JPH01241540A - Direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the max. optical density for the preferable photographic density of the title material, and to reduce the generation of stain, and to improve the stability with age of the sensitive material by incorporating a compd. which has an oxidizing property capable of cleaving a single bond and does not release a substance having a photographic effect, in a supporting body. CONSTITUTION:At least the direct positive emulsion having a hydrazine type nucleus-forming inner latent image, and the compd. which has the oxidizing property capable of cleaving the single bond by being reduced and does not release the substance having the photographic effect are incorporated in the supporting body. The compd. is the oxidative compd. capable of cleaving the single bond by being reduced. For example, the cleavable single bond is a nitrogen-oxygen bond, a nitrogen-nitrogen bond or a nitrogen-sulfur bond. Thus, the lack of the max. density, the generation of the stain, the generation of the stain at the min. optical density part and the deterioration of the stability with age are prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION (Technical Field of Application of the Invention) The present invention relates to a photographic material having an internal latent image type positive silver halide emulsion. In particular, the present invention relates to the above-mentioned photographic material containing a compound that acts as a nucleation accelerator.

(Prior Art) Attempts have heretofore been made to directly obtain positive images by utilizing various development effects. Regarding these, T, H, Jam
Written by es ” The Theory or
the Photographic Process'
(4'Lh edition) 182~p 19
1, but all of them provided insufficient photographs. In contrast, in recent years, it has become possible to obtain positive light-sensitive materials with high sensitivity and good discrimination by using an internal latent image type direct positive emulsion that has not been fogged in advance in combination with a nucleating agent. For example, it is described in US Pat. No. 3,761°276.

The nucleating agent used here must be sufficiently stable during storage of the photosensitive material and have sufficient activity to generate surface fog nuclei during development, and hydrazine compounds are effective. Are known.

However, this hydrazine-based nucleating agent has a problem in that its activity may not be fully expressed depending on how it is used.

For example, in photographic materials made by coating an internal latent image type direct positive emulsion on a support with low oxygen permeability, such as a polyethylene terephthalate support, the nucleation effect of the hydrazine compound is insufficient. It is known that a phenomenon occurs in which sufficient image density cannot be obtained.

As a technology to solve this problem, rResearch
A method using a strong oxidizing agent such as ferricyanide in a silver halide emulsion, as described in Disclosure J Magazine Maru 16929 (1978) and Na 16936 (1978), and U.S. Patent No. 4,341.8
A method using a quinone oxidizing agent in a silver halide emulsion layer as described in No. 58, and a method using an azo compound as described in JP-A-60-173541 have been proposed.

However, the first method has problems such as insufficient maximum density and the occurrence of stains, the second method causes stains to occur in the lowest density area, and the third method deteriorates the stability of the photosensitive element over time. There is a problem.

(Object of the Invention) Therefore, the object of the present invention is to provide a novel nucleation accelerator that provides a maximum density desirable for photography, does not cause staining in the lowest density area, and has excellent stability over time. There is a particular thing. Furthermore, it is an object of the present inventors to provide an internal latent image type positive silver halide photographic light-sensitive material containing such a nucleation accelerator. A direct positive emulsion characterized by having a hydrazine-based nucleating agent internal latent image type direct positive emulsion and an oxidizing compound that causes single bond cleavage when reduced and does not release any photographic effect. It has been found that the above objects can be effectively achieved by a silver halide photographic light-sensitive material.

The above nucleation accelerator used in the present invention has the following general formula (
Compounds represented by the following are preferred.

The compound represented by general formula (I) is an oxidizing compound whose single bond is cleaved upon reduction, and the single bond cleaved here is a nitrogen-oxygen bond, a nitrogen-nitrogen bond, or a nitrogen-sulfur bond. be.

In the formula, R1, R1 and R3 are substituents other than hydrogen atoms, and at least one of them represents an electron-accepting group.

X represents an oxygen atom, a sulfur atom, or R'-N<.

R4 represents a substituent other than a hydrogen atom or a simple bond. When X is R'-N<, at least one of R1-R4 represents an electron-accepting group.

R1 and R1, R1 and Rff, R3 and R4, and R4 and R1 may be bonded to each other to form a ring.

-S The compound represented by formula (1) is preferably one represented by general formula (b) mainly from a synthetic viewpoint.

General formula (■) In the formula, Rs represents a group bonded to X and N to form a 3- to 8-membered heterocycle.

R'' and R4, R' and R', R' and R' 4:l
a may be bonded to each other to form a ring.

Examples of the groups RI SR1, R3 and R4 include the groups described below.

Nitro group, cyano group, carboxy group, sulfo group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), alkyl group, aralkyl group (optionally substituted alkyl group, aralkyl group) Methyl group, trifluoromethyl group, benzyl group, chloromethyl group, dimethylaminomethyl group, ethoxycarbonylmethyl group, aminomethyl group, acetylaminomethyl group, ethyl group, 2-(4-dodecanoylaminophenyl)ethyl group, Carboxyethyl group, allyl group, 3.3.3-)lichloroprobyl group,
n-propyl group, 1so-propyl group, n-butyl group,
1so-butyl group, 5ec-butyl group, t-butyl group,
n-pentyl group, 5ec-pentyl group, 1-pentyl group, cyclopentyl group, n-hexyl group, 5ec-hexyl group, t-hexyl group, cyclohexyl group, n-octyl group, 5ec-octyl group, t-octyl group , n-decyl group, n-undecyl group, n-dodecyl group, n-tetradecyl group, n-benzodecyl group, n-hexadecyl group,
5ec-hexadecyl group, t-hexadecyl group, n-octadecyl group, t-octadecyl group, etc.), alkenyl group (optionally substituted alkenyl group).

For example, vinyl group, 2-chlorovinyl group, 1-methylvinyl group, 2-cyanovinyl group, cyclohexen-1-yl group, etc.), alkynyl group (optionally substituted alkynyl group).

For example, ethynyl group, 1-propynyl group, 2-ethoxycarbonylethynyl group), aryl group (optionally substituted aryl group, etc.), phenyl group, naphthyl group, 3-hydroxyphenyl group, 3
-chlorophenyl group, 4-acetylaminophenyl group,
4-hexadecanesulfonylaminophenyl group, 2-methanesulfonyl-4-nitrophenyl group, 3-nitrophenyl group, 4-methoxyphenyl group, 4-acetylaminophenyl) Lt group, 4-methanesulfonylphenyl group,
2゜4-dimethylphenyl group, 4-tetradecyloxyphenyl group, etc.), heterocyclic group (optionally substituted heterocyclic group 0, e.g. ■-imidazolyl group, 2-furyl group, 2-pyridyl group, 5- Nitro-2-pyridyl group, 3-pyridyl group, 3,5-dicyano-2-pyridyl group, 5-tetrazolyl group, 5-phenyl-1-tetrazolyl group, 2-benzthiazolyl group,
2-benzimidazolyl group, 2-benzoxasilyl group, 2-oxazolin-2-yl group, morpholino group, etc.)
, Acyl group (optionally substituted acyl group 0 For example, acetyl group, propionyl group, butyroyl group, 1so-butyroyl group, 2,2-dimethylpropionyl group, benzoyl L3.4-dichlorobenzoyl group, 3-acetylamino- 4-methoxybenzoyl group, 4-methylbenzoyl group, etc.), Su/L/honyl group (optionally substituted sulfonyl group. For example, methanesulfonyl group, ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonyl group, butanesulfonyl group) group, n-octanesulfonyl group,
n-dodecanesulfonyl group, n-hexadecanesulfonyl group, benzenesulfonyl group, 4-toluenesulfonyl group, 4-n-V decyloxybenzenesulfonyl group, etc.), carbamoyl group (optionally substituted carbamoyl group 0, etc.), carbamoyl group , methylcarbamoyl group, dimethylcarbamoyl group, bis-(2-methoxyethyl)
Carbamoyl group, diethylcarbamoyl group, cyclohexylcarbamoyl group, di-n-octylcarbamoyl group, 3-dodecyloxypropylcarbamoyl group, hexadecylcarbamoyl group, 3-(2,4-di-t-pentylphenoxy)propylcarbamoyl group, 3-octanesulfonylaminophenylcarbamoyl group, di-n-octadecylcarbamoyl group, etc.), sulfamoyl group (
Sulfamoyl group which may be substituted, for example, sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, bis-(2-methoxyethyl)sulfamoyl group, diethylsulfamoyl group, di-n-butylsulfamoyl group group, methyl-n-octylsulfamoyl
, n-hexadecylmethylsulfamoyl group, 3-ethoxypropylmethylsulfamoyl group, N-phenyl-N-methylsulfamoyl group, 4-decyloxyphenylsulfamoyl group, methyloctadecylsulfamoyl group Such).

At least one of R1 to R4 represents an electron-accepting group.

The electron-accepting group may be any group as long as it accepts electrons, but those represented by the following formula (EAG) are preferred.

Formula (RAG) ■, represents an atomic group forming a 3- to 8-membered ring together with Z+ and Zt, and n is an integer from 3 to 8.
: Zs Za Zs-1Vh: 23 Z
a-Zs Za-1Vq knee Zs Za Zs
Zh-Z, -1V@: Zs Za 25 Z
h-ZvZs-.

Sub Sub I Zz~Zs each represents -C-1-N-1-0-Sub -S-1 or -8O1-, and Sub is a simple bond (π bond), a hydrogen atom, or a substituent described below. Sub represents the general formula ( In A), the Hammett substituent constant σ of the substituent
, the sum of +0.09 or more, more preferably +0.3
above, most preferably +0.45 or above.
Select b.

Examples when Sub is a substituent are listed below (each preferably has 0 to 40 carbon atoms).

Substituted or unsubstituted alkyl groups (e.g. methyl group, ethyl group, 5ec-butyl group, t-octyl group, benzyl group, cyclohexyl group, chloromethyl group, dimethylaminomethyl group, n-hexadecyl group, trifluoromethyl group, 3 .3.3-Trichloropropyl group, methoxycarbonylmethyl group, etc.) Substituted or unsubstituted alkenyl group (e.g. vinyl group, 2-chlorovinyl group, 1-methylvinyl group, etc.), substituted or unsubstituted alkynyl group ( For example, ethynyl group, 1-propynyl group, etc.), cyano group, nitro group, halogen atom (fluorine, chlorine, bromine, iodine), substituted or unsubstituted heterocyclic residue (2-pyridyl group, l-imidazolyl group) , benzothiazole-2-
yl group, morpholino group, benzoxazol-2-yl group), sulfo group, carboxyl group, substituted or unsubstituted aryloxycarbonyl or alkoxycarbonyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxycarbonyl group) , 2-methoxyethoxycarbonyl group, phenoxycarbonyl group, 4-cyanophenylcarbonyl group, 2-chlorophenoxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group (e.g., carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, methyl Hexadecylcarbamoyl group, methyloctadecylcarbamoyl group, 2
, 4゜6-dolychlorophenylcarbamoyl group, N-ethyl-N-phenylcarbamoyl group, 3-hexadecylsulfamoylphenylcarbamoyl group, etc.), hydroxyl group, substituted or unsubstituted ab group (e.g. phenylazo group, p -methoxyphenylazo group, 2-cyano-
4-methanesulfonylphenylazo group, etc.), substituted or unsubstituted aryloxy or alkoxy groups (e.g. methoxy group, ethoxy group, dodecyloxy group, benzyloxy group, phenoxy group, 4-methoxyphenoxy group, 3-acetylaminophenoxy group) 3-methoxycarbonylpropyloxy group, 2-trimethylammonioethoxy group, etc.) sulfino group, sulfeno group, mercapto group, substituted or unsubstituted acyl group (e.g. acetyl group, trifluoroacetyl group, n-butyroyl group, t-
butyroyl group, benzoyl group, 2-carboxybenzoyl group, 3-nitrobenzoyl group, formyl group, etc.), substituted or unsubstituted teryl or alkylthio group (e.g. methylthio group, ethylthio group, [-octylthio group, hexadecylthio group) , phenylthio group, 2,4.5-
) dichlorophenylthio group, 2-methoxy-5-t-octylphenylthio group, 2-acetylaminophenylthio group, etc.), substituted or unsubstituted aryl group (e.g. phenyl group, naphthyl group, 3-sulfophenyl group, 4-
methoxyphenyl group, 3-lauroylaminopheno group), substituted or unsubstituted sulfonyl group (e.g. methylsulfonyl group, chloromethylsulfonyl group, n-octylsulfonyl group, n-hexatecylsulfonyl group, 5
ec-octylsulfonyl group, p-)luenesulfonyl group, 4-chlorophenylsulfonyl group, 4-dodecylphenylsulfonyl group, 4-dodecyloxyphenylsulfonyl group, 3-nitrophenylsulfonyl group, etc.) substituted or unsubstituted sulfinyl group (e.g. methylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, 4-nitrophenylsulfinyl group, etc.), substituted or unsubstituted amino groups (e.g. methylamino group, diethylamino group, amino group, methyloctadecylamino group, phenylamino group) group, ethylphenylamino group,
3-tetradecylsulfamoylphenylamino group, acetylamino group, trifluoroacetylamino group, N-
Hexadecyl acetylamino group, N-methylbenzoylamino group, methoxycarbonylamino group, phenoxycarbonylmethylamino group, N-methoxyacetylamino group, amidinoamino group, phenylaminocarbonylamino group, 4-cyanophenylaminocarbonylamino group,
N-ethylethoxycarbonylamino group, N-methyldodecylsulfonylamino group, N-(2-cyanoethyl)
-p-toluenesulfonylamino group, hexadecylsulfonylamino group, trimethylammonio group, etc.), substituted or unsubstituted sulfamoyl group (e.g. dimethylsulfamoyl group, sulfamoyl group, hexadecylsulfamoyl group, methyloctadecylsulfamoyl group), Famoyl group, methylhexadecylsulfamoyl group, 2-cyanoethylhexadylsulfamoyl group, phenylsulfamoyl group, N-(3,4-dimethylphenyl)-N-octylsulfamoyl group, dibutylsulfamoyl group moyl group,
Substituted or unsubstituted acyloxy groups such as dioctadecylsulfamoyl group, bis-(2-methoxycarbonylethyl)sulfamoyl group (e.g., acetoxy group, benzoyloxy group, chloroacetoxy group, etc.),
Examples include substituted or unsubstituted sulfonyloxy groups (eg, methinosulfonyloxy, Lp-toluenesulfonyloxy, p-chlorophenylsulfonyloxy, etc.).

More specific examples of electron-accepting groups include aryl groups substituted with at least one electron-withdrawing group (e.g., 4-nitrophenyl group, 2-nitro-4-N-methyl-N -octadecylsulfamoylphenyl group, 2-N
, N-dimethylsulfamoyl-4-nitrophenyl group, 2-cyano-4-octadecylsulfonylphenyl group, 2゜4-dinitrophenyl group, 2,4.6-dolycyanophenyl group, 2-nitro-4-N -Methyl-N-octadecylcarbamoylphenyl group, 2-nitro-5-octylthiophenyl group, 2,4-dimethanesulfonylphenyl group, 3.5-dinitrophenyl group, 2-chloro-4
-nitro-5-methylphenyl group, 2-nitro-3,5
-dimethyl-4-tetradecylsulfonylphenyl group,
2.4-dinitronaphthyl group, 2-ethylcarbamoyl-4-nitrophenyl group, 2.4-bis-dodecylsulfonyl-5-trifluoromethylphenyl group, 2.3,
4,5.6-pentafluorophenyl group, 2-acetyl-4-nitrophenyl group, 2.4-diacetylphenyl group, 2-nitro-4-fluoromethylphenyl group, etc.), substituted or unsubstituted hetero ring (e.g. 2-
Pyridyl group, 2-pyrazyl group, 5-nitro-2-pyridyl group, 5-N-hexadecylcarbamoyl-2-pyridyl group, 4-pyridyl group, 3,5-dicyano-2-pyridyl group, 5-dodecylsulfonyl group -2-pyridyl group, 5-
Cyano-2-pyrazyl group, 4-nitrothiophene-2-
yl group, 5-nitro-1,2-dimethylimidazole-
4-yl group, 3.5-diacetyl-2-pyridyl group, 1
-dodecyl-5-carbamoylpyridinium-2-yl group, etc.), substituted or unsubstituted quinones (e.g., 1
, 4-benzoquinon-2-yl group, 3.5.6-)samethyl-1,4-benzoquinon-2-yl group, 3-methyl-1,4-naphthoquinon-2-yl group, 3,6-simethyl-5 -hexadylthio-1,4-benzoquinone-2
-yl group, 5-pentadecyl-1゜2-benzoquinone-
4-yl group) or, in addition to the vinyllobes listed above, nitroalkyl groups (e.g. 2-nitro-2-
propyl group, nitroalkenyl group (e.g., 2-nitroethynyl group), monovalent group of α-diketo compound (e.g., 2-oxopropanoyl group, etc.), nitroalkane,
Examples include nitroalkenes.

As mentioned above, R5 is bonded to a nitrogen atom and an oxygen atom, and 3 to
This represents the atomic group necessary to form an 8-membered heterocycle, and below are some examples of this heterocycle.

R4 represents the same meaning as above, and R6-R13 represents a hydrogen atom or the same meaning as Sub above.

However, the content of the present invention is not limited to the above examples of heterocycles, and any substituents can be selected for the heterocycles.

Specific compound examples are described below, but the present invention is not limited thereto.

C0NHCHHzC1liCHtOC+ zLs+31
f4
1C0NHC+J33 C0NH+CHz±JC+5Hzq ■ NO1 NO7 NO! Fff (b) ■ ■ SO□CH3 C0NHC+Jgs oz CONHC+allis NO□ c+tH1% C1@83? Regarding the synthesis of the compound used in the present invention, when X is oxygen, see Japanese Patent Application Laid-Open No. 62-215270, and when X is 1-N- containing a nitrogen atom, see Japanese Patent Application No. 62-34.
No. 953, when X is a sulfur atom, JP-A No. 62-
It can be synthesized by referring to the synthesis method described in No. 244048 and Japanese Patent Application No. 62-34954.

The compound of general formula (1) may be added in the silver halide emulsion layer or in a layer adjacent thereto, but it is preferably contained in the emulsion layer.

The amount of the compound of the present invention added is necessary and sufficient to promote nucleation, but specifically, 1 g of silver in a silver halide emulsion is added.
0.01 snol to 20 +1 IIOI, preferably 0.05 ssol to 5 ms+ol.

The compound of the present invention can be dispersed in a hydrophilic colloid as a carrier by various methods depending on the type of the compound. It can be dissolved in an alkaline aqueous solution and then added to a hydrophilic colloid solution for dispersion. On the other hand, compounds that are difficult to dissolve in aqueous media but easy to dissolve in organic solvents can be dispersed by the following method.

(2) A method in which a solution of a compound dissolved in a substantially water-insoluble high-boiling solvent is added to a hydrophilic colloid solution for dispersion.This method is described, for example, in U.S. Pat.
, No. 533,514 and No. 2゜801.171. Further, if necessary, a low boiling point solvent or an organic solvent easily soluble in water may be used, and these solvents are removed by volatilization by drying, washing with water, etc.

■ A method of dissolving a compound in a water-miscible solvent and then dispersing it in a hydrophilic colloid solution. This method is described, for example, in JP-A-53-13
No. 8726.

(2) A method in which a hydrophilic polymer is used in place of the high-boiling point solvent or in combination with the high-boiling point solvent in (1) above. Regarding this method, for example, US Pat. No. 1 619.195, West German Pat.
No. 957.467.

(1) A method of dissolving a compound in a water-miscible solvent and then gradually adding aqueous latex to this solution to obtain a dispersion in which the compound is contained in latex particles.This method is described in, for example, Japanese Patent Application Laid-Open No. 51-59943. It is described in.

In addition, hydrosil, a lipophilic polymer described in Japanese Patent Publication No. 51-39835, may be added to the hydrophilic colloid dispersion obtained above.

Dispersion of the compounds of this invention is significantly aided by the use of surfactants as emulsification aids. Useful surfactants are described, for example, in the above-mentioned patent specifications and in Japanese Patent Publication No. 39-492.
No. 3, US Pat. No. 3,676.141.

A typical hydrophilic colloid used to disperse the compound or coloring material of the present invention is gelatin, but gelatin may be partially or completely replaced with a synthetic hydrophilic colloid.

The support used in the photosensitive material of the present invention is not particularly limited as long as it has good dimensional stability, but polyester supports with poor oxygen permeability, such as polyethylene and polycarbonate supports, In particular, the use of a polyethylene terephthalate support is most effective.

The inner layer type direct positive silver halide emulsion that can be used in the present invention is not particularly limited, and conventionally known ones can be used. A silver halide inner core doped with metal ions, chemically sensitized, or both, and a silver halide exterior covering at least the photosensitive sites of the inner core. “Core/shell type” halogenation consisting of acid (shell)! 1. Emulsions and the like can be used, but it is particularly preferable to use core/shell type emulsions.

In order to dope the core of the core/shell silver halide grains used in the present invention with metal ions, for example, cadmium salt, zinc salt, lead salt, thallium salt, etc. A method can be adopted in which a metal ion source such as iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or a complex salt thereof is allowed to coexist.

The metal ion is usually 10-h per 111 moles of halide.
Use in a molar or higher proportion. The core silver halide may be chemically sensitized using one or more of noble metal sensitizers, sulfur sensitizers, and reduction sensitizers instead of or in addition to the metal ion doping described above, especially metal sensitization. Sulfur sensitization increases sensitivity. The method of treating silver halide of the core and coating the surface of the silver halide grains constituting the core with silver halide serving as a shell is known, for example, as described in U.S. Pat. No. 3,206,316 and U.S. Pat. , No. 317, 322,
The methods described in Patent No. 3,367.778 (excluding the step of fogging the particle surface) and Patent No. 3.761,276 can be advantageously applied.

The ratio of silver halide in the core to tm halide in the shell is arbitrary, but the ratio of the latter to 1 mole of the former is usually 0.
It is preferable to use 5 to 8 moles.

The silver halides in the core and shell preferably have the same composition, but may have different compositions. In the present invention, silver halides in the core and shell include, for example, silver bromide and iodide. Silver, silver chloride, silver chlorobromide, silver bromoiodide, silver iodide, etc. can be used. Preferred silver halides consist of at least 50 mole percent silver bromide, most preferred when both the core and shell are silver bromide.

Although core/shell silver halide grains having a variety of grain sizes may be used in the present invention, the average grain diameter is about 0.
．． Core/shell silver halide grains of 1 to 2.5 microns, preferably about 0.2 to 2.5 microns, and preferably about 0.8 to 2.0 microns give good results.

Core/shell silver halide grains may have regular crystal structures such as cubic or octahedral, or irregular crystal structures such as spherical or plate-like.
lar), or a composite of these crystal forms, or even a mixture of particles of various crystal forms.

Examples of plate-shaped internal latent image type core/shell silver halide emulsions include, for example, European Patent No. 79583 and British Patent No. 21.
11706A and 2110831A are useful.

Such core/shell silver halide grains of the present invention are dispersed in a binder in a known manner.

As a binder it is advantageous to use gelatin, but
Other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate esters, sodium nialginate, starch derivatives, etc. t1! Derivatives and the like can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Photo,
Oxygen-treated gelatin as described in Japan, N116.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. As gelatin derivatives, various compounds such as acid halides, t11 anhydride, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples include U.S. Patent No. 2,614,928,
No. 3.132°945, No. 3,186,846, No. 3,312.553, British Patent No. 861,414, No. 1.

No. 033.189, No. 1,005,784, Special Publication No. 4
2-26845, etc.

As the gelatin graft polymer, a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, their esters and amides, etc., acrylonitrile, styrene, etc. is grafted onto gelatin. can be used. In particular,
Preferred are graft polymers of gelatin with polymers that have some degree of compatibility with gelatin, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates, examples of which are described in U.S. Pat. No. 2,763,625. No. 2,83
1. , No. 767, 2. 956. It is described in issues such as No. 884.

Typical synthetic hydrophilic polymer substances are, for example, patented in West Germany.
(OLS) No. 2,312.708, U.S. Patent No. 3,620
, No. 751, 3. 879. No. 205, Special Publication No. 43
-7,561. In addition, for the purpose of improving the passage of processing liquids, in the photographic emulsion layer, etc., inert grains (substantially non-swellable in aqueous alkali, compatible with gelatin, and substantially non-film forming) are added. (preferably polymer latex) may also be included. As the polymer latex, for example, acrylic acid or methacrylic acid-based polymer (homopolymer or copolymer) latex or styrene-based polymer (homopolymer or copolymer) latex can be used.

The photographic emulsion used in the present invention does not require chemical sensitization of the silver halide grain surfaces, but may be chemically sensitized to some extent, and the photographic emulsion may be spectrally sensitized with methine dyes or the like.

Hydrazine-based nucleating agents that can be used in the present invention include the hydrazines described in U.S. Patent Nos. 2,588,982 and 2,563.785; Hydrazone neck; US Patent 3, 7
18,470, which has a fogging effect (nu
creating) substituent in the dye molecule; U.S. Pat.
No. 27, No. 4.245,037, No. 4,255.51
No. 1, No. 4,266.013, No. 4,276.364
Thiourea-bonded acylhydrazine compounds described in British Patent No. 2,012,443; U.S. Patent No. 4,
374,923; and U.S. Pat. No. 4,080,270,
No. 4.278,748, British Patent No. 2,011,391
Typical examples include acylhydrazine compounds in which a thioamide ring or a heterocyclic group such as triazole or tetrazole described in Section B etc. is bonded as an adsorption group.

The amount of nucleating agent used herein is preferably such that the photographic emulsion of this invention will provide a sufficient maximum of 4 degrees when developed in a surface developer. In practice, the appropriate content may vary over a wide range, depending on the properties of the silver halide emulsion used, the chemical structure of the nucleating agent, and the development conditions, but the appropriate content may vary over a wide range, but approximately 21% per mole in the photographic emulsion. 0
．． A range of 1-5g is practically useful, preferably! ! 1
From about 0.5 to about 2 grams per mole.

The light-sensitive material of the present invention can be used for both black and white photography and color photography. Specific uses of this photosensitive material include photosensitive materials for scene use, photosensitive materials for printing, photosensitive materials for printing, photosensitive materials for X-rays, photosensitive materials for black and white photography, photosensitive materials for diffusion transfer, and heat-developable photosensitive materials. The photosensitive material of the present invention can be used in a wide range of fields, such as materials, photosensitive materials for silver dye bleaching, and photosensitive materials for movies.

When the photosensitive material of the present invention is used for color, various coloring materials are used in the photosensitive material.One of the most representative coloring materials is a coupler. The coupler preferably has a hydrophobic group called a ballast group in its molecule and is non-diffusive.The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor upon development (so-called DIR coupler).The coupler may be a coupler in which the product of the campling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, benzoylacetanilide and pivaloylacetanilide compounds are particularly useful.

As the magenta coloring coupler, pyrazolone compounds, indashilon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly useful.

Also useful are pyrazolotriazole compounds, pyrazoloimidazole compounds, and pyrazolopyrazole compounds.

As the cyan coloring coupler, phenolic compounds, naphthol compounds, etc. can be used.

In addition, colored couplers, DIR couplers (particularly DIR couplers that release highly diffusible development-inhibiting substances), etc. can be used in combination.

In addition to the DIR coupler, the light-sensitive material may contain a compound that releases a development inhibitor upon development; for example, U.S. Pat. Nos. 3,297,445 and 3,379,529
Those described in OLS No. 2,417,914, and Japanese Patent Application Laid-open Nos. 52-15271 and 53-9116 can be used.

Two or more types of couplers can be contained in the same layer.

The same compound may be contained in two or more different layers.

The coupler is generally 2 x 104 per mole of silver in the emulsion layer.
moles to 5 x 10-' moles, preferably I x
10-'' moles to 5 X 10-'' moles are added.

Further, when the photosensitive material of the present invention is used for color diffusion transfer, either a positive type or a negative type can be used as the coloring material, but it is preferable to use a negative type coloring material. The coloring material itself is non-diffusible (non-mobile) under alkaline conditions (in the developer), but as a result of development,
It is advantageous to use colorants of the type that release diffusible dyes (or their precursors). Diffusible dye-releasing coloring materials include couplers and redox compounds that release diffusible dyes, and these are used not only for color diffusion transfer methods (wet method) but also as described in JP-A No. 58-58543. It is also useful as a coloring material for heat-developable sensitive materials (dry method), such as those shown in

The diffusible dye-releasing redox compound (hereinafter referred to as "DRR compound") can be represented by the following general formula.

Here, DYE represents a dye or its precursor, and Y represents a component that provides a compound having diffusivity different from that of the above compound under alkaline conditions. Depending on the function of Y, compounds are broadly classified into negative-type compounds that are diffusible in the silver developed area and positive-type compounds that are diffusible in the undeveloped area.

Specific examples of negative-type Y include those that oxidize and cleave as a result of development to release a diffusible dye.

Specific examples of Y include U.S. Pat. No. 3,928.312 and U.S. Pat.
No. 93,638, No. 4.076.529, No. 4.15
No. 2,153, No. 4,055,428, No. 4,053
, No. 312, No. 4,198゜235, No. 4,179,
No. 291, No. 4,149.892, No. 3,844,7
No. 85, No. 3゜443.943, No. 3,751,40
No. 6, No. 3,443,939, No. 3,443,940
No. 3,628,952, No. 3,980,479, No. 4,183,753, No. 4. 142. 891
No. 4,278,750, No. 4,139°379, No. 4,218,368, No. 3,421.964,
4,199,355, 4゜199.354, 4,135,929, 4.336,322, 4
, No. 139,389, JP-A No. 53-50736, No. 5
No. 1-104343, No. 54-130122, No. 53
-110827, 56-12642, 56-1
No. 6131, No. 57-4043, No. 57-650,
No. 57-20735, No. 53-69033, No. 54
-130927, 56-164342, 57-
119345 etc.

Among Y of the negative dye-releasing redox compound, a particularly preferable group is an N-1-substituted sulfamoyl group (the N-substituent is a group derived from an aromatic hydrocarbon ring or a heterocycle). Typical groups for Y are illustrated below, but are not limited to these.

H NH3(h- H C4H9(t) For positive-type compounds, Angewante Hemi International Edesitane Ingredients (An
gev, Chem, In5t, Ed, Engl, ),
22.191 (1982).

A specific example is a compound (dye developer) that is initially diffusible under alkaline conditions but becomes non-diffusible after being oxidized by development.U.S. Pat. The ones listed are representative.

Another type is one that releases a diffusible dye by self-closing under alkaline conditions, but substantially ceases to release the dye when oxidized during development. For specific examples of Y having such a function, see U.S. Pat.
54-130927, U.S. Patent No. 3,421,964,
4°199.355, etc.

Another type is one that does not itself release any pigment, but
Some release dyes when reduced.

This type of compound is used in combination with an electron donor,
The diffusible dye can be released imagewise by reaction with the remaining electron donor imagewise oxidized by silver development. Regarding atomic groups having such functions, for example, U.S. Pat.
18.368, JP 53-110827, U.S. Patent 4
゜278.750, 4,356,249, 4゜35
8.525, JP 53-110827, JP 54-13
0927, 56-164342, Public Technical Report 87-61
99, European Patent Publication No. 220746A2, etc.

On the other hand, specific examples of the dye represented by the general formula DYE are described in the following literature.

Example of yellow dye: U.S. Pat. No. 3,597,200, U.S. Pat. No. 3,309°199
No. 4,013,633, No. 4,245.028, No. 4,156,609, No. 4゜139.383,
No. 4,195,992, No. 4,148,641, No. 4,148,643, No. 4,336,322: JP-A-51-114930, No. 56-71072: R
e5earchDisclosure 7630 (
1978) and No. 16475 (1977).

Example of magenta dye: U.S. Pat. No. 3,453,107, U.S. Pat. No. 3,544°545
No. 3,932,380, No. 3,931.144, No. 3,932,308, No. 3954.476,
4,233,237, 4,255,509, 4,250.246, 4,142,891, 4
, No. 207,104, No. 4,287.292: JP-A No. 52-106.727, No. 52-106727, No. 53-23,628, No. 55-36,804, No. 5
No. 6-73,057, No. 56-71060, No. 55-
What is described in No. 134.

Examples of cyan dyes: U.S. Pat. No. 3,482,972, U.S. Pat. No. 3,929°760
No. 4,013,635, No. 4.268.625, No. 4,171,220, No. 4゜242.435,
No. 4,142,891, No. 4,195,994, No. 4,147,544, No. 4,148,642; British Patent No. 1,551°138; No. 52-8827, No. 53-47823, No. 53
-143323, 54-99431, 56-7
No. 1061; European Patent (RPC) No. 53°037, No. 53, 040 + Re5earch Dis
Closure No. 17.630 (1978) and Closure No. 16.475 (1977).

The amount of these colorants applied is generally about 1Xl0-' to 1XIO
-”mol/bo is appropriate, preferably 2X10-4~
2XIO-"mol/'rd.

In the present invention, the coloring material may be contained in the silver halide emulsion layer combined therewith, or may be contained in a layer adjacent to the emulsion layer on the exposed side or on the opposite side.

In the present invention, when using a DRR compound as a coloring material, any silver halide developer (or electron donor) can be used as long as it can cross-oxidize it, but 3-pyrazolidone is especially Preferably.

When the sensitive material of the present invention is used for a film unit for diffusion transfer method, it is preferable to process it with a viscous developer.
This viscous developer is a liquid composition containing processing components necessary for developing the silver halide emulsion (and forming a diffusion transfer dye image), and the solvent is mainly water, and other solvents include methanol,
Hydrophilic solvents such as methyl cellosolve may also be included.

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

These polymers may have at least one voice in the treatment composition at room temperature.
Preferably, it is used to give a viscosity of about 500 to 1000 voices.

The above treatment composition is described 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 the container by filling it into a container that can be ruptured by pressure, such as those described in Japanese Patent Application No. 056,492, No. 3, 152.515, and the like.

When 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; 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.

Example 1 The following layers (11
A photosensitive sheet coated with ~aO was prepared.

+11 The following cyan DRR compound (0,36m-m
ol/rd), tricyclohexyl phosphate
(0,09g/+tf), and gelatin (0,4
4 g/rd).

SO! ■ -CdL (2) Isolation layer containing 0.4 g/rd gelatin (3
) red-sensitive internal latent image type direct reversal silver bromide emulsion (root amount 0
．． 5g/rrr), gelatin (0.78g/rd
), a layer containing the following nucleating wI (27 μg/m).

+412.5-Di(tert-pentadecyl)hydroquinone (0,71 g/n()), layer containing poly-(t-butylacrylamide) (0,35 g/rrr) and gelatin (0,4 g/m).

(5) Layer containing gelatin (0.2 g/rrr).

(6) The following magenta DRR compound (0.49, g /
r+(), tricyclohexyl phosphate (0,
08g/n? ), a layer containing 2,5-tert-pentadecylhydroquinone (0,01 g/rd) and gelatin (0,5 g/rrf).

(7) Green-sensitive internal latent image direct reversal silver bromide emulsion (silver content 0.34 g/r+?), gelatin (0.66 g/r+?)
g/rd), the same nucleating agent as layer (2) (12,9μ
g/n? ) and sodium pentadecylhydroquinone sulfonate (0,04 g/n?).

(812,5-di(tert-pentadecyl)hydroquinone (0,85g/nf), copolymer of vinylpyrrolidone and vinyl acetate (molar ratio 7:3) (0,24
g/+y? ) and gelatin (0,4 g/n?).

(9) Layer containing gelatin (0,25 g / n ().

0I The following Yel:I-DRR compound (0,48g
/rd), tricyclohexyl phosphate (0
,03g/i), and gelatin (0,43g/r
d) a layer containing.

(il+ blue-sensitive internal latent image type direct reversal silver bromide emulsion (
Silver] amount 0.84g/n (), gelatin 7 (0.9g
/n? ), the same nucleating agent as layer (2) (29■/=> and sodium pentadenylhydroquinone sulfonate (0,
05 g/m').

Layer containing beaten gelatin (1.0 g/rrr).

A rupturable container was filled with 0.8 g of a treatment solution having the following composition.

A dye image-receiving sheet was prepared by sequentially applying the following layers 0 to 01 above a white support on which a treatment solution and a carbon blank layer and a titanium white layer were sequentially applied on the back side.

Difference a 80:20 of acrylic acid and butyl acrylate (
(weight ratio) copolymer (22glrd) and 1°4-bis(2,3-epoxypropoxy)-butane (0,44glrd)
g/rd).

Oa Acetylcellulose (100g of acetylcellulose is hydrolyzed to produce 39.4g of acetyl groups.) (3,8g/n?) and a 60:40 (weight ratio) copolymer of styrene and maleic anhydride. (molecular weight approximately 50,000) (0,2 g/m) and 5-(β-cyanoethyl 1,000)-1-phenyltetrazole (0,115 g
/n? ).

Q! 9 Copolymer latex of vinylidene chloride, methyl acrylate and acrylic acid in a ratio of 85:12:3 (weight ratio) (2.5 g/n?) and polymethyl methacrylate latex (particle size 1-3 microns) (0.05 g) /
A layer containing n().

0 groans Mordant below <3.0g #) and gelatin (3,0
g/n? ) containing a mordant layer.

0η Peeling layer containing the following compound (0,05g/rd).

lh C0OHC00CJ* The photosensitive sheet was used as a sample, and each of the compounds listed in Table 1 was added to N(3) in an amount of 65 μ+mol/n? Samples B, C, and D were prepared.

For comparison, Sample E containing the same amount of diphenylquinone, which is a nucleation accelerator disclosed in U.S. Pat. Sample F was prepared by adding the same amount of the following Compound X as an agent.

After exposing samples A to F, they were overlapped with the dye image-receiving sheet, and during this time the processing liquid was spread to a thickness of 60 μm using a pressing member to obtain a transferred color image.

The obtained sensitometry results are shown in Table-1.

Sample (A) without the compound of the present invention has a low maximum Rt1 degree and provides insufficient photographic performance, but samples B and C in which the compound of the present invention 8.15.32 is added to the red sensitive layer.
, D, the maximum R1 degree increases greatly, and it can be seen that satisfactory photographic properties are obtained.

Also, in samples E and F to which known compounds were added,
Although there is an improvement in the maximum R1 degree, there are disadvantages such as an increase in yellow stain and an increase in the minimum density of R in F.

In contrast, the compound of the present invention is superior in that it does not have the disadvantage of reducing the whiteness of the white background.

2. Sheet retention - Samples A-F prepared in Example 1 were heated at 60°C, 20% RH,
After aging under the conditions of 45° C. and 70% RF, sensitometry was performed to perform a compulsory preservability test. The results are shown in Table 2.

In Sample F using a known nucleation accelerator, the photographic properties deteriorated in the storage test, whereas Compound 8.
It can be seen that Samples B, C, and D containing 15.32 have fewer such adverse effects (and provide stable performance).

Example-3 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic window optical material was prepared by coating the following layers from the 1st layer to the 14th layer on the front side (0 micron) and the 15th layer to the 16th layer on the back side. The polyethylene coating side of the first layer contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(angry light layer composition) The components and coating amounts in g/rd are shown below.

Regarding silver halide, the coating amount is shown in terms of silver. The emulsions used in each layer were prepared according to the manufacturing method of emulsion EMI.

However, as the emulsion for the 14th layer, a Lippmann emulsion without surface chemical sensitization was used.

1st layer (antihalation layer) Black colloidal silver 0.10 gelatin
1. 30 Second layer (intermediate layer) Gelatin 0.70 Third layer (low sensitivity red sensitive layer) Silver bromide spectrally sensitized with red sensitizing dye (ExS-1,2°3) (average grain size 0.30) 3 μ, size distribution [coefficient of variation] 8%, octahedral) 0.60 Silver chlorobromide spectrally sensitized with red sensitizing dye (ExS-1,23) (silver chloride 5 mol%, average grain size 0) .45μ, 10% size distribution, octahedron > 0.10 gelatin 1.00 cyan coupler (E
xC-1) 0.11 cyan coupler (ExC-
2) 0.10 anti-fading agent (Cpd-2,3゜4.13 equivalent) 0.12 power puller dispersion medium (Cpd-5) 0.13 coupler? Container (Solv-7゜2.3 equivalent) 0.06 4th layer (high sensitivity red-sensitive layer) Silver bromide (average particle Size 0.60μ, size distribution 15%, octahedral) 0.14 gelatin
1.00 cyan coupler (Ex
C-1) 0.15 cyan coupler (ExC-2
) 0.15 Anti-fade agent (Cpd ~ 2.3° 4.13 equivalents) 0.15 Power puller dispersion medium (Cpd-5) 0.03 Coupler solvent (S
olv-7゜2.3 equivalent) 0.10 5th layer (intermediate layer) Gelatin 1.00 Color mixing prevention agent (Cpd-7) 0.08 Color mixing prevention agent solvent (
SOIV-4°5 etc. 0.16 Polymer Latex (Cpd-8) 0.10 6th layer (low sensitivity)! Sensitive layer) Silver bromide spectrally sensitized with green sensitizing dye (ExS-3) (average grain size 0.25 μ, grain size distribution 8%, octahedral) 0.04 green sensitizing dye (ExS-3) Silver bromide (average grain size 0.4-5μ, grain size distribution 11%, octahedral) spectrally sensitized with 0.06 gelatin 0.80 magenta coupler (
ExM- 1, 2 etc. 0.11 anti-fading agent (
Cpd-9) 0.10 stain inhibitor (C
pd-1 0.22 equivalent) 0.014 Stain inhibitor (Cpd-23) 0.001 Stain inhibitor (Cpd-12) 0.01 Force puller dispersion medium (C
pd-5) 0.05 coupler solvent (Solv-
4゜6 equivalent) 0.15 No. 77J (
High sensitivity green sensitivity N) Brominated gelatin spectrally sensitized with green sensitizing dye (ExS-3°4) (average particle size 0.8 μ, particle size distribution 16%, octahedral 3 0.10 gelatin)
0.80 magenta coupler (E
xM- 1,2) 0.11 anti-fading agent (Cpd-9) 0.10 anti-stain agent (Cpd-1 0,22 equivalent) 0.013 anti-stain agent (Cpd-23) 0.001 anti-stain agent (Cpd-12) 0.01 force puller dispersion medium (Cp
d-5) 0.05 coupler solvent (Solv-4
゜6 equivalent) 0.15th, 8th layer (
Intermediate layer) 9th layer (yellow filter layer) same as 5th layer Yellow colloid 11 0.20 Gelatin 1.00 Color mixing prevention agent (Cpd
-7) 0.06 color mixing inhibitor solvent (Solv
- 4,5 equivalents) 0.15 Polymer latex (Cpd-8) 0.10 10th layer (intermediate layer) Same as 5th layer, 11th layer (low intensity blue sensitive layer) Blue sensitizing dye ( Silver bromide (average grain size 0.4-5μ, grain size distribution 8%, octahedral) spectrally sensitized with 0.07 blue sensitizing dye (ExS-5°6) Sensitized silver bromide (average grain size 0.60μ, grain size distribution 14%, octahedral) 0.10 gelatin 0.50 yellow coupler (
ExY-1) 0.22 Stain inhibitor (Cpd-
11) 0.001 anti-fading agent (Cpd-6)
0.10 coupler dispersion medium (Cpd-5)
0.05 Coupler solvent (Solv-2) 0.05
12th layer (high sensitivity blue sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5°6) (average grain size 1.2 μ, grain size distribution 21%, octahedron) 0. 25 gelatin
1,00 yellow coupler (E
xY-1) 0.41 stain inhibitor (Cpd-1
1) 0.002 anti-fading agent (Cpd-6)
0.10 coupler dispersion medium (cpa-5) 0
．． 05 coupler solvent (Solv-2) 0.10 13th layer (ultraviolet absorbing layer) gelatin 1.50 ultraviolet absorber (cpct-i.

3.13 equivalents') 1.00 Color mixing inhibitor (Cpd-6°14 equivalents) 0.06 Dispersion medium (C
pd-5) 0.05 ultraviolet absorber solvent (
Solv- 1, 2 equivalent > 0.15 Irradiation prevention dye (Cpd-15, 16 equivalent > 0.02 Irradiation prevention dye (Cpd-17, 18 equivalent) 0.02 14th layer (protective layer) Fine particle salt Silver bromide (silver chloride 97 mol%, average size 0.2μ) O,OS Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.02 polymethyl methacrylate particles (average particle size 2. 4 microns), silicon oxide (average particle size 5 microns) equivalent to 0.05 gelatin
1.50 gelatin hardener (H-1
) 0.17 15th layer (back layer) Gelatin 2.50 16th layer (
Back protective layer) Polymethyl methacrylate particles (average particle size 2.4 microns), silicon oxide (average particle size 5 microns) equivalent amount 0.05 gelatin
2.00 gelatin hardener (H-1)
0.11 How to make emulsion EMI An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75°C over 15 minutes with vigorous stirring.
Octahedral silver bromide grains with an average grain size of 0.40 microns were obtained. To this emulsion, 0.3 g of 3.4-dimethyl-1,3-thiazoline-2-thione, 6 μg of sodium thiosulfate, and 7 μg of chloroauric acid (tetrahydrate) were sequentially added per mole of silver.
Chemical sensitization treatment was performed by heating at °C for 80 minutes. The grains thus obtained were used as cores and further grown in the same precipitation environment as in the first time, to finally obtain an octahedral monodisperse core/shell silver bromide emulsion with an average grain size of 0.7 microns. The coefficient of variation in particle size was approximately 10%. This emulsion contains 1.5 μm of sodium thiosulfate per mole of silver and 1.5 μm of sodium thiosulfate per mole of silver.
A chemical sensitization treatment was carried out by adding 5 μm of chloroauric acid (tetrahydrate) and heating at 60° C. for 60 minutes to obtain an internal latent image type silver halide emulsion.

In each photosensitive layer, ExZK-1 was used as a nucleating agent at a rate of 4.2X 10-' mol/Ag mol based on the coating amount of silver halide, and the nucleating accelerator listed in Table 3 was used. Furthermore, each layer contains alkanol XC (Bupo) as an emulsification dispersion aid.
nt) and sodium alkylbenzenesulfonate, succinate ester and Mage4a as coating aids.
F 120 (manufactured by Dainippon Ink Co., Ltd.) was used. Silver halide and colloidal silver containing layers contain (
Cpd-19, 2o, 21) was used. This sample was designated as sample number Il&Ll-4. The compounds used in the examples are shown below.

xS-1 xS-2 xS-3 ExS-4 ExS-5 (CL)ko0ffH ExS-6 503-5O3H-N(CzHs)s pd-t pa-z Cpd-3 Cpd-4 pct-s CONHCJ*( t) Cpd-6 Cpd-7 H 噸H Cpd-8 Polymethylacrylate pd-9 Cpd-10 Cpd-11 H 譬H Cpd-12 srI order ([) cpa-13 Cpd-14 H ■ Cpd-ts Cpd -ts I (cHz) 5s03K (C)Iri, S
O, Kpd-17 Cpd-18 Cpd-19 Cpd-20 H Cpd-21 Cpd-23 H ■ xC-1 I xC-2 fl)l xM-1 ExM 2 ExY-1 Cρ 5olv-1 di(2-ethylhexyl ) Phthalate 5o
lv-2) Linonylbosphate 5olv-3 di(3-methylhexyl) phthalate 5o
lv-4 tricresyl bosphate 5 olv-5 dibutyl phthalate 5 olv-6) lyoctyl phosphate 5 olv-7 di(2-ethylhexyl) sebacate H-11,2-bis(vinylsulfonylacetamido)ethane xZK-1 H As above After subjecting the color photosensitive material prepared in the above steps to J-7 di-exposure (3200, 0.1 second, 100 CMS), processing step A was carried out. The magenta density of the obtained color image was measured.

Color development 90 seconds 38℃ Bleach-fixing 40#33〃 Washing (1) 40' 33〃 Washing +21 40 seconds 33℃ Washing +31 15#33s Drying 30-80# Washing water replenishment method is in the washing bath (3) A so-called countercurrent replenishment method was adopted in which the overflow liquid from the water washing bath (3) was introduced into the water washing bath (2), and the overflow liquid from the water washing bath (2) was introduced into the water washing bath +ll. At this time, the amount of bleach-fix solution carried from the bleach-fix bath for photosensitive materials to the washing bath +11 is 35 d/rd.
The ratio of the amount of washing water replenished to the amount of bleach-fix solution brought in was 9.1 times.

The composition of each treatment liquid was as follows.

For the elbow Mother liquid ethylenediaminetetraacetic acid kismethylenephosphonic acid 0.5g diethylene glycol 10-benzyl alcohol
12.0Mi potassium bromide
0.65g Sodium sulfite 2.4
gN,N-diethylhydroxylamine 4.0g triethylenediamine (1゜4-diazabicyclo[2゜2.2]octane) 4.0gN-ethyl-N-(β-methanesulfonamidoethyl) -3-methylaniline sulfate 5.6g Potassium carbonate 27.0g Fluorescent brightener (
Diaminostilbene type) Add 1.0g of water and adjust to IOOadpH (25°C)
10.501m Mother liquor ethylenediaminetetraacetic acid 2 sodium dihydrate 4. Og ethylenediaminetetraacetic acid・Fe ([[[) ・Ammonium dihydrate salt 46. Og ammonium thiosulfate (700g/J 155mff
1 Sodium p-toluenesulfinate 20.0g Sodium bisulfite 12.0g Ammonium bromide
50.0g ammonium nitrate
30. OgpH (25℃) 6.2
A mixed bed column filled with tap water and H-type strongly acidic cation exchange resin (Amberlite IR-120B, manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-400, manufactured by Rohm and Haas). Water was passed through the flask to reduce the concentration of calcium and magnesium ions to 3/l or less, and then sodium dichloride isocyanurate 20*/12 and sodium sulfate 1.5 g/l were added. The pH of this solution is 6.5
It was in the range of ~7.5.

Table 3 *l Addition amount 3.2X 10-' mol/Ag mol Nos. 1 to 7 using the nucleation accelerator of the present invention have higher Dmax< and lower D+sin than Comparative Example Magnet 4. It was true.

Claims (3)

[Claims] (1) At least a hydrazine-based nucleating agent, an internal latent image type direct positive emulsion, and an oxidizing compound that causes cleavage of single bonds when reduced, which have a photographic effect, are not released on the support. A direct positive silver halide photographic light-sensitive material characterized by having a compound. (2) In item 1, the oxidizing compound that cleaves a single bond when reduced is a compound that cleaves an N-X bond (a bond between nitrogen and oxygen, nitrogen and nitrogen, or nitrogen and sulfur). The direct positive silver halide photographic light-sensitive material according to item 1, characterized in that it is represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1, R^2, and R^3 are substituents other than hydrogen, and at least one of them has an electron-accepting group. represent. X represents an oxygen atom, a sulfur atom, or the following group R^4-■- (here, R^4 represents a group other than a hydrogen atom or a simple bond). If X is R^4-■- then R^
At least one of 1 to R^4 represents an electron-accepting group. R^1 and R^5, R^2 and R^3, R^3 and R^4, R
^4 and R^1 may each be bonded to each other to form a ring. (3) The direct-positive silver halide photographic material according to item 2, wherein the compound represented by general formula (I) is represented by general formula (II). General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ In the formula, R^5 represents a group that is bonded to X and N to form a 3- to 8-membered heterocycle. Other meanings have the same meaning as stated in Section 2. In general formula (II), at least one of R^3, R^4, and R^5 represents an electron-accepting group.