JPH0391737A - Direct positive photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the direct positive color image having the max. density and the min. density and good color reproducibility by using a specific yellow coupler and specific nucleation accelerator. CONSTITUTION:The compd. expressed by general formula [I] and the compd. expressed by general formulas [II] and/or [III] are incorporated into the direct positive photographic sensitive material having at least one layer of internal latent image type silver halide emulsion layers which are to previously fogged on a base, by which the color reproducibility is enhanced. In the formulas, X is preferably a nitrogen atom and is a heterocyclic group combined with a coupling active position or an aryloxy group. Q denotes the atom group necessary forming a 5- or 6-membered heterocycle. Q' denotes the atom group necessary for forming a 5- or 6-membered heterocycle can form imino group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a direct positive photographic light-sensitive material and a method for producing direct positive and dual image forms with excellent image quality.

[Conventional technology]

A method is known in which a positive image is directly obtained by using an internal latent image type silver halide emulsion that has not been fogged in advance, and performing surface development after or while performing fogging treatment after image exposure. The above-mentioned internal latent image type silver halide photographic emulsion is a type of silver halide photographic emulsion in which photosensitive nuclei are mainly inside the silver halide grains, and a latent image is mainly formed inside the grains by exposure. say. Various techniques are known so far in this technical field.
For example, U.S. Patent Nos. 2,592,250 and 2,46
No. 6.957, No. 2,491.815, No. 2.588
, No. 982, No. 3317.322, No. 3,761.2
No. 66, No. 3,761,276, No. 3,796.57
7 and British Patent No. 1,151.363, 115
The main ones are those described in the specifications of No. 0.553 and No. 1,011,062. Using these known methods, it is possible to produce photosensitive rice grains with relatively high sensitivity as a direct positive type. For the detailed structure of the direct positive image formation mechanism, for example,
T. H. James, The Theory of
The Photographic Process J (Theτheo
ry of the Photographic Pr
), 4th edition, Chapter 7, pages 182 to 193, and US Pat. No. 3,761,276.
In other words, due to the surface desensitization effect caused by the so-called internal latent image generated inside the silver halide by the initial imagewise exposure, fog nuclei are selectively generated only on the surface of the silver halide grains in the unexposed areas. Then, a photographic image (direct positive image) is created in the unexposed area by applying a normal so-called surface development process.
is expressed.

As mentioned above, as a means for selectively producing fog nuclei, a method of applying a second exposure to the entire surface of the photosensitive layer, which is generally called "one-light fogging method" (for example, British Patent No. 1,151,
363) and a nucleating agent (U
A method using a creating agent) is known. This latter method is discussed, for example, in Research Disclosure (Research Disclosure).
Closure) Magazine, Volume 151, Shame 15162 (
Published in November 1976), pages 76-78.

In order to form a direct positive color image, after subjecting the internal latent image type silver halide photosensitive material to capri processing, or performing surface color development processing while performing fogging processing, then bleaching,
It can be fixed (or bleached and fixed) to achieve the precepts. After the bleaching and fixing treatments, washing and/or stabilizing treatments are usually performed.

[Problem to be solved by the invention]

In direct positive image formation using a photofog method or a chemical fog method, the development speed is slower and processing time is longer than in the case of a normal negative type.
And/or? & Methods have been used to shorten the processing time by increasing the temperature. However, there is a problem in that when the pH is high in -a, the minimum image density of the direct positive image obtained increases.

Furthermore, under high pH conditions, the developing agent tends to deteriorate due to air oxidation, and the pH tends to drop due to the absorption of carbon dioxide gas in the air. As a result, there is a problem in that the developing activity is significantly reduced. Another method for increasing the development speed of direct positive images is the use of hydroquinone derivatives (U.S. Pat. Nos. 3 and 2).
27.552), those using merkabuto compounds having carboxylic acid groups or sulfonic acid groups (Japanese Patent Application Laid-open No. 170-1982)
No. 843) and the like are known, but the effects of using these compounds are small, and no technique has been found to effectively directly increase the maximum density of a positive image. In particular, it was desired to obtain a high maximum image density without increasing the minimum image density. Furthermore, compared to the conventional negative-positive method in which a negative photosensitive material is layered twice, direct-positive images cannot use masking technology, so color reproducibility may be a problem.

Accordingly, a primary object of the present invention is to provide a direct positive color imaging method that provides high maximum image density without increasing minimum image density.

A second object of the present invention is to provide a method for forming a direct positive color image with excellent color reproducibility. [Means for Solving the Problems] The object of the present invention is to provide a direct positive photographic light-sensitive material having at least one internal latent image type silver halide emulsion layer that is not pre-fogged on a support, which has the following general formula: CI)
This has been achieved by a direct positive photographic material containing a compound represented by the formula (■) and/or (Ill) below.

General formula (1) [wherein, R1 is an aryl group or a tertiary alkyl group,
2 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, R is a group that can be substituted on the benzene ring, and X is a hydrogen atom or an aromatic group. e represents a group that can be separated by a coupling reaction with an oxidized product of a primary amine developer, and e represents an integer of O to 4, respectively. however,
When l is plural, the plural R2s may be the same or different. ] General formula (n) In the formula, Q represents an atomic group necessary to form a 5- or 6-membered heterocycle. This heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring. R! represents a divalent linking group consisting of an atom or atomic group selected from hydrogen, carbon, nitrogen, oxygen, and sulfur atoms, and R! A represents an organic group containing at least one thioether group, amino group, ammonium group, ether group, or heterocyclic group.

n represents 0 or l, and m represents 0, 1 or 2.

M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions.

General formula Cm) In the formula, Q' represents an atomic group necessary to form a 5- or 6-membered heterocyclic ring, and L, R'', n,
M has the same meaning as in general formula (II) above. p represents l or 2.

The compound represented by general formula (1) will be explained in detail below.

In general formula (1), R1 preferably has 6 carbon atoms
~24 aryl groups (e.g. phenyl, P-tolyl, 0
-tolyl, 4-methoxyphenyl, 2-methoxyphenyl, 4-butoxyphenyl, 4-octyloxyphenyl, 4-hexadecyloxyphenyl, l-naphthyl)
or a tertiary alkyl group having 4 to 24 carbon atoms (for example, t
-butyl, L-pentyl, L-hexyl, 1 1
3 3-tetramethylbutyl, 1-adamantyl, 1
．． 11 nt-2-chloroethyl, 2-phenoxy-2-propyl, bicyclo(2,2.23octan-1-yl).

In general formula (1), R2 is preferably a fluorine atom,
Alkyl groups having 1 to 24 carbon atoms (e.g. methyl, ethyl, isopropyl, L-butyl, cyclopentyl, n-
octyl, n-hexadecyl, benzyl), C6-C24 aryl groups (e.g. phenyl, p-tolyl,
〇Motolyl, 4-methoxyphenyl), number of carbon atoms 1 ~
24 alkoxy groups (e.g. methoxy, ethoxy, poxy, n-octyloxy, n-tetradecyloxy,
penzyloxy, methoxyethoxy), carbon number 6~
24 aryloxy groups (e.g. phenoxy, p-tolyloxy, 0-tolyloxy, P-methoxyphenoxy, p-dimethylaminophenoxy, m-pentadecylphenoxy), dialkylamino groups having 2 to 24 carbon atoms (e.g. dimethylalyloxy), ξ, diethylaξ, pyrrolidino, bilidino, morpholino), an alkylthio group having 1 to 24 carbon atoms (e.g. methylthio, butylthio, n-octylthio, n-hexadecylthio) or an arylthio group having 6 to 24 carbon atoms ( For example, phenylthio, 4-
Methoxyphenylthio, 4-t-butylphenylthio,
4-dodecyl phenylthio).

In the general formula [1], R is preferably a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group having 1 to 24 carbon atoms (e.g. methyl, t-butyl, n-dodecyl), Aryl groups having 6 to 24 carbon atoms (e.g. phenyl, p-tolyl, p-dodecyloxyphenyl), alkoxy groups having 1 to 24 carbon atoms (e.g. methoxy, n-butoxy, n-octyloxy, n-tetra decyloxy, penzyloxy, 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. ethoxycarbonyl, dodecyloxycarbonyl, 1-(dodecyloxycarbonyl)ethoxycarbonyl], aryloxycarbonyl group having 7 to 24 carbon atoms (e.g., phenoxycarbonyl, 4-L-octylphenoxycarbonyl, 2 4-di-t-bentylphenoxycarbonyl), carbonamide group having 1 to 24 carbon atoms [e.g. acetamido, pivaloylamino,
Penzamide, 2-ethylhexanamide, tetradecanamide, 1 (2,4-di-t-pentylphenoxy)
butanamide, 3-(2,4-di-L-bentylphenoxy)butanamide, 3-dodecylsulfonyl-2-methylpropanamide], sulfonamide ξ-do group having 1 to 24 carbon atoms (e.g. methanesulfonamide, ρ -toluenesulfonamide, hexadecanesulfonamide), carbamoyl groups with 1 to 24 carbon atoms (e.g. N-methylcarbamoyl, N-tetradecylcarbamoyl, N,N
- dihexyl group, N-octadecyl-N-methylcarbamoyl, N-phenylcarbamoyl), sulfamoyl group having 0 to 24 carbon atoms (e.g. N-methylsulfamoyl, N-phenylsulfamoyl, N-acetylsulfamoyl), moyl, N-probanoylsulfupmoyl, N-hexadecylsulfamoyl, N,N-dioctylsulfamoyl) alkylsulfonyl groups having 1 to 24 carbon atoms (e.g. methylsulfonyl, penzylsulfonyl, hexadecylsulfonyl) ), number of carbon atoms 6-24
arylsulfonyl group (e.g. phenylsulfonyl,
ρ-Tolylsulfonyl, p-dodecylsulfonyl, p-
methoxysulfonyl), ureido groups having 1 to 24 carbon atoms (e.g. 3-methylureido, 3-phenylureido, 3-dimethylureido, 3-tetradecylureido), sulfamoylamino groups having 0 to 24 carbon atoms (
For example, N,N-dimethylsulfamoylate),
Alkoxycarbonylamino group having 2 to 24 carbon atoms (
For example, methoxycarponylamino, isobutoxycarponylamino, dodecyloxycarbonylamino)nitro groups, heterocyclic groups having 1 to 24 carbon atoms (e.g. 4-biridyl, 2-chenyl, phthalimide, octadecylsuccinimide), cyano group, an acyl group having 1 to 24 carbon atoms (e.g. acetyl, benzoyl, dodecanoyl), an acyloxy group having 1 to 24 carbon atoms (e.g. acetoxy,
penzoyloxy, dodecanoyloxy), an alkylsulfonyloxy group having I to 24 carbon atoms (e.g. methylsulfonyloxy, hexadecylsulfonyloxy) or an arylsulfonyloxy group having 6 to 24 carbon atoms (4Mt p-toluenesulfonyloxy) , P-dodecylphenylsulfonyloxy).

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

When X represents a heterocyclic group bonded to the coupling active position with a nitrogen atom, X represents a heterocyclic group selected from oxygen atom, sulfur atom, nitrogen atom, phosphorus atom, selenium atom, and tellurium atom in addition to the nitrogen atom. 5-7 which may contain atoms
A monocyclic or condensed heterocyclic ring whose members may be substituted; examples include succinimide, maleic acid, phthalimide, diglycolic acid, virol, pyrazole, imidazole, 1.2 4- triazole,
Tetrazole, indole, penzopyrazole, penzimidazole, penzotriazole, ξdazolidine-
2 4-dione, oxazolidine-2,4-dione, thiazolidine-2. 4-';one, imidazolidin-2-one, oxazoline-2-one, thiazoline-2-one
one, penzimidazolin-2-one, penzoxapurin-2-one, penzothiazolin-2-one, 2-viroline-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2. 6-dioxypurine, parabanic acid, 1.2.4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyridone, 6
-viridazone, 2-pyrazune, etc., and these heterocyclic groups may be substituted. Examples of substituents include hydra
In addition to xyl group, carboxyl group, sulfo group, amino group (e.g., agarino, N-methylamino, N,N-dimethylano, NN-diethylamino, anilino, virolidino, biveridino, morpholino), examples of the above R. There are substituents listed as.

When X represents a ryoloxy group, X has 6 carbon atoms.
-24 aryloxy groups, which may be substituted with a group selected from the above-mentioned substituent group when X is a heterocyclic group. Substituents include carboxyl group, sulfo group, cyano group, nitro group, alkoxy carbonyl group, halogen atom, carbonamide group, sulfonado group, carbamoyl group, sulfamoyl group, alkyl group, alkylsulfonyl group, arylsulfonyl group, or Acyl groups are preferred.

Next, examples of particularly preferably used substituents in the present invention will be described for each of the above-mentioned substituents R, R2, R3 and X.

In the general formula (H), R1 is particularly preferably a 2- or 4-alkoxyaryl group (for example 4-methoxyphenyl, 4-butoxyphenyl, 2-methoxyphenyl) or an L-butyl group, most preferably an L-butyl group. In the general formula [[], 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 [1], R is particularly preferably an alkoxy group, a carbonamide group or a sulfonamide group. In the general formula (1), 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 (IA).

General formula CIA] General formula CIA) In the smell, Z is R, R4 R, Rs Rs R & RS
R&RvR&O RsRw
Represents Rho Rl. Here, R4,
RS, Rl and R represent a hydrogen atom, 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 amino group, and R and R represent a hydrogen atom , represents an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group, or an alkoxycarbonyl group, and R1. and R. represents a hydrogen atom, an alkyl group, or an aryl group. R.I.O. and R.I.O. may be combined with each other to form a benzene ring, R4 and R. , R, and R! , R6 and R or R4 and R may be bonded to each other to form a ring (eg, cyclobutane, cyclohexane, cyclohebutane, cyclohexene, pyrrolidine, viveridine).

Among the heterocyclic groups represented by the general formula (IA), particularly preferred are those in which Z is RS
R6 RS R6 R is a heterocyclic group.

The total number of carbon atoms in the heterocyclic group represented by general formula (IA) is 2 to 24, preferably 4 to 20, more preferably 5 to 24.
It is l6. Examples of the heterocyclic group represented by the general formula (iA) include a succinimide group, a maleinide group, a phthalide ξ-do group, a l-methylidazolidine-24-dion-3-yl group, and a l-pendylimidazo group. Lysine-2,4-dion-3-yl group, 5,5-dimethyloxazoli. Dine-2,4-dione-3-yl group, 5-methyl-5-brobyloxazolidine-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, l,2.4-triapridine-3.5-dione-4-yl group, 1-methyl-2-phenyl group 1.2
．． 4-triazolidine-3,5-dione-4-yl group,
1-benzyl-2-phenyl-1,2,4-triazolidine-3,5-dione-4-yl group, 5-hexyloxy-l-methylimidazolidine-2,4-dione-3-
yl group, l-benzyl-5-ethoxyimidazolidine-
There are 2,4-dione-3-yl group and 1-benzyl-5-dodecyloxy-dazolidine-2,4-dione-3-yl group. Among the above heterocyclic groups, imidazolidine-24
A monodione-3-yl group (e.g. l-pendylimidazolidine-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-penzyloxyphenylsulfonyl), enoxy group, 4-(4-hyFOxyphenylsulfonyl)
Phenoxy group, 2-chloro 4-(3-chloro-4-hydroxyphenylsulfonyl) phenoxy group, 4-methoxycarbonylphenoxy group, 2-chloro-4-methoxycarbonylphenoxy group, 2-acetamido 4-methoxycarbonylphenoxy group , 4-isobroboxycarbonylphenoxy group, 4-cyanophenoxy group, 2-
(N-(2-hydroxyethyl)carbamoyl)phenoxy group, 4-nitrophenoxy group, 2,5-dichlorophenoxy group, 2,3,5-trichlorophenoxy group,
4-methoxycarbonyl-2-methoxyphenoxy L4
-(3-carboxypropanamido)phenoxy group is the most preferred example. In the coupler represented by the general formula (1), the substituent R may form a dimer or a multimer of more than two molecules bonded to each other via 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. When the coupler represented by the general formula (1) forms a multimer, an addition polymer having a yellow dye-forming coupler residue is an ethylenically unsaturated compound 'p! A typical example is a single or copolymer of J (yellow colored heptamer). In this case, the multimer contains repeating units of general formula (IB), and one or more types of yellow coloring repeating units represented by 1M formula (IB) may be contained in the multimer, and the copolymerization rate is It may also be a copolymer containing one or more non-color-forming ethylene type monomers.

General formula (IB) In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a chlorine atom, A represents -CONH-, -COO, or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group, and -CONH-, -NHCON
H-, -NHCOO- -NIICO-, -0CON
H- -Nll-, coo- -oco-, 1C
O-, -O- -S-, -SO. -NHSOz- or -SOINH-. a, bSc are O or l
shows. Q represents a yellow coupler residue represented by the general formula (1) from which a hydrogen atom has been removed. As the multimer, a copolymer of the following non-color-forming ethylene-like hepanomer of a yellow color-forming heptanomer represented by a coupler unit of the general formula (rB) is preferred. Non-color-forming ethylene monomers that do not couple with the oxidation products of aromatic primary amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (for example, methacrylic acid, etc.). amides or esters derived from (e.g., acrylamide, methacrylamide, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methyl acrylate,
Ethyl acrylate, n-probyl acrylate, n-
butyl acrylate, L-butyl acrylate, iso
-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, methacrylonitrile・Aromatic vinyl compounds (
For example styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (
(e.g. vinyl ethyl ether), maleic acid ester,
Examples include N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and -4-vinylpyridine. Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. Two or more types of 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 (18)
The ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to The agent can be selected such that its compatibility with gelatin, its flexibility, thermal stability, etc. are favorably influenced. The yellow polymeric coupler used in the present invention is obtained by dissolving a lipophilic polymeric coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the above general formula [IB] in an organic solvent, and dissolving it in an aqueous gelatin solution. It can be made by emulsifying and dispersing it in the form of latex, or it can be made directly by emulsion polymerization. U.S. Patent No. 3,45 describes a method for emulsifying and dispersing a lipophilic polymer coupler 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 R and X represented by the general formula (1) are shown below, but the present invention is not limited thereto. Specific example of X (1> (2) (3) (4) (5) (6) (7) (9) (l1> (8) (lO>(12> H) (13) (14) (15) (16) 0 (19) (20) (21) (22) Specific example of R3 (30) (32> (23) (31) (33> CHs CHs (36) (37) C-th H3, NHCOCHxCHCOOClh -NHSO1CtJts -n (38) (39) (40) (41) CH, -COOC+Jgs -COOCHCOOC+ !His ku42) (43) -CONHC.Htq -OC@U.〒-n (44) (45) -COJI(Cl {t)sOc+Jzs-NHCOC+
sHs+ (47) (48) In the table of specific examples of the yellow dye-form coupler represented by the general formula (1), the numbers in parentheses represent the numbers assigned to the specific examples of X and R, and the numbers in brackets [ ] The numbers 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 to several types, or may be used in combination with a known yellow dye type coupler. Although the coupler of the present invention can be used in any layer of the light-sensitive material, it is preferably used in the light-sensitive silver halide emulsion layer or a layer adjacent thereto, and 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 method of gathering precepts described in Specification No. 23047 is applied. The amount of the coupler of the present invention used in the light-sensitive material is from 1 x IO-'' mol to 1 mol per 1, preferably IX
IO-' moles to 5X10-3 moles, more preferably 2X
IO-' mol to 10-3 mol.

The compounds represented by the general formulas (II) and [III] used in the present invention act as nucleation accelerators, and the nucleation accelerator does not substantially function as a nucleation agent. However, it refers to a substance that promotes the action of a nucleating agent to increase the maximum density of a direct positive image and/or speeds up the development time required to obtain a constant direct positive image density. The above general formulas (n) and (1) will be further explained. In the general formula [■], Q is preferably an atom necessary to form a 5- or 6-membered heterocyclic ring composed of at least one of carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms, and selenium atoms. Represents a group. This heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle include tetrazoles, triazoles, isudazoles, thiadiazoles, oxadiazoles, selenadiazoles, oxazoles, thiazoles, penzoxazoles, penzuthiazoles, penzimidazoles, pyrimidines, etc. can be mentioned. Further, the heterocycle may include a nitro group, a halogen atom (for example,
chlorine, bromine>, mercabuto group, cyan group, substituted or unsubstituted alkyl group (e.g., methyl, ethyl, proyl, t-butyl, cyanoethyl), aryl group (e.g., phenyl, 4-methanesulfonamidophenyl, 4-methylphenyl, 3,4-dichlorophenyl,
naphthyl), alkenyl groups (e.g. allyl), ar,
(M,t, benzyl, 4-methylbenzyl, phenethyl), sulfonyl group (e.g. methanesulfonyl, ethanesulfonyl, P-toluenesulfonyl), carbamoyl group (e.g. unsubstituted rubamoyl, methyl rubamoyl, phenylcarbamoyl), sulfamoyl groups (e.g., unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl), carbonamide groups (e.g., acetamide, penzamide), sulfonamide groups (e.g., methanesulfonamide, benzenesulfonamide, P -toluenesulfonamide), acyloxy groups (e.g. acetyloxy, penzoyloxy), sulfonyloxy groups (e.g. methanesulfonyloxy), ureido groups (e.g. unsubstituted ureido, methylureido, ethylureido, phenylureido) ,
Thiourido group (e.g., thioureido with no W?#!)
methylthioureido>, acyl groups (e.g. acetyl,
benzoyl), oxycarbonyl group (e.g. methoxycarbonyl, phenoxycarbonyl), oxycarbonylamino group (e.g. methoxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino), carboxylic acid or salt thereof , a sulfonic acid or a salt thereof, a hydroxyl group, etc., but it is preferable that it is not substituted with a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, or a hydroxyl group in terms of the nucleation promoting effect. Preferred heterocycles represented by Q include tetrazoles, triazoles, imidazoles, thiadiazoles, and oxadiazoles. M is a hydrogen atom, an alkali metal atom (e.g., sodium, potassium), an ammonium group (e.g., trimethylammonium, dimethylbenzylammonium}, a group that can become M=H or an alkali metal atom under alkaline conditions (e.g., acetyl, cyanoethyl, Methanesulfonylethyl>. L represents a divalent linking group consisting of an atom or atomic group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of divalent linking groups include R4^ O
0 RS^ R4A R7^ R8^ R9^ R R l l A RIlA 0 [1 -N-CO- R SO2 O O 1111 -C- -SO 11 0 -OS- etc. Here, the heterocycle 11 0 Q is linked to the left side of the linking group. These linking groups are a linear or branched alkylene group (for example, methylene, ethylene, propylene, butylene, hexylene, 1-methylethylene), or a substituted or 4;l? I! may be bonded via a substituted arylene group (phenylene, naphthylene). R0, RS^, R-^, R? ＾、R８＾、R9＾、Ri
ll^Rll^ R I 2-
methylphenyl>, substituted or unsubstituted alkenyl groups (e.g., bropenyl, l-methylvinyl), or substituted or unsubstituted aralkyl groups (e.g., benzyl,
represents phenethyl. Rh represents an organic group containing at least one thioether group, amino group (including salt form), ammonium group, ether group, or hetero N group (including salt form). Examples of such organic groups include groups selected from substituted or unsubstituted alkyl groups, alkenyl groups, aralkyl groups, or ryoryl groups combined with the above groups. It's okay. For example, dimethylaminoethyl group, aminoethyl group, diethylaminoethyl group, dibutylaminoethyl group,
Hydrochloride of dimethylanopropyl group, dimethylaminoethylthioethyl group, 4-dimethylaminophenyl group, 4
-dimethylagonobenzyl group, methylthioethyl group, ethylthiobrobyl group, 4-methylthio3-cyanophenyl group, methylthiomethyl group, trimethylammonioethyl group, methoxyethyl group, methoxyethoxyethoxyethyl group, methoxyethylthioethyl group , 3,4-dimethoxyphenyl group, 3-chloro-4-methoxyphenyl group, morpholinoethyl group, 1-idazolylethyl group, morpholinoethylthioethyl group, pyrrolidinoethyl group, biveridinopropyl group, 2-pyridylmethyl group −(1
Examples include -idazolyl)ethylthioethyl group, pyrazolylethyl group, triazolylethyl group, methoxyethoxyethoxyethoxyethyl group, and the like. n represents O or l, m represents 0, 1 or 2. In the general formula (ill3, L% R!A...n, M are synonymous with those in the general formula [■], p represents l or 2, and Q' is a 5- or 6-membered iminosilver form. Represents the atomic group necessary to define the member heterocycle.

Represents an atomic group necessary to form a 5- or 6-membered heterocycle preferably selected from carbon, nitrogen, oxygen, sulfur, and selenium. This heterocycle may also be fused with a carbon aromatic ring or a heteroaromatic ring. Examples of the heterocycle represented by Q' include indazoles, penzimidazoles, penzotriazoles, penzoxazoles, penzuthiazoles, imidazoles, thiazoles, oxazoles, triazoles, tetrazoles, and tetrazoles. Examples include azaindenes, triazaindenes, diazaindenes, birazoles, and indoles. The compound represented by the general formula (n) is represented by the following general formula [■
], (V), [■], and [■] are preferably used. General formula (IV) In the formula, M% R''% L% n has the same meaning as that in general formula (U). X represents an oxygen atom, a sulfur atom or a selenium atom, with a sulfur atom being preferred.

General formula (V) R' In the formula, R' is a hydrogen atom, a halogen atom (for example, chlorine,
Bromine>, nitro group, merkabuto group, unsubstituted amino group, each substituted or unsubstituted alkyl group (e.g. methyl, ethyl>, alkenyl group (e.g. ethyl, flobenyl, l)
-methylvinyl>, aralkyl group (e.g. benzyl,
phenethyl), a ryol group (e.g., phenyl, 2-methylphenyl), or →L}-. R'.
is a hydrogen atom, an unsubstituted amino group, or →Lh. Represents R' island. R' and R' →Lt. When representing R"^, they may be the same or different. However, at least one of R' and R' represents →LtofiR". M% R”% L% n is each represented by the above general formula (II)
are synonymous with each of . General formula (Vl) In the formula, R″′ represents →L←1 R3^.

M1 R3 Todoroki L and n each have the same meaning as each of the above general formula (II). General formula [■] R/l/ In the formula, Rl4^ and R''^ are hydrogen atoms, halogen atoms,
Represents a substituted or unsubstituted amino group, a nitro group, a substituted or unsubstituted alkyl group, alkenyl group, aralkyl group, or aryl group. However, M and R'' have the same meaning as each of the above general formulas [VI]. Specific compounds represented by general formulas (Ill) to [■] of the present invention are shown below, but the compounds of the present invention are It is not limited to this. R1.2 CLCHxSCL RI04 R,., A-34 CM.CHON((J{s)z In the present invention, nucleation represented by the above general formula (If) and CIO) The accelerator is contained in the light-sensitive material, but it is preferably contained in the internal latent image type silver halide emulsion layer and other rough aqueous colloid layers (intermediate layer, protective layer, etc.). Particularly preferred is a silver halide emulsion layer or a layer adjacent thereto.The amount of the nucleation accelerator added is 104 to 104 per mole of silver halide.
to-'' moles are preferred, more preferably to-' to 1
It is 0-2 moles. In addition, when the nucleation accelerator is added to the processing solution, that is, the developer or its pre-bath, io-'-to-'
mol is preferred, and more preferably 10-' to io-' mol.

Furthermore, two or more types of nucleation accelerators can also be used together. As the nucleating agent used together with the nucleating accelerator, at least one of the compounds represented by the following general formulas (N-1) and (N-I[) is used. General formula (N-1) In general formula (N-1), Z1 represents a nonmetallic atom group necessary to form a 5- to 6-membered heterocycle, RIM is an aliphatic group, and REN is a hydrogen atom. , is an aliphatic group or an aromatic group. Z+, R", R" may be substituted,
In addition, REN is further combined with a heterocyclic ring completed by Zi,
You may also use the ring as a precept.

However, at least one of the groups represented by [;jlN, RtH and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or
It forms a 6R ring with 2N and forms a dihydropyridinium skeleton. Y is a counterion for charge balance, n
is 0 or 1. General formula (N-I1) RSNR6N In the general formula (N-n), R1N represents an aliphatic group, aromatic group, or heterocyclic group, and R4N represents a hydrogen atom, an alkyl group,
Represents an aralkyl group, aryl group, alkoxy group, aryloxy group, or ξno group, and G represents a carbonyl group, sulfonyl group, sulfoxy group, phosphoryl group, or iminomethylene group (HN=C<>, RS) l and R6
Both N's are hydrogen atoms, or one is a hydrogen atom and the other is an alkylsulfonyl group, an arylsulfonyl group, or an acyl group. However, Q, R4NSR6
The hydrazone structure (including N and hydrazine nitrogen)
)N − N = C<->. Furthermore, the groups mentioned above may be substituted with substituents if possible. In general formula (N-1), the heterocycle completed by Z1 is, for example, quinolinium, penzothiazolium, penzimidazolium, viridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, penzoselenazolium, Imidazolium, tetrazolium, indolenium, virolinium, acridinium, phenanthridinium, isoquinolinium, oxazolium,
Examples of the substituent of Z1 include naphthoxazolium and penzoxazolium nuclei; group, alkylthio group, arylthio group,
Azyloxy group, acylamino group, sulfonyl group, sulfonyloxy group, sulfonylamino group, carboxyl group, acyl group, carbamoyl group, sulfamoyl group, sulfo group, cyano group, ureido group, urethane group, carbonate ester group, hydrazine group, Examples include a hydrazone group and an imino group. As the substituent for Zl, for example, at least one substituent is selected from the above substituents, but if two or more substituents are selected, they may be the same or different, and the above substituents may be further substituted with these substituents. You can. Furthermore, as a substituent for Z, Z
It may contain a heterocyclic quaternary ammonium group which is activated by +. In this case, it takes a so-called dimer structure. Preferred heterocycles for Z1 include quinolinium, penzothiazolium, penzimidazolium, pyridinium, acridinium, phenanthridinium, and isoquinolinium nuclei. More preferred are quinolinium and penzothiazolium, and most preferred is quinolinium.

RIM and the aliphatic group of RIM are unsubstituted alkyl groups having 1 to 18 carbon atoms and alkyl moieties having 1 to 18 carbon atoms.
substituted alkyl groups. Examples of the substituent include those described as the substituent for Z1. The aromatic group represented by RtN has 6 to 20 carbon atoms, such as phenyl group and naphthyl group.
Examples of the substituent include those described as the substituent for Z1. REN is preferably an aliphatic group, most preferably a methyl group, a substituted methyl group, or a ring formed by bonding with a heterocycle completed with 2.

Rllll, R! At least one of the groups represented by N and Z1 has an alkynyl group, an acyl group, a hydrazine group, or a hydrazone group, or RIM and R!
H forms a 6-membered ring and forms a dihydrobiridinium core, but these may be substituted with the groups mentioned above as substituents for the group represented by Z. R I N, R! , N and at least one of the substituents to the ring represented by Z1 is an alkynyl group or an acyl group, or RIM and R1 are connected to form a dihydrobiridinium bone core. Preferably, it further preferably contains at least one alkynyl group, most preferably a probargyl group.

The adsorption-promoting group to silver halide that RIM, R2N and zl substituents have is X'-(L'). It is preferable to use the expression . Here, X+ is a group promoting adsorption to silver halide, Ll is a divalent linking group, and m is 0 or 1. Preferred examples of the adsorption-promoting group to silver halide represented by XI include a thioamide group, a mercabuto group, and a 5- or 6-membered nitrogen-containing heterocyclic group. These may be substituted with the substituents for Zl. The thioamide group is preferably an acyclic thioamide group (e.g., thiourethane group, thiourido group, etc.). The mercabuto group of .4-triazole, 2-merkabuto-1.
3.4-thiadiazole, 2-merkabuto-1.3.4
-oxadiazole, etc.) are preferred. The 5- to 6-membered nitrogen-containing heterocycle represented by X1 is composed of a combination of nitrogen, oxygen, sulfur and carbon,
Preferably, those that produce ξinosilver, such as penzotriazole and aminothiatriazole, are preferred. The divalent linking group represented by Ll includes 05N, S,
An atom or atomic group containing at least one type of O.
Specifically, for example, alkylene group, alkenylene group, alkynylene group, arylene group, -O- -S- -
NH- -N= -CO-SOz (these groups may have a substituent), etc., alone or in combination.

Examples of combinations include -CO- -CNH--NHS
OzNH-, O 11 →alkylent CNH]arylene}-Sol NH-0 11 →arylene}-NHCNH- →arylene}-CNH, and the like are preferred. Counter ions Y for charge balance include, for example, bromide ions, chloride ions, iodide ions, p-toluenesulfonate ions,
Examples include ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion, boron tetrafluoride ion, and phosphorus hexafluoride ion.

These compounds and their synthesis methods are described, for example, in Research Disclo
sure) Magazine Ko 22.534 (published January 1983,
50-54), and patents cited in Doko 23.213 (Published August 1983, pages 267-270), Japanese Patent Publications No. 49-38,164, No. 52-19.452, No. 52-47. , No. 326, JP-A-52-69.613,
No. 52-3.426, No. 55-138.742, No. 60-11.837, U.S. Patent No. 4,306,016
No. 4,471,044. Specific examples of the compound represented by general formula (N-1) are listed below, but the invention is not limited thereto. (N-1-1) (N-1-2) (N-1-3) (N-1 4) (N-1-5> S (N l 6) CH I C Mi CD (N-1- 7) SH (N 1-8) (N 1 9) CH.CmiCH (N-1-10) (N-1-11) q}I CH.CmiCll (N-1-12) CII. C Mi CH (N-1-13) SH (N-1-14) (N-1-15) S (N-1-16> (N-1-17) (N-1-18) Cll zc E Cll (N-1 1 9> (N-1-20) CH.Cmi CI1 CIlzC = CB Furthermore, in the general formula (N-11), RffN is preferably an aromatic group, an aromatic heterocycle, or an aryl substituted It is a methyl group, more preferably an aryl group (for example, a phenyl group, a naphthyl group, etc.). R3'' may be substituted with a substituent, and examples of the substituent include the following. The groups may be further substituted, such as alkyl groups, aralkyl groups, alkoxy groups, alkyl or aryl groups, substituted danno groups, acylamino groups, sulfonylamino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups. , carbamoyl group, aryl group, alkylthio group, arylthio group,
These include sulfonyl groups, sulfinyl groups, hydroxyl groups, halogen atoms, cyano groups, sulfo groups, carboxyl groups, and phosphoric acid amide groups. Among these, ureido groups and sulfonylamino groups are particularly preferred. These groups may be linked to each other to form a ring when possible.

R4N is preferably a hydrogen atom, an alkyl group (for example, a methyl group), an aralkyl group (for example, a 2-hydroxybenzyl group, etc.), or an aryl group (for example, a 2-hydroxymethylphenyl group, etc.), and in particular a hydrogen atom and an A group is preferred. As the substituent for R4N, in addition to the substituents listed for R)N, for example, an acyl group, an acyloxy group,
Alkyl or aryloxy carbonyl groups, alkenyl groups, alkynyl groups and nitro groups can also be used. These substituents may be further substituted with these substituents. If possible, these groups may be linked to each other to form a ring. R3N or R4N, especially RffN, may contain a diffusion-resistant group such as a coupler, or may have a group X2→L'')-v that promotes adsorption to the surface of the silver halide grain. In particular, it is preferable to link with a ureido group or a sulfonylamino group.Here, X! is of the general formula (N-
It has the same meaning as XI in 1), and is preferably a thioamide group, mercabuto group, or a 5- to 6-membered nitrogen-containing heterocyclic group. ◆L2 represents a divalent linking group, and the general
a mt, which has the same meaning as L1 in N-1), is O or 1. Even more preferable X! is an acyclic thioamide group (e.g., thioureido group, thiourethane group, etc.), a cyclic thio-do group (i.e., a nitrogen-containing heterocycle substituted with merkabuto x, e.g., a 2-merkabutothiadiazole group, a 3-merkabuto-1
．． 2.4-}lyazole group, 5-merkabutotetrazole group, 2-merkabuto-1.3.4-oxadiazole group, 2-merkabutopenzoxazole group, etc.), or nitrogen-containing heterocyclic group (e.g. (penzotriazole group, penzimidazole group, indazole group, etc.). As X2, a mercabuto-substituted nitrogen-containing heterocycle or a nitrogen-containing heterocycle in the form of iminosilver is preferable. Hydrogen atoms are preferred as R 5N and R hH. Moreover, as G, a carbonyl group is most preferable.

As general formula 1:N-If), W &
Those having an ii group, and those having a ureido group or a sulfonylamino group are preferable. The synthesis method for (N-I1) is based on examples of hydrazine-based nucleating agents having a silver halide adsorption group, such as U.S. Pat. No. 4,031,127, No. 3,718,470
No. 4.269927, No. 4,276,364
No. 4,278,748, No. 4,385.10
No. 8, No. 4,459.347, No. 4,478,92
No. 2, No. 4,560,632, British Patent No. 2,011
, No. 391B, JP-A-54-74,729, JP-A No. 55-
No. 163,533, No. 55-74.536, and No. 6
0-179.734 etc. Other hydrazine-based nucleating agents include, for example, JP-A No. 5
7-86.829, U.S. Pat. No. 4,560,638, U.S. Pat. No. 4,478.928, and U.S. Pat.
No. 785 and No. 2,588,982. Specific examples of the compound represented by the general formula (N-n) are shown below, but the present invention is not limited thereto. (N-1■-1) 0 (N-ff-2) 0 (N-11-3) (N-I1 4) (N-11 5) (N-n-6) (N-11-7) ( N-n-8) ■ (N-1f-9) 0 0 ■ (N-n-10) 0 S (N-1-11) S (N-1-12) O (N-It-13) ( N-I1-14) (N 11-1 5) (N-n 16) 0 Cll! Of{ (N~■17) (N-n-18) (N1■-19) O CI. OR In the present invention, when a compound represented by 1m formula (N-13 and (N-■)) is contained in a photographic light-sensitive material,
Hydrophilic colloids can be prepared as solutions in water-miscible organic solvents such as alcohols (e.g. methanol, ethanol), esters (e.g. ethyl acetate), ketones (e.g. acetone), or as an aqueous solution if water-soluble. Just add it to the solution. When added to a photographic emulsion, it may be added at any time from the start of chemical training to before coating, but it is preferably added after chemical training is completed. In the present invention, the general formula (N
The nucleating agents represented by -1) and (N-I1) may be contained in the hydrophilic colloid layer welded to the silver halide emulsion layer, but are preferably contained in the silver halide emulsion layer. ．． The addition position differs depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent, and the development conditions, so it can vary over a wide range.
A range of from about IXIO-' moles to about IXIO-' moles per mole of silver in the silver emulsion is practical in practice, with a preferred range from about fXIO-' to about 1.times.10@1 moles per mole of silver. As the nucleating agent of the present invention, (N-1) is preferable, and among (N-1), it is preferable that the ring is formed by bonding with a heterocycle whose RfM is 21.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The silver halide grains in photographic emulsions may be so-called regular grains with regular crystal structures such as cubic, octahedral, or tetradecahedral, or may have irregular crystal shapes such as spherical or twin. It may be one with crystal defects such as crystal planes, or a composite form thereof. Also, a mixture of various crystal forms may be used. The grain size of the silver halide may be fine grains of about 0.1 micron or less, large grains with a projected area diameter of about 10 microns, monodisperse emulsion with a narrow distribution, or polydisperse with a wide distribution. It can also be an emulsion. It is preferable to use a monodisperse emulsion in terms of pam adjustment and image quality control. The silver halide photographic emulsion used in the present invention can be produced by a known method, for example, Research Disclosure, 1
76@, NCL17643 (December 1978), 2
pp. 2-23, “1. Emulsion Production (Emulsion Pr.
1187, No. 118716 (January 1979)
, 648 may be followed. The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by P. Glafkide, published by Paul Montell.
s, Chimie et PhysiqueP
photographique paul montel
, 1967), "Photographic Emulsion Chemistry" by G.F. Duffin, published by Focal Press.
, Photographic Emulsion C
bemtsLry(Focal Press. 1
9 6 6) ), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V.L.Z.
Elikmaa et al. , Making
and CoatingPhotography
c Emulsion. Focal Press.
1964) and others. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed under an excess of silver ions (so-called back-mixing method). PA in the liquid phase in which silver halide is produced as a form of simultaneous mixing method
It is also possible to use a method in which g is kept constant, that is, the so-called controlled double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In addition, known silver halide solvents (for example, ammonia, rhodankali or Showa 54-100717
It is also possible to perform physical training in the presence of thioethers and thione compounds (described in No. 2003 or JP-A-54-155828, etc.). This method also yields a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution. The above-mentioned silver halide emulsion consisting of regular grains can be obtained by controlling pAg and pH in the grain shape. For more information, please see Photographic Science
and Engineering (Photographic
Science and Engineering) Volume 6, pages 159-165 (1962); Journal of Photographic Science (Journal
of Photographic Science),
12, pp. 242-251 (1964), U.S. Patent No. 3
, 655,394 and British Patent No. 1,413,74
It is stated in No. 8. Monodisperse emulsions that can be preferably used in the present invention include emulsions in which silver halide grains have an average grain diameter of greater than about 0.05 microns, and at least 95% by weight of the silver halide grains are within ±40% of the average grain diameter. is typical.
Further, it is possible to use an emulsion in which the average grain diameter is 0.15 to 2 microns, and at least 95% by weight or at least 95% by number of silver halide grains are within the range of ±20% of the average grain diameter. Methods for producing such emulsions are described in U.S. Pat. No. 3,574,628 and U.S. Pat.
No. 4 and British Patent No. 1.413748. Also, JP-A-48-8600, JP-A No. 51-3902
No. 7, No. 51-83097, No. 53-137133, No. 54-48521, No. 54-99419, No. 5
Monodisperse emulsions such as those described in No. 8-37635 and No. 5B-49938 can also be preferably used. Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in the book by Gutt, Photographic Science and Engineering (Cut
Off, Photographic Science
and Engineering), Volume 14, 248
-257 pages (1970): U.S. Patent No. 4.43422
No. 6, No. 4,414,310, No. 4,433,048
No. 4,439,520 and British Patent No. 2.11
It can be easily adjusted by the method described in No. 2,157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, and the above-mentioned US Pat. No. 4,434,226
It is detailed in the issue. In the particle shape control process, it is also possible to use particles whose crystal shape is controlled by using sensitizing dyes or certain additives. The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1.027.1.
No. 46, U.S. Patent No. 3,505,068, U.S. Patent No. 4,44
4.877 and Japanese Patent Application No. 58-248469. Further, silver halides having different compositions may be bonded by an epitaxial bond, or may be bonded to a compound other than silver halide, such as silver rhodan or lead oxide. These emulsion grains are described in U.S. Pat.
No. 4,459,353, British Patent No. 2.038.79
No. 2, U.S. Patent No. 4,349,622, U.S. Patent No. 4,395
．． No. 478, No. 4,433,501, No. 4 463
．． No. 087, No. 3,656,962, No. 3,852,
No. 067, JP-A-59-162540, etc. Furthermore, chemical ripening occurs on the crystal surface, producing Ag as a photosensitive nucleus.
．． It is also possible to use a material having a so-called latent type grain structure in which silver halide is further surrounded by silver halide after forming a grain (such as s, Agn, Au, etc.). Silver halide grain shape precept or physics V! Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. may coexist in the pre-preparation process. In the present invention, it is preferable to use an internal latent image type emulsion that has not been fogged in advance and to use a nucleating agent before or during processing to directly obtain a positive color light-sensitive material. 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 the silver halide grains are not fogged in advance and the latent image is mainly formed inside the grains. However, more specifically, a silver halide emulsion is uniformly coated on a transparent support, and then a zero
．． When exposed for a fixed time of 0.01 to 10 seconds and developed for 6 minutes at 20°C in the following developer A (internal type developer), the maximum density measured by the usual photographic density measurement method is the same as above. A silver halide emulsion having a density at least 5 times greater than the maximum density obtained when a silver halide emulsion coated and exposed in the same manner is developed at 18°C for 5 minutes in the following developer B (surface type developer). Preferably, and more preferably, those having a concentration that is at least 10 times greater.

Surface developer B Metol 2.5g 2-ascorbic acid 10g NaBox 4Hz O
35g KBr
Add Ig water to 1l
Internal developer A Metol 2g Sodium sulfite (
anhydrous) 90g hydroquinone
8g Soda carbonate (monohydrate) 52.
5gKBr 5gKI
O. Add 5g water
Specific examples of Ifi internal latent image type emulsions include British Patent No. 1011062, U.S. Patent No. 2.592.250, and U.S. Patent No. 2,456.943.
Examples of the core/shell type silver halide emulsions include convergence type silver halide emulsions and core/shell type silver halide emulsions described in JP-A-47-32813; No. 47-32814, No. 5
No. 2-134721, No. 52-156614, No. 53
-60222, 53-66218, 53-66
No. 727, No. 55-127549, No. 57-1366
No. 41, No. 58-70221, No. 59-208540
No. 59-216136, No. 60-10764 1
No. 60-247237, No. 61-2148, No. 61-3137, Special Publication No. 56-18939, No. 5B
-1412, 58-1415, 58-6935
No. 5B-108528, patent application No. 61-36424
No., U.S. Pat. No. 3,206,313, U.S. Pat. No. 3,317,322,
No. 3761266, No. 3761276, No. 3850
No. 637, No. 3923513, No. 4035185,
Examples include emulsions described in 4395478, 4504570, European Patent No. 0017148, and Research Disclosure Magazine 16345 (November 1977). To remove soluble root salts from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation, ultrafiltration, etc. are used. The emulsion used in the present invention is usually one that has been subjected to physical examination, chemical P or spectral sensitization. Additives used in such processes are described in the aforementioned Research Disclosure Nal 7643 (December 1978) and Research Disclosure Nal 18716 (November 1979), and the relevant sections are summarized in the table below. ．． Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures, and the locations listed are shown in the table below. Additive type RD17
643 RD18716l Chemical sensitizer
Page 23 Page 648 Right column 2rfI! ．． Increasing agent
Same as above 3 Spectral sensitizer 23
~Page 24 Page 648 Right column ~Supersensitizer
Page 649 Right column 4 Brightening agent Page 24 5 Antifogging agent Pages 24-25 and stabilizer 6 Light absorber, filter dye UV absorber 7 Stain inhibitor 8 Dye image stabilizer 9 Hardener 10 Binder 1 Plasticizer , Lubricant l2 Coating aid, page 649, right column, page 649, right column - page 650, left column, page 650, left to right column, page 651, left column, page 650, right column, page 25-26, page 25, right column, page 25, page 26, page 26. Page 27 Pages 26-27 Surfactant 13 Static Page 27 Page 650 Right Column Inhibitor In the present invention, various color couplers can be used in addition to the above compound (11). Generates or releases a substantially non-diffusible dye through a coupling reaction with an oxidized product of an oxidized color developer.
Preferably, the compound is a compound which is itself substantially non-diffusible. Typical examples of useful color couplers include naphthol or phenolic compounds, virazolone or virazoloazole compounds, and open chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that can be used in the present invention can be found in "Research Disclosure", Vol. 17.
643 (published in December 1978), Section P25■-D, 18717 (published in November 1979), and the compounds described in Japanese Patent Application No. 61-32462 and the patents cited therein. Among the yellow couplers that can be used in the present invention, representative examples include oxygen atom elimination type and nitrogen atom elimination type yellow two-equivalent couplers, which can be used in combination with those shown in [I] above. In particular, .alpha.-pivaloylacetanilide couplers are preferred because they provide excellent color fastness, especially light fastness, while .alpha.-penzoylacetanilide couplers are preferred because they provide high color density. The 5-virazolone-based magenta coupler that can be preferably used in the present invention is a 5-virazolone-based coupler in which the 3-position is substituted with an arylamino group or an acyl-amino group (especially a sulfur atom-eliminating type two-equivalent coupler). ．． More preferred are birazoloazole-based couplers, and among them birazolo(5,l-c)(1,2.4)triazoles described in U.S. Pat. No. 3,125.067 are preferred; The imidazo(1.2-b) birazoles described in U.S. Pat. No. 4,500,630 are more preferred in terms of the low yellow side absorption of the dye and the light fastness, and the imidazo(1.2-b) birazoles described in U.S. Pat. The pyrazolo(1,5-b)(1,2.4)}riazole described above is particularly preferred.Cyan couplers that can be preferably used in the present invention include:
U.S. Patent Nos. 2,474,293 and 4,052,21
Naphthol-based and phenol-based couplers described in US Pat. .5
-Diacylamino-substituted phenolic couplers are also preferred from the viewpoint of color image fastness. Colored couplers to correct unnecessary absorption in the short wavelength range of the generated dyes, couplers in which coloring dyes have appropriate diffusivity, non-coloring couplers, DIR couplers that release development inhibitors along with the coupling reaction, and Polymerized couplers can also be used. Typical usage amounts for color couplers range from 0.001 to 1 mole per mole of photosensitive halide iIl, preferably 0.001 to 1 mole for yellow couplers. Ol to 0.5
mole, for magenta cobbler, 0.03 mole to 0.03 mole.
3 mol, and 0.002 to 0.00 for cyan coupler.
It is 3 moles. A color enhancer can be used in the present invention for the purpose of improving the color development of the coupler. Representative examples of the compounds include those described in Japanese Patent Application No. 61-32462, pages 374-391. The coupler of the present invention is dissolved in an organic solvent with a high boiling point and/or a low boiling point, and is added to an aqueous solution of gelatin or other hydrophilic colloid by stirring at high speed with a homogenizer, by mechanical atomization using a colloid mill, or by ultrasonication. Emulsification and dispersion is performed using the technology used, and this is added to the emulsion layer. In this case, it is not necessary to use a high boiling point organic solvent, but it is preferable to use the compounds described on page 1.
The coupler of the present invention can be dispersed in a hydrophilic colloid by the method described in . The light-sensitive material of the present invention preferably contains one or more compounds capable of reacting with and fixing formaldehyde gas, such as those listed below. The compound used in the present invention that reacts with formaldehyde gas and fixes it (hereinafter referred to as formalin scavenger) is a compound represented by the following general formula (SI), [S■], and has an active hydrogen defined below. The equivalent molecular weight per unit is 300 or less. General formula (Sl) H R+s X Rxs where R. and R. represents hydrogen, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, or an ajuno group; and I? zs may take the form of a ring,
Rl! sR! At least one of 3 is an acyl group,
Alkoxy is carbonyl group, carbamoyl group or ξno group. X represents -CH- or -N-. R, 3
represents hydrogen, an alkyl group, a substituted alkyl group, an aryl group, or a substituted aryl group, and may form a bicyclic ring with a phenyl group. n represents an integer of 2 or more. Two or more formalin scavengers used in the present invention may be used in combination. The formalin scavenger of the present invention is contained in at least one of the silver halide emulsion layer, undercoat layer, protective layer, intermediate layer, filter layer, antihalation layer, and other auxiliary layers of a silver halide color photographic light-sensitive material. However, the object of the present invention is achieved regardless of whether it is added to a silver halide emulsion layer containing a magenta polymer coupler whose photographic performance deteriorates when it comes into contact with formaldehyde gas, a layer closer to the support or a layer farther from the support. It is achieved. In order to add the formalin scavenger used in the present invention into these layers, it is necessary to add the formalin scavenger used in the present invention to the coating liquid for forming the layers.
The formalin scavenger can be added as it is or dissolved in a suitable concentration in a solvent that does not have an adverse effect on the silver halide color photographic light-sensitive material, such as water or alcohol. Alternatively, the formalin scavenger can be dissolved in a high boiling point organic solvent and/or a low boiling point organic solvent, emulsified and dispersed in an aqueous solution, and then added. The formalin scavenger may be added at any time during the manufacturing process, but it is generally preferable to add the formalin scavenger immediately before application. The amount added is suitably 0.01 to 10 g per one silver halide photographic color light-sensitive material, preferably 0.05 to 5 g. When the light-sensitive material of the present invention is a color light-sensitive material, various antifading agents can be used. Examples of organic antifading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, subirochromans,
p-Alkoxyphenols, hindered phenols mainly including bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and phenolic water of each of these compounds
Representative examples include ether or ester derivatives in which the I group is silylated or alkylated. Also, (bissalicylaldoximato)nickel complex and (bis-N
, N-dialkyldithiorubamato)nickel complexes can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
As described in U.S. Pat. No. 4,268,593,
Compounds containing both hindered fruit and hindered phenol partial structures in the same molecule give good results. In addition, in order to prevent deterioration of magenta dye images, especially deterioration caused by light, substitution of subiroindanes as described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-09835 is recommended. chromans give favorable results. The purpose of these compounds can be achieved by co-emulsifying them with the corresponding color coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight. In order to prevent cyan dye images from deteriorating due to heat and especially light, it is effective to introduce ultraviolet absorbers into the layers on both sides adjacent to the cyan coloring layer. Furthermore, UV absorbers can be added to hydrophilic colloid layers such as protective layers. The light-sensitive material of the present invention may contain dyes that inhibit irradiation and halation, antistatic agents, slipperiness improvers, and the like.

Representative examples of these additives are described in Research Disclosure journals NCL 17643 (published December 1970) and 18716 (published November 1979). The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be chosen arbitrarily as necessary. The preferred layer arrangement order is: red sensitivity, green sensitivity, blue sensitivity from the support side; blue sensitivity, green sensitivity, red sensitivity from the support side; blue sensitivity, red sensitivity, green sensitivity from the support side; or green sensitivity, red sensitivity from the support side. Sensitivity, blue sensitivity. Further, each of the above-mentioned emulsion layers may be made up of two or more emulsion layers having different sensitivities, or a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, the red-sensitive emulsion layer contains a cyan-type coupler, the green-sensitive emulsion layer contains a magenta-type coupler, and the blue-sensitive emulsion layer contains a yellow-type coupler.

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 layer,
It is preferable to provide an auxiliary layer such as a white reflective layer as appropriate.

Among the light-sensitive materials of the present invention, when the latent type emulsion which is not fogged in advance is used, p-phenylenediamine-based Developed with a surface developer containing a color developer,
By bleaching and fixing, it is possible to directly form a positive color image. In particular, the photosensitive material of the present invention is advantageous in that good direct positive color images can be obtained even when using a low pH color developer having a pH of 11.5 or less. In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. It will be done. Useful flexible supports include films made from semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate complex, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α- Paper coated or laminated with 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, U.S. Patent No. 2,681,294, U.S. Pat.
Multiple layers may be applied simultaneously by the method described in, for example, 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 (
It is advantageous to use colorants of the type that are non-migratory) but release a diffusible dye (or its precursor) as a result of development. These diffusible dye-releasing coloring materials (DRR compounds) include couplers and redox compounds that release diffusible dyes, and these are used in the color diffusion transfer method (wet method).
It is useful not only as a coloring material for heat-developable photosensitive materials (dry method) as described in JP-A-58-58543, for example. When the photosensitive material of the present invention is used in a color diffusion transfer method, the photographic emulsion may be coated integrally on the same support on which the image-receiving layer is coated, or it may be coated on a separate support. may be coated on.

Further, the silver halide photographic emulsion layer (light-sensitive element) 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. 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 copiers, color hard copies for storing CRT images, and photosensitive materials for plate inspection of plate-formed films in color printing. The present invention also applies to “Research Disclosure” magazine N [L17123 (19
It can also be applied to black-and-white light-sensitive materials using a three-color coupler mixture, as described in the publication (published in July 1978). The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N,N-jethylaniline, 3 -methyl-4-amino-N-ethyl-N
-β-Hydroxyethylaniline, 3-methyl=4-amino-N-ethyl-N-β-methanesulfonic acid-ethylaniline, 3-methyl-4-amino-N-ethyl-N
Examples include monoβ-methoxychetylaniline and their sulfates, hydrochlorides, or P-toluenesulfonates.
Two or more of these compounds can be used in combination depending on the purpose. The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors such as bromide salts, iodide salts, penzimidazoles, penzothiazoles or merkabut compounds or It generally contains antifoggants, etc. In addition, if necessary, hydroxylamine, diethylhydroxylamine,
Sulfites, hydrazines, phenylse ξ carbazides,
Triethanolamine, catechol sulfonic acids, triethylenediamine (1,4-diazabisic acid [22.2
] Various preservatives such as octane), organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers,
Competitive couplers such as caprase agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-virazolidone, viscosity-imparting agents, aminobolycarboxylic acids, polyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids. Various cattle rate agents, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediastrawtetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-
1.1-diphosphonic acid, nitrilo-N,N,N-}rimethylenephosphonic acid, ethylenediamine-N,N,N'N
Typical examples include '-tetramethylenephosphonic acid, ethylene diamine di(O-hydroxyphenylacetic acid), and salts thereof. p of these color developing solutions
H is generally 9 to 12, and 9.5 to 1
1.5 is preferred. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is usually less than 11 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be reduced to 300. It can also be less than one. 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. The amount of replenishment can also be reduced by using means to suppress the accumulation of bromide ions in the developer. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, processing in two consecutive bleach-fix baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (III) and cobalt (I).
[), chromium (Vl), fJil (■), and other polyvalent metal compounds, peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide: dichromate; organic complex salts of iron ([1) or cobalt <1), such as ethylenedionetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1. Agonopolycarbonate M such as 3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.; persulfate bromate; manganate; nitrobenzenes, etc. may be used. Can be done. Bleach accelerators may be used in the bleaching solution, bleach-fixing solution, and their pre-baths, if necessary. The silver halide color photographic light-sensitive material of the present invention can be washed with water and/or after desilvering treatment.
Or, it is common to go through a stabilization process. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the material used, such as a coupler), the purpose, the temperature of the washing water, and the number of washing tanks (number of stages).
A wide range of settings can be made depending on replenishment methods such as , counterflow, forward flow, and various other conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is as follows:
the Society of Motton Pic
ture and Television Engine
ers Volume 64, P. 24B-253 (May 1955
You can obtain it using the method described in the monthly 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 at 5 to 40°C is selected. Furthermore, the photosensitive material of the present invention can also be processed directly with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-open No. 57-8.543 and 5-14.
All known methods described in No. 834, No. 60-220,345 can be used. Various chelating agents and antifungal agents can also be added to this stabilizing bath. The above washing and/
Alternatively, the overflow liquid resulting from replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

Various processing conditions in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate the processing and shorten the processing time, or conversely, lower the temperature to improve image quality and stability of the processing solution. It is possible to attain the precepts. The smaller the amount of replenishment in each treatment step, the better. The amount of replenisher is 0.0% compared to the conventional amount brought in per unit area of photosensitive material. 1 to 50 times is preferable, more preferably 3 to 3 times
It is 0 times.

The latent type emulsion-containing light-sensitive material of the present invention can directly produce a positive image by developing it using a surface developer. A surface developer is one in which the development process is substantially induced by a latent image or fog on the surface of silver halide grains. Although it is preferred not to include silver halide solubilizers in the developer solution, unless the internal latent image contributes substantially to the completion of development by the surface development centers of the silver halide grains, silver halide solubilizers (e.g. sulfite (salt) may be included. The developing solution may contain sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, sodium metaborate, etc. as an alkaline agent and a buffering agent. The content of these agents is
The pH of the developer is 9 to 13, preferably 10 to 11.
Choose 2. The developer also contains, for example, penzimidazoles, such as 5-nitropenzimidazole; benzotriazoles, such as penzotriazole, 5-
It is advantageous to include methyl-benzotriazoles, compounds commonly used as anti-capri agents.

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 containing the processing components necessary for developing the silver halide emulsion (and the format of the spreading transfer dye image).
The C medium is mainly water, and may also contain other hydrophilic solvents such as methanol and methyl cellosolve. Preferably, the treatment composition contains a hydrophilic polymer such as high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose. These polymers are preferably used so as to give the treated material a viscosity of 1 void or more, preferably about 500 to 1000 voids, at room temperature.

The above-mentioned treated knitted sole is disclosed in U.S. Patent No. 2,543.181,
No. 2,643,886, No. 2,653,732, No. 2,723,051, No. 3 056.491, No. 3
It is preferable to use it by filling it into a container that can be ruptured by pressure, such as those described in Japanese Patent No. 056,492 and No. 3.152.515.

(Examples) The present invention will be explained in detail in Examples below, but the present invention is not limited thereto.

Example-1 Gion support laminated on both sides with polyethylene (thickness 10
A sample lot of a color photographic light-sensitive material was prepared by coating the following 1st layer to 14th layer on the front side of 0 micron) and layer 15 to 16th layer on the back side. Titanium oxide is used as a white pigment in the polyethylene on the coating side of the first layer, and v&tc
o. Contains 0.003g/E) of ultramarine blue as a bluing material (
The chromaticity of the surface of the support is ss. in Lm, am, be system.
o, 0.20, -0.75. ). (Photosensitive layer composition) The components and coating amounts (in g/rrf units) are shown below. For silver halide, the coating amount is shown in terms of silver. The emulsions used in each layer were made according to the manufacturing method of emulsion EMI. However, the emulsion for the 14th layer was a Lippmann emulsion that was not surface chemically sensitized. 1st layer (antihalation layer) Black colloidal silver ...0.1
0 Gelatin ・・・・・・0.70
2nd layer (middle N) Gelatin 0.70
3rd layer (low sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1.2.3) (average grain size 0.25μ, size distribution [coefficient of variation] 8%, 0.04 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1.2.3) (silver chloride 5 mol%, average particle size 0.40μ
, size distribution 10%, octahedron)...0.08 Gelatin...i. oo
Cyan coupler (ExC-1, 2, 3 1:1:0.
2) ...0.3
0 Anti-fading agent (Cpd-1, 2, 3, 4, etc.!)...
・・0. 1 8 Coupler dispersion medium (Cpd-6) ...0.0
3 coupler solvents (Solv-1, 2, 3 equivalents)...
・・0. 12 4th layer (high sensitivity red sensitive layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1.2.3) (average grain size 0.60μ, size distribution 15%)
, octahedron) ...0.14 gelatin
...1.00 cyan coupler (ExC-1, 2, 3 1:1:0.2)
・・・・・・0.30 Anti-fading agent (Cpd
-1, 2, 3, 4 equivalents)...0.18 Coupler dispersion medium (Cpd-6)...0.0
3 coupler solvents (Solv-1, 2, 3 equivalents)...
...0.12 No. 511 (intermediate layer) Gelatin ...1.00 Color mixing prevention agent (Cpd-7) ...0.08
Color mixing inhibitor solvent (Solv-4, 5 equivalents)...
0,l6 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)
......Silver chlorobromide spectrally sensitized with 0.04 green sensitizing dye (ExS-4) (silver chloride 5 mol%, average particle size 0.40μ, size distribution 1O%,
Octahedron) ...0.06 Gelatin ...
・0, 80 magenta coupler (ExM-1, 2, 3, etc. 1) 0.11 Antifading agent (equal amounts of Cpd-5 and 9) 0.15 Stain Inhibitor (CPd-10, 11, 12 i.4:
t:i ratio) ...0.025 Coupler dispersion medium (Cpd-6) ...0.05 Coupler solvent (Solv-4, 6 equivalents) ...0 ．．
15 7th layer (high-sensitivity green-sensitive layer) Silver bromide (
Average particle size 0.65 μ, size distribution 16%, octahedral) ...0.10 gelatin
・・・・・・0.80 Magenta Cobra (ExM-1, 2, 3 equivalent) ・・・・・・0.11 Antifading agent (Cpd-5, 9 equivalent) ・・・・・・0.15 Stain inhibitor (Cpa-B, l1, l2 1.41:
1 ratio)...0.0.25 Coupler dispersion medium (Cpd-6)...0.05 Coupler solvent (Solv-4, 6 equivalents)...0 .15 8th layer (intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow Colloy l -・-・-0. 1
2 Gelatin ・・・・・・0.
70 Color mixing prevention agent (Cpd-7) ・・・・・・0
．． 03 Color mixing inhibitor solvent (Solv4, 5 equivalent)...
...0.10 Polymer latex (Cpd-8) ...0.07 10th layer (intermediate layer) 11th layer (low sensitivity blue sensitive layer) same as the 5th layer Blue sensitizing dye (ExS Silver bromide spectrally sensitized with -5, 6) (average grain size 0.40 μ, size distribution 8%, octahedral) ...0.07 blue sensitizing dye (ExS-5, 6) Silver chlorobromide spectrally sensitized with silver chloride (silver chloride 8 mol%, average grain size 0.60μ, size distribution 11
%, octahedron)...0.14 Gelatin...0.80
Yellow coupler (ExY-1, 2 etc!!k) Anti-fade agent (Cpd-14) Anti-stain agent (Cpd-15) Coupler dispersion medium (Cpd-6) Coupler solvent (Solv-2) 12th layer (high sensitivity Blue sensitizing dye (ExY-1, 6) Blue sensitizing dye (SnxS-5, silver bromide (average grain size 0. Distribution 18%, octahedral) Gelatin yellow coupler (ExY-1, 6) with spectral sensitization of 85μ, size ...0.15 ...0.60 2nd place!) ...0.30 ...0.10 Anti-fading agent (Cpd-14) Anti-staining agent (Cpd-15) Coupler dispersion medium (Cpd-6) Coupler solvent (Solv-2) 13th layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (Cpd-2, 4, ...0. ... ...0. ...0. ...0. ...0. ...0. ...0. ...0.・0.007 05 10...1.00 16 equivalent)...0. 50 Color mixing prevention agent (Cpd-7, 17 equivalent) ...0. 03 minute defeat medium (Cpd-6) ・・・・・・0.0
2 UV absorber solvent (Solv-2, 7 equivalents)...
・・0. 08 Anti-irradiation dye (Cpd-18, l9, 20
, 2L'l3 in a ratio of 10:10:13:15:20)
...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 ...0.
01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
...0.05 gelatin
...1.80 Gelatin hardening agent (H-1, H-2 equivalent) ...0.18 15th layer (back layer) Gelatin ...2.50
Ultraviolet absorber (Cpd-2, 4, l6 equivalent)...
・0.50 dye (equal amounts of Cpd-18, 19, 20, 21, l3)
・・・・・・0.06 1st
6 layers (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. 1 4 How to make emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was stirred vigorously into an aqueous gelatin solution and added simultaneously over a period of 15 minutes at 75"C to form an octahedral bromide with an average grain size of 0.40μ. Silver particles were obtained. 0.3 g of 3,4-dimethyl-
1. Sequentially add 3-thiazoline 2-thione, 6 parts of sodium thiosulfate and 7 ffig of chloroauric acid (tetrahydrate) 75
Chemical sensitization was carried out by heating at °C for 80 minutes. The particles obtained in this way were used as cores and further grown in the same precipitation environment as the first time, and the final average particle size was 0.7.
A monodisperse octahedral core/shell silver bromide emulsion of μ was obtained. The coefficient of variation in particle size was approximately 10%. S to this emulsion!
I. per 11 moles. 5■ Sodium thiosulfate and 1.
5 mg of chloroauric acid (tetrahydrate) was added and heated at 60°C for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion. Each photosensitive layer contains ExZK-1 and ExZK- as nucleating agents.
2 was used in an amount of 10-'101 feces weight percent based on silver halide. Furthermore, each layer contains alkanol XC (D
upon) and sodium alkylbenzenesulfonate, succinate ester and Magef as coating aids.
ac F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. CPd-23, 24, 25) was used as a stabilizer in the silver halide and colloidal silver containing layers. This sample was designated as sample number 101. The compounds used in the examples are shown below.

ExS-1 SO, SGff+?・N(CJs)s ExS-2 ExS-3 ExS-4 已xs-5 I SO3H-N(Cdb), ExS-6 CPd 1 Cpd-2 all14HノCpd-3 cp d-4 Cpd-5 Cpd 6 CONHC4Hw(t) Cpd 7 0H cP d-8 −+CH. -Cllt. COOCJ+s Cpd 9 jitts し■1 cpct l1 Cpd -12 Cpd -13 cpct 14 cpct 15 Oi+ Cpd 16 Cpd-17 0H Cpd -18 SO,κ SO,κ Cpd 19 Cpd-20 SOJ C p d-21 503K S03K SOJ Cpd-23 0H Cpd-24 OH C , d -25 EXC-1 EXC 2 Lf EXC-3 EXM-1 EXM-2 IH 7(t) EXM 3 EXY-1 Cl EXY-2 C1 3o1v-1 Solv -2 3o1v-3 Solv-4 Solv-5 Solv-5 '3o1v-7 1{-1 H-2 巳xZK-1 Di(2-ethylhexyl) sebacate trinonyl phosphate di(3-methylhexyl) phthalate tri cresyl phosphate dibutyl phthalate trioctyl phosphate di(2-ethylhexyl) phthalate 1,2-bis(vinylsulfonylacetamido)ethane 4 6-dichloro 2-hydroxy-1,3,5-triazine Na salt 7-(3-ethoxythio) nylaminobenzamide)-9 monomethyl-IO-prohagi-1,2,3.4-tetrahydroacridinium trifluoromethanesulfonateExZK-2 2 - (4 - (3 - (3
-(3-(5-(3-(2-chloro5-(1-dodecyloxycarbonylethoxycarbonyl)phenylcarbamoyl)-4-hydroxy-1-naphthylthio}tetrazol-1-yl)phenyl)ureido]benzene Next, the yellow coupler in the 11th and 12th layers of sample 101 was replaced with the yellow coupler of the present invention shown in Table 1 in an equimolar amount, and a nucleation accelerator was added. Added sample 102~
109 was produced.

Table 1: The amount added is 3.0% per liter of silver halide in the silver halide emulsion layer. Samples 101 to 109 obtained as above, which were made into OXIO-'monochrome, were subjected to normal wedge exposure (3200K O.1 seconds 10 CMS), and then processed using the method described below using an automatic developing machine. The tank was continuously processed until the cumulative amount of liquid refilled was three times the tank capacity. Processing process Time Temperature Mother liquor 9'l volume
Replenishment amount color development 135 seconds 38°C 1 5
ffi 3GOd/rrf bleach fixing 40〃33
〃3〃300 Washing (1) 40 〃33〃3〃 Washing (2) 40〃33〃3〃320〃Drying 30#80〃 The method of replenishing the washing water is to replenish it to the washing bath (2) and (
A so-called counter-current replenishment system was adopted in which the overflow liquid from step 2) was introduced into the washing bath (1). At this time, the amount of bleach fixing solution brought into the washing bath (1) from the bleach-fixing bath for photosensitive materials is 3
The reduction was 5%/%, 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 solution was as follows. D-sorbitol 0.15 g 0.20 g Sodium naphthalene sulfonate 0.15 g 0.20 g
Formalin condensate ethylenediaminetetrakis 1.5g 1.
58 Methylenephosphonic acid Diethylene glycol Benzyl alcohol Potassium bromide Penzotriazole Sodium sulfite NN-Bis(carboxymethyl)hydrazine D-Glucose triethanolamine N-ethyl-N-(β-methanesulfonamidoethyl) 3-Methyl-4-amino Aniline sulfate potassium carbonate optical brightener (diaminostilbene type) 12.0d 16. f) d 13.5d 18.0d 0.85g 0.003g 0.004g 2.4g 3.2g 6.0g 8.0g 2.0g 2.4g 6.0g 8.0g 6.4g 8.5g 30. 0 g 25.0 g 1.0 g 1.2 g pH (25°C) 10.25 10.75 Reduction U Otsu 4 liquid ethylenediaminetetraacetic acid, 2 4.0g Same as mother liquor, sodium dihydrate, ethylenediaminetetraacetic acid・70.0 gFe(I
II) ・Ammonium dihydrate ammonium thiosulfate (70 180lli!O
g/1 Sodium p-toluenesulfinate 20. O g Thorium Sodium Bisulfite 20.0 g 5-Merkabuto-1.3,4 0.5 g Monotriazole Ammonium Nitrate IO. Add og water to 1000dpH (25"C)
6.20 extracts mother liquor,
Add the replenisher and tap water to H-type strongly acidic cation exchange resin (Amberlite IR-1.20B manufactured by Rohm and Haas).
and OH type anion exchange resin (Amberlite IR-
Water was passed through a mixed bed column packed with 400) to reduce the concentration of calcium and magnesium ions to 3/l or less,
Subsequently, 20 μ/l of sodium dichloride isocyanurate and 1. 5g/j! was added. The pH of this solution was in the range of 6.5 to 7.5. Maximum image density (Dmax) and minimum image density (Ilain) of the yellow image obtained by developing in this way
was measured using λwax. In addition, λmax+60n
The ratio of Dmax at m to Daiax at λIlax was measured and summarized in Table 2. Table 2 As is clear from Table 2, samples 103 to 103 according to the present invention
Sample No. 109 had a higher maximum image density and a lower minimum image density than Comparative Samples 101 and 102, and was preferable. In addition, Samples 103 to 109 according to the present invention had good absorption edges on the long wavelength side and were favorable in terms of color reproduction. Example-2 The sample obtained in Example 1 was treated with N- in a color developing solution.
Ethyl-N-(β-methanesulfonamidoethyl)-3
-N-ethyl-N-(β-methanesulfonadeξdoethyl)-4 instead of methyl-4-aminoaniline sulfate
-aminoaniline sulfate or N-ethyl-N-(β
Example 1 was repeated except that the processing solution was replaced with an equimolar amount of 4-aminoaniline sulfate (hydroxyethyl)-4-aminoaniline sulfate, and the same results as in Example 1 were obtained.

〔Effect of the invention〕

By using the constitution of the claims, in particular, a specific yellow coupler and a specific nucleation accelerator, the maximum concentration (
It is possible to obtain a direct positive color image with high D (old X) and low minimum density (Da+in) and good brown color reproducibility.

Claims (1)

[Scope of Claims] A direct positive photographic light-sensitive material having at least one internal latent image type silver halide emulsion layer that is not pre-fogged on a support, comprising a compound represented by the following general formula [I], and a compound represented by the following general formula [I]; A direct positive photographic material containing a compound represented by formula [II] and/or [III]. [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [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 class 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. ] [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Q represents the atomic group necessary to form a 5- or 6-membered heterocycle. Further, this heterocycle may be fused with a carbon aromatic ring or a heteroaromatic ring. L represents a divalent linking group consisting of an atom or atomic group selected from a hydrogen atom, a carbon atom, a nitrogen atom, an oxygen atom, and a sulfur atom, and R^3^A represents a thioether group, an amino group,
Represents an organic group containing at least one ammonium group, ether group, or heterocyclic group. n represents 0 or 1, and m represents 0, 1 or 2. M represents a hydrogen atom, an alkali metal atom, an ammonium group, or a group that cleaves under alkaline conditions. [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Q' represents the atomic group necessary to form a 5- or 6-membered heterocycle capable of forming iminosilver, and L, R^3^A
, n, and M have the same meanings as in the general formula [II]. p represents 1 or 2.