. Phenylene
diamine and etherified naphthols e.g. 4-methoxynaphthol-1, have
also been described as reducing agents for this purpose. Compounds
suitable for use as light-sensitive compounds are heavy metal salts
which form traces of the free metal on exposure to light,
especially light-sensitive silver salts such as silver halides
which form silver by a photolytic reaction on exposure to light.
These photolytic heavy metal nuclei initiate the redox
reaction.
The materials used in the said process also have the above
mentioned disadvantage of being relatively unstable in storage due
to the sensitivity of the reducing agents to oxidation by
atmospheric oxygen. To obtain sufficient stability in storage for
practical requirements, it is, therefore, necessary to take
additional steps to protect the reducing agents against the action
of atmospheric oxygen. This is achieved mainly by the addition of
antioxidants.
It is among the present objects of the invention to provide a
photographic material which contains silver salt and embedded
developer substance suitable for wet or dry development processes,
which developers should have a sufficiently powerful development
action and sufficient resistance to oxidation in order to enable
photographic images of high quality to be produced from a material
of sufficient stability in storage.
It has now been found that compounds of the following general
formula are eminently suitable developer substances or reducing
agents for this purpose: ##SPC1##
wherein
n = 0 or 1;
R.sub.1, r.sub.2, r.sub.3, r.sub.4, r.sub.5 and R.sub.6 = hydrogen
or alkyl groups having up to 9 carbon atoms, preferably methyl
groups;
R.sub.3 and R.sub.4 or R.sub.4 and R.sub.5 may be joined together
to complete a carbocyclic ring system having 5, 6 or 7 carbon atoms
which can contain a double bond and/or which can be substituted by
alkyl groups having up to 4 carbon atoms;
R.sub.6 may further stand for an alkoxy group having up to 6 carbon
atoms or a tertiary amino group of the following formula:
##SPC2##
wherein
R.sub.7 and R.sub.8 represent alkyl having up to 6 carbon atoms or
are together the ring members required for completing a 5-membered,
6-membered or 7-membered ring which may contain an oxygen atom or a
nitrogen atom as ring member in addition to the nitrogen atom
already present;
R.sub.9 and R.sub.10 = hydrogen, alkyl or alkoxy having up to 6
carbon atoms, preferably methyl or tertiary alkyl groups, and, at
least one of them represents a hydroxyl group;
R.sub.11 and R.sub.12 = hydrogen, alkyl or alkoxy having up to 9
carbon atoms, preferably methyl or tertiary alkyl groups,
cycloalkyl such as cyclopentyl or cyclohexyl, aralkyl such as
benzyl or phenyl ethyl, or aryl, especially a phenyl ring, or a
group of the formula: ##SPC3##
wherein
R.sub.7 and R.sub.8 have the meanings already indicated.
The following are examples of suitable compounds:
1) 2-methyl-6-hydroxy-chroman,
2) 2,2-dimethyl-6-hydroxy-chroman,
3) 2,2,3-trimethyl-6-hydroxy-chroman,
4) 2,2-dimethyl-7-tert-butyl-6-hydroxy-chroman,
5) 2,2-dimethyl-8-tert-butyl-6-hydroxy-chroman,
6) 2,2-dimethyl-7-tert-amyl-6-hydroxy-chroman,
7) 2,2-dimethyl-7-tert-octyl-6-hydroxy-chroman,
8) 2,2-dimethyl-7-cyclopentyl-6-hydroxy-chroman,
9) 2,2-dimethyl-7-cyclohexyl-6-hydroxy-chroman,
10) 2,2-dimethyl-7-(1'-methylcyclohexyl)-6-hydroxy-chroman,
11) 2,2-dimethyl-7-(2'-phenyl ethyl)-6-hydroxy-chroman,
12) 2,2-dimethyl-7-(2'-methyl-2'-phenyl
ethyl)-6-hydroxy-chroman,
13) 2,2-dimethyl-7-phenyl-6-hydroxy-chroman,
14) 2,2,7-trimethyl-6-hydroxy-chroman,
15) 2,2,3,4-tetramethyl-6-hydroxy-chroman,
16) 2,2,5-trimethyl-7,8-dimethoxy-6-hydroxy-chroman,
17) 2,2,5,7,8-pentamethyl-6-hydroxy-chroman,
18) 2-dimethylamino-3,3-dimethyl-5-hydroxy-coumaran,
19) 2-diethylamino-3,3-dimethyl-5-hydroxy-coumaran,
20) 2-pyrrolidino-3,3-dimethyl-5-hydroxy-coumaran,
21) 2-piperidino-3,3-dimethyl-5-hydroxy-coumaran,
22) 2-morpholino-3,3-dimethyl-5-hydroxy-coumaran,
23) 2-morpholino-3,3-dimethyl-6-tert-butyl-5-hydroxy-coumaran,
24) 2-pyrrolidino-3,3-dimethyl-6-tert-butyl-5-hydroxy-coumaran,
25) 2-piperidino-3,3-dimethyl-6-tert-butyl-5-hydroxy-coumaran,
26) 2-morpholino-3,3-dimethyl-6-tert-octyl-5-hydroxy-coumaran,
27) 2-morpholino-3,3-dimethyl-6-phenyl-5-hydroxy-coumaran,
28)
2-pyrrolidino-3,3-(spiro-cyclohexen-(3')-yl)-5-hydroxy-coumaran,
29) 2-morpholino-3,3-(spiro-cyclohexyl)-5-hydroxy-coumaran,
30)
2-piperidino-3,3-(spiro-cyclohexen-(3')-yl)-5-hydroxy-coumaran,
31)
2-morpholino-3,3-(spiro-3'-methyl-cyclohexen-(3')-yl)-5-hydroxy-coumaran,
32)
2-morpholino-3,3-dimethyl-6-morpholino-methyl-5-hydroxy-coumaran,
33)
2-morpholino-3,3-(spiro-4'-methyl-cyclohexen-(3')-yl)-5-hydroxy-coumaran,
34)
2-morpholino-3,3-(spiro-4'-methyl-cyclohexen-(3')-yl)-6-morpholino-methyl-
5-hydroxy-coumaran,
35) 2-morpholino-2,3-tetramethylene-5-hydroxy-coumaran,
36) 2,2-dimethyl-7-hydroxy-coumaran,
37) 2,2-dimethyl-6-tert-butyl-7-hydroxy-coumaran,
38) 2-methoxy-3,3-dimethyl-5-hydroxy-coumaran,
39) 2-methoxy-3,3-dimethyl-6-tert-octyl-5-hydroxy-coumaran,
40) 2-ethoxy-3,3-dimethyl-5-hydroxy-coumaran,
41) 2-methoxy-3,3-(spiro-4-methyl-cyclohexen-(3'
)-yl)-5-hydroxy-coumaran,
42) 2-n-butyloxy-3,3-dimethyl-6-tert-butyl-5-hydroxy-coumaran,
43) compound of the constitution: ##SPC4##
The process of preparing the compounds to be used according to the
invention is known and has been described inter alia in U.S. Pat.
No. 3,160,637 and in German Patent Specification No. 1,163,837.
The photographic materials according to the invention which contain
one or more of the foregoing developer substances are not in
principle subject to any restrictions as regards their photographic
application. They may be used wherever light-sensitive materials
which contain developer substances are required. They may be used
both for wet and for dry processing methods.
The optimum developer substances for any given photographic process
can be selected by means of simple tests.
The materials according to the invention may contain both silver
halides and organic silver salts, e.g. the silver salts of
carboxyalkylthio derivatives or silver salts of carboxylic acids as
described in British Patent Specification Nos. 1,111,492 and
1,110,046 or mixtures of these silver salts. These silver salts are
sufficiently light-sensitive if precipitated in the presence of a
protective colloid such as gelatin.
Any silver halide emulsions may be used for producing the silver
halide emulsion layers, such as silver chloride, silver bromide or
silver chlorobromide emulsions, and they may also contain up to 10
mols percent of silver iodide. These emulsions may contain 0.05 to
0.5 mol of silver halide per litre. For wet processing and for
thermal development, the layers may contain the organic silver
salts of carboxyalkylthio derivatives described in British Patent
Specification No. 1,111,492 instead of silver halides or in
admixture with silver halides.
The binder used for the photographic layers is preferably gelatin
but this may be partly or completely replaced by other natural or
synthetic binders. Suitable natural binders are, e.g. alginic acid
and its derivatives such as salts, esters or amides, cellulose
derivatives such as carboxymethyl cellulose, alkyl cellulose such
as hydroxyethyl cellulose, starch or its derivatives such as ethers
or esters or carrageenates. Suitable synthetic binders are, e.g.
polyvinyl alcohol, partially saponified polyvinyl acetate or
polyvinyl pyrrolidone and the like.
The binder mixtures of gelatin and cellulose acetate described in
German Auslegeschrift No. 2,000,926 may also be used, the gelatin
solution for the layer being in that case mixed in the presence of
phthalic acid in quantities of 10 to 50 percent by weight, based on
the total amount of solids in the mixture, with cellulose acetate
having an acetic acid content of between 30 and 50 percent by
weight. The emulsions may also be chemically sensitized, e.g. by
adding compounds which contain sulfur, such as allyl
isothiocyanate, allyl thiourea or sodium thiosulfate and the like,
at the stage of chemical ripening. Reducing agents may also be used
as chemical sensitizers, e.g. the tin compounds described in
Belgian Patent No. 493,464 and 568,687, polyamines such as
diethylene triamine or formamidine sulfinic acid derivatives, e.g.
according to Belgian Patent No. 547,323.
Noble metals and noble metal compounds, e.g. gold, platinum,
palladium, iridium, ruthenium and rhodium, are also suitable for
use as chemical sensitizers. This method of chemical sensitization
has been described in the article by R. Koslowsky, Z. Wiss. Phot.
46, 65-72 (1951).
The emulsions may also be sensitized with polyalkylene oxide
derivatives, e.g. with polyethylene oxide having a molecular weight
of between 1000 and 20,000, with condensation products of alkylene
oxides and the aliphatic alcohols, glycols or cyclic dehydration
products of hexitols or with alkyl substituted phenols, aliphatic
carboxylic acids, aliphatic amines, aliphatic diamines and amides.
The condensation products have a molecular weight of at least 700
and preferably more than 1000. These sensitizers may, of course, be
combined in order to achieve special effects, as described in
Belgian Patent No. 537,278 and in British Patent Specification No.
727,982.
The emulsions may also be spectrally sensitized, e.g. with the
usual polymethine dyes such as merocyanines, basic or acid
carbocyanines, rhodacyanines, hemicyanines, styryl dyes or
oxonoles. Sensitizers of this type have been described in the work
by F. M. Hamer "The Cyanine Dyes and Related Compounds" (1964).
The emulsions may contain the usual stabilizers, e.g. homopolar or
salt-type compounds of mercury which have aromatic or heterocyclic
rings, such as mercaptotriazoles, simple mercury salts, sulfonium
mercury double salts and other mercury compounds. Azaindenes are
also suitable for use as stabilizers, especially tetra- or
penta-azaindenes and especially those which are substituted with
hydroxyl or amino groups.
Compounds of this type have been described in the article by Birr,
Z. Wiss. Phot. 47, 2 - 58(1952). Other suitable stabilizers are
e.g. heterocyclic mercapto compounds such as phenyl
mercaptotetrazole, quaternary benzothiazole derivatives,
benzotriazoles or the substituted 4-aminobenzotriazoles described
in British Patent No. 919,061.
The emulsions may be hardened for wet processing in the usual
manner, for example with formaldehyde or halo-substituted aldehydes
which contain a carboxyl group, such as mucobromic acid, diketones,
methane sulfonic acid esters or dialdehydes.
When using the light-sensitive materials according to the invention
for heat copying processes, it is advisable also to add other
substances, for example matting agents such as starch ether,
dextrin, colloidal silicic acid or finely dispersed silicon
dioxide, aluminum oxide or titanium dioxide. For some heat copying
processes it has been found especially advantageous to add
substances which impart a certain moisture to the light-sensitive
layer and/or the image receiving layer during the heat development.
This group of substances includes substances which split off water
at elevated temperature or hydrophilic compounds which increase the
residual moisture of the layer. Substances of the first mentioned
type are ureas, caprolactam, .beta.-nitroethanols or
.beta.-cyanoethanols as described in German Patent Specification
No. 1,174,159 or salts which form clearly defined hydrates, such as
sodium acetate, sodium citrate or sodium sulfate. Compounds of the
second type mentioned include glycols, polyethylene glycols,
glycerol, sorbitol or mono- or oligo-saccharides. These substances
are added to the casting solutions for the light-sensitive layer in
such quantities that the dry layer contains about 0.1 to
25g/m.sup.2 of these substances.
The light-sensitive layer may be arranged on any layer support such
as paper, synthetic resin, fabric or metal. For development at
elevated temperature, the layer support must be stable at the usual
temperatures employed.
In certain cases, it is advantageous to interpose an intermediate
layer between the support and the emulsion layer. Intermediate
layers of this type which are suitable for development at elevated
temperature have been described e.g. in German Patent Specification
No. 1,189,383.
The developer substances to be used according to the invention may
be added to the emulsion layers which contain silver salts or to
the intermediate layers in amounts of 50 to 1000 g, preferably 100
to 700 g, per mol of silver salt.
These photographic materials can be developed simply by the action
of an alkaline solution after exposure to light and are, therefore,
suitable both for use as negative material for the silver salt
diffusion process and as copying material for processing in the
two-bath process and for conventional processing by fixing and
washing.
When the developer substances to be used according to the invention
have been embedded in the photographic layer, they are
differentiated from known developer substances such as
hydroquinone, aminophenol or p-methylaminophenol etc. by their
improved resistance to oxidation. Furthermore, the photographic
materials produced with these developer substances have less
fog.
The compounds to be used according to the invention and the
photographic materials containing them are especially suitable for
a heat copying process of the following type.
A photographic recording material for the production of copies by
the dry process contains as oxidizing agent a silver salt which is
substantially insensitive to light, a reducing agent and a
light-sensitive heavy metal compound which on exposure forms metal
nuclei by photolysis, thus initiating the redox reaction on
heating, the reducing agent used being one or more of the compounds
according to the invention represented by the general formula
indicated, which compounds are capable of reducing the
light-sensitive silver salt at temperatures of between 50.degree.C
and 160.degree.C in the presence of the photolytically produced
heavy metal nuclei.
Suitable oxidizing agents of the image-producing redox system are
silver salts of organic acids which, under the conditions of the
process, are either insensitive to light or sensitive to light only
to a negligible extent, e.g. silver saccharide, silver
5-chlorosalicylic aldoxime, silver 5-nitrosalicylic aldoxime or,
preferably, a silver salt of a long chained fatty acid having up to
30 carbon atoms, e.g. silver stearate, silver palmitate or silver
behenate or the silver salts of aliphatic carboxylic acids
containing a thioether group as described in U.S. Patent No.
3,330,663. Silver salts of the last mentioned kind are
light-insensitive if prepared in the absence of protective colloids
such as gelatin.
The light-insensitive silver salt serving as oxidizing agent
generally is used in a molar ratio of between 1:1 and 1:10 with
respect to the above-defined reducing agent.
Suitable light-sensitive heavy metal salts which when exposed to
light form metal nuclei capable of initiating the image-producing
redox reaction are e.g. inorganic or organic salts of silver,
mercury or gold. The heavy metals of the sub-group Ib of the
Periodic System of Elements are preferred, especially silver salts
and among these again the silver halides.
The most suitable light-sensitive heavy metal salts for any given
redox system can easily be determined by a few simple laboratory
tests. Thus, for example, the metal salt may be mixed with the
components of the redox reaction in the form of its aqueous
suspension. If it is to be suitable, it must not undergo any change
in the dark but when the mixture is exposed to UV light, it should
undergo discoloration within a few seconds. If both these
conditions are fulfilled, the heavy metal salt is suitable for the
redox system.
The light-sensitive heavy metal salt is used in comparatively small
quantities of about 0.05 to 0.2 percent by weight, based on the
weight of the oxidizing agent. This proportion of light-sensitive
salt is sufficient in most cases but a higher or lower percentage
may, of course, also be used.
The light-sensitive heavy metal salt, e.g. silver halide, should be
present in such small quantities that the photolytically produced
heavy metal nuclei are capable of initiating the redox reaction,
but at the same time the concentration of the silver halide is so
low that the metal nuclei formed do not cause any discoloration of
the copying material, or only to a negligible extent.
The silver halide may be added to the casting solution for the
layer which contains the components of the redox reaction or it may
be formed in situ in the casting solution, e.g. by precipitation of
the silver halide in the mixture. The silver ions for the
precipitated silver halide may in that case be derived mainly from
the silver salt which is not light-sensitive.
The silver salts which are not light-sensitive and which are
present as oxidizing agents may be obtained in a known manner
exactly like the silver halide by precipitation of silver salt
solutions, e.g. by the precipitation of silver nitrate with the
alkali metal salts of the organic acids preferably in the absence
of protective colloids. The free acid may, of course, be present
during precipitation but, in order to obtain highly transparent
layers, it is advantageous to have only a slight excess of free
acid present or even to use stoichiometric quantities of the
organic acid and the silver salt.
Various methods may be used for preparing silver halides from the
light-insensitive silver salts. For example, the surface of the
light-insensitive silver salts may be treated with vapors of
hydrohalic acids, e.g. hydrochloric acid, hydrobromic acid or
hydriodic acid. The quantity of silver halide produced on the
surface may be kept within the required limits by adjusting the
concentration of the hydrogen halide in the vapor phase and the
treatment time.
The light-insensitive silver salts of the organic acids may, of
course, also be treated with a solution containing halogen ions,
such as chloride ions, bromide ions or iodide ions. These halogen
ions may be obtained from the hydrohalic acids themselves or from
their salts, in particular their ammonium, alkali metal, or
alkaline earth metal salts.
The reaction of the light-insensitive silver salts with the
compounds which give off halogen ions is preferably carried out
with the silver salts in the form of a suspension in a volatile,
non-aqueous liquid, although also the dry salts may be reacted, for
example with hydrogen halide vapors.
In addition to hydrohalic acids and their salts, e.g. the alkali
metal salts, ammonium salts and alkaline earth metal salts already
mentioned above and other metal salts, e.g. zinc salts and mercury
salts, there may also be used for formation of the light-sensitive
silver halides ionisable organic halogen compounds, e.g.
triphenylmethyl chloride, triphenylmethyl bromide, 2-bromo-2-methyl
propane, 2-bromo-butyric acid, 2-bromoethanol or benzophenone
dichloride.
The materials according to this embodiment of the invention are
preferably prepared by formation of the light-sensitive silver
halides from the light-insensitive silver salts of the organic
acids. This enhances the capacity of the silver halides to produce
photolytic silver nuclei which are especially effective in
initiating the redox reaction. Although useful materials can also
be obtained by preparing the silver halides separately and
subsequently mixing them with the light-insensitive silver salts,
the photolytic heavy metal nuclei formed from such mixtures are
generally not so active.
To prepare the material according to the invention, the components
for the redox reaction and the light-sensitive heavy metal are used
together with a suitable binder. The binders used are preferably
organic polymers such as copolymers of vinyl chloride and vinyl
acetate or of butadiene and styrene, polyethylene, polyamides,
polyisobutylene, polyvinyl chloride, polyvinylidene chloride,
polyvinyl pyrrolidone, polystyrene, chlorinated rubber, polyvinyl
butyral, polymers of acrylic acid or methacrylic acid esters or
copolymers of the derivatives of acrylic acid and methacrylic acid,
cellulose derivatives such as nitro cellulose, cellulose acetates,
cellulose propionates or mixtures thereof such as cellulose
acetobutyrates.
The light-sensitive layer may be used as a self-supporting layer
but it is preferably applied to a suitable layer support. The layer
support must be stable at the processing temperatures of between
60.degree.C and 200.degree.C. Suitable supports are e.g. sheets or
foils of paper, cellulose acetate, polyethylene terephthalate,
textile fabrics, metal foils or glass. Where paper supports are
used, the paper may contain the usual suxiliary layers such as
baryta layers and/or polyethylene layers.
The concentration of the reducing agent and of the oxidizing agent
in the layer may vary within wide limits.
Proportions by weight of 4:1 to about 1:1 between the components of
the redox reaction and the binder have generally been found
sufficient.
The thickness of the light-sensitive layer may also be adapted to
the requirements of the given reproduction process. Layer
thicknesses of between 5 and 100 microns are generally sufficient
for the usual requirements. The layer supports have the usual
thicknesses of between about 0.1 and 0.8 mm.
Also in this embodiment of the invention the light-sensitive layers
may be spectrally sensitized by the addition of dyes.
The usual white pigments such as silicon dioxide and toners such as
phthalazone, phthalazone derivatives and phthalimide may be added
to the light-sensitive layers.
The photographic materials according to the invention are processed
in a known manner. Image-wise exposure is carried out with the
usual light sources used in photographic work, e.g. mercury lamps,
iodine quartz lamps or simple incandescent lamps. The type of light
source used depends on the spectral sensitivity of the heavy metal
salt. In the preferred method using silver halides, the usual
incandescent lamps are sufficient. The exposure time is a few
seconds.
The exposed material is then uniformly heated to a temperature of
between about 60.degree.C and 160.degree.C. The time and
temperature required for the heat treatment depends on the nature
of the redox system. Periods of between 3 and 80 seconds are
generally sufficient. A dark brown to black image is formed which
is ready for immediate use.
Example 1
Light-sensitive material:
An equimolar mixture of silver behenate and behenic acid is
prepared by precipitating silver nitrate with a solution of sodium
behenate and behenic acid in alcohol and water. The precipitate is
carefully washed and dried.
The suspension used for preparation of the layer is prepared by
treating the mixture described below in a ball mill for 12
hours:
240 ml of methanol,
125 ml of a 10% solution of polyvinyl-n-butyral in methanol,
20 ml of a 10% solution of poly-N-vinyl pyrrolidone in
methanol,
30 g of an equimolar mixture of silver behenate and behenic
acid,
10 ml of a 1% methanolic solution of ammonium bromide,
1.2 g of phthalazone, and
15 g of 2,2-dimethyl-7-tert-butyl-6-hydroxy-chroman (Compound
4).
The above mixture is applied to a conventional paper support at a
concentration of 100 g/sq.m and dried at room temperature.
Processing:
The light-sensitive layer is exposed through a transparent
original. The source of light used is a 750 Watt UV lamp at a
distance of 5 cm. The exposure time is 2 seconds and the distance
from the source of light 5 cm. The material is then heated to a
temperature of 80.degree.C for 5 seconds.
A black-brown negative image of the original is obtained.
Similar results are obtained when using e.g. Compound 38 or
Compound 24 instead of the compound described above.
Example 2
Light-sensitive material:
Suspension for bottom layer:
1.8 g of a mixture of silver behenate and behenic acid (molar ratio
1:1),
3 g of cellulose acetate,
3 g of phthalazone,
4.5 ml of calcium bromide solution (1 g dissolved in 100 ml of
methanol),
5.7 ml of mercury-II-acetate solution (1 g + 1 ml of glacial acetic
acid dissolved in 100 ml of methanol),
3 ml of a solution of
1-methyl-3-allyl-5-[2'-(3"-ethyl-benzoxazolylidene-(2")-ethylidene]-2-thio
hydantoin (0.01 g dissolved in 100 ml of chloroform),
0.15 g of silicon dioxide,
55 g of acetone,
1 g of copolymer of vinyl chloride and vinyl acetate 88:12
dissolved in 20 g of butyl acetate.
Top layer:
10 g of polyvinyl butyral,
1.5 g of phthalazone,
5 g of 2-methoxy-3,3-dimethyl-5-hydroxy coumaran (Compound 38),
100 ml of methanol.
The suspension for the bottom layer is ground in a ball mill for
about 16 hours and then applied on baryta paper and dried. The
silver application is 0.3 to 0.4 g/m.sup.2.
The top layer is cast on the dry bottom layer. The amount of
reducing agent applied is 0.5 to 1.5 g/m.sup.2.
Instead of Compound 38, the following reducing agents may be added
to the top layer:
6 g of Compound 23,
6 g of Compound 25,
4 g of Compound 36,
5 g of Compound 4, or
5 g of a mixture of Compounds 4 and 5.
The reducing agents may also be added to the suspension for the
bottom layer instead of that for the top layer, and ground with
this suspension in a ball mill for about one-half hour, e.g.:
8 g of Compound 43,
8 g of Compound 33.
Processing:
The light-sensitive material is exposed with tungsten lamps for 3
to 30 seconds depending on the intensity of the lamps and the
required gradation, and developed by heat. The development time
varies from 3 to 80 seconds according to the height of the
temperature within the range of 60.degree.C to 160.degree.C and the
apparatus used. The apparatus used for development may be heatable
presses, drying drums, rollers or the apparatus described in
Belgium Patent No. 628,174 or in French Patents Nos. 1,512,332;
1,416,752 or 1,419,101 or the usual commercial apparatus. To
protect the photographic layer and to produce a high gloss image,
the layer surface of the material may be kept in contact with a
polyester foil during the heat development.
The images obtained on development are brown or brownish black to
neutral black images on a white to yellow ground, depending on the
developer substance used and the processing conditions.
Example 3
Light-sensitive material:
The following substances are added to 1 kg of a silver chloride
gelatin emulsion which contains 0.2 mol of silver halide with a
silver iodide content of less than 0.1 mols %:
20 mg of 1-phenyl-5-mercaptotetrazol (1% in alcohol),
125 g of sodium acetate (cryst.) (1:1 dissolved in water),
5 g of colloidal silicic acid,
20 g of Compound 4 or Compound 38 dissolved in methanol, and
5 ml of saponin (30% aqueous solution).
The pH of the emulsion is adjusted to 5.1 with sulfuric acid. The
emulsion is applied on a baryta paper in a known manner and dried.
Silver application 1.2 g/m.sup.2.
Processing:
After exposure the rear surface of the coated paper is placed in
contact for 0.5 to 60 seconds with a metal or synthetic resin
surface heated to 90 to 200.degree.C or with a liquid heat transfer
agent. The apparatus used for development may be conventional heat
development apparatus or heatable presses, drying drums, rollers or
the apparatus described in Belgian Patent No. 628,174 or the
image-wise exposed negative may be exposed to infra-red radiation
for about 10 to 180 seconds.
A dark brown image is obtained.
The well-covered silver image has little sensitivity to light. It
may be stabilized by fixing and washing in water or by bathing it
in an alcoholic solution of 2,5-dimercapto-1,3,4-thiadiazole or
1-phenyl-5-mercaptotetrazole.
Example 4
Light-sensitive material:
A paper is coated with a solution of:
100 g of the sodium salt of polyurea sulfonic acid prepared by
polyaddition of the sodium salt of
4,4'-diaminodiphenylethane-2,2'-disulfonic acid with tolylene
diisocyanate,
125 g of cane agar, and
2.5 litres of water.
After this coating is dried it is covered with a coating of the
following silver halide gelatin emulsion:
1 kg of a silver chloride gelatin emulsion which contains, per kg
of emulsion, 0.2 mol of silver halide with a silver iodide content
of less than 0.1 mols %,
200 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene (dissolved in
alcohol),
50 mg of benzotriazole (dissolved in alcohol),
100 g of sodium acetate (cryst.) (1:1 dissolved in water),
20 g of Compound 23 or Compound 4 dissolved in methanol,
3 g of colloidal silicic acid, and
5 ml of saponin (30% aqueous solution).
The pH of the emulsion is adjusted to 4.9 with sulfuric acid.
Silver application 1.2 g/m.sup.2.
The material is exposed and processed as described in Example 3 and
a brownish black image is obtained.
Example 5
The following substances are added to 1 kg of an unwashed silver
chlorobromide gelatin emulsion which contains per kg 0.18 mol of
silver halide (20 mols % AgBr):
2.7 ml of a 40% citric acid solution,
30 mg of 1-phenyl-5-mercaptotetrazole (1% in alcohol),
3 g of colloidal silicic acid and 1 litre of a 10% solution of
phthalic acid in methanol.
This emulsion is added with stirring to a solution of 3 litres of a
3 percent solution of a cellulose acetate (acetate group content 40
percent by weight) in acetone/water (1:4) and 1 litre of a 10
percent solution of phthalic acid in methanol and 60 g of Compound
38 or 60 g of Compound 43, and the emulsion is then applied to a
baryta paper. Silver application 1.2 g/m.sup.2.
The material is exposed and processed as described in Example 3 and
a brown image is obtained.
The exposed material may also be developed for 1 minute in 10
percent sodium hydroxide solution and fixed and washed in the usual
manner. A black, well-covered image is obtained.
Example 6
2 ml of a 40 percent aqueous citric acid solution are added to 1
litre of a 10 percent aqueous gelatin solution, and the solution is
heated to 40.degree.C. 22 g of
2-n-octylthio-5-carboxymethylthio-1,3,4-thiadiazole dissolved in
the equimolar quantity of sodium hydroxide solution are then added
and the solution is precipitated with 100 ml of a 10 percent silver
nitrate solution with vigorous stirring, and 1 litre of a 10
percent solution of phthalic acid in methanol is added with
stirring. This emulsion is added with stirring to a solution of 2
litres of a 3 percent solution of a cellulose acetate (acetate
group content 40 percent by weight) in acetone/water (4:1) and 200
ml of a 10 percent solution of phthalic acid in methanol and 50 g
of Compound 38 or 50 g of Compound 25, and the emulsion is then
applied to a layer support as in Example 3. Silver application 0.6
g/m.sup.2. If desired, 10.2 g of 3-carboxymethylthio-1,2,4-triazole
may be used instead of 22 g of
2-n-octylthio-5-carboxymethylthio-1,3,4-thiadiazole.
The material is processed as described in Example 3 and a brownish
black image is obtained.
The exposed material may also be developed for 1 minute in a 10
percent sodium carbonate solution and fixed and washed in the usual
manner. A black image is obtained.
Example 7
The following substances are added to 1 kg of a silver chloride
gelatin emulsion which contains, per kg of emulsion, 0.2 mol of
silver halide which has a silver iodide content of less than 0.1
mols percent:
2.7 ml of a 40% aqueous citric acid solution,
40 mg of 1-phenyl-5-mercaptotetrazole (1% in alcohol),
10 ml of a 30% formaldehyde solution,
25 ml of a 10% aqueous saponin solution, and
20 g of Compound 23, or
20 g of Compound 43 dissolved in methanol.
The emulsion is applied to baryta paper in a known manner and
dried. Silver application 1.3 g/m.sup.2.
The exposed material is developed in a 10 percent aqueous sodium
carbonate solution for one minute and fixed and washed in the usual
manner. A well-covered black image is obtained.
Example 8
The exposed material described in Example 7 may also be brought
into contact with the image-receiving layer described hereinafter
in a commercial apparatus conventionally used for the silver salt
diffusion process, and developed in the following activator
solution:
Anhydrous sodium sulfite 40.0 g anhydrous sodium phosphate 30.0 g
sodium hydroxide 1.5 g sodium thiosulfate cryst. 1.0 g potassium
bromide 1.0 g made up with water to 1 litre
The two layers are separated after a contact time of 15 to 30
seconds.
A black image with good whites is obtained.
Image-receiving material:
A layer of baryta is applied from the follwing solution to a layer
support of paoer (80 g/m.sup.2):
6 ml of a 50% aqueous suspension of barium sulfate,
20 ml of a 10% aqueous gelatin solution,
8 ml of a 50% aqueous emulsion of polyvinyl acetate, water up to
100 ml.
The baryta layer is dried and then coated with an image-receiving
layer from the following casting solution:
4.5 g of propylene glycol alginate,
12.5 mg of silver sulfide in the form of an aqueous colloidal
solution,
20 ml of a 50% aqueous gelatin solution,
1.5 ml of a 30% aqueous solution of potassium bromide,
1.2 ml of a 30% aqueous solution of saponin,
7.5 g of sodium thiosulfate,
made up with water to 300 ml.
The layer is applied in such a thickness that it contains about 1.1
g of sodium thiosulfate per m.sup.2.
A layer of the following casting solution is then applied to the
aforesaid image-receiving layer:
3.5 g of sodium alginate,
10 g of sodium thiosulfate,
0.8 ml of a 30% aqueous potassium bromide solution,
8 ml of a 30% aqueous saponin solution,
0.5 ml of a 1% alcoholic solution of
3-mercapto-4,5-dimethyl-1,2,4-triazole,
made up with water to 350 ml.
This layer is applied in such thickness that it contains about 0.6
g of sodium thiosulfate per m.sup.2.
Example 9
A light-sensitive photographic material comprising a silver
chloride gelatin emulsion layer on a support, which emulsion layer
contains per kg of casting solution 0.2 mol of silver halide with
less than 0.1 mol percent of silver iodide (silver application 1.3
g/m.sup.2) and Compound 38 or Compound 43 (20 g/kg of emulsion) is
exposed image-wise and developed in the following activator
solution in an ordinary commercial two bath apparatus:
60 g of sodium hydroxide,
50 g of anhydrous sodium sulfite
2 g of potassium bromide,
made up with water to 1 litre.
The developed material is treated with the following stabilizer
solution:
250 g of ammonium thiocyanate,
80 g of potassium metabisulfite,
20 ml of acetic acid,
20 g of the sodium salt of the cyclohexanone bisulfite adduct,
made up with water to 1 litre.
A grey-black image with good whites is obtained.
If the above mentioned emulsion is mixed with phthalic acid and
cellulose acetate as described in Example 5, a black image is
obtained.
* * * * *