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Description  |
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FIELD OF THE INVENTION
This invention relates to a silver halide photographic material and, more
particularly, to a silver halide photographic material having improved
image stability and improved stability in its preparation.
More particularly, it relates to a photographic light-sensitive material
which provides a photographic image having improved antifungal and
antibacterial properties.
BACKGROUND OF THE INVENTION
Many bactericides and antifungal agents used for killing bacteria and fungi
are generally known, as described in, for example, Biseibutsu no Mekkin,
Sakkin, Bobai Gijutsu ("Techniques of Sterilization, Pasteurization, and
Fungicides of Microorganisms") compiled by Eisei Gijustu-kai ("Saninitary
Technology Society") (published in 1982). In the field of silver halide
photography, however, relatively few agents are known, and they have
undesirable side effects such as reduction in photographic sensitivity.
There are few agents which show satisfactory bactericidal and fungicidal
effects when used in a small amount. For example, JP-A-60-263938 (The term
"JP-A" as used herein means an "unexamined published Japanese
Publication") discloses compounds effective as antifungal agent.
JP-B-58-48892 (the term "JP-B" as used herein means an "examined Japanese
Patent publication") discloses various compounds as antibacterial agents
with some efficacy. However, these agents are still insufficient.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a silver halide
photographic material with sufficient antifungal and antibacterial
properties, without adversely affecting the silver halide light-sensitive
material or silver halide photographic image formed after development
processing, and to prevent deterioration of photographic pictures caused
by generation or growth of fungi and bacteria.
It has now been found that this and other objects of the present invention
can be attained by a silver halide photographic material composed of a
support having thereon at least one light-sensitive silver halide emulsion
layer, wherein the material contains the combination of (i) at least one
compound represented by formula (I) and (ii) at least one compound
represented by formulae (II) and/or (III):
##STR7##
wherein R.sub.1 represents hydrogen, a substituted or unsubstituted alkyl
group, a substituted or unsubstituted aryl group or a substituted or
unsubstituted aralkyl group, X represents a halogen atom, a nitro group, a
hydroxyl group, a cyano group, a lower alkyl group, a lower alkoxy group
--COR.sub.2,
##STR8##
or --SO.sub.3 M; R.sub.2 represents hydrogen, --OM, a lower alkyl group,
an aryl group, an aralkyl group, a lower alkoxy group, an aryloxy group,
an aralkyloxy group or
##STR9##
R.sub.3 and R.sub.4, which may be the same or different, each represents
hydrogen, a lower alkyl group, an aryl group, an aralkyl group,
--COR.sub.7 or --SO.sub.2 R.sub.7 ; R.sub.5 and R.sub.6, which may be the
same or different, each represents hydrogen, a lower alkyl group, an aryl
group or an aralkyl group; R.sub.7 represents a lower alkyl group; an aryl
group or an aralkyl group; M represents hydrogen, an alkali metal atom or
a monovalent cation; m represents 0 or an integer of 1 to 4; n represents
0 or an integer of 1 to 4; and Z represents an atomic group necessary for
forming a thiazolyl ring;
##STR10##
wherein R.sub.8 represents a lower alkylene group; X is the same as X in
formula (I); p represents 0 or 1, and q represents 0 or an integer of 1 or
5;
##STR11##
wherein R.sub.9 represents hydrogen, a substituted or unsubstituted alkyl
group, a substituted or unsubstituted alkenyl group, a substituted or
unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a
heterocyclic group,
##STR12##
R.sub.10 and R.sub.11, which may be the same or different, each represents
hydrogen, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group, a cyano group, a heterocyclic group, a
substituted or unsubstituted alkylthio group, a substituted or
unsubstituted arylthio group, a substituted or unsubstituted
alkylsulfonyloxy group or a substituted or unsubstituted alkylsulfonyl
group; R.sub.10 and R.sub.11 may be linked to form an aromatic ring; and
R.sub.12 and R.sub.13, which may be the same or different, each represents
hydrogen, a substituted or unsubstituted alkyl group, a substituted or
unsubstituted aryl group or a substituted or unsubstituted aralkyl group.
DETAILED DESCRIPTION OF THE INVENTION
The compounds to be used in the present invention are described in greater
detail below.
In the general formula (I), R.sub.1 represents hydrogen, a substituted or
unsubstituted alkyl group (for example, methyl, ethyl, 2-hydroxyethyl,
2-cyanoethyl, n-hexyl), a substituted or unsubstituted aryl group (for
example, phenyl, p-chlorophenyl) or a substituted or unsubstituted aralkyl
group (for example, benzyl, p-methoxybenzyl).
X represents a halogen atom (for example, chlorine, bromine, iodine), a
nitro group, a hydroxyl group, a cyano group, a lower alkyl group (alkyl
group containing 1 to 5 carbon atoms, for example, methyl, ethyl, butyl,
t-butyl, t-pentyl), a lower alkoxy group (alkoxy group containing 1 to 5
carbon atoms, for example, methoxy, ethoxy, butoxy), --COR.sub.2 (for
example, carboxyl, acetyl, ethoxycarbonyl, butoxycarbonyl, carbamoyl,
##STR13##
(for example, amino, dimethylamino, acetamido, methanesulfonamido) or
--SO.sub.3 M (for example, sulfo).
R.sub.1 preferably represents hydrogen, X preferably represents an alkyl
group containing 1 to 3 carbon atoms, an amino group, a nitro group, a
sulfo group, a halogen atom or a hydroxy group, m preferably represents 1
or 2, n preferably represents 0, and the thiazole ring formed by Z
preferably represents a 5-thiazolyl group.
Specific examples of the compounds represented by formula (I) are
illustrated below, but the present invention is not to be construed as
being limited thereto.
##STR14##
The compounds represented by formula (I) is disclosed, e.g., in
JP-A-57-157244, JP-A-57-190949, JP-A-60-260951, and JP-A-60-263938.
In formula (II), R.sub.8 represents an alkylene group (for example,
methylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene).
In formula (II), X preferably represents a lower alkyl group, an
alkoxycarbonyl group or a halogen atom.
Specific examples of the compounds represented by formula (II) are
illustrated below, the present invention is not to be construed as being
limited thereto.
##STR15##
The compounds represented by formula (II) is a commercially available
product.
In formula (III), R.sub.9 represents a hydrogen, straight or branched
chain, substituted or unsubstituted alkyl group (for example, methyl,
ethyl, tert-butyl, n-octadecyl, 2-hydroxyethyl, 2-carboxyethyl,
2-cyanoethyl, sulfobutyl, N,N-dimethylaminoethyl), a substituted or
unsubstituted cyclic alkyl group (for example, cyclohexyl,
3-methylcyclohexyl, 2-oxocyclopentyl), a substituted or unsubstituted
alkenyl group (for example, allyl, methylallyl), a substituted or
unsubstituted aralkyl group (for example, benzyl, p-methoxybenzyl,
o-chlorobenzyl, p-iso-propylbenzyl), substituted or unsubstituted aryl
group (for example, phenyl, naphthyl, o-methylphenyl, m-nitrophenyl,
3,4-dichlorophenyl), a heterocyclic group (for example, 2-imidazoly,
2-furyl, 2-thiazolyl, 2-pyridyl),
##STR16##
R.sub.10 and R.sub.11 each represents hydrogen, a substituted or
unsubstituted alkyl group (for example, methyl, ethyl, chloromethyl,
2-hydroxyethyl, tert-butyl or n-octyl), a substituted or unsubstituted
cyclic alkyl group (for example, cyclohexyl, 2-oxocyclopentyl), a
substituted or unsubstituted aryl group (for example, phenyl,
2-methylphenyl, 3,4-dichlorophenyl, naphthyl, 4-nitrophenyl,
4-aminophenyl, 3-acetamidophenyl), a cyano group, a heterocyclic group
(for example, 2-imidazolyl, 2-thiazolyl, 2-pyridyl), a substituted or
unsubstituted alkylthio group (for example, methylthio, 2-cyanoethylthio,
2-ethoxycarbonylthio), a substituted or unsubstituted arylthio group (for
example, phenylthio, 2-carboxyphenylthio, p-methoxyphenylthio), a
substituted or unsubstituted alkylsulfonyloxy group (for example,
methylsulfonyloxy or 2-hydroxyethylsulfonyloxy) or a substituted or
unsubstituted alkylsulfonyl group (for example, methylsulfonyl,
2-bromoethylsulfonyl), with R.sub.10 and R.sub.11 being optionally linked
to each other to form an aromatic ring (for example, benzene,
naphthalene).
R.sub.12 and R.sub.13 each represents hydrogen, a substituted or
unsubstituted alkyl group (for example, methyl, ethyl, iso-propyl,
2-cyanoethyl, 2-n-butoxycarbonylethyl, 2-cyanoethyl), a substituted or
unsubstituted aryl group (for example, phenyl, naphthyl, 2-methoxyphenyl,
m-nitrophenyl, 3,5-dichlorophenyl, 3-acetamidophenyl) or a substituted or
unsubstituted aralkyl group (for example, benzyl, phenethyl,
p-iso-propylbenzyl, o-chlorobenzyl, m-methoxybenzyl).
R.sub.9 preferably represents hydrogen, and an alkyl group, and R.sub.10
and R.sub.11 each preferably represents hydrogen, an alkyl group, an aryl
group, and a cyano group.
Specific examples of the compounds represented by the general formula (III)
are illustrated below, but the present invention is not to be construed as
being limited thereto.
##STR17##
The compounds represented by formula (III) is disclosed, e.g., in U.S. Pat.
No. 2,870,015 and French Pat. No. 1,555,416.
Of the above-described compounds, a combination of (I-1) and (II-1), a
combination of (I-1) and (II-9), and a combination of (I-1) and (II-11)
are particularly preferred.
The present invention can be applied to, for example, color negative films,
color reversal films, color positive films, color papers, color reversal
papers, black-and-white negative films, black-and-white papers,
microfilms, lith films, X-ray films, color and black-and-white
light-sensitive materials for diffusion transfer process, and silver
dye-bleach type light-sensitive materials.
The antifungal and antibacterial effects can be obtained by adding the
compounds represented by formulae (I), (II) and (III) to any one of, or
more than one of, silver halide emulsion layers, gelatin interlayers and
protective colloidal layers in these light-sensitive materials.
It is preferred that the compounds represented by formula (I) is added to a
protective layer which is farthest from the support and the compounds
represented by formulae (II) and (III) is added to a light-sensitive layer
(e.g., a protective layer, an interlayer layer, an antihalation layer) or
all photographic layer which constitutes a photographic material.
The compound represented by formula (I) is added in an amount of preferably
0.01 to 30 mg/m.sup.2, particularly preferably 0.2 to 10 mg/m.sup.2.
The compound represented by formula (II) is added in an amount of
preferably 1 to 3000 mg/m.sup.2, particularly preferably 50 to 1000
mg/m.sup.2.
The compound represented by formula (III) is added in an amount of
preferably 0.1 to 300 mg/m.sup.2, particularly preferably 1 to 50
mg/m.sup.2.
In incorporating the compounds represented by formulae (I), (II), and (III)
in photographic light-sensitive materials, they are preferably added as a
solution in an organic solvent such as methanol, ethanol, ethylene glycol,
diethylene glycol, triethylene glycol, benzyl alcohol, ethanolamine,
diethanolamine or triethanolamine, or in an emulsified state.
The combined use of the compound of the present invention represented by
formula (I) and at least one compound selected from the compounds
represented by formulae (II) and (III) is effective against all fungi
growing in silver halide photographic images, but is particularly
effective against the following fungi: Aspergillus niger, Aspergillus
gracilis, Aspergillus penicilloides, Pulluraria pullulanes, Chaetomium
globosum, Cladosporium resinae, Aspergillus flavus, Aspergillus oryzac,
Penicillium citrinum, Penicillium luteum, Trichoderma uiride, Aspergillus
restrictus, Aspergillus glaucus, Chrysosporium, Aspergillus versirolor,
Eurotium rubrum, Eurotium tonophilum, and Arthrium Pestalotia.
The silver halide incorporated in the photographic emulsion layers of the
photographic light-sensitive material of the present invention is silver
chloride, silver bromide, silver iodide, silver iodobromide, silver
iodochloride or silver iodochlorobromide.
The silver halide grains in the photographic emulsion may have a regular
crystal form such as cubic, octahedral or tetradecahedral, an irregular
form such as spherical or tabular, a form with crystal defects such as a
twin plane, or a composite form thereof.
As to the grain size of silver halide grains, both fine grains of not
larger than about 0.2 .mu.m and large-sized grains of up to about 10 .mu.m
in projected area diameter may be used. The emulsion may be a
polydispersed emulsion or a monodispersed emulsion.
The silver halide photographic emulsion used in the present invention may
be prepared according to processes described in, for example, Research
Disclosure (RD) No. 17643 (Dec., 1978), pp. 22-23, "I. Emulsion
preparation and types" and ibid., No. 18716 (Nov., 1979), p. 648;
Glafkides, Chimie et Phisique Photographiique, pages 329 to 425; (Paul
Montel, 1967), G. F. Duffin, Photographic Emulsion Chemistry, pages 57 to
82 (Focal Press, 1966), V. L. Zelikman et al, Making and Coating
Photographic Emulsion pages 69 to 87 (Focal Press, 1964), etc.
Monodispersed emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394
and British Pat. No. 1,413,748, etc. are also preferred.
Tabular grains of about 5 or more in aspect ratio are also useful in the
present invention. Such tabular grains may be easily prepared according to
processes described in, for example, Gutoff, Photographic Science and
Engineering, vol. 14, pp. 248-257 (1970), U.S. Pat. Nos. 4,434,226,
4,414,310, 4,433,048, 4,439,520 and British Pat. No. 2,112,157.
The crystal structure may be a uniform structure, a structure wherein the
inner portion and the outer portion differ in halide composition, or a
layered structure, or silver halide crystals different from each other may
be joined to each other by epitaxial joined or, further, crystals
conjuncted to other compounds than silver halide, such as silver rhodanide
or lead oxide, may be used.
In addition, a mixture of grains of various crystal forms may also be used.
The silver halide emulsions are usually subjected to physical ripening,
chemical ripening, and spectral sensitization before use. Additives to be
used in these steps are described in Research Disclosure Nos. 17643 and
18716, as described in the following table.
Known photographic additives that can be used in the present invention are
also described in the above-described two Research Disclosures as
summarized in the following table.
______________________________________
Kind of Additive RD 17643 RD 18716
______________________________________
1. Chemical sensitizer
p. 23 p. 648, right col.
2. Sensitivity-raising agent "
3. Spectrally sensitizing
pp. 23-24 p.648, right col.
agent and Supersensitizing to
agent p. 649, right col.
4. Whitening agent p. 24
5. Antifoggant and Stabilizer
pp. 24-25 p. 649, right col.
6. Light-absorbing agent,
pp. 25-26 p. 649, right col.
Filter dye, and UV ray to
absorbent p. 650, left col.
7. Stain-preventing agent
p. 25, right
p. 650, left to
col. right col.
8. Dye image stabilizer
p. 25
9. Hardener p. 26 p. 651, left col.
10. Binder p. 26 p. 651, left col.
11. Plasticier and Lubricant
p. 27 p. 650, right col.
12. Coating aid and Surfactant
pp. 26-27 "
13. Antistatic agent p. 27 "
______________________________________
Various color couplers may be used in the present invention, and specific
examples thereof are described in the patents disclosed in the foregoing
Research Disclosure (RD), No. 17643, VII-C to G.
As yellow couplers, those described in, for example, U.S. Pat. Nos.
3,933,501, 4,022,620, 4,326,024 and 4,401,752, JP-B-58-10739, British Pat.
Nos. 1,425,020 and 1,476,760 are preferred.
As magenta couplers, 5-pyrazolone type and pyrazoloazole type compounds are
preferred including those described in, for example, U.S. Pat. Nos.
4,310,619, 4,351,897, European Pat. No. 73,636, U.S. Pat. Nos. 3,061,432
and 3,725,067, Research Disclosure, No. 244220 (Jun., 1984),
JP-A-60-33552, Research Disclosure, No. 24230 (Jun., 1984), JP-A-60-43659,
U.S. Pat. Nos. 4,500,630 and 4,540,654.
As cyan couplers, there are illustrated phenolic and naphtholic couplers,
and those described in U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233,
4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002,
3,758,308, 4,334,011, and 4,327,173, West German patent application (OLS)
No. 3,329,729, European Pat. No. 121,365A, U.S. Pat. Nos. 3,446,622,
4,333,999, 4,451,559, 4,427,767, and European Pat. No. 161,626A, etc. are
preferable.
As colored couplers for correcting unnecessary absorption of colored dyes,
those described in Research Disclosure, No. 17643, Item VII-G, U.S. Pat.
No. 4,163,670, JP-B-57-39413, U.S. Pat. Nos. 4,004,929, 4,138,258, and
British Pat. No. 1,146,368 are preferred.
As couplers capable of forming colored dyes with a suitable diffusibility,
those described in U.S. Pat. No. 4,366,237, British Pat. No. 2,125,570,
European Pat. No. 96,570, and West German patent application (OLS) No.
3,234,533 are preferred.
Typical examples of polymerized dye-forming couplers are described in U.S.
Pat. Nos. 3,451,820, 4,080,211, and 4,367,282, British Pat. No. 2,102,173,
etc.
Couplers capable of releasing a photographically useful residue upon
coupling reaction are also preferably used in the present invention. As
DIR couplers capable of releasing a development inhibitor, those described
in the patents mentioned in the foregoing RD 17643, Item VII-F,
JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, and U.S. Pat. No.
4,248,962 are preferred.
As couplers capable of imagewise releasing a nucleating agent or a
development accelerator upon development, those described in British Pat.
Nos. 2,097,140 and 2,131,188, JP-A-59-157638 and JP-A-59-170840 are
preferred.
Further couplers to be used in the light-sensitive material of the present
invention include, for example, competitive couplers described in U.S.
Pat. No. 4,130,427, etc.; polyequivalent couplers described in U.S. Pat.
Nos. 4,283,472, 4,338,393, 4,310,618, etc.; DIR redox compound-releasing
couplers described in JP-A-60-185950, etc.; and couplers capable of
re-acquiring color after being released which are described in European
Pat. No. 173,302A.
The couplers to be used in the present invention may be introduced into
light-sensitive materials by various known dispersing processes.
Examples of high-boiling point organic solvents to be used in the
oil-in-water dispersion process are described in, for example, U.S. Pat.
No. 2,322,027.
Steps and advantages of the latex dispersion process and specific examples
of latexes for impregnation are described in U.S. Pat. No. 4,199,363, West
German patent application (OLS) Nos. 2,541,274 and 2,541,230.
Suitable supports to be used in the present invention are described in, for
example, the above-mentioned RD, No. 17643, p. 28 and ibid., No. 18716, p.
647, right to column to p. 648, left column.
The color photographic material of the present invention may be development
processed according to common processes described in the foregoing RD, No.
17643, pp. 28-29 and ibid., No. 18716, p. 651, left column to right
column.
The color developer to be used for development processing light-sensitive
materials of the present invention is preferably an alkaline aqueous
solution containing an aromatic primary amine color developing agent as a
major component. As the color developing agents, p-phenylenediamine
compounds are preferably used, though aminophenol compounds are also
useful. Typical examples thereof include
3-methyl-4-amino-N,N-diethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-methanesulfonamidoethylaniline,
3-methyl-4-amino-N-ethyl-N-.beta.-methoxyethylaniline, and sulfates,
hydrochlorides or p-toluenesulfonates thereof. These compounds may be used
as a combination of two or more depending upon the purpose.
The color developer generally contains a pH buffer agent such as an alkali
metal carbonate, borate or phosphate, a development inhibitor or
antifoggant such as a bromide, an iodide, a benzimidazole, a benzothiazole
or a mercapto compound. If necessary, various preservatives such as
hydroxylamine, diethylhydroxylamine, hydrazine sulfites,
phenylsemicarbazides, triethanolamine, catecholsulfonic acids,
triethylenediamine (1,4-diazabicyclo(2,2,2)octane), etc.; organic solvents
such as ethylene glycol, diethylene glycol, etc.; development accelerators
such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
amines, etc.; dye-forming couplers; competitive couplers; fogging agents
such as sodium borohydride; auxiliary developing agents such as
1-phenyl-3-pyrazolidone; viscosity-imparting agents; various chelating
agents represented by aminopolycarboxylic acids, aminopolyphosphonic acid,
alkylphosphonic acids, and phosphonocarboxylic acids such as
ethylenediaminetetraacetic acid, nitrilotriacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid,
nitrilo-N,N,N-trimethylenephosphonic acid,
ethylenediamine-N,N,N'N'-tetramethylenephosphonic acid,
ethylenediamine-di(o-hydroxyphenylacetic acid) and salts thereof, may be
added to the color developer.
In conducting reversal processing, usually black-and-white development is
conducted before color development. This black-and-white developer
includes known black-and-white developing agents such as dihydroxybenzenes
(for example, hydroquinone), 3-pyrazolidones (for example,
1-phenyl-3-pyrazolidone) and aminophenols (for example,
N-methyl-p-aminophenol) alone or as a combination thereof.
These color developer and black-and-white developer generally have a pH of
9 to 12. These developers are replenished generally in amounts of up to 3
liters per m.sup.2 of light-sensitive materials, though depending upon the
kind of color photographic light-sensitive materials to be processed. The
replenishing amount may be reduced to not more than 500 ml by decreasing
the bromide ion concentration in the replenisher. In the case of
decreasing the replenishing amount, contact area between the solution and
the air within the processing tank be preferably minimized to thereby
prevent vaporization and air oxidation of the solution. In addition, the
replenishing amount may also be decreased by employing means of depressing
accumulation of bromide ion in the developer.
Color-developed photographic emulsion layers are usually bleached.
Bleaching may be conducted independently or simultaneously with fixing
(bleach-fixing). In order to promote the processing, bleach-fixing may be
conducted after bleaching. Further, it is possible to use two continuous
bleach-fixing baths, to fix before bleach-fixing or to bleach-fix after
bleach-fixing, as desired. As the bleaching agent, compounds of polyvalent
metals such as iron(III), cobalt(III), chromium (VI), copper(II), etc.,
peracids, quinones, nitro compounds, and the like are used. As typical
bleaching agents, ferricyanides; dichromates; organic complex salts of
iron(III) or cobalt(III), for example, complex salts of
aminopolycarboxylic acids such as ethylenediaminetetraacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,
methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol
ether diaminetetraacetic acid or of organic acids such as citric acid,
tartaric acid and malic acid; persulfates; bromide acid salts;
permanganates; nitrobenzenes; etc. may be used. Of these, iron (III)
aminopolycarboxylates including iron (III) ethylenediaminetetraacetate and
persulfates are preferred in view of rapid processing and prevention of
environmental pollution. Further, iron (III) aminopolycarboxylate complex
salts are particularly useful in both an independent bleaching solution
and a bleach-fixing solution.
The bleaching or bleach-fixing solution containing these iron(III)
aminopolycarboxylate complex salts usually has a pH of 5.5 to 8, but may
have a lower pH for accelerating the processing.
A bleach accelerator may be used in the bleaching solution, bleach-fixing
solution, or pre-baths thereof. As specific examples of useful bleach
accelerators, there are illustrated mercapto group- or disulfido
group-containing compounds described in, for example, U.S. Pat. No.
3,893,858, West German Pat. Nos. 1,290,812 and 2,059,988, JP-A-53-32736,
JP-A-53-57831, JP-A-53-37418, JP-A-53-72623, JP-A-53-95630, JP-A-53-95631,
JP-A-53-10423, JP-A-53-124424, JP-A-53-141623, JP-A-53-28426, and Research
Disclosure, No. 17129 (Jul., 1978); thiazolidine derivatives described in
JP-A-50-140129; thiourea derivatives described in JP-B-45-8506,
JP-A-52-20832, JP-A-53-32735, U.S. Pat. No. 3,706,561, etc.; iodides
described in West German Pat. No. 1,127,715, and JP-A-58-16235;
polyoxyethylenes described in West German Pat. Nos. 966,410 and 2,748,430;
polyamines described in JP-B-45-8836; compounds described in
JP-A-49-42434, JP-A-49-59644, JP-A-53-94927, JP-A-54-35727, JP-A-55-26506,
JP-A-58-163940; and bromide ion. Of these, mercapto group- or disulfido
group-containing compounds are preferable due to their great accelerating
effect, and compounds described in U.S. Pat. No. 3,893,858, West German
Pat. No. 1,290,812 and JP-A-53-95630 are particularly preferred. In
addition, those compounds which are described in U.S. Pat. No. 4,552,834
are also preferred. These beach accelerators may be incorporated into the
photographic materials.
These bleach accelerators are particularly effective in bleach-fixing color
light-sensitive materials for photographing use.
Fixing agents include, for example, thiosulfates, thiocyanates, thioether
compounds, thioureas and a large amount of an iodide salt. Of these,
thiosulfates are generally used, with ammonium thiosulfate being most
widely used. As preservatives for the bleach-fixing solution, sulfites,
bisulfites or carbonyl-bisulfite adducts are preferred.
After removal of silver, the silver halide color photographic material of
the present invention is generally subjected to a water-washing step
and/or stabilizing step. The amount of water used in the water-washing
step may be selected in a wide range depending upon the characteristics of
the light-sensitive material (resulting from, for example, materials such
as couplers), end-use, temperature of the washing water, number (step
number) of washing tanks, manner of replenishment (countercurrent manner
or direct current manner), and other various conditions. Of these, the
number of water-washing tanks and the amount of washing water can be
determined according to the method described in Journal of the Society of
Motion Picture and Television Engineers vol. 64, pp. 248-253 (May, 1955).
The multistage countercurrent manner described in the above-described
publication permits to marked reduction of the amount of washing water but
since the standing time of water within the tanks is prolonged, there
arises a problem of adhesion of floating matter produced as a result of
growth of bacteria. In order to solve the problem in processing the color
light-sensitive material of the present invention, the technique of
reducing the level of calcium ion and magnesium ion described in
JP-A-62-288838 may be effectively employed. In addition,
chlorine-containing bactericides (for example, sodium chloroisocyanurate
and bactericides described in Bokin Bobai no Kagaku ("Chemistry of
bactericides and fungicides") written by Hiroshi Horiguchi, Biseibutsu no
Mekkin, Sakkin, Bobai Gijutsu ("Techniques of Sterilization,
Pasteurization, and Fungicides of Microorganisms") compiled by Eisei
Gijustukai ("Sanitary Technology society") and Bokin Bobaizai Jiten ("Book
of Bactericides and Fungicides") compiled by Nippon Bokin Bobai Gakkai
("Japan Bactericide and Fungicide Society"), such as benzotriazoles may be
used.
The washing water to be used for processing the light-sensitive material of
the present invention has a pH of 4 to 9, preferably 5 to 8. The washing
temperature and washing time may be variously selected depending upon the
characteristics and end-use of light-sensitive materials, but, as a
general guide, a washing temperature of 15.degree. to 45.degree. C. and a
washing time of 20 seconds to 10 minutes is typical, with a washing
temperature of 25.degree. to 40.degree. C. and a washing time of 30
seconds to 5 minutes being preferred. Further, the light-sensitive
material of the present invention may be directly processed with a
stabilizing solution in place of the above-described washing with water.
In such stabilizing processing, all known techniques described in
JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 may be employed.
In addition, stabilizing processing may be conducted subsequent to the
above-described water-washing processing. For example, a stabilizing bath
containing formalin and a surfactant can be used as a final bath for
processing color light-sensitive materials for photographic use. To this
stabilizing bath may also be added various chelating agents and antifungal
agents.
An over-flow solution produced as a result of replenishment of the washing
water and/or stabilizing solution may be re-used in other steps such as
silver-removing step.
Color developing agents may be incorporated in the silver halide color
photographic material of the present invention for the purpose of
simplifying and accelerating the processing. Various precursors of the
color developing agents to be incorporated are preferably used. For
example, These include indoaniline compounds described in U.S. Pat. No.
3,342,597; Schiff base type compounds described in U.S. Pat. No. 3,342,599
and Research Disclosure Nos. 14,850 and 15,159; aldol compounds described
in Research Disclosure No. 13,924; metal salt complexes described in U.S.
Pat. No. 3,719,492; and urethane compounds described in JP-A-53-135628.
The silver halide color photographic material of the present invention may
contain, if necessary, various 1-phenyl-3-pyrazolidones for the purpose of
accelerating color development. Typical examples thereof are described in,
for example, JP-A-56-64339, JP-A-57-144547 and JP-A-58-115438.
Various processing solutions in the present invention are used at
temperatures of 10.degree. C. to 50.degree. C. Temperatures of 33.degree.
C. to 38.degree. C. are standard, but higher temperatures may be employed
for accelerating processing and shortening processing time, or lower
temperature may be employed to improve image quality or stability of
processing solutions. In addition, processing using cobalt intensification
or hydrogen peroxide intensification described in West German Pat. No.
2,226,770 or U.S. Pat. No. 3,674,499 may be conducted for saving silver of
light-sensitive materials.
Growth of fungi and bacteria can be markedly prevented by incorporation of
the compound represented by the general formula (I) and the compound
represented by the general formula (II) and/or (III) in photographic
light-sensitive materials. This effect is suprisingly greater than that
obtained by independently using the compounds of the general formulae (I),
(II) and (III).
The present invention is now illustrated in more detail with reference to
the following examples which, however, are not to be construed as limiting
the scope of the present invention in any way. Unless otherwise indicated,
all parts, percents and ratios are by weight.
EXAMPLE 1
A color light-sensitive material composed of a subbed cellulose triacetate
film support having provided thereon the layers of the following
formulations, referred to as Sample 101, was prepared.
Formulation of light-sensitive layer:
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