FIELD OF THE INVENTION
[0001] The present invention relates to a novel process for forming an image which comprises
imagewise forming a mobile dye by heating in a substantially water-free condition
and transferring the dye into a dye fixing layer using water. More particularly, the
present invention relates to a process for forming an image, wherein a small amount
of water is used in transferring an imagewise formed dye into a dye fixing layer.
BACKGROUND OF THE INVENTION
[0002] A photographic process utilizing a silver halide has heretofore been widely used
due to its excellent photographic characteristics such as sensitivity, control of
gradation, etc., as compared with other photographic processes such as an electrophotographic
process or a diazo photographic process. In recent years, with respect to image formation
process for light-sensitive materials using a silver halide, a technique capable of
easily and quickly obtaining an image. has been developed by changing the conventional
wet development process using, for example, a developing solution, into a dry development
process such as a process using heat.
[0003] A heat-developable light-sensitive material has been known in the field of this technique.
Such heat-developable light-sensitive materials and processes therefor are described
in, for example, Shashin Koqaku no Kiso, Corona Co., Ltd., pages 553-555,
Eizo Joho, April 1978, page 40, Neblet- ts Handbook of Photography and Reprography,
4th Ed., Van Nostrand Reinhold Co., pages 32-33, U.S. Patents 3,152,904, 3,301,678,
3,392,020 and 3,457,075, British Patents 1,131,108 and 1,167,777, and Research Disclosure,
June 1978, pages 9-15 (RD-17029).
[0004] Namely processes for obtaining color images by a dry process have been proposed.
[0005] With respect to processes for forming color images by the reaction of an oxidation
product of a developing agent with a coupler, it has been proposed to use a p-phenylenediamine
type reducing agent and a phenolic coupler or an active methylene coupler as described
in U.S. Patent 3,531,286, a p-aminophenol-type reducing agent as described in U.S.
Patent 3,761,270, a sulfonamidophenol type reducing agent as described in Belgian
Patent 802,519 and Research Disclosure, pages 31 and 32 (Sept. 1975) and the combination
of a sulfonamidophenol type reducing agent and a 4-equivalent coupler as described
in U.S. Patent 4,021,240.
[0006] These processes, however, are disadvantageous in that turbid color images are formed,
because a reduced silver image and a color image are simultaneously formed on the
exposed area after heat-development. In order to eliminate these disadvantages, there
have been proposed a process which comprises removing a silver image by liquid processing
or a process which comprises transferring only the dye to another layer, for example,
a sheet having an image receiving layer. However, the latter process is not desirable
because it is not easy to transfer only the dye as distinguishable from unreacted
substances.
[0007] Another process which comprises introducing a nitrogen containing heterocyclic group
into a dye, forming a silver salt and releasing a dye by heat-development has been
described in Research Disclosure, No. 16966, pages 54 to 58 (May 1978). According
to this process, clear images cannot be obtained, because it is difficult to control
the release of dyes from nonexposed areas, and thus it is not a conventionally applicable
process.
[0008] Also, processes for forming a positive-working color image by a silver.dye bleach
process utilizing heat, with useful dyes and methods for bleaching have been described,
for example, in Research Disclosure, No. 14433, pages 30 to 32 (April 1976), ibid.,
No. 15227, pages 14 and 15 (
Dec. 1976) and U.S. Patent 4,235,957.
[0009] However, this process requires an additional step and an additional material for
accelerating bleaching of dyes, for example, heating with a superposed sheet with
an activating agent. Furthermore, it is not desirable because the resulting color
images are gradually reduced and bleached by coexisting free silver during long periods
of preservation.
[0010] Moreover, a process for forming a color image utilizing a leuco dye has been described,
for example, in U.S. Patents 3,985,565 and 4,022,617. However, this process is not
desirable because it is difficult to stably incorporate the leuco dye in the photographic
material and coloration gradually occurs during preservation.
[0011] Furthermore, these processes described above generally have disadvantages that a
relatively long period of time is required for development and only images having
a high level of fog and a low density are obtained.
SUMMARY OF THE INVENTION
[0012] The present invention provides a novel process for obtaining a visible image by transferring
a dye which is imagewise obtained by heating in a substantially water-free condition
into a dye fixing layer and overcomes the problems involved in the conventional materials.
[0013] Accordingly, an object of the present invention is to provide a novel process for
forming an image by transferring a mobile hydrophilic dye released by heating in a
substantially water-free condition into a dye fixing layer using a small amount of
water to obtain a dye image.
[0014] Another object of the present invention is to provide a novel process for obtaining
a smear-free, uniform and sharp color image.
[0015] These objects of, the present invention are attained by a process for forming an
image which comprises
heating a light-sensitive material comprising a support having thereon at least a
light-sensitive silver halide, a binder and a dye releasing redox compound which is
reductive to the light-sensitive silver halide and capable of releasing a hydrophilic
dye upon reaction with the light-sensitive silver halide by heating, after imagewise
exposure or simultaneously with imagewise exposure, in a substantially water-free
condition to imagewise form a mobile dye; and transferring the mobile dye into a dye
fixing material using water, wherein when the dye is transferred, the amount of water
present in all the coating of the light-sensitive material and dye fixing material
is within a range of from 0.1 time the total weight of all the coatings to the difference
obtained by subtracting the total weight of all the coatings from the weight of water
corresponding to the maximum swollen volume of all the coatings.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The maximum amount of water required to transfer the dye imagewise formed by heating
to the dye fixing layer depends on the total thickness of the light-sensitive material
and dye fixing material when swollen.
[0017] One of the features of the present invention is that the mobile dye is transferred
with water in an amount not exceeding the total weight of water corresponding to the
swollen volume of the light-sensitive material and dye fixing material when those
are sufficiently swollen by applying a sufficient amount of water; in other words,
the mobile dye is transferred in the condition that the coatings of the light-sensitive
material and dye fixing material are not sufficiently swollen. If the amount of water
exceeds the above specified upper limit, a smear occurs on the color image transferred
and this is undesirable.
[0018] The minimum amount of water is sufficient if such can transfer the dye. The preferred
minimum amount is 0.1 time the total weight of all the coatings of the light-sensitive
material and image-receiving material in a dry state and in this amount, the dye released
can be completely transferred.
[0019] The coatings are unstable in a swollen state. Depending on conditions, a smear may
occur locally. In order to prevent such smearing, the amount of water is preferably
0.8 time or less the difference obtained by subtracting the amount of water corresponding
to the total weight of all the coatings from the amount of water corresponding to
the maximum swollen volume of all the coatings of the light-sensitive and dye fixing
materials.
[0020] The amount of water in the present invention is an amount of water present in all
the coatings at the time of transferring. The amount of water is controlled within
the range as specified above by applying water in a previously determined amount falling
within the above specified range or by applying a sufficient amount of water and then
adjusting the amount of water within the specified range by squeezing by means of,
e.g., rollers, or drying by heating.
[0021] Any binder can be used in the preparation of the coatings of the present invention
so long as transferring the dye with water can be made. These coatings can contain
a light-sensitive silver halide, a dye releasing redox compound, a mordant, a high
boiling organic solvent, and the like. Those additives do not change the nature of
the present invention described above.
[0022] In the case of a coating (4 g/m2) with gelatin as a binder, assuming that its thickness
in a swollen state is 12 p, the amount of water required for transferring the dye
is from 0.4 to 8 ml per square meter of the coating.
[0023] The maximum swollen volume can be determined as follows:
A light-sensitive material or dye fixing material having a coating to be measured
is immersed in water for transferring and sufficiently swollen. When sufficiently
swollen, the thickness of the coating to be measured is determined by measuring the
length of the cross-section by means of, e.g., a microscope. By multiplying the thickness
as determined above by the surface area of the coating to be measured, the maximum
swollen volume can be obtained.
[0024] A method of measuring a degree of swelling is described in Photographic Science Engineering,
Vol. 16, page 449 (1972).
[0025] The degree of swelling of a gelatin coating greatly varies depending on a degree
of hardening of the coating. The degree of hardening is usually controlled so that
the thickness of the coating in a maximum swollen state is 2 to 6 times the thickness
thereof in a dry state.
[0026] The photographic light-sensitive material of the present invention may contain inorganic
or organic hardeners in hydrophilic colloid layers such as a photographic emulsion
layer. Examples of the hardeners which can be used include chromium salts (e.g., chromium
alum and chromium acetate), aldehydes (e.g., formaldehyde, glyoxal, and glutaraldehyde),
N-methylol compounds (e.g., dimethylol urea and methyloldimethyl hydantoin), dioxane
derivatives (e.g., 2,3-dihydroxydioxane), active vinyl compounds (e.g., 1,3,5- triacryloyl-hexahydro-s-triazine
and l,3-vinylsulfonyl-2-propanol), active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine),
and mucophenoxyhalogeno acids (e.g., mucochloric acid and mucophenoxychloric acid).
These compounds can be used alone or in mixtures thereof.
[0027] Water may be applied to either of the dye fixing material or the light-sensitive
material. Alternatively, water may be applied to both the dye fixing material and
the light-sensitive material.
[0028] In the process of the present invention, water may be applied in any suitable manner.
Water may be jetted through a small hole, or the material can be wet with water using
a web roller. In addition, a procedure in which pods containing water are smashed
may be used. The present invention is not limited to these methods.
[0029] The water as used herein is not limited to "pure water" and includes water in a sense
widely and customarily used.
[0030] General drinking water, industrial water, etc. can be used in the present invention.
With regard to water which is used as the general drinking water, there are the water
quality standards for tap water as adopted in U.S.A. and the water quality standards
as prescribed by WHO (World Health Organization). Water satisfying these standards,
of course, can be used in the process of the present invention. In addition, water
ordinarily used in various industries can be used in the process of the present invention.
The standards for quality of water used in various industries are described in, for
example, Eisei Kogaku Handbook, Asakura Shoten, page 356 (1967). Water satisfying
the above standards can be used as the water intended in the present invention, even
though it is underground water or river water, or water to which medicines are added
for some purpose.
[0031] The term "dye image" as used herein includes both multicolor and monocolor dye images.
The monocolor dye image includes a multicolor image obtained by mixing at least two
dyes.
[0032] According to the image formation process for the present invention, a silver image
and in the portion corresponding the silver image, a mobile dye and a silver image,
are simultaneously given by merely heating after imagewise exposure.
[0033] That is, when the light-sensitive material is imagewise exposed and heat developed
in a substantially water- free condition, a redox reaction occurs between a light-sensitive
silver halide and/or an organic silver salt oxidizing agent and a reducing dye releasing
redox compound with the exposed light-sensitive silver halide as a catalyst and a
silver image is formed on the exposed area. In this step, the dye releasing redox
compound is oxidized by the organic silver salt oxidizing agent to form its oxidation
product. As a result, a hydrophilic mobile dye is released and a silver image and
mobile dye are formed on the exposed area. The presence of a dye releasing aid at
this stage accelerates the above described reaction. By transferring the thus formed
mobile dye using a small amount of water into the dye fixing layer, the dye image
is formed.
[0034] The above explanation has been given in a case where a negative-working emulsion
is used. In the case of an autopositive-working emulsion, the same is applicable with
the exception that the silver image and mobile dye are formed on the non-exposed area.
[0035] The redox reaction between the light-sensitive silver halide and the dye releasing
redox compound and the subsequent dye releasing reaction according to the present
invention are characterized in that such occur at high temperature and also in a substantially
water-free dry condition. The term "high temperature" as used herein means a temperature
of 80°C or more. The term "substantially water-free dry condition" means a condition
which is in an equilibrium state with respect to water in air but with no addition
of water from outside the system. This condition is described in T.H. James edit.,
The Theory of the Photographic Process, 4th ed., Macmillan, page 374. Showing a sufficient
reactivity even in a substantially water-free dry condition can be confirmed by the
fact that the reactivity of a test sample does not drop even if it is vacuum dried
at 1
0-3 mmHg for one day.
[0036] The dye releasing reaction has conventionally been believed to occur
due to the attack ofanucleophilic reagent and is usually carried out in a liquid having
a pH of at least 10. Therefore, it is unexpected that high reactivity can be obtained
at high temperature and also in a substantially water-free dry condition. The dye
releasing redox compound of the present invention can undergo a redox reaction with
a silver halide without the help of the so-called auxiliary developing agent. This
is an unexpected result which could not be anticipated from the knowledge of conventional
wet development system which is carried out at temperatures near ordinary temperature.
[0037] The above-described reactions proceed smoothly particularly in the presence of an
organic silver salt oxidizing agent, producing a high image density. It is therefore
particularly preferred in the present invention that such an organic silver salt oxidizing
agent is used in combination.
[0038] It is unexpected from conventional teachings that in the process of the present invention,
a sharp dye image can be formed by applying a small amount of water within the above
specified range when transferring the mobile dye imagewise formed into the dye fixing
layer.
[0039] The dye releasing redox compound which releases a hydrophilic diffusible dye used
in the present invention is a compound described in European Patent Ap
plica- tion (OPI) No. 76,492 as a dye releasing compound and is represented by the
following general formula:

wherein R
a represents a reducing group capable of being oxidized by the silver halide; and D
represents an image forming dye portion containing a hydrophilic group.
[0040] The above-described compound is oxidized corresponding to or reversely corresponding
to latent image distributed imagewise in the silver halide and releases imagewise
a mobile dye.
[0041] The detail definitions of Ra and D, examples of the specific compounds and synthesis
examples thereof are described in European Patent Application (OPI) No. 76,492.
[0042] As the dye releasing redox compounds used in the present invention, the compounds
as described, for example, in U.S. Patent 4,055,423, Japanese Patent Application (OPI)
Nos. 12642/81, 16130/81, 16131/81, 650/82 and 4043/82, U.S. Patents 3,928,312 and
4,076,529, U.S. Published Patent Application B 351,673, U.S. Patents 4,135,929 and
4,198,235, Japanese Patent Application (OPI) No. 46730/78, U.S. Patents 4,273,855,
4,149,892, 4,142,891 and 4,258,120, etc., are also effective in addition to the above-described
compounds.
[0043] Further, the dye releasing redox compounds which release a yellow dye as described,
for example, in U.S. Patents 4,013,633, 4,156,609, 4,143,641, 4,165,987, 4,148.,643,
4,183,755, 4,246,414, 4,268,625 and 4,245,023, Japanese Patent Application (OPI) Nos.
71072/81, 25737/81, 138744/80, 134849/80, 106727/77, 114930/76, etc., can be effectively
used in the present invention.
[0044] The dye releasing redox compounds which release a magenta dye as described, for example,
in U.S. Patents 3,954,476, 3,932,380, 3,931,144, 3,932,381, 4,268,624 and 4,255,509,
Japanese Patent Application (OPI) Nos. 73057/81, 71060/81, 134850/80, 40402/80, 36804/80,
23628/78, 106727/77, 33142/80 and 53329/80, etc., can be effectively used in the present
invention.
[0045] The dye releasing redox compounds which release a cyan dye as described, for example,
in U.S. Patents 3,929,760, 4,013,635, 3,942,987, 4,273,708, 4,148,642, 4,183,754,
4,147,544, 4,165,238, 4,246,414 and 4,268,625, Japanese Patent Application (O
PI) Nos. 71061/81, 47823/78, 8827/77 and 143323/78, etc., can be effectively used in
the present invention.
[0046] Two or more of the dye releasing redox compounds can be used together. In these cases,
two or more dye releasing redox compounds may be used together in order to represent
the same color or in order to represent black color.
[0047] The dye releasing redox compounds are suitably used in a range from 10 mg/m
2 to 15 g/m
2 and preferably in a range from 20 mg/m2 to 10 g/m
2 in a total.
[0048] The dye releasing redox compound used in the present invention can be introduced
into a layer of the light-sensitive material by known methods such as a method as
described in U.S. Patent 2,322,027. In this case, an organic solvent having a high
boiling point or an organic solvent having a low boiling point as described below
can be used. For example, the dye releasing redox compound is dispersed in a hydrophilic
colloid after dissolved in an organic solvent having a high boiling point, for example,
a phthalic acid alkyl ester (for example, dibutyl phthalate, dioctyl phthalate, etc.),
a phosphoric acid ester (for example, diphenyl phosphate, triphenyl phosphate, tricresyl
phosphate, dioctylbutyl phosphate, etc.), a citric acid ester (for example, tributyl
acetylcitrate, etc.), a benzoic acid ester (for example, octyl benzoate, etc.), an
alkylamide (for example, diethyl laurylamide, etc.), an aliphatic acid ester (for
example, dibutoxyethyl succinate, dioctyl azelate, etc.), a trimesic acid ester (for
example, tributyl trimesate, etc.), etc., or an organic solvent having a boiling point
of about 30°C to 160°C, for example, a lower alkyl acetate such as ethyl acetate,
butyl acetate, etc., ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone,
β-ethoxyethyl acetate, methyl cellosolve acetate, cyclohexanone, etc. The above-described
organic solvents having a high boiling point and organic solvents having a low boiling
point may be used as a mixture thereof.
[0049] Further, it is possible to use a dispersion method using a polymer as described in
Japanese Patent Publication No. 39853/76 and Japanese Patent Application (OPI) No.
59943/76. Moreover, various surface active agents can be used when the dye releasing
redox compound is dispersed in a hydrophilic colloid. For this purpose, the surface
active agents illustrated in other part of the specification can be used.
[0050] In the present invention, if necessary, a reducing agent may be used. The reducing
agent in this case is the so-called auxiliary developing agent, which is oxidized
by the silver halide and/or the organic silver salt oxidizing agent to form its oxidized
product having an ability to oxidize the reducing group R
a in the dye releasing redox compound.
[0051] Examples of useful auxiliary developing agents include the compounds specifically
described in European Patent Application (OPI) No. 76,492.
[0052] The silver halide used in the present invention includes silver chloride, silver
chlorobromide, silver chloroiodide, silver bromide, silver iodobromide, silver chloroiodobromide
and silver iodide, etc.
[0053] In the embodiment of the present invention in which the organic silver salt oxidizing
agent is not used together with but the silver halide is used alone, particularly
preferred silver halide is silver halide partially containing a silver iodide crystal
in its grain. That is, the silver halide which shows the X-ray diffraction pattern
of pure silver iodide is particularly preferred.
[0054] In photographic materials a silver halide containing two or more kinds of halogen
atoms can be used. Such a silver halide is present in the form of a completely mixed
crystal in a conventional silver halide emulsion. For example, the grain of silver
iodobromide shows X-ray diffraction pattern at a position corresponding to the mixed
ratio of silver iodide crystal and silver bromide crystal but not at a position corresponding
to pure silver iodide crystal and pure silver bromide crystal separately.
[0055] Particularly preferred examples of silver halide used in the present invention include
silver chloroiodide, silver iodobromide, and silver chloroiodobromide each containing
silver iodide crystal in its grain and showing X-ray diffraction pattern of silver
iodide crystal.
[0056] The process for preparing those silver halides is explained taking the case of silver
iodobromide. That is, the silver iodobromide is prepared by first adding silver nitrate
solution to potassium bromide solution to form silver bromide particles and then adding
potassium iodide to the mixture.
[0057] Two or more kinds of silver halides in which a particle size and/or a halogen composition
are different from each other may be used in mixture.
[0058] An average particle size of the silver halide used in the present invention is preferably
from 0.001 µm to 10 µm and more preferably from 0.001 µm to 5 µm.
[0059] The silver halide used in the present invention may be used as is. However, it may
be chemically sensitized with a chemical sensitizing agent such as compounds or sulfur,
selenium or tellurium, etc., or compounds of gold, platinum, palladium, rhodium or
iridium, etc., a reducing agent such as tin halide, etc., or a combination thereof.
The details thereof are described in T.H. James, The Theory of the Photographic Process,
the Fourth Edition, Chapter 5, pages 149 to 169.
[0060] In the particularly preferred embodiment of the present invention, an organic silver
salt oxidizing agent is used together. The organic silver salt oxidizing agent is
a silver salt which forms a silver image by reacting with the above-described image
forming substance or a reducing agent coexisting, if necessary, with the image forming
substance, when it is heated to a temperature of above 80°C and, preferably, above
100°C in the presence of exposed silver halide. By coexisting the organic silver salt
oxidizing agent, the light-sensitive material which provides higher color density
can be obtained.
[0061] The silver halide used in this case is not always necessarily to have the characteristic
in that the silver halide contains pure silver iodide crystal in the case of using
the silver halide alone. Any silver halide which is known in the art can be used.
[0062] Examples of such organic silver salt oxidizing agents include those described in
European Patent Application (OPI) No. 76,492.
[0063] A silver salt of an organic compound having a carboxy group can be used. Typical
examples thereof include a silver salt of an aliphatic carboxylic acid and a silver
salt of an aromatic carboxylic acid.
[0064] In addition, a silver salt of a compound containing a mercapto group or a thione
group and a derivative thereof can be used.
[0065] Further, a silver salt of a compound containing an imino group can be used. Examples
of these compounds include a silver salt of benzotriazole and a derivative thereof
as described in Japanese Patent Publication Nos. 30270/69 and 18416/70, for example,
a silver salt of benzotriazole, a silver salt of alkyl substituted benzotriazole such
as a silver salt of methylbenzotriazole, etc., a silver salt of a halogen substituted
benzotriazole such as a silver salt of 5-chlorobenzotriazole, etc., a silver salt
of carboimidobenzotriazole such as a silver salt of butylcarboimidobenzotriazole,
etc., a silver salt of 1,2,4-triazole or 1-H-tetrazole as described in U.S. Patent
4,220,709, a silver salt of carbazole, a silver salt of saccharin, a silver salt of
imidazole and an imidazole derivative, and the like.
[0066] Moreover, a silver salt as described in Research Disclosure, Vol. 170, No. 17029
(June, 1978) and an organic metal salt such as copper stearate, etc., are the organic
metal salt oxidizing agent capable of being used in the present invention.
[0067] Methods of preparing these silver halide and organic silver salt oxidizing agents
and manners of blending them are described in Research Disclosure, No. 17029, Japanese
Patent Application (OPI) Nos. 32928/75 and 42529/76, U.S. Patent 3,700,458, and Japanese
Patent Application (O
PI) Nos. 13224/74 and 17216/75.
[0068] A suitable coating amount of the light-sensitive silver halide and the organic silver
salt oxidizing agent employed in the present invention is in a total of from 50 mg/m
2 to 10 g/m
2 calculated as an amount of silver.
[0069] The light-sensitive silver halide and the organic silver salt oxidizing agent used
in the present invention are prepared in the binder as described below. Further, the
dye releasing redox compound is dispersed in the binder described below.
[0070] The binder which can be used in the present invention can be employed individually
or in a combination thereof. A hydrophilic binder can be used as the binder according
to the present invention. The typical hydrophilic binder is a transparent or translucent
hydrophilic colloid, examples of which include a natural substance, for example, protein
such as gelatin, a gelatin derivative, etc., a cellulose derivative, a polysaccharide
such as starch, gum arabic, etc., and a synthetic polymer, for example, a water-soluble
polyvinyl compound such as polyvinyl alcohol, polyvinyl pyrrolidone, acrylamide polymer,
etc. Another example of the synthetic polymer compound is a dispersed vinyl compound
in a latex form which is used for the purpose of increasing dimensional stability
of a photographic material.
[0071] The silver halide used in the present invention can be spectrally sensitized with
methine dyes or other dyes. Suitable dyes which can be employed include cyanine dyes,
merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine
dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Of these dyes, cyanine dyes,
merocyanine dyes and complex merocyanine dyes are particularly useful. Any conventionally
utilized nucleus for cyanine dyes, such as basic heterocyclic nuclei, can be contained
in these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus,
a pyrrole nucleus, an oxazole nucleus, a thiazolenucleus, a selenazole nucleus, an
imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc., and further, nuclei
formed by condensing alicyclic hydrocarbon rings with these nuclei and nuclei formed
by condensing aromatic hydrocarbon rings with these nuclei, that is, an indolenine
nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole
nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus,
a benzimidazole nucleus, a quinoline nucleus, etc., are appropriate. The carbon atoms
of these nuclei may also be substituted.
[0072] As nuclei having a ketomethylene structure, 5- or 6-membered heterocyclic nuclei
such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione
nucleus, a thiazolidin-2,4-dione nucleus, a rhodanine nucleus, a thiobarbituric acid
nucleus, etc., may also be used in merocyanine dyes and complex merocyanine dyes.
[0073] These sensitizing dyes can be employed individually, and can also be employed in
combination thereof. A combination of sensitizing dyes is often used, particularly
for the purpose of supersensitization. Representative examples thereof are described
in U.S. Patents 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293,
3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862
and 4,026,707, British Patents 1,344,281 and 1,507,803, Japanese Patent Publication
Nos. 4936/68 and 12375/78, Japanese Patent Application (OPI) Nos. 110618/77 and 109925/77,
etc.
[0074] The sensitizing dyes may be present in the emulsion together with dyes which themselves
do not give rise to spectrally sensitizing effects but exhibit a supersensitizing
effect or materials which do not substantially absorb visible light but exhibit a
supersensitizing effect. For example, aminostilbene compounds substituted with a nitrogen-containing
heterocyclic group (e.g., those described in U.S. Patents 2,933,390 and 3,635,721),
aromatic organic acid-formaldehyde condensates (e.g., those described in U.S. Patent
3,743,510), cadmium salts, azaindene compounds, etc., can be present. The combinations
described in U.S. Patents 3,615,613, 3,615,641, 3,617,295 and 3,635,721 are particularly
useful.
[0075] A support used in the light-sensitive material or used as the dye fixing material,
if desired, according to the present invention is that which can endure at the processing
temperature. As an ordinary support, not only glass, paper, metal or analogues thereto
may be used, but also an acetyl cellulose film, a cellulose ester film, a polyvinyl
acetal film, a polystyrene film, a polycarbonate film, a polyethylene terephthalate
film, and a film related thereto or a plastic material may be used. Further, a paper
support laminated with a polymer such as polyethylene, etc., can be used. The polyesters
described in U.S. Patents 3,634,089 and 3,725,070 are preferably used.
[0076] In the present invention, various kinds of dye releasing activators can be used.
The dye releasing activator means a substance which accelerates the oxidation-reduction
reaction between the light-sensitive silver halide and/or the organic silver salt
oxidizing agent and dye releasing redox compound, or accelerates release of a dye
by means of its nucleophilic action to the oxidized dye releasing redox compound in
the dye releasing reaction subsequently occurred, and a base and a base precursor
can be used. It is particularly advantageous to use these dye releasing activators
in order to accelerate the reactions in the present invention.
[0077] Examples of preferred bases are amines which include trialkylamines, hydroxylamines,
aliphatic polyamines, N-alkyl substituted aromatic amines, N-hydroxyalkyl substituted
aromatic amines and bis[p-(dialkylamino)phenyl]methanes. Further, betaine tetramethylammonium
iodide and diaminobutane dihydrochloride as described in U.S. Patent 2,410,644, and
urea and organic compounds including amino acids such as 6-aminocaproic acid as described
in U.S. Patent 3,506,444 are useful. The base precursor is a substance which releases
a basic component by heating. Examples of typical base precursors are described in
British Patent 998,949. A preferred base precursor is a salt of a carboxylic acid
and an organic base, and examples of the suitable carboxylic acids include trichloroacetic
acid and trifluoroacetic acid and examples of the suitable bases include guanidine,
piperidine, morpholine, p-toluidine and 2-picoline, etc. Guanidine trichloroacetate
as described in U.S. Patent 3,220,846 is particularly preferred. Further, aldonic
amides as described in Japanese Patent Application (OPI) No. 22625/75 are preferably
used because they decompose at a high temperature to form bases.
[0078] These dye releasing activators can be used in an amount of a broad range. A useful
range is u
p to 50% by weight based on the amount of a dry layer coated of the light-sensitive
material. A range of 0.01% by weight to 40% by weight is more preferred.
[0079] It is advantageous to use a compound represented by the general formula described
below in the heat-developable color photographic material in order to accelerate development
and accelerate release of a dye.

wherein A
1, A
2, A3 and A
4, which may be the same or different, each represents a hydrogen atom or a substituent
selected from an alkyl group, a substituted alkyl group, a cycloalkyl group, an aralkyl
group, an aryl group, a substituted aryl group and a heterocyclic group; and A
1 and A
2 or A3 and A4 may combine with each other to form a ring.
[0080] The above-described compound can be used in an amount of broad range. A useful range
is up to 20% by weight based on the amount of a dry layer coated of the light-sensitive
material. A range of 0.1% by weight to 15% by weight is more preferred.
[0081] It is advantageous to use a water releasing compound in the present invention in
order to accelerate the dye releasing reaction.
[0082] The water releasing compound means a compound which releases water by decomposition
during heat development. These compounds are particularly known in the field of printing
of fabrics, and NH
4Fe(SO
4)
2·12H
2O, etc., as described in Japanese Patent Application (OPI) No. 88386/75 are useful.
[0083] Further, in the present invention, it is possible to use a compound which activates
development and stabilizes the image at the same time. Particularly, it is preferred
to use isothiuroniums including 2-hydroxyethylisothiuronium trichloroacetate as described
in U.S. Patent 3,301,678, bisisothiuroniums including l,8-(3,6-dioxaoctane)bis(isothiuronium
trifluoroacetate), etc., as described in U.S. Patent 3,669,670, thiol compounds as
described in German Patent Application (OLS) No. 2,162,714, thiazolium compounds such
as 2-amino-2-thiazolium trichloroacetate, 2-amino-5-bromoethyl-2-thiazolium trichloroacetate,
etc., as described in U.S. Patent 4,012,260, compounds having a-sulfonyl- acetate
as an acid part such as bis(2-amino-2-thiazolium)-methylene-bis(sulfonylacetate),
2-amino-2-thiazolium phenylsulfonylacetate, etc., as described in U.S. Patent 4,060,420,
and compounds having 2-carboxycarboxamide as an acid part as described in U.S. Patent
4,088,496.
[0084] In the present invention, it is possible to use a thermal solvent. The term "thermal
solvent" means a non-hydrolyzable organic material which melts at a temperature of
heat treatment and melts at a lower temperature of heat treatment when it is present
together with other components. Preferred examples of thermal solvents include compounds
which can act as a solvent for the developing agent and compounds having a high dielectric
constant which accelerate physical development of silver salts. Examples of preferred
thermal solvents include those described in European Patent Application (OPI) No.
76,492.
[0085] In the present invention, though it is not always necessary to further incorporate
substances or dyes for preventing irradiation or halation in the light-sensitive material,
because the light-sensitive material is colored by the dye releasing redox compound,
it is possible to add filter dyes or light absorbing materials, etc., into the light-sensitive
material, as described in Japanese Patent Publication No. 3692/73 and U.S. Patents
3,253,921, 2,527,583 and 2,956,879, etc., in order to further improve sharpness. It
is preferred that these dyes have a thermal bleaching property. For example, dyes
as described in U.S. Patents 3,769,019, 3,745,009 and 3,615,432 are preferred.
[0086] The light-sensitive material used in the present invention may contain, if necessary,
various additives known for the heat-developable light-sensitive materials and may
have a layer other than the light-sensitive layer, for example, an antistatic layer,
an electrically conductive layer, a protective layer, an intermediate layer, an antihalation
layer, a strippable layer, etc.
[0087] The photographic emulsion layer and other hydrophilic colloid layers in the light-sensitive
material of the present invention may contain various surface active agents for various
purposes, for example, as coating aids, or for prevention of electrically charging,
improvement of lubricating property, emulsification, prevention of adhesion, improvement
of photographic properties (for example, acceleration of development, rendering hard
tone or sensitization), etc.
[0088] For example, it is possible to use nonionic surface active agents such as saponin
(steroid saponin), alkylene oxide derivatives (for example, polyethylene glycol, polyethylene
glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene
glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan
esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone,
etc.), glycidol derivatives (for example, alkenylsuccinic acid polyglycerides, alkylphenol
polyglycerides, etc.), polyhydric alcohol aliphatic acid esters or saccharide alkyl
esters, etc.; anionic surface active agents containing acid groups such as a carboxy
group, a sulfo group, a phospho group, a sulfate group, a phosphate group, etc., such
as alkylcarboxylic acid salts, alkylsulfonate salts, alkylbenzenesulfonate salts,
alkylnaphthalenesulfonate salts, alkyl sulfuric acid esters, alkylphosphoric acid
esters, N-acyl-N-alkyl- taurines, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene
alkylphenyl ethers, polyoxyethylene alkylphosphoric acid esters, etc.; ampholytic
surface active agents such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric
acid esters or phosphoric acid esters, alkylbetaines, amine oxides, etc.; and cationic
surface active agents such as alkylamine salts, aliphatic or aromatic quaternary ammonium
salts, heterocyclic quaternary ammonium salts such as pyridinium salts, imidazolium
salts, etc., aliphatic or heterocyclic phosphonium salts, aliphatic or heterocyclic
sulfonium salts, etc.
[0089] Of the above-described surface active agents, polyethylene glycol type nonionic surface
active agents having a recurring unit of ethylene oxide in their molecules may be
preferably incorporated into the light-sensitive material. It is particularly preferred
that the molecule contains 5 or more of the recurring units of ethylene oxide.
[0090] The nonionic surface active agents capable of satisfying the above-described conditions
are well known as to their structures, properties and methods of synthesis. These
nonionic surface active agents are widely used even outside this field. Representative
references relating to these agents include: Surfactant Science Series, Vol. 1, Nonionic
Surfactants (edited by Martin
J. Schick, Marcel Dekker Inc., 1967), and Surface Active Ethvlene Oxide Adducts (edited
by Schoufeldt N. Pergamon Press, 1969). Among the nonionic surface active agents described
in the above-mentioned references, those capable of satisfying the above-described
conditions are preferably employed in connection with the present invention.
[0091] The nonionic surface active agents can be used individually or as a mixture of two
or more of them.
[0092] The polyethylene glycol type nonionic surface active agents can be used in an amount
of less than 100% by weight, preferably less than 50% by weight, based on a hydrophilic
binder.
[0093] The light-sensitive material of the present invention may contain a cationic compound
containing a pyridinium salt. Examples of the cationic compounds containing a pyridinium
group used are described in PSA Journal Section B 36 (1953), U.S. Patents 2,648,604
and 3,671,247, Japanese Patent Publication Nos. 30074/69 and 9503/69, etc.
[0094] In the photographic light-sensitive material and the dye fixing material of the present
invention, the photographic emulsion layer and other binder layers may contain inorganic
or organic hardeners. It is possible to use chromium salts (chromium alum, chromium
acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol
compounds (dimethylol- urea, methylol dimethylhydantoin, etc.), dioxane derivatives
(2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloylhexahydro-s-triazine,
1,3- vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine,
etc.), mucohalo
genic acids (mucochloric acid, mucophenoxychloric acid, etc.), etc., which are used
individually or as a combination thereof.
[0095] Examples of various additives include those described in Research Disclosure, Vol.
170, No. 17029 (June, 1978), for example, plasticizers, dyes for improving sharpness,
antihalation dyes, sensitizing dyes, matting agents, fluorescent whitening agents
and fading preventing agents, etc.
[0096] If necessary, two or more layers may be coated at the same time by the method as
described in U.S. Patent 2,761,791 and British Patent 837,095.
[0097] Various means for exposure can be used in the present invention. Latent images are
obtained by imagewise exposure by radiant rays including visible rays. Generally,
light sources used in this invention include tungsten lamps, mercury lamps, halogen
lamps such as iodine lamps, xenon lamps, laser light sources, CRT light sources, fluorescent
tubes and light-emitting diodes, etc.
[0098] In the present invention, after the heat-developable color photographic material
is exposed to light, the resulting latent image can be developed by heating the whole
material to a suitably elevated temperature, for example, about 80°C to about 250°C
for about 0.5 second to about 300 seconds. A higher temperature or lower temperature
can be utilized to prolong or shorten the heating time, if it is within the above-described
temperature range. Particularly, a temperature range of about 110°C to about 160°C
is useful.
[0099] As the heating means, a simple heat plate, iron, heat roller, heat generator utilizing
carbon or titanium white, etc., or analogues thereto may be used.
[0100] In the present invention, a specific method for forming a color image by heat development
comprises transfer of a hydrophilic mobile dye. For this purpose, the heat-developable
color photographic material of the present invention is composed of a support having
thereon a light-sensitive layer (I) containing at least silver halide, if necessary,
an organic silver salt oxidizing agent, a dye releasing redox compound which is also
a reducing agent for the organic silver salt oxidizing agent and a binder, and a dye
fixing layer (II) capable of receiving the hydrophilic diffusible dye formed in the
light-sensitive layer (I).
[0101] The above-described light-sensitive layer (I) and the dye fixing layer (II) may be
formed on the same support, or they may be formed on different supports, respectively.
The dye fixing layer (II) can be stripped off the light-sensitive layer (I). For example,
after the heat-developable color photographic material is exposed imagewise to light,
it is developed by heating uniformly and thereafter the dye fixing layer (II) or the
light-sensitive layer (I) is peeled apart. Also, when a light-sensitive material having
the light-sensitive layer coated on a support and a fixing material having the dye
fixing layer (II) coated on a support are separately formed, after the light-sensitive
material is exposed imagewise to light and uniformly heated, the mobile dye can be
transferred on the dye fixing layer (II) by superposing the fixing material on the
light-sensitive layer.
[0102] Further, there is a method wherein only the light-sensitive layer (I) is exposed
imagewise to light and heated uniformly by superposing the dye fixing layer (II) on
the light-sensitive layer (I).
[0103] The dye fixing layer (II) can contain, for example, a dye mordant in order to fix
the dye. In the present invention, various mordants can be used, and polymer mordants
are particularly preferred. In addition to the mordants, the dye fixing layer may
contain the bases, base precursors and thermal solvents. In particular, it is particularly
preferred to incorporate the bases or base precursors into the dye fixing layer (II)
in the cases wherein the light-sensitive layer (I) and the dye fixing layer are formed
on different supports.
[0104] Preferred polymer mordants used in the present invention can be polymers containing
secondary and tertiary amino groups, polymers containing nitrogen-containing heterocyclic
moieties, polymers having quaternary cation groups thereof, having a molecular weight
of from 5,000 to 200,000, and particularly from 10,000 to 50,000.
[0105] For example, vinylpyridine polymers and vinyl- pyridinium cation polymers as disclosed
in U.S. Patents 2,548,564, 2,484,430, 3,148,061 and 3,756,814, etc., polymer mordants
capable of cross-linking with gelatin as disclosed in U.S. Patents 3,625,694, 3,859,096
and 4,128,538, British Patent 1,277,453, etc., aqueous sol type mordants as disclosed
in U.S. Patents 3,958,995, 2,721,852 and 2,798,063, Japanese Patent Application (OPI)
Nos. 115228/79, 145529/79 and 126027/79, etc., water-insoluble mordants as disclosed
in U.S. Patent 3,898,088, etc., reactive mordants capable of forming cobalent bonds
with dyes used as disclosed in U.S. Patent 4,168,976 (Japanese Patent Application
(OPI) No. 137333/79), etc., and mordants disclosed in U.S. Patents 3,709,690, 3,788,855,
3,642,482, 3,488,706, 3,557,066, 3,271,147 and 3,271,148, Japanese Patent Application
(OPI) Nos. 71332/75, 30328/78, 155528/77, 125/78 and 1024/78, etc., can be illustrated.
[0106] In addition, mordants disclosed in U.S. Patents 2,675,316 and 2,882,156 can be used.
[0107] The dye fixing layer (II) can have a white reflective layer. For example, a layer
of titanium dioxide dispersed in gelatin can be provided on the mordant layer on a
transparent support. The layer of titanium dioxide forms a white opaque layer, by
which reflection color images of the transferred color images which can be observed
through the transparent support is obtained.
[0108] Typical dye fixing material used in the present invention is obtained by mixing the
polymer containing ammonium salt groups with gelatin and applying the mixture to a
transparent support.
[0109] The transfer of dyes from the light-sensitive layer to the dye fixing layer can be
carried out using a dye transfer assistant. Examples of useful dye transfer assistant
include water and an alkaline aqueous solution containing sodium hydroxide, potassium
hydroxide and an inorganic alkali metal salt. Further, a solvent having a low boiling
point such as methanol, N,N-dimethylformamide, acetone, diisobutyl ketone, etc., and
a mixture of such a solvent having a low boiling point with water or an alkaline aqueous
solution can be used. The dye transfer assistant can be employed by wetting the image
receiving layer with the transfer assistant or by incorporating it in the form of
water of crystallization or microcapsules into the material.
EXAMPLE 1
[0110] A method of preparing a silver iodobromide is described below.
[0111] 40 g of gelatin and 26 g of potassium bromide (KBr) were dissolved in 3,000 ml of
water and the solution was stirred while maintaining the temperature at 50°C. A solution
containing 34 g of silver nitrate dissolved in 200 ml of water was then added to the
above prepared solution over 10 minutes. Subsequently, a solution containing 3.3 g
of potassium iodide (KI) dissolved in 100 ml of water was added thereto over 2 minutes.
[0112] By controlling the pH of the resulting silver iodobromide emulsion, precipitates
were formed and excess salts were removed. The pH of the emulsion was adjusted to
6.0 and 400 g of the silver iodobromide emulsion was obtained.
[0113] A method of preparing a silver benzotriazole emulsion is described below.
[0114] 28 g of gelatin and 13.2 g of benzotriazole were dissolved in 3,000 ml of water and
the solution was stirred while maintaining the temperature at 40°C. A solution containing
17 g of silver nitrate dissolved in 100 ml of water was then added to the above prepared
solution over 2 minutes.
[0115] By controlling the pH of the resulting silver benzotriazole emulsion, precipitates
were formed and excess salts were removed. The pH of the emulsion was adjusted to
6.0 and 400 g of the silver benzotriazole emulsion was obtained.
[0116] The method of preparing a gelatin dispersion of a dye releasing redox compound is
described below.
[0117] 5 g of magenta dye releasing redox compound of the following formula:

0.5 g of sodium 2-ethyl-hexylsuccinate sulfonate, and 5 g of tri-cresyl phosphate
(TCP) were weighed and added to 30 ml of ethyl acetate and dissolved therein by heating
at about 60°C to form a uniform solution. This solution was mixed with 100 g of a
10 wt% aqueous solution of lime-treated gelatin and then dispersed at 10,000 rpm for
10 minutes using a homogenizer.
[0118] This dispersion is designated a dispersion of the magenta dye releasing redox compound.
[0119] A method of preparing light-sensitive coatings A and B is described below.

dissolved and the resulting mixture solution was coated on a polyethylene terephthalate
film in a wet thickness of 30 µm and dried.

[0120] The above components (i) to (iv) were mixed and coated on the above prepared coating
layer as a protective layer in a wet thickness of 25 µm to produce a light-sensitive
coating A.

[0121] The above components (a) to (f) were mixed and dissolved and the resulting mixture
solution was coated on a polyethylene terephthalate film in a wet thickness of 30
µm and dried. A protective layer having the same formulation for the coating A was
provided to produce a light-sensitive coating B.
[0122] A method of preparing a dye fixing material is described below.
[0123] 10 g of poly(methylacrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride (the
ratio of methyl acrylate to vinylbenzylammonium chloride is 1:1) was dissolved in
200 ml of water and the solution was uniformly mixed with 100 g of 10 wt% aqueous
solution of lime-treated gelatin. This mixture solution was uniformly coated on a
paper support with a titanium-dispersed polyethylene laminated thereon in a wet thickness
of 90 pm. The sample was dried to be used as a dye fixing material having a mordant
layer.
[0124] The light-sensitive coatings A and B were each imagewise exposed at 2,000 lux for
10 seconds using a tungsten lamp and then uniformly heated for 20 seconds on a heat
block which had been heated at 130°C.
[0125] Water was applied onto the coating side of the dye fixing material in an amount of
80 ml per square meter of the coating. Each of the light-sensitive coatings A and
B which had been heat treated as described above was superposed on the dye fixing
material in such a manner that the coating surface of the coating and dye fixing material
were in contact with each other.
[0126] They were heated for 6 seconds on a heat block which had been heated at 80°C and
the dye fixing material was peeled away from the light-sensitive material, whereby
a negative-working magenta color image was formed on the dye fixing material.
[0127] This magenta image had a remarkable color smear and could not be said to be a sharp
image.
[0128] The same procedure as above was repeated except that water was applied onto the coating
side of the dye fixing material in an amount of 10 ml per square meter of the coating
layer. As a result, a sharp and smear-free magenta image could be formed.
[0129] The weights of the light-sensitive coatings A and B and the coating of the dye fixing
material were about 4 g/m
2, about 4 g/m
2, and about 5 g/m
2, respectively. The maximum swollen thicknesses in the water used were 12 µm, 12 µm
and 14 µm, respectively. Hence, the amount of water in the above described system
was 0.9 to 17 ml/m
2.
EXAMPLE 2
[0130] The light-sensitive coating A prepared in Example 1 was exposed and then heated in
the same manner as in Example 1.
[0131] Water was applied onto the coating side of the dye fixing material in various amounts:
0.5 ml, 1.2 ml, 2.1 ml, 2.7 ml, 4.4 ml, 7.8 ml, 9.3 ml, 15 ml and 20.5 ml, each being
per square meter of the coating.
[0132] The light-sensitive material and the dye fixing material were superposed in such
a manner that their coating surfaces were in contact with each other and then heated
for 6 seconds on a heat block which had been heated at 80°C. The dye fixing material
was peeled away from the light-sensitive material. The maximum density of the magenta
color image formed on the dye fixing material was measured with a Macbeth reflection
densitometer (RD-519). The results were as follows:

[0133] When water was applied in an amount of 20
..5 ml/m
2, smears were recognized on the image.
[0134] The maximum swollen thickness of the light-sensitive coating A and the dye fixing
material of Example 1 was 26 µm, and the total amount of all the coatings was 9 g/m
2. Therefore, the range as specified in the present invention of this material is 0.9
ml/m
2 to 17 ml/m
2. It can be seen from the above results that within this range the dye can be sufficiently
transferred satisfactorily without causing any smears.
EXAMPLE 3
[0135] The procedure of Example 2 was repeated except for using water in an amount of 2.72
ml and varying the heating time on the heat block. As a result, the maximum density
of 1.85 could be obtained by heating for 12 seconds.
[0136] Also, the procedure of Example 2 was repeated except for using water in an amount
of 1.2 ml. As a result, the maximum density of 1.60 could be obtained by heating for
30 seconds.
[0137] It can be seen from the above results that when the amount of water applied is small,
a sharp and smear-free image can be formed by increasing the heating time for transferring
the dye.
EXAMPLE 4
[0138] In the light-sensitive coating A of Example 1, only the weight of the protective
layer was changed to 14 g/m
2 (the maximum swollen thickness was 40 pm).
[0139] Using this light-sensitive coating, the procedure of Example 2 was repeated. When
water was applied in an amount of 2.1 ml or more, a sufficiently high color density
could be obtained. Even when the amount of water applied was 20.5 ml, a sharp and
smear-free image could be obtained.
[0140] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope thereof.