JPH0338638A - Direct positive color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a sensitive material not causing changes of max. density and min. density due to a change of the pH of a color developing soln. by using a specified yellow coupler and a specified pyrazoloazole magenta coupler in combination in a direct positive color photographic sensitive material contg. unfogged internal latent image type silver halide particles. CONSTITUTION:At least one kind of compd. represented by general formula I and at least one kind of compd. represented by general formula M-II are incorporated as photosensitive materials into a direct positive color photographic sensitive material. The compd. represented by the formula I is typically a homo- or copolymer of an addition-polymerizable ethylenic unsatd. compd. having a residue of a yellow dyestuff forming coupler. The compd. represented by the formula M-II is known as a pyrazoloazole coupler. The occurrence of a re-reversal negative image is inhibited by incorporating Mn, Cu, Zn, Cd, Pd, Bi or a group VIII metal of the periodic table into unfogged internal latent image type silver halide particles in the sensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic material, and more particularly to a direct positive color photographic material having excellent stability in photographic processing performance.

[Conventional technology]

Generally, photographic methods for directly obtaining positive color photographic images using silver halide color photographic materials are well known.

Excluding special methods, the methods used to create positive images using conventionally known direct positive silver halide photographic materials can be mainly divided into two types, considering their practical usefulness. can.

One type uses a pre-coupled silver halide emulsion and uses solarization or the Burschel effect to destroy fog nuclei (?I!J images) in the exposed area, thereby creating a positive image directly in the developing machine. It's something you get.

The other type uses an internal latent image type silver halide emulsion that has not been couplered in advance, and after image exposure, fogging treatment is performed, or surface development is performed while fogging treatment is performed to directly obtain a positive image. .

The above-mentioned internal latent image type silver halide photographic emulsion refers to a type of silver halide photographic emulsion that has photosensitive nuclei mainly inside the silver halide grains, and a latent image is mainly formed inside the grains upon exposure. .

Various techniques are known to date in this technical field. For example, U.S. Patent No. 2.592.250, U.S. Pat.
, No. 588.982, No. 3゜317.322, No. 3,
761.266, 3.761.276, 3.7
The main ones are those described in British Patent No. 96,577 and the specifications of British Patent No. 1.151.363, British Patent No. 1.150.553, and British Patent No. 1,011,062.

Further, regarding the direct positive image formation mechanism njlB, see, for example, T. H. James, "The Theory
Photographic Process” (The Theor
y of the Photographic Pro
cess), 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761.276.

In other words, fog nuclei are selectively generated only on the surface of silver halide grains in unexposed areas by a surface desensitization effect based on a so-called internal latent image generated inside silver halide by the first image AM light. It is believed that a photographic image (direct positive image) is then formed in the unexposed area by subjecting it to a normal so-called surface development process.

As mentioned above, as a means for selectively generating fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called "photofogging method" (for example, British Patent No. 1.151,
363) and a nucleating agent (n
A method using a nucleating agent is known. Regarding this latter method, for example, ``Research Disclosure
mouth 1 closure) magazine, volume 151, blood 15162
(published November 1976), pages 76-78.

Color-forming dyes using cyan, magenta, and yellow couplers used in conventional silver halide color photographic materials have unnecessary JilJ absorption, and therefore their color reproducibility tends to be impaired. Therefore, couplers that form image dyes with low side absorption have been studied.

For example, JP-A No. 63-123047 discloses a yellow coupler that exhibits a sharp absorption subtractor of coloring dyes, has excellent coloring properties, has little fog, and has little variation in coloring properties depending on the pH of the color developer. ing.

It is also known that the coloring dye of the pyrazoloazole magenta coupler has a sharper visible absorption spectrum than that of the 5-pyrazolone magenta coupler.

[Problem to be solved by the invention]

However, according to research conducted by the present inventors, particularly in direct positive color photographic materials, when the above-mentioned yellow coupler and pyrazoloazole magenta coupler are used together, the formation of coloring dyes by each coupler depends on the pH of the color developer. It fluctuates greatly due to fluctuations, especially at the highest concentration (
Do+ax) and minimum concentration (Dmin) fluctuate greatly, and a solution to these problems has been desired.

Therefore, the object of the present invention is to increase the maximum density (Daax) and minimum density (Dmin) by varying the pH of the color developer.
) The object of the present invention is to provide an excellent direct positive color photographic material without any variation in color.

[Means to solve the problem]

The object of the present invention is to provide a direct positive color photographic light-sensitive material containing on a support at least one layer of unfogged internal latent image type silver halide grains and a color image-forming coupler, the light-sensitive material having the following general formula: The internal latent image type silver halide grains contain at least one compound represented by [I] and at least one compound represented by general formula [M-■], and the at least one internal latent image type silver halide grain is Mn, Cu.

This was achieved using a direct positive color photographic material characterized by incorporating at least one member selected from the group consisting of Zn, Cd, Pd, Bi, and metals belonging to Group 1 of the Periodic Table.

[In the formula, R1 is an aryl group or a tertiary alkyl group,
1 is a fluorine atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an alkylthio group, or an arylthio group, and R3 is Rt! on the benzene stage. ! X represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized product of an aromatic primary amine developer, and an integer from 11EO to 4, respectively. However, when 1 is plural, the plural R3s may be the same or different. ] General formula [M-n] [In the formula, R1° represents a hydrogen atom or a substituent. Y.

represents a hydrogen atom or a leaving group. Za, Zb and Zc represent methine, substituted methine, =N- or -NH-, and Za
One of the -Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond.

The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. This includes the case where a dimer or more multimer is formed with R1° or Y, and the case where a dimer or more multimer is formed with the substituted methine when Za, Zb or Zc is a substituted methine. ] JP-A No. 63-231451 discloses that a silver halide color photographic light-sensitive material containing the above yellow coupler and pyrazoloazole magenta coupler exhibits excellent color reproducibility, dye image storage stability, and color development. However, there is no mention of direct positive color photographic materials, and the problems and solutions of the present invention when used in direct positive color photographic materials cannot be found.

The compound represented by the general formula [■] used in the present invention will be explained in more detail.

General formula [! ], R6 preferably has 6 carbon atoms
~24 aryl groups (e.g. phenyl, p-)lyl, 0
-) Lyle, 4-methoxyphenyl 2-methoxyphenyl, 4-butoxyphenyl 4-octyloxyphenyl,
4-hexadecyloxyphenyl, 1-naphthyl) or tertiary alkyl groups having 4 to 24 carbon atoms (e.g. t-butyl, t-pentyl, t-hexyl, 1.1.3.3-
Tetramethylbutyl, ■-adamantyl, 1.1=dimethyl-2-chloroethyl, 2-phenoxy-2-propyl, bicyclo(2,2,2)o99-l-yl).

In the general formula ([1, R3 is preferably a fluorine atom,
Alkyl groups having 1 to 24 carbon atoms (e.g. methyl, ethyl, isopropyl, t-butyl, cyclopentyl, n-
octyl; For example, methoxy, ethoxy,
butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy), aryloxy groups having 6 to 24 carbon atoms (e.g. phenoxy, p-
) Lyloxy, o-tolyloxy, p-methoxyphenoxy, p-dimethylaminophenoxy, m-pentadecylphenoxy>, dialkylamino group having 2 to 24 carbon atoms (e.g. dimethylamino, diethylamino, pyrrolidino, piperidino, morpholino), carbon Number of atoms 1-24
alkylthio groups (e.g. methylthio, butylthio, n
-octylthio, n-hexadecylthio) or arylthio groups having 6 to 24 carbon atoms (e.g. phenylthio,
4-methoxyphenylthio, 4-t-butylphenylthio, 4-dodecylphenylthio).

In the general formula [■], R5 is preferably a halogen atom (e.g., fluorine, chlorine, bromine, iodine), carbon atom number 1
~24 alkyl groups (e.g. methyl, t-butyl, n-
dodecyl), an aryl group having 6 to 24 carbon atoms (e.g. phenyl, p-)UR, p-dodecyloxyphenyl)
, alkoxy groups having 1 to 24 carbon atoms (e.g. methoxy, n-butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy), aryloxy groups having 6 to 24 carbon atoms (e.g. phenoxy, pt-butylphenoxy, 4-butoxyphenoxy), alkoxycarbonyl groups having 2 to 24 carbon atoms [e.g. ethoxy carbonyl, dodecyloxycarbonyl, l-(dodecyloxycarbonyl)ethoxycarbonyl], 7 to 24 carbon atoms Aryloxycarbonyl groups (e.g. phenoxycarbonyl, 4-t-octylphenoxycarbonyl, 2,4-di-t-pentylphenoxycarbonyl), carbonamide groups having 1 to 24 carbon atoms [e.g. acetamide, pivaloylamino, benzamide, 2- Ethylhexanamide, tetradecanamide, 1-(2,4-di-1-pentylphenoxy)butanamide, 3-(2,4-di-t-pentylphenoxy>butanamide, 3-dodecylsulfonyl-2-methylprohanamide), Sulfonamide groups having 1 to 24 carbon atoms (e.g. methanesulfonamide, p-toluenesulfonamide, hexadecanesulfonamide), carbamoyl groups having 1 to 24 carbon atoms (e.g. N-methylcarbamoyl, N-tetradecylcarbamoyl, N , N-dihexyl-rubamoyl, N-dioctadecyl-N-methylcarbamoyl, N-7enylcarbamoyl), sulfamoyl group having 0 to 24 carbon atoms (e.g. N-methylsulfamoyl, N-phenylsulfamoyl, N-acetylsulfamoyl, N-propanoylsulfamoyl, N-hexadecylsulfamoyl, NlN-dioctylsulfamoyl), alkylsulfonyl groups having 1 to 24 carbon atoms (e.g. methylsulfonyl, benzylsulfonyl, hexadecylsulfamoyl), decylsulfonyl), 6 to 24 carbon atoms
alkylsulfonyl group (sidelight lf phenylsulfonyl, p-)IJ lsulfonyl, p-dodecylsulfonyl,
p-methoxysulfonyl), ureido groups having 1 to 24 carbon atoms (e.g. 3-methylureido, 3-phenylureido, 3.3-dimethylamino, 3-tetradecylureido), sulfur groups having 0 to 24 carbon atoms moylamino group (e.g. N,N-dimethylsulfamoylamino), alkoxycarbonylamino group having 2 to 24 carbon atoms (e.g. methoxycarbonylamino, isobutoxycarbonylamino, dodecyloxycarbonylamino), nitro group, number of carbon atoms 1-24 heterocyclic groups (e.g. 4-pyridyl, 2-thienyl, phthalimide, octadecylsuccinimide), cyano groups, acyl groups having 1-24 carbon atoms (e.g. acetyl, benzoyl, dodecanoyl), 1-24 carbon atoms acyloxy groups (e.g. acetoxy,
benzoyloxy, dodecanoyloxy), alkylsulfonyloxy groups having 1 to 24 carbon atoms (e.g. methylsulfonyloxy, heisubylsulfonyloxy) or arylsulfonyloxy groups having 6 to 24 carbon atoms (e.g. p-)luenesulfonyl oxy, p-dodecylphenylsulfonyloxy).

In general formula [I], l is preferably an integer of 1 or 2.

In general formula [I], , bromine, iodine), 1 to 24 carbon atoms
a heterocyclic group bonded to the coupling active position at the nitrogen atom of
Aryloxy group having 6 to 24 carbon atoms, 6 carbon atoms
~24 arylthio groups (e.g. phenylthio, p-t
butylphenylthio, p-chlorophenylthio, p-carboxyphenylthio), acyloxy groups having 1 to 24 carbon atoms (e.g. acetoxy, benzoyloxy, dodecanoyloxy), alkylsulfonyloxy groups having 1 to 24 carbon atoms (e.g. methylsulfonyloxy, butylsulfonyloxy, dodecylsulfonyloxy), arylsulfonyloxy groups having 6 to 24 carbon atoms (e.g. benzenesulfonyloxy, p-chlorophenylsulfonyloxy), or heterocyclic oxy groups having 1 to 24 carbon atoms (e.g. 3-pyridyloxy, 1 phenyl-1,2
, 3,4-tetrazol-5yloxy), and more preferably a heterocyclic group or an aryloxy group bonded to the coupling active position through a nitrogen atom.

When X represents a nitrogen ring group bonded to the coupling active position with a nitrogen atom, X may contain a heteroatom selected from oxygen, sulfur, nitrogen, phosphorus, selenium, and tellurium in addition to the nitrogen atom. A 5- to 7-membered optionally substituted monocyclic or fused heterocyclic ring, such as succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole,
l.

2.4-) lyazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazolidine-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione,
imidazolidin-2-one, oxazolin-2-one,
Thiazolin-2-one, benz imidacillin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidacillin-5-one, indoline-2,3-one dione, 2.6-
Cyoxypurine, parabanic acid, 1.2゜4-triacylidine-3,5-dione, 2-pyridone, 4-pyridone,
Examples include 2-pyrimidone, 6-pyridazone, 2-pyrazone, etc., and these heterocyclic groups may be substituted. Examples of substituents include hydroxyl group, carboxyl group, sulfo group, amino group (e.g. amino, N-methylamino, N.

In addition to N-dimethylamino, N,N-diethylamino, anilino, pyrrolidino, piperidino, morpholino), there are substituents listed as examples of R5 above.

When X represents an aryloxy group, X has 6 carbon atoms
-24 aryloxy groups, and when X is a heterocyclic group, it may be substituted with a group selected from the above-mentioned substituent groups. Substituents include carboxyl group, sulfo group,
Preferred are a cyano group, a nitro group, an alkoxycarbonyl group, a halogen atom, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkyl group, an alkylsulfonyl group, an arylsulfonyl group, or an acyl group.

Next, examples of substituents particularly preferably used in the present invention will be described for each of the above-mentioned substituents R+, R2, Rs and X.

In general formula (13), R1 is particularly preferably a 2- or 4-alkoxyaryl group (e.g. 4-methoxyphenyl, 4-butoxyphenyl, 2methoxyphenyl) or a t-butyl group, most preferably a t-butyl group. .

In general formula [1], R2 is particularly preferably a methyl group, ethyl group, alkoxy group, aryloxy group or dialkylamino group, most preferably a methyl group, ethyl group, alkoxy group, aryloxy group or dimethylamino group. .

In the general formula [■], %R3 is particularly preferably an alkoxy group, a carbonamide group or a sulfonamide group.

In the general formula [■], X is particularly preferably a heterocyclic group or an aryloxy group bonded to the coupling active position through a nitrogen atom.

When X represents the above-mentioned heterocyclic group, X is preferably represented by the following general formula [■].

General formula [■] °·Z-' 4 In the general formula [■], Z represents -0-C-Rs Rs 6 Rs R. Here, R4, Rs, Re and R9 are water i
i-child represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or an amiki group, and R8 and R1 are a hydrogen atom, an alkyl group, an aryl group, or an alkylsulfonyl group. represents a group, an arylsulfonyl group, or an alkoxycarbonyl group, and R1° and R
o represents a hydrogen atom, an alkyl group or an aryl group.

RIO and Ro may be combined with each other to form a benzene ring. R1 and Rs, Rs and Rs, R- and R? or R4
and R. may be combined with each other to form m (eg, cyclobutane, cyclohexane, cyclohebutane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by the general formula [11], particularly preferred are those in which Z is represented by the general formula (n).

The total number of carbon atoms in the heterocyclic group represented by general formula (Il) is 2 to 24, preferably 4 to 20, more preferably 5 to
It is 16. Examples of the *syh group represented by the general formula (I[] are succinimide group, maleimide group, butylimide group, l-methylimidazolidine-2,4-dione-3-yl group, l-benzylimidazolidine-2, 4-
Dione-3-yl group, 5,5-dimethyloxazolidin-2゜4-dione-3-yl group, 5-methyl-5-propyloxazolidin-2,4-dione-3-yl group, 5
, 5-dimethylthiazolidine-2,4-dione-3-yl group, 5,5-dimethylimidazolidine-2,4-dione-3-yl group, 3-methylimidazolidinetrione-
1-yl group, 1.2゜4-triacylidin-3,5-dione-4-yl group, 1-methyl-2-phenyl-1,2
, 4-triacylidin-3,5-dione-4-yl group,
1 benzyl-2-phenyl-1,2,4-)lyasiridin-3,5-dione-4-yl group, 5-hexyloxy-1-methylimidazolidine-2゜4-dione-3-yl group, 1 -benzyl-5-ethoxyimidazolidine-2
, 4-dione-3-yl group, and l-benzyl-5-dodecyloxyimidazolidin-2,4-dione-3-yl group.

Among the above heterocyclic groups, imidazolidine-2,4-dione-3-yl group (e.g. l-benzyl-imidazolidine-
2,4-dione-3-yl group) is the most preferred group.

When X represents an aryloxy group, 4-carboxyphenoxy group, 4-methylsulfonylphenoxy group, 4-
(4-benzyloxyphenylsulfonyl) phenoxy group, 4-<4-hydroxyphenylsulfonyl) phenoxy group, 2-chloro-4-<3-90 rho 4-hydroxyphenylsulfonyl) phenoxy group, 4-methoxycarbonylphenoxy group, 2-chloro-4-methoxycarbonylphenoxy group, 2-acetamido-4-methoxycarbonylphenoxy group, 4-isopropoxycarbonylphenoxy group, 4-cyanophenoxy group, 2-C
N-(2-hydroxyethyl)carbamoyl]phenoxy group, 4-nitrophenoxy group, 2.5-dichlorophenoxy group, 2.3゜5-trichlorophenoxy group, 4-
Methoxycarbonyl-2-methoxyphenoxy group, 4-
(3-carboxypropanamide) phenoxy group is the most preferred example.

The coupler represented by the one-shell formula [I] may form a dimer or a multimer of more than two molecules bonded to each other via a substituent R9, 2 or a group having a valence of two or more. In this case, the number of carbon atoms in each substituent group may be outside the range specified above.

-G When the coupler represented by formula [I] forms a multimer, a typical example is a single or copolymer of an addition polymer ethylenically unsaturated compound (yellow color-forming monomer) having a yellow dye-forming coupler residue. In this case, the multimer contains a repeating unit represented by the following general formula (111), and the multimer may contain one or more types of yellow coloring repeating units represented by the general formula [I], A copolymer containing one or more non-color-forming ethylene type monomers as a copolymerization component may also be used.

General formula [In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, A represents a -CONH-1-CO rho or a substituted or unsubstituted) unilene group, and B represents a Represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, L is -CON)I-1-NHCON
H-1-NHCOO--NHCO-1-0CONH--
NH-1C00-~oco--co-1-o--s--
So.

-N) ISO, - or -Sro2NH-, aS
bSc indicates 0 or 1. Q represents a yellow coupler residue represented by the general formula [1] with two molecules removed.

As the multimer, a copolymer of a yellow color-forming monomer represented by a coupler unit of general formula [111] and the following non-color-forming ethylene-like monomer is preferred.

Examples of non-color-forming ethylene monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-Chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Amides or esters derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-
Butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, 1so-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate , ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylatrile,
Aromatic vinyl compounds (such as styrene and its derivatives, such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (such as vinyl ethyl ether), maleic esters, N-vinyl-2-pyrrolidone, N-
Examples include vinylpyridine and 2- and -4-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more kinds of the non-color-forming ethylene monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the general formula 1 [1]
The ethylenically unsaturated monomer to be copolymerized with the vinylic monomer corresponding to It can be selected so that its compatibility with gelatin, its flexibility, thermal stability, etc. are favorably influenced.

The yellow polymer coupler used in the present invention is -
It can also be made by dissolving a lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the Takeshi formula (Iff) in an organic solvent and dispersing it in the form of a latex in an aqueous gelatin solution. Alternatively, it may be produced by direct emulsion polymerization.

U.S. Patent No. 3,45 discloses a method for emulsifying and dispersing lipophilic polymer couplers in an aqueous gelatin solution in the form of latex.
No. 1.820, and U.S. Pat. No. 4,08 for emulsion polymerization.
The methods described in No. 0,211 and No. 3,370.952 can be used.

Specific examples of the yellow dye-forming couplers R3 and X represented by the general formula [13] are shown below, but the present invention is not limited thereto.

A specific example of X is shown below.

(1) <2> (3) (4) (5) (6) (7) (8) (9) Shini (11) (12) (13) ■ (14) mouth (18) (20) (21) (15) (17) (22) (23) (24) A specific example of R1 is shown below.

(25) CH.

NtlCOCHC-)11t-n-NHCOC)IC)ICH,C,)1. -tCaH+
5 (CHz) 2cHcH2cJs-t (36) (37) CL C1゜01 Mushroom-NHCOCHffCHCO口C8゜-NHSOa [IJas-n (38) (39) (41> [H3 COOC1J-s COOCHC mouth 0C12H2s ~ C0NHC+J2m (42 ) (43) (44) -CON)I (CL)30 [IJ25-NHCOC,
S)1. .

(47) (48) Specific examples of the yellow dye-forming coupler represented by the general formula [11] are listed below for each substituent in the structural formula.

In the table, the numbers in (>) represent the numbers assigned to the specific examples of X and R5, and the numbers in [] represent the substitution positions on the anilide group.

The coupler of the present invention may be used alone, or may be used in combination of two or several kinds, or may be used in combination with a known yellow dye-forming coupler.

The couplers of the present invention can be used in any layer of the light-sensitive material, but are preferably used in the light-sensitive silver halide emulsion layer or a layer adjacent thereto, most preferably in the light-sensitive silver halide emulsion layer.

The coupler of the present invention can be synthesized by conventionally known synthesis methods.
The synthesis method described in No. 23047 can be mentioned.

The amount of the coupler of the present invention used in the light-sensitive material is 1X10-' mol-10-2 mol per 1 m'', preferably 1X10-' mol to 5XIO-' mol, more preferably 2X10-' mol-101 mol. It is.

Next, the compound represented by the general formula [:M-II) will be explained in detail below.

General Formula [In General Formula 1: M-113, Rho represents a hydrogen atom or a substituent. Y represents a hydrogen atom or a leaving group, and particularly preferably a halogen atom or an arylthio group. ZaSZb
and Zc represent methine, substituted methine, =N- or -NH-, one of the Za-Zb bond and the 2b-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is part of an aromatic compound. This includes the case where R1° or Y forms a dimer or more multimer, and when ZaSZb or Zc is a substituted methine, the case where the substituted methine forms a dimer or more multimer.

The compound represented by formula -a [M-I11 is known as a pyrazoloazole coupler. Among the pyrazoloazole couplers of the present invention, U.S. Patent No. 4,500,63
Imidazo [I.

2-b] Pyrazoles are preferred, as described in U.S. Pat. No. 4.54
Pyrazolo(1,5-b)N, 2.
4]) Riazole is particularly preferred.

In addition, a branched alkyl group as described in JP-A-61-65245 is 2.3% of the pyrazolotriazole ring.
or a pyrazolotriazole coupler directly linked to the 6-position, a pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group containing a sulfonamide group in the molecule as described in JP-A No. 61-6i5246; It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position, such as those described in European Patent Publication Nos. 226.849 and 294.785.

Specific examples of the pyrazoloazole coupler represented by the general formula [M-11] are listed below, but the present invention is not limited thereto.

In the present invention, Mn, Cu, and Zn5Cct are added to internal latent image type silver halide grains that have not been fogged in advance.

Contains at least one member selected from the group consisting of Pd, Bi, and metals belonging to Group Ⅰ of the periodic table. Mn%Cu, Zn on internal latent image type silver halide grains that have not been fogged in advance
It is known from US Pat. No. 4,395,478 that the generation of re-inverted negative images can be suppressed by incorporating at least one member from the group consisting of 5Cds Pds Bi or metals belonging to Group 1 of the periodic table. However, nothing is mentioned about the effect of the present invention when the yellow coupler of the present invention and the pyrazoloazole magenta coupler are used in combination.

Mn%Cu, Zn, Cd, Pd, Bi contained in the internal latent image type silver halide grains which are not fogged in advance of the present invention
Alternatively, the amount of the metal belonging to Group U of the periodic table is preferably 10-9 to 1O-2 mol per mol of silver halide,
More preferably 104 to 10-3 mol.

Among the metals mentioned above, particular preference is given to using lead, iridium and bismuth.

There is no particular restriction as to where the metal is incorporated in the unfogged internal latent image type silver halide emulsion used in the present invention, but in the internal latent image type emulsion having a core/shell type structure, , is preferably built into the core.

When these metals are mixed with a silver ion solution and an aqueous halogen solution to form silver halide particles, the metal ions can be made to coexist in the form of an aqueous solution or an organic solvent solution and incorporated into the particles. Alternatively, after forming the particles, metal ions are added in the form of an aqueous or organic solvent solution; 1. Thereafter, it may be further covered with silver halide.

A method of incorporating these metals is described in U.S. Patent No. 3.7.
It is described in No. 61.276, No. 4.39-5.478, and JP-A-59-216136.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surfaces of silver halide grains are not fogged in advance and latent images are mainly formed inside the grains. However, more specifically, a silver halide emulsion is deposited on a transparent support in a certain amount (0.5~
3 g/m'') and add 0.01 to 10
When exposed for a fixed time of seconds and developed for 5 minutes at 18°C in the following developer A (internal type developer), the maximum density measured by the usual photographic density measuring method is the same as above.
Il! Preferably, the emulsion has a density at least 5 times greater than the maximum density obtained when a silver halide emulsion exposed in the same manner with a cloth is developed in the following developer B (surface type developer) at 20°C for 6 minutes. , more preferably at least 10 times greater concentration.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
5gKI
O, add 5g water
1i Surface developer B Metol 2.5g L-ascorbic acid 10gNa BO2.4
Add 35 g of Ha O, 1 g of KBr, and water to make an internal type emulsion.
Conversion type silver halide emulsions described in the specifications in U.S. Patent Nos. 3,761,276 and 3,85
No. 0,637, No. 3,923.513, No. 4,035
．． No. 185, No. 4,395.478, No. 4,504,
No. 570, JP-A-52-156614, JP-A No. 55-12
No. 7549, No. 53-50222, No. 56-2268
No. 1, No. 59-208540, No. 60-107641
No. 61-3137, patent application No. 61-32462,
Research Disclosure Magazine Aim 23510 (19
The core/shell type silver halide emulsion described in the patent disclosed in P2S5 (published in November 1983) can be mentioned.

The shapes of the silver halide grains used in the present invention include regular crystals such as cubes, octahedrons, dodecahedrons, and tetradecahedrons, irregular crystal shapes such as spherical shapes, and length/thickness. The ratio value is 5
In particular, an emulsion in which 8 or more tabular grains account for 50% or more of the total projected area of the grains may be used. It may also be a composite of these various crystal forms, or an emulsion made from a mixture thereof.

The composition of silver halide includes silver chloride and silver bromide mixed silver halide, and the silver halide preferably used in the present invention does not contain silver iodide or contains less than 3 mol% of salt (
silver bromide, silver chloride or silver bromide.

The average grain size of silver halide grains (in the case of spherical or nearly spherical grains, the grain diameter is taken as the grain size, and in the case of cubic grains, the length is taken as the grain size, respectively, and expressed as an average based on the projected area) is 1.5 μm or less. O.lam or more is preferred, and particularly preferred is 1.2 μm or less and 0.2 μm or more. Particles! **lyo fi<a mo wide, a, i awa,
6. Good, in order to improve elegance, sharpness, etc., 90% of all particles are within ±40% of the average particle size, preferably within ±30%, most preferably within ±20% of the average particle size in terms of particle number or weight. As mentioned above, it is particularly preferable to use a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution of 95% or more in the present invention.

In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes or multiple types of monodisperse silver halide emulsions with the same size but different sensitivities are used in an emulsion layer having substantially the same color sensitivity. The particles can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The silver halide emulsion used in the present invention can be chemically sensitized inside or on the grain by sulfur or selenium sensitization, reduction sensitization, noble metal sensitization, etc. alone or in combination. For detailed examples, see Research Disclosure magazine Na17643III (published December 1978).
It is in the patent described on page 23 etc.

The photographic emulsions used in the present invention are spectrally sensitized with photographic sensitizing dyes in a conventional manner. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. Detailed examples can be found in patents such as those described in Research Disclosure magazine Na17643-rV (published December 1978), pages 23-24.

The photographic emulsion used in the present invention may contain an antifoggant or a stabilizer for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. For detailed examples, see Research Disclosure Magazine 1k17643-V.
l (published December 1978) and E, J, 81r
“Author = Stabilization of Photo
graphic 5ilverHailde em
ulsion” (Focal Pleas), 19
It is written in the 1974 edition.

In the present invention, various color couplers can be used in combination to directly form a positive color image. A color coupler is a compound that generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized form of an aromatic primary amine color developer, and is itself a substantially non-diffusible dye. Preferably, it is a compound. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open chain or 'ass ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in combination in the present invention can be found in Research Disclosure magazine, k17643 (published December 1978), p.25.
, (1)-ri section, No. 118717 (issued in November 1979) and Japanese Patent Application No. 61-32462, and the patents cited therein.

Card couplers for correcting unnecessary absorption in the short wavelength range of the generated dyes, couplers whose coloring dyes have appropriate diffusivity, colorless couplers, and DIR couplers that release a development inhibitor upon coupling reaction. or polymerized couplers can also be used.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

A color antifogging agent or a color mixing inhibitor can be used in the light-sensitive material of the present invention.

Representative examples of these are JP-A-62-215272 No. 185~
It is described on page 193.

A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. A typical example of a compound is JP-A No. 6
Examples include those described in No. 2-215272, pages 121 to 125.

The photosensitive material of the present invention includes a cross-agent for preventing irradiation and halation, an ultraviolet absorber, a plasticizer, a fluorescent whitening agent, a matting agent, an air fog prevention agent, a fabric auxiliary agent, a hardening agent, and a charging agent. It is possible to add inhibitors, slip property improvers, etc. Typical examples of these additives are listed in Research Disclosure magazine k17643 ■~x■ (published December 1978)
p25-27, and 18716 (November 1979)
Published in May), pages 647-651.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one edge-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred layer arrangement order is red-sensitive, green-sensitive, blue-sensitive from the support side, or edge-sensitive, red-sensitive, blue-sensitive from the support side. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same color sensitivity. . Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the edge-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation agent,
It is preferable to appropriately provide auxiliary layers such as a back layer and a white reflective layer.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure Magazine 17643, Section V (2).
Published in December 1978) on page 28, European Patent No. 0,102,253, and JP-A-61-97655.
It is coated on the support described in No. Also, Research Disclosure Magazine N117643 Section XV p28-291.
: The coating method described can be used.

The present invention can be applied to various color photosensitive materials.

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing images on CRTs. The present invention also applies to Research Disclosure magazine 11h1712.
3 (published in July 1978), it can also be applied to black-and-white photosensitive materials using a mixture of three color couplers.

The fogging treatment of the present invention is carried out by the following "photofogging method" and/or "chemical fogging method". The entire surface exposure in the "light fogging method" of the present invention, that is, the fogging exposure is performed during the image ms post-light development process and/or the development process. The imagewise exposed light-sensitive material is immersed in a developer solution or a pre-bath of the developer solution, or is taken out from the solution and exposed before drying, but it is most preferable to expose the material in the developer solution.

As a light source for fogging exposure, a light source within the wavelength range to which the photosensitive material is sensitive may be used, and generally any of fluorescent lamps, tungsten lamps, xenon lamps, sunlight, etc. can be used.

These specific methods are described, for example, in British Patent No. 1,151.
No. 363, Special Publication No. 45-12710, No. 45-127
No. 09, No. 58-6936, JP-A No. 48-9727, No. 56-137350, No. 57-129438,
No. 58-62652, No. 58-60739, No. 58
-70223 (corresponding U.S. Patent No. 4,440°851)
, No. 58-120248 (corresponding European Patent No. 89101A
2) etc.

Photosensitive materials sensitive to all wavelength ranges, such as color photosensitive materials, are disclosed in Japanese Patent Application Laid-open No. 56-137350 and No. 58-702.
A light source with high color rendering properties (as close to white as possible) as described in No. 23 is preferable.The illuminance of the light is 0.01 to 200.
0 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. For light-sensitive materials that use emulsions with higher sensitivity, exposure at lower illuminance is preferable. The illuminance may be adjusted by changing the luminous intensity of the light source, or by changing the exposure using various filters, the distance between the photosensitive material and the light source, or the angle between the photosensitive material and the light source. Further, the illuminance of the fogging light can be increased continuously or stepwise from low illuminance to high illuminance.

It is preferable to immerse the light-sensitive material in a developer solution or its pre-bath solution, and irradiate the material after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material. The time from penetration into the liquid to light fogging exposure is as follows:
Generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, more preferably 10 seconds to 30 seconds.

The exposure time for fogging is generally 0.01 seconds to 2 minutes.
Preferably 0.1 seconds to 1 minute, more preferably 1 second to 4 minutes
It is 0 seconds.

In the present invention, the nucleating agent used in the so-called "chemical fogging method" can be contained in the light-sensitive material or in the processing solution for the light-sensitive material. Preferably, it can be incorporated into the photosensitive material.

Here, the term "nucleating agent" refers to a substance that acts during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance to directly improve the formation of a positive image. In the present invention, fogging using a nucleating agent is particularly preferred.

When incorporated into a light-sensitive material, it is preferably added to the internal bath type silver halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to other layers, e.g. , an intermediate layer, an undercoat layer or a back layer.

When the nucleating agent is added to the processing solution, it may be contained in the developer solution or a low pH prebath as described in JP-A-58-178350.

Furthermore, two or more types of nucleating agents may be used in combination.

Nucleating agents that can be used in the present invention include, for example:
"Research Disclosure" magazine, N112253
4 (January 1983) pp. 50-54, same magazine, N111
5162 (November 1976) pp. 76-77, same magazine, k
23510 (November 1983), pages 346-352, quaternary heterocyclic compounds, hydrazine compounds, etc. may be mentioned. In particular, nucleating agents represented by the general formula [N-■] or [N-4] described in JP-A-64-59351 are preferred.

As the nucleation promoter for promoting the action of the nucleation agent that can be used in the present invention, tetrazaine having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group is used. Examples include denes, triabindenes, pentazaindenes, and the compounds described in JP-A-63-106656, pages 5 to 16.

The nucleation accelerator can be contained in the light-sensitive material or in the processing solution, but it can be contained in the internal latent image type silver halide emulsion and other hydrophilic colloid layers (intermediate layer, protective layer, etc.) in the light-sensitive material. It is preferable to contain it. Particularly preferred is a layer in or adjacent to a silver halide emulsion.

The amount of nucleation accelerator added is 10-" per mole of silver halide.
~10-2 mol is preferred, more preferably 10-'~
It is 1O-2 mole.

Further, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, the amount is preferably 10 to 10-3 mol, more preferably 10-7 to 10-' mol per 1Il.

Moreover, two or more kinds of nucleation accelerators can also be used together.

Known photographic additives that can be used in the present invention include the aforementioned Research Disclosure N117643 (January 1978).
(February) and N111879 (It month), and are summarized in the table below.

Additive type RO17643 1 Chemical sensitizer page 23 2 Sensitivity enhancer 3 Spectral sensitizer page 23-24 Supersensitizer 4 Whitening agent page 24 5 Antifoggant, page 24-25 Stabilizer 6 Light absorber , pages 25-26 Filter dyes, UV absorbers 7 Anti-stain agents page 25 Right grip 8 Dye image stabilizers page 25 9 Hardeners page 26 10 Binders page 26 11 Plasticizers, lubricants page 27 12 Coating aids, 26 ~27 pages 716 (19 Relevant parts RD18716 Page 648 right column Same as above Page 648 Right column ~ Page 649 Right column Page 649 Right column Page 649 Right column ~ Page 650 Left column Page 650 Left to right column Page 651 Left column Same as above Page 650 Right column Same as above Surfactant 13 Static Page 27 Same as above Inhibitor In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers may be formed on a flexible support such as plastic film, paper, or cloth commonly used in photographic light-sensitive materials. It is applied to a rigid support such as glass, ceramic, metal, etc. Useful flexible supports include cellulose nitrate, cellulose acetate, cellulose acetate complex, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc. These include films made of semi-synthetic or synthetic polymers, papers coated with or laminated with baryta layers, or α-olefin polymers (eg, polyethylene, polypropylene, ethylene/butene copolymers), etc.

The support may be colored using dyes or pigments.

Various known methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used to coat the silver halide photographic emulsion layer and other hydrophilic colloid layers.

In addition, as necessary, US Patent Nos. 2,681,294, 2,761,791, 3,526,528,
Multiple layers may be applied simultaneously by methods such as those described in No. 08947.

Furthermore, when the photosensitive material of the present invention is used for color diffusion transfer, a dye developer can be used as a coloring material.
The coloring material itself is alkaline (in the developer) and non-diffusible (
non-migratory), but the result of development is a diffusive color! ! It is advantageous to use colorants of the type that release (or their precursors). Diffusible dye-releasing coloring materials (DRR compounds) include couplers and redox compounds that release diffusible dyes, and these are used not only for the color diffusion transfer method (wet method) but also for example It is also useful as a coloring material for heat-developable sensitive materials (dry method) as described in No. 58543.

When the photosensitive material of the present invention is used in a color diffusion transfer method, the photographic aperture may be coated integrally on the same support on which the image-receiving layer is coated, or may be coated on a separate support. It may be coated on top.

Further, the silver halide photographic emulsion layer (sensitivity S) and the image receiving layer (image receiving element) may be provided in a combined form as a film unit, or may be provided as separate and independent photographic materials. Further, the form of the film unit may be one that is integrated throughout the process of exposure, development, and viewing of the transferred image, or may be of a type that is peeled off after development, but the latter type is preferred for the present invention. is more effective.

The present invention can be applied to various photographic materials.

For example, typical examples include color reversal film for slides or television, color reversal paper, and instant color film. It can also be applied to full-color copying machines and color hard copies for storing CR7 images. The present invention also applies to “Research Disclosure” Magazine 17123 (1978
It can also be applied to black-and-white photosensitive materials using a mixture of three-color couplers, such as those described in J.

The color developer used for developing the photosensitive material of the present invention is as follows:
Preferred is an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component.

As this color developing agent, aminophenol compounds are also useful, but p-fuynylenediamine compounds are preferably used, and a representative example thereof is 3-methyl-4
-amino-N,N-diethylaniline, 3-methyl-4
-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Methanesulfonamidoethylaniline, 3-methyl-4
-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

Color developers may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds, or fogging agents. It generally contains an inhibitor. In addition, as necessary, hydroxylamine, diethylhydroxylamine, sulfites, hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (l,4-diazabicycloC2,2,2)
Various preservatives such as octane) @, Koyo Range Recall,
Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, 1-phenyl-3-pyrazolidone. auxiliary developing agents, viscosity-imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, etc. Acetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-
11-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine-N.

Representative examples include N,N',N'-tetramethylenephosphonic acid, ethylene diamine di(0-hydroxyphenylacetic acid NI), and salts thereof.

The pH of these color developers is generally 9 to 12, preferably 9.5 to 11.5. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but it is generally less than tX per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be reduced to less than 300. It can also be done. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be carried out simultaneously with the fixing process, or may be carried out separately.

Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As a bleaching agent, for example, iron (III
), cobalt (III), chromium (Vl), jl
Compounds of polyvalent metals such as (II), peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide: dichromate; organic complex salts of iron(1) or cobal);
For example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, l,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; Persulfates; bromates; permanganates; nitrobenzenes and the like can be used.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process varies widely depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is Jour
nalor the 5ociety of Moti
on Picture and Television
Bnginaers Vol. 64, P, 248-253 (1
It can be determined by the method described in May 955 issue).

The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Laid-Open Nos. 57-8,543 and 58-14.8
All known methods described in No. 34, No. 60-220.345 can be used.

Various hand-rate agents and antifungal agents can also be added to this stabilizing bath. The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

Various processing solutions in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, and conversely, lower temperatures can improve image quality and stability of processing solutions. can be achieved.

The smaller the amount of replenishment in each treatment step, the better. The amount of replenisher is preferably 0.1 to 50 times, more preferably 3 to 3 times, the amount of prebath brought in per unit area of the photosensitive material.
It is 0 times.

A positive image can be directly obtained from the photographic material containing an internal bath type emulsion of the present invention by developing it using a surface developer. A surface developer is one in which the development process is substantially induced by latent images or fog nuclei on the surface of silver halide grains.

Although it is preferable not to include a silver halide solubilizer in the developer, as long as the internal latent image does not substantially contribute to the completion of development by the surface development centers of the silver halide grains,
Silver halide solubilizers (eg sulfites) may also be included.

The developer contains alkaline agents and! One buffering agent may include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, 13-sodium phosphorus, sodium metaborate, and the like. The content of these agents is
The developer paste H is 9 to 13, preferably the pH is 10 to 11.
Choose 2.

The developer also contains, for example, benzimidazoles, such as 5-
Nitrobenzimidazole; it is advantageous to include benzotriazoles, such as benzotriazole, 5-methyl-benzotriazoles, compounds commonly used as antifoggants.

When the photosensitive material of the present invention is used for a film unit for diffusion transfer method, it is preferably processed with a viscous developer.

This viscous developer is a liquid composition containing the processing components necessary for developing the silver halide emulsion (and the format of the diffusion transfer dye image), and the solvent is mainly water, other methanol,
Hydrophilic solvents such as methyl cellosolve may also be included.

Preferably, the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose.

These polymers may be present in the treatment composition at room temperature of 1 poise or more;
Preferably, it is used to give a viscosity of about 500 to 1000 poise.

The above treatment composition is described in US Pat. No. 2,543.181;
2,643,886, 2,653゜732, 2,723.051, 3,056.491, 3
It is preferable to use the container by filling it into a container that can be ruptured by pressure, such as those described in Japanese Patent Application No. 056,492, No. 3, 152.515, and the like.

Example-1 Hereinafter, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited only to these examples.

Emulsions C-1 to C-6 used in Examples were prepared as follows.

C-iI Aqueous solution of potassium bromide and silver nitrate at 0.1 per tB mole
Add 5 g of 3,4-dimethyl-1,3-thiazoline-2-thione to an aqueous gelatin solution without vigorous stirring.
They were added simultaneously at 5°C over a period of about 15 minutes to obtain an octahedral monodispersed silver bromide emulsion with an average grain size of 0.35 μm. For this emulsion! Chemical sensitization was carried out by adding 5 ml of sodium thiosulfate and 8 m of chloroauric acid (tetrahydrate) per mole of II and heating at 75° C. for 80 minutes. Using the thus obtained silver bromide grains as cores, they were further grown in the same precipitation environment as the first time, to finally obtain an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7 μm. The coefficient of variation in particle size was approximately 10%.

This emulsion contains 1.0% per mole of silver. 5111g of sodium thiosulfate and 1.5cm of gold chloride! Add (tetrahydrate salt) and 60'
A chemical sensitization treatment was performed by heating at C for 60 minutes to obtain an internal latent image type halogenated emulsion C-1.

Emulsion C-1 was prepared in exactly the same manner as Emulsion C-1, except that the metal compounds shown in Table 1 were added to each emulsion during core formation.
2 to C-4 were prepared. The amount added is the final core/
The amount added per mole of shell silver bromide is shown.

Emulsion C-5 was prepared in exactly the same manner as Emulsion C-3 except that a metal compound was added during shell formation.

Table 1 Preparation of sample 101 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic material was prepared by coating the following layers from layer 1 to 14 on the front side of the film (0 micron) and layer 15 to layer 16 on the back side.

Titanium oxide (4 g/m
') as a white pigment, and a trace amount of ultramarine (0.003 g/m2) as a dye for bluing (the chromaticity of the surface of the support is L'', 88.0°O, 20, - in b1 system). 0,7
It was 5. ).

(Photosensitive layer composition) Below, 1=component and coating amount<g/d unit) is shown. Regarding silver halide, the coating amount is shown in terms of bells.

The emulsions used in each layer were prepared according to the manufacturing method of emulsion C-t. However, the emulsion for the 14th layer was a Lippmann emulsion that was not surface chemically sensitized.

11 layers (antihalation layer - black colloidal silver...0.10 gelatin...0.70 second
Layer (middle layer) Gelatin...0.70'
jlJ3 layer (low sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 0.25 μ, size distribution coefficient of variation 18%, octahedral) ...0.04 Silver chlorobromide spectrally sensitized with red sensitized color # (EXS-1, 2, 3) (silver chloride 5 mol%, average particle size 0.4
0μ, size distribution 10%, octahedron)...0.0
8 Gelatin...1.00 cyan coupler IExc-1,2,3 l:1:0.2)
...0.30 anti-fading agent (
Cp d -1,2,3,4 equivalent)...0.1
8 Anti-stin agent (Cp d-5) 0.0
03 force puller dividing medium (Cpd-6>・・・0.0
3 coupler solvent (Solv-1, 2, 3 equivalents)...
...0.12 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3) (average grain size 0.60μ, size distribution 15%)
, octahedron) ・Old...0, 14 gelatin
...1.00 cyan coupler (
ExC-1, 2, 3 1:l:0.2)
・Old...0.30 week color inhibitor (Cp d -1,2
, 3, 4 equivalents...0,18 Coupler dispersion medium (Cpd-6)...0.03 Coupler solvent (Solv-1, 2, 3 equivalents)...・
0.12 5th layer (intermediate layer) Gelatin...1.00 Color mixing inhibitor (Cpd-7)...O, Oa color mixing inhibitor solvent (Solv-4, 5 equivalent)・・・－・・0
．． 16 Polymer latex (Cpd-8) ...0.10 6th layer (low sensitivity green sensitive layer) Silver bromide (spectral sensitized with green sensitizing dye (ExS-4)
Average particle size 0.25μ, size distribution 8%, octahedral)
...0.04 green sensitizing dye (Ex
Silver chlorobromide spectrally sensitized with S-4) (silver chloride 5 mol%,
Average particle size 0.40μ, size distribution 10%, octahedral)...0.06 Gelatin...0.80 Magenta coupler (ExM-1>...0.11 Antifading agent (equal amount of Cp d -9,26)...
・0.15 stain inhibitor (Cpd-10111, 12, 13 at 1
0:7:7:1 ratio) ...--0,025 force puller dispersion medium (Cpd-6) = 0.05 coupler solvent (S
olv-4,6 equivalent)...0.15 7th layer (high sensitivity green sensitive layer) Silver bromide spectrally sensitized with green sensitizing color Jl (ExS-4) (average grain size 0.65μ, size distribution 16%, octahedron) ...0.10 gelatin
...0.80 Magenta coupler (ExM-1) ...0.11 Antifading agent (Cp d -9,26 equivalent) ...
0.15 Anti-staining agent (Cpd-10, 11, 12, 13 at 1
0:7:? :1 ratio> ...0.025 force puller dispersion medium (Cp d -6) ...0.05 coupler solvent (Solv-4,6 etc. 1i) ... 0.
15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloidal silver (particle size 100A) Gelatin color mixture prevention agent (Cp d -7) ......Ol ...・・0゜・・・・・・0゜2 0 3 Color mixture prevention agent solvent (Solv4.5 equivalent)・・・・・・0
．． 10 Polymer latex (Cpd-8) ...0.0? ! ! 10th layer (intermediate layer) 11th layer (low sensitivity blue sensitive layer) same as the 5th layer Silver bromide spectrally sensitized with blue sensitizing dye (ExS-5, 6) (average grain size 0.40μ, size Distribution 8%, octahedral> ...0.07 blue sensitizing dye (E
Silver chlorobromide (silver chloride 8 mol%, average grain size 0.60μ, size distribution 11
%, octahedron)...0.14 Gelatin...0.80 Yellow coupler (ExY-1)...0.35 Antifading agent (Cpd-14)... ...0.10
Stain inhibitor (Cp d -5,15 in a 1:5 ratio)
...0.007 Force puller dispersion medium (Cp d -6) ...0.05
Coupler solvent (Solv-2)...0. IO 12th layer (high sensitivity blue sensitive layer) Blue sensitized color, silver bromide spectrally sensitized with I (ExS-5,6> (average grain size 0.85μ, size distribution 18%,
Octahedron) ...0.15 gelatin
...0.60 yellow coupler (
ExY-1) ...0.30 Antifading agent (Cpd-14) -----...0. 1
0 stain inhibitor (Cpd-5,15 in 1:5 ratio)
・・・・・・0.007 Force Blur dispersion medium (Cpd-6) ・・・0.05 Coupler solvent (SolV-2) ・・・0.10 13th layer (ultraviolet absorption layer ) Gelatin...1.00 Ultraviolet absorber (Cp d -2,4,16 equivalent)...
...0.50 Color mixing prevention agent (Cpd-7, 17 equivalent) ...0.03 Dispersion medium (Cpd-6) ...0.02
Ultraviolet absorber solvent (Solv-2, 7 equivalent)...
・0.08 Anti-irradiation dye (Cpd-18, 19, 20
, 21, 27 in a 10:10:13:15:20 ratio)
・・・・・・0.05 14th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average size 0.1
μ) ...0.03 Acrylic modified copolymer of polyvinyl alcohol (molecular weight 50.0
00) Equivalent amount of 0.01 polymethyl methacrylate particles (average particle size 2.4μ) and silicon oxide (average particle size 5μ)
...0.05 gelatin ...
...1.80 Gelatin hardening agent (H-1, H-2 equivalent)
...0.18 15th layer (back layer) Gelatin ...2.50 Ultraviolet absorber (Cp d -2,4,16 equivalent) ...
・・0.50 Dye (Equivalent amount of Cpd-18, 19, 20, 21, 27)
・・・・・・0.06 16th layer (
Back protective layer) Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
...0.05 gelatin
・・・・・・2.00 Gelatin hardening agent (H-
1, H-2 equivalent)...0.14 Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
2 to 1O1O-2% by weight relative to silver halide,
Cpd-22 was used as a nucleation accelerator to''% by weight. Furthermore, in each layer, alkanol XC (
Dupon) and sodium alkylbenzenesulfonate as coating aids, succinate ester and Mag
efacF120 (manufactured by Dainippon Ink Co., Ltd.) was used. Silver halide and colloidal silver containing layers contain Cp as a stabilizer.
d-25) was used. This sample was designated as sample number 101. The compounds used in the examples are shown below.

xS-1 ・N (CaHs) 3 xS-3 xS-4 xS-5 goose 5OsH-N(C2Hs)3 ExS-6 Cpd-1 Cpd-2 Shi411・(1) Cpd-3 Cpd-4 Cpd-5 H H Cpd-6 Cpd-7 H H Cpd-8 (CL-Ci.

0OCJs Cp d -9 Shit13 ShiHa Cp d -11 Cp d -12 Cpd -13 Cpd -14 Cpd -15 H H H Cpd -16 Cpd-17 H Ul'I Cpd -18 03K Cpd to SOs ~ 19 Cp d -20 Cp d to SOl -21 SO, K 04K Cpd -22 Cpd 5 Cp d -26 Cpd Yu27 H (:HiCOOK CH, EXC-1 to COO Ll EXC-2 1 EXC-3 XM-1 XY -1 OC=Hs(n) 1 olv-1 olv-2 olv-3 olv-4 olv-5 Sol v-6 olv-7 -1 -2 xZK-1 Di(2-ethylhexyl)sepacate trinonyl phosphate Di(3-methylhexyl) phthalate Tricresyl phosphate Dibutyl phthalate Trioctyl phosphate Di(2-ethylhexyl) phthalate 1,2-bis(vinylsulfonylacetamido)ethane 4.6-dichloro-2-hydroxy-1,3,5 -) Lyazine Na salt 7-(3-ethoxythiocarbonylaminobenzamide)-9-methyl-10-propargyl-1゜2.3.4-tetrahydroacridinium trifluoromethane Ex2-2 Ruphonate 2- [4- (3-C3-(3-C5-(3-C2-chloro-5-(l-dodecyloxycarbonylethoxycarbonyl)phenylrubamoyl]-4-hydroxy-1-naphthylthio)tetrazol-1-yl]phenyl)ureido ] Benzenesulfonamido) phenyl 3-1-formylhydrazine Creation of samples 102 to 117 3rd layer, 4th layer, 6th layer, 7th layer, 11th layer of sample 101
The emulsions of the layers and the 12th layer were manufactured as shown in Table 1, and the magenta couplers of the 6th and 7th layers, 11th Jil and 12th
Samples 102 to 11 were prepared in exactly the same manner as Sample 101 except that the yellow couplers in the layers were changed to the compounds shown in Table 1.
7 was created.

The amount of coupler added in each of Samples 102 to 117 was made equal to that in each layer of Sample 101.

Samples 101 to 117 thus prepared were exposed to light using an enlarger through a color reversal film which had been photographed and developed using Macbeth's color chart, and developed using the following color developer A.

We then compared their color reproducibility, especially for yellow. Samples 101-117 were also exposed through a light wedge and developed using color developer A as described below.

Further, it was exposed in the same manner and developed using color developer B as described below. The maximum and minimum image densities of magenta and yellow were measured.

These results are shown in Table 1.

Processing process Time Temperature Mother liquor tank capacity Replenishment amount Color development 135 seconds 38℃ 151 300yd
/rd bleach fixing 40〃33〃3〃300〃Washing (1
) 40 N 33〃3//Washing (2) 40〃33
〃3〃320〃Dry! 30〃80” The method of replenishing the flushing water is to replenish the flushing bath (2) and
A so-called countercurrent replenishment system was adopted in which the overflow liquid of 2) was led to the washing bath (1). At this time, the amount of bleach-fix solution brought into the washing bath (1) from the bleach-fix bath for photosensitive materials is 3
5ml/m'', and the ratio of the amount of washing water replenished to the amount of bleach-fix solution brought in was 9.1 times.

The composition of each treatment liquid was as follows.

Color developer A D-Sorbit 0.15g 0.
20g Sodium naphthalene sulfonate 0.15g
O, 20g0g Ramurmarine condensate Ethylenediamine Tetrakis methylene phosphonic acid Diethylene glycol Benzyl alcohol Potassium bromide Benzotriazole Sodium sulfite N,N-bis(carboxymethyl)hydrazine D-Glucose triethanolamine )- 3-Methyl-4-aminoaniline sulfate potassium carbonate optical brightener (diaminostilbene type) 1.5g 1.5g 12.0d 16.0d 13.5d 18.0af 0.85g 0,003g 0.004g 2.4g 3.2g 6.0g 8.0g 2.0g 2.4g 6.0g 8.0g 64g 8.5g 30.0g 25.0g 1.0g 1.2g pH (25°C) 10.40 11. 00 Bleach-fix solution Ethylenediaminetetraacetic acid, disodium, dihydrate Ethylenediaminetetraacetic acid, Fe(III), ammonium, dihydrate ammonium thiosulfate (700 g/1) p-) Sodium luenesulfinate Sodium bisulfite 5-mercapto- 1,3,4 Add monotriazole ammonium nitrate water and pH (25℃) Mother solution Replenisher 4.0g Same as mother solution 70.0g 18 (Ig+j! 20.0g 20.0g 0.5g 10.0g 000d 6.20 Washing water Both the mother liquor and the replenisher are tap water filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite rR-400 manufactured by Rohm and Haas). Water was passed through the column to reduce the concentration of calcium and magnesium ions to 3μ/l or less, and then 20IIIg/i of sodium isocyanurate dichloride and 1.5g/l of sodium sulfate were added.The pH of this solution was 6. It was in the range of .5 to 7°5.

Color developer B Change the amount of potassium carbonate in Color developer IA and adjust the pH to l.
The results are the same except that 094 was changed to 10.0. From the results in Table 1, it can be seen that compared to the comparative example, the present invention achieves high color development without increasing fluctuations in Di+ax and Dmin with respect to pH fluctuations of the color developer. It is clear that the color reproducibility has been improved.

Example 2 Samples 201 to 217 were prepared by removing the nucleating agent ExZK-l from Samples 101 to 117 of Example 1.

These samples 201 to 216 were subjected to imagewise exposure in the same manner as in Example 1, and then developed in the same manner as in Example 1, except that the development was performed while uniformly fogging exposure with light.

Table 2 shows their color reproducibility, Dmax, and low 1n values.

The results in Table 2 show that, compared to the comparative example, the present invention exhibits high color development without increasing fluctuations in Dmax and Dmin with respect to fluctuations in pH of the color developer, and has improved brown color reproducibility. It is clear that there are.

Example 3 Similar results to Examples 1 and 2 were obtained when manganese, zinc 7, copper, and cadmium were used in place of the metal compound lead acetate in Emulsion C-2 of Examples 1 and 2.

(Effects of the Invention) According to the present invention, Dma
A direct positive color photographic material with excellent color reproducibility can be obtained without fluctuations in x and Dmin.

Although it is difficult to maintain a constant pH of a color developing solution, the direct positive color photographic material of the present invention has great practical advantages.

Claims (1)

[Scope of Claims] A direct positive color photographic light-sensitive material containing on a support at least one layer of unfogged internal latent image type silver halide grains and a color image-forming coupler, the light-sensitive material having the following general formula [ I] and at least one compound represented by the general formula [M-II], and at least one of the internal latent image type silver halide grains contains Mn, Cu, Zn, Cd, Pd
, Bi, and a metal belonging to Group VIII of the Periodic Table. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 is an aryl group or a tertiary alkyl group,
R_2 is a fluorine atom, alkyl group, aryl group, alkoxy group, aryloxy group, dialkylamino group, alkylthio group, or arylthio group, R_3 is a group that can be substituted on the benzene ring, and X is a hydrogen atom or an aromatic group. l represents a group that can be separated by a coupling reaction with an oxidized product of a primary amine developer, and l represents an integer of 0 to 4, respectively. However, when l is plural, the plural R_2 may be the same or different. ] General formula [M-II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1_8 represents a hydrogen atom or a substituent. Y_
4 represents a hydrogen atom or a leaving group. Za, Zb and Zc
represents methine, substituted methine, =N- or -NH-, Z
One of the a-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. The case where the Zb-Zc bond is a carbon-carbon double bond includes the case where it is a part of an aromatic ring. R_1_9 or Y_4
When forming a dimer or more multimer, Za, Zb
Alternatively, when Zc is a substituted methine, this includes the case where the substituted methine forms a dimer or more multimer. ]