JPS63296039A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the gradation and the shelf stability of the titled material by providing with a layer contg. a specified dyestuff and a layer contg. a hydrazine derivative in the titled material. CONSTITUTION:The titled material is composed of one or more layers of silver halide emulsion layers and a hydrophilic colloidal layer, and a layer which does not contain said dyestuff is provided between said emulsion layer and the hydrophilic colloidal layer. And, the hydrazine derivative (for example, a compd. shown by formula III) is incorporated in the colloidal layer of the titled material such as the photosensitive emulsion layer. In the formula, PWR is a group capable of releasing a group (Time)t-LA by reduction. Time is a group capable of releasing a group LA, LA is a group having the absorption max. of a light of 310nm, (t) is 0 or 1. And, the dyestuff shown by formula I (such as a compd. shown by formula II) is incorporated in a surface protective layer or a halation resistant layer.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a novel light-absorbing material that can be well contained in a light-sensitive material layer and that can be decolorized so as not to cause residual color contamination during development. The present invention relates to a silver halide photographic material having at least one layer containing a compound.

(Prior Art) Generally, in silver halide photographic materials, for the purpose of adjusting sensitivity, improving safelight safety, adjusting the color temperature of light, preventing halation, or adjusting the sensitivity balance in multilayer color light-sensitive materials, etc. It has been conventional practice to include light-absorbing compounds in silver halide emulsion layers or other hydrophilic colloid layers to absorb light at specific wavelengths.

For example, silver halide photographic light-sensitive materials are formed by forming a hydrophilic colloid layer such as a photosensitive silver halide emulsion layer on a support. When performing symmetrical exposure, it is necessary to control the spectral composition of light incident on the silver halide emulsion layer in order to improve photographic sensitivity. In such cases, a dye capable of absorbing light in a wavelength range that is not needed by the silver halide emulsion layer is usually added to the hydrophilic colloid layer that is located on the side farther from the support than the photosensitive silver halide emulsion layer. A method is used in which the filter is made into a single layer by incorporating it to transmit only light in the target wavelength range.

In particular, silver halide photographic materials used in the photolithography process, more specifically light-sensitive materials for bright room use.

To increase safety against safelight light, dyes that absorb UV light and visible light are added to the photosensitive layer or to the layer between the light source and the photosensitive layer.

It is also added to the hydrophilic colloid layer between the photosensitive silver halide emulsion layer and the support to prevent halation.

The dye used for this purpose must be decolorized during photographic processing and easily eluted from the silver halide photographic light-sensitive material to prevent substantial residual color staining caused by the dye after photographic processing. It should not have any negative effects on the emulsion such as fogging or desensitization, it should not diffuse from the colored layer to other layers, it should have good absorption spectrum characteristics according to its intended use, and it should also be able to be used in solution. Alternatively, it must satisfy conditions such as excellent stability over time in silver halide photographic materials and no deterioration.

When the layer containing the above-mentioned dye functions as a filter layer and an antihalation layer, it is necessary to selectively color that layer so that the coloring does not substantially spread to other layers. This is because substantially coloring the other layers not only has harmful spectral effects on the other layers, but also sterilizes the effectiveness of the filter layer as an antihalation layer. Further, if the dye added to a certain layer for the purpose of preventing irradiation diffuses and colors other layers, the same problem as described above will occur.

As a new dye that solves these problems, the patent application
0-244.873, 61-88625, 61-1
30342, 62-43704 by reduction reaction,
Compounds have been proposed that release diffusible dyes. These compounds are diffusion resistant, remain in the layer in which they are added and do not diffuse into other layers, and can be quickly decolored by development, so all of the above problems are solved.

However, when these compounds are used in photosensitive materials containing hydrazine derivatives as nucleating agents, they may cause problems such as softer gradations and large changes in sensitivity when the photosensitive materials are stored at high temperatures. The problem was discovered.

(Objective of the Invention) Therefore, the first object of the present invention is to dye a layer dyed with a dye and to suppress the diffusion of the dye to other layers by at least 1N''.
It is an object of the present invention to provide a silver halide photographic material having good gradation that can be decolorized during photographic processing.

A second object of the present invention is to provide a silver halide photographic material with good stability over time.

(Structure of the Invention) The above object of the present invention is to have on a support at least one silver halide emulsion layer and a hydrophilic colloid layer containing a compound represented by the general formula (I), and the at least one layer of halogen A hydrophilic colloid layer containing substantially no compound represented by the general formula (I) is provided between the silver oxide emulsion layer and the hydrophilic colloid layer containing the compound represented by the general formula (I). and a silver halide photographic light-sensitive material characterized in that at least one of these hydrophilic colloid layers or other hydrophilic colloid layers contains a hydrazine derivative.

General formula [! ] PWR (Time To LLA In the formula, PWR is reduced to ('l'ime)-represents a group that releases 2LA.

Time represents a group that is released from PWR as (Time)-t LA and then releases LA through a subsequent reaction.

represents an integer of 0 or 1.

LA represents a group having a light absorption maximum at 310 nm or more.

Next, the compound of general formula (I) used in the present invention will be explained.

First, PWH will be explained in detail.

PWR releases a photographic reagent through an intramolecular nucleophilic substitution reaction after being reduced as disclosed in U.S. Pat. No. 4,139,389 or U.S. Pat. It may correspond to a portion containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound, or may correspond to a portion containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center,
No., JP-A-59-101649 or JP-A-61-
As disclosed in No. 88257, it corresponds to the part containing the electron-accepting quinonoid center and the carbon atom that connects it to the photographic reagent in a compound that eliminates the photographic reagent by an intramolecular electron transfer reaction after being reduced. Also, Japanese Patent Application Laid-Open No. 142530/1983, U.S. Patent No. 4.343.893, U.S. Pat. No. 4,619
, 884, the aryl group substituted with an electron-withdrawing group and the atom (sulfur atom or carbon or a nitrogen atom), and may also correspond to a moiety containing a nitrogen atom).
It may correspond to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom that connects the photographic reagent with the nitro group as disclosed in No. 50,223, or This corresponds to the geminal dinitro moiety in the dinitro compound that β-eliminating the photographic reagent after electron acceptance and the carbon atom-containing moiety that connects it to the photographic reagent described in U.S. Pat. No. 4,609.610. However, in order to more fully achieve the object of the present invention, the compound of general formula (I) is preferably represented by general formula (II).

General formula (n) EAG In the general formula [■], I EAG (Time)-t LA is Rt, Rz or EAG
(to combine with one)

Z is an oxygen atom (-0-), a sulfur atom (-S-)■ Represents a group (-N-) containing a nitrogen atom.

EAG represents a group that accepts and takes electrons from reducing substances,
Bonds to nitrogen atoms. As EAG, the following general formula (A)
Or a group represented by (B) is preferable.

General formula (A) General formula (B) In general formula (A), Sub "zl is -C- or -Ng"Vn' is Zr
, represents an atomic group forming a 3- to 8-membered ring together with Zz, and n' represents an integer of 3 to 8, but Vs; Zs, Va i Z3-Za
, Vs iZs Z4 ZS , Vai
Zs Z4-Zs-Zh, vv; zl
Z4 Zs-26-Z? , Vsi Zs
Za Zs-26Z? It is Zl-.

28 to Z are -〇- and -N-, respectively.

■ Sub -O-, -S-, or -SO! - represents Sub
Sub represents a simple bond (π bond), a hydrogen atom, or a substituent described below.Sub may be the same or different, and may be bonded to each other to form a 3- to 8-membered In the general formula (A), the sum of Hammett substituent complete failure σ of the substituents is +0.09 or more,
More preferably +0.3 or more, most preferably +0.
Select Sub so that it is 45 or more.

Examples when Sub is a substituent are listed below. (The number of carbon atoms is preferably 0 to 40 in each case.) 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-)lichloroprobyl group, methoxycarbonylmethyl group, etc.), substituted or unsubstituted alkenyl groups (e.g. vinyl group, 2-chlorovinyl group, 1 -methylvinyl group, etc.), substituted or unsubstituted alkynyl groups (e.g. ethynyl group, l-propynyl group, etc.), cyano group, nitro group, halogen atom (fluorine, chlorine, bromine, iodine), substituted or unsubstituted Terocyclic residue (2-pyridyl group, 1-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-methoxyethylcarbonyl group, phenoxycarbonyl group,
4-cyanophenylcarbonyl group, 2-chlorophenoxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group (e.g. carbamoyl group, methylcarbamoyl group, diethylcarbamoyl group, methylhexadecylcarbamoyl group, methyloctadecylcarbamoyl group, fesolcarbamoyl group) i, 2.4.6-trichlorophenylcarbamoyl group, N-ethyl-N-phenylcarbamoyl group, 3-hexadecylsulfamoylphenylcarbamoyl group, etc.), hydroxyl group, substituted or unsubstituted azo group (e.g. phenylazo 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,
rl-butyroyl group, t-butyroyl group, benzoyl group, 2-carboxybenzoyl group, 3-nitrobenzoyl group, formyl group, etc.), substituted or unsubstituted aryl or alkylthio group (e.g. methylthio group, ethylthio group, t-octylthio group) group, hexadecylthio group, phenylthio group, 2.4.5-trichlorothio group, 2-methoxy-5-t-octylphenylthio group, 2-acetylaminophenylthio group), substituted or unsubstituted aryl group (e.g. phenyl group, naphthyl group, 3-sulfophenyl group, 4-methoxyphenyl group, 3-lauroylaminophenyl group), substituted or unsubstituted sulfonyl group (e.g. methylsulfonyl group, chloromethylsulfonyl L n-octylsulfonyl group, n-hexadecylsulfonyl group, 5ec-octylsulfonyl group, p-
toluenesulfonyl group, 4-chlorophenylsulfonyl group, 4-dodecylphenylsulfonyl group, 4-dodecyloxyphenylsulfonyl group, 4-nitrophenylsulfonyl group), substituted or unsubstituted sulfinyl group (e.g. methylsulfinyl group, dodecylsulfinyl group) , phenylsulfinyl group, 4-nitrophenylsulfinyl group), substituted or unsubstituted amino groups (e.g. methylamino group, diethylamino group, methyloctadecylamino group, phenylamino group, ethylphenylamino group, 3-tetradecylsulfinyl group) Famoylphenylamino group, acetylamino group, trifluoro acetylamino group, N-hexadecylacetylamino group, N-methylbenzoylamino group, methoxycarbonylamino group, phenoxycarbonylmethyl group, N-methoxyacetylamino group, amidinoamino group group, phenylaminocarbonylamino group, 4-cyanophenylaminocarbonylamino group, N-ethylethoxycarbonylamino group, N-methyldodecylsulfonylamino group, N-(2-cyanoethyl)-p-toluenesulfonylamino group, hexadecyl sulfonylamino group, trimethylammonio group, etc.),
Substituted or unsubstituted sulfamoyl group (e.g. dimethylsulfamoyl group, hexadecylsulfamoyl group,
Sulfamoyl group, methyloctadecylsulfamoyl group, methylhexadecylsulfamoyl group, 2-cyanoethylhexadecylsulfamoyl group, phenylsulfamoyl group, N-(3,4-dimethylphenyl)-N-
octylsulfamoyl group, dibutylsulfamoyl group, dioctadecylsulfamoyl group, bis(2-methoxycarbonylethyl)sulfamoyl group, etc.), substituted or unsubstituted acyloxy groups (e.g. acetoxy group,
benzoyloxy group, decyloxy group, chloroacetoxy group, etc.), and substituted or unsubstituted sulfonyloxy groups (eg, methylsulfonyloxy group, p-toluenesulfonyloxy group, p-chlorophenylsulfonyloxy group, etc.).

In general formula (B), n'' represents an integer of 1 to 6, LJ+ i'/+, Us; -Y+
Yz, IJs ;'/+ Yz Ys, U
a i Y+ Yz YsYa, Us
i-'/I Ya Yx Ya-Ys +, U
h i'! '+ Yz Y3 Ya Y
s-Y.

Sub' Y, ~Y, each represents 10-3ub' or Sub'Sub' represents a simple bond (σ bond, π bond) or a substituent of Sub described in general formula (A), general formula CB
), the sum of the Hammett substituent constants σ of the substituents is +0.
Sub' is selected so that it is at least 09, more preferably at least +0.3, and most preferably at least +0.45.

A more specific example of EAG is an aryl group substituted with at least one electron-withdrawing group (fM, t)
Nitrophenyl group, 2-nitro-4-N-methyl-N-
Octadecylsulfamoylphenyl group, 2-N, N-
dimethylsulfamoyl-4-nitrophenyl group, 2-
cyano-4-occudecylsulfonylphenyl group, 2.
4-dinitrophenyl ak, 2,4.6-)lycyanophenyl group, 2-nitro-4-N-methyl-N-octadecylcarbamoylphenyl group, 2-nitro-5-octylthiophenyl group, 2.4- Dimethanesulfonylphenyl 13.5-dinitrophenyl group, 2-chloro-4-nitro-5-methylphenyl group, 2-nitro3.5-dimethyl-4-tetradecylsulfonylphenyl M, 2.
4-dinitronaphthyl group, 2-ethylcarbamoyl-4
-nitrophenyl 1.2.4-bis-dodecylsulfonyl-5-trifluoromethylphenyl group, 2°3.4.
5.6-pentafluorophenyl group, 2-acetyl-4
-nitrophenyl l, 2,4-diacetylphenyl group,
2-nitro-4- ) IJ fluoromethylphenyl group, etc.), substituted or unsubstituted heterocycles (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-2-pyridyl group, 5-cyano-2
-pyrazyl group, 4-nitrothiophen-2-yl group, 5
-nitro-1,2-dimethylimidazol-4-yl group, 3.5-diacetyl-2-pyridyl group, ■-dodecyl-5-carbamoylpyridinium-2-yl group, etc.),
Substituted or unsubstituted quinones (e.g. 1,4-benzoquinon-2-yl group, 3.5°6-drimethyl-1.4
-benzoquinon-2-yl group, 3-methyl-1,4-naphthoquinon-2-yl group, 3,6-dimethyl-5-hexadecylthio-1,4-benzoquinon-2-yl group, 5
-pentadecyl-1,2-benzoquinon-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),
Examples include monovalent groups (for example, 2-oxopropanoyl group) of α-diketo compounds.

R1, Rff and R3 represent a group other than a hydrogen atom or a simple bond.

R1 and R are preferably substituted or unsubstituted alkyl groups, aryl groups, heterocyclic residues, acyl groups, sulfonyl groups, and the like.

R1 is preferably a substituted or unsubstituted acyl group or sulfonyl group. *R', R'' and R3 may be bonded to each other to form a 5-8 true ring.

Furthermore, in order to achieve the object of the present invention, general formula (II)
Among the metals represented by the formula (III), those represented by the general formula (III) are more preferable.

General formula CII+) RAG In the general formula (III), (1) RAG (Time)-2LA is bonded to at least one of R' and RAG. Regarding the moiety corresponding to PWH in general formula (m), Y is a divalent linking group, preferably -C- or -8ot-, and X is 10-1-S-1 or - as in R above. It represents N-, preferably an oxygen atom.

R4 represents an atomic group that combines with X and Y to form a 5- to 5-membered monocyclic or condensed heterocycle including a nitrogen atom.

(Preferable examples including the bonding position of Time and 2LA will be described.

CwH+s CH-CH! CHx -4Time)-vLA Time represents a group that releases LA through a subsequent reaction without causing cleavage between N-X.

t represents an integer of 0 or 1, and when t=0, Time represents a simple combination.

An example of Time is JP-A No. 61-236549.
Examples include those described as me.

Preferred examples of Time in the present invention will be specifically described below. In the compound of the present invention, (this) means bonding to the PWR side (*) (*) means bonding to the LA side.

cHt
C! Hs (Iω (chief), l II cHs 0 (book) -3-CH- (monkey) (rate) C00Ct Hs (38) LA is 310
It is a dye that represents a group having an absorption maximum in nm or more and is used in silver halide photographic light-sensitive materials, such as azomethine dyes, styryl dyes, butadiene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, These are hemicyanine dyes, diarylmethane dyes, triarylmethane dyes, azomethine dyes, azo dyes, metal chelate dyes, anthraquinone dyes, stilbene dyes, chalcone dyes, and indophenol dyes.

Specific examples of the compound represented by the general formula (I) used in the present invention are shown below, but the present invention is not limited to these.

Compound Examples ■-11 ■-13 The compounds of the present invention emit dyes as described in US Pat. No. 4,139.
No. 389, No. 4,139.379, JP-A-59-18
5333, U.S. Patent No. 4,
No. 232.107, JP-A No. 59-101649, No. 6
1-88257, methods for synthesizing compounds disclosed in U.S. Pat. No. 4,343.893 and U.S. Pat.
No. 0゜223, No. 4,609.610, Patent Application 1986-
It can be easily synthesized by binding to the PWR moiety with reference to the compound synthesis method disclosed in No. 244873 and No. 61-88625.

The compound of general formula (I) used in the present invention can be added to the layer in a necessary amount depending on the purpose, but it is preferably used in an optical density range of 0.05 to 3.0. The specific amount of dye varies depending on the dye, but is generally between 10-"g/rrr and 3,000 g/rd, especially 10-"
Preferred amounts can be found in the range from 1.0 g/nf to 1.0 g/rd.

The compound of general formula (I) according to the invention can be incorporated into the hydrophilic colloid layer by various known methods.

For example, these compounds can be dissolved or dispersed in gelatin by dissolving them in a suitable solvent [e.g., alcohol (methanol, ethanol, propatool), acetone, methyl ethyl ketone, methyl cellosolve, dimethyl formamide, cyclohexanone, ethyl acetate]. Alternatively, it can be dissolved in an oil with an even higher boiling point and added as an emulsified dispersion in the form of fine oil droplets. As the oil, known oils such as tricresyl phosphate, diethyl phthalate, dibutyl phthalate, and triphenyl phosphate can be used.

As another dispersion method, U.S. Patent No. 4,512°969
, JP 51-59,943, JP 51-39, 85
As described in Section 3, the compound of the present invention is dissolved in a water-miscible organic solvent, and then mixed with a polymer latex that can be swelled with the organic solvent to form a compound containing a small amount of organic solvent (
By removing a portion of both, a stable dispersion can be prepared and used. Alternatively, a dispersion of the compound of the present invention in water may be prepared using a media dispersion machine such as a ball mill or a colloid mill, and the dispersion may be mixed with an aqueous gelatin solution for use. At this time, as a dispersion aid,
It is effective to use a variety of well-known surfactants. Examples of surfactants are described in Japanese Patent Publication No. 51-39.853.

The compound of general formula (I) according to the present invention can be contained in an intermediate layer, a photosensitive layer, a protective layer, an overcoat layer, etc. When the photosensitive material of the present invention has two or more photosensitive layers, substantially A hydrazine derivative can be contained in the photosensitive layer that bears an image, and a compound of the general formula (RI) can be contained in the photosensitive layer that contributes less to the other image. Preferably, the compound of the general formula (I) is added to the support. A non-photosensitive hydrophilic colloid layer (e.g. a surface protective layer) outside the photosensitive layer furthest from the support, or a non-photosensitive hydrophilic colloid between the support and the photosensitive layer closest to the support. The layer containing the compound represented by the general formula (I) of the present invention, which is preferably included in the layer, is mainly composed of:
Since it is decomposed and eluted by hydroquinone, sulfite, or alkali in the developer, it does not color or stain photographic images.

Gelatin is most preferred as the hydrophilic colloid, and various known gelatins may be used. Alternatively, gelatin that has undergone modification such as phthalation or sulfonylation can also be used. Moreover, if necessary, it can be used after being subjected to desalting treatment.

The mixing ratio of the compound of general formula (I) of the present invention and gelatin varies depending on the structure and amount of the compound, but is 1/1.
Preferred ratios can be found in the range 0'' to 1/3.

Examples of the hydrazine derivatives used in the present invention include hydrazine derivatives having a sulfinyl group described in US Pat. No. 4,478,928 and compounds represented by the following general formula (rV).

General formula (TV) Re　　　-N　HN　H-CHO In the formula, R0 represents an aliphatic group or an aromatic group.

In general formula (IV), the aliphatic group represented by Ro preferably has 1 to 30 carbon atoms, particularly 1 to 30 carbon atoms.
~20 straight chain, branched or cyclic alkyl groups. The branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein; , an alkoxy group, a sulfoxy group, a sulfonamide group, a carbonamide group, or the like.

For example, t-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, imidazolyl group,
Examples include a tetrahydrofuryl group and a morpholino group.

In the general formula (rl/), the aromatic group represented by R+ is a monocyclic or bicyclic ring group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be monocyclic or bicyclic.
may be condensed with a ru group to form a heteroaryl group.

For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrrolidyl group, quinoline ring,
Examples include an inquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring, among which those containing a benzene ring are preferred.

Particularly preferred as Ro is an aryl group.

The aryl group or aromatic group of Ro may have a substituent.

Typical π substituents include linear, branched or cyclic alkyl groups (preferably those with 1 to 20 carbon atoms), aralkyl groups (preferably monocyclic or bicyclic alkyl groups with 1 to 3 carbon atoms) ), alkoxy groups (preferably those with 1 to 20 carbon atoms), substituted amino groups (preferably those with 1 to 20 carbon atoms),
~20 alkyl group substituted), acylamino group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms)
, ureido group (preferably one having 1 to 30 carbon atoms)
and so on.

-Ro in the IC formula (rV) may have a ballast group, which is commonly used in immobile photographic additives such as couplers, incorporated therein.The ballast group has a carbon number of 8 or more and is suitable for photographic properties. It is a group that is relatively inert to the above, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like.

Ro in the -C formula (■) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include the groups described in US Pat. No. 4,385,108, such as thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups.

Synthesis methods for these compounds are described in JP-A No. 53-20921,
No. 53-20922, No. 53-66732, No. 53
-20318 etc.

In the present invention, when the compound represented by general formula (IV) is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but it is preferably contained in a non-photosensitive hydrophilic colloid layer (for example, a protective layer, intermediate layer, filter layer, antihalation layer, etc.).Specifically, if the compound used is water-soluble, it may be contained in an aqueous solution, or if it is poorly water-soluble, it may be contained in alcohols or esters. ,
As a solution of water-miscible organic solvents such as ketones,
It can be added to the hydrophilic colloid solution. When added to the silver halide emulsion layer, it can be added at any time from the start of chemical ripening to before coating, but it can be added between the end of chemical ripening and before coating. It is preferable to add it to a coating liquid prepared for coating.

The content of the compound represented by the general formula (IV) of the present invention is determined by the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, and the relationship between the layer containing the compound and the silver halide emulsion layer. It is desirable to select the optimum amount depending on the type of antifoggant compound, etc., and the test method for selection is well known to those skilled in the art. Mol or I
A range of 10-' moles, especially from 10-s to 4×10-" moles, is used.

Specific examples of the compound represented by the general formula (IV) are shown below, however, the present invention is not limited to the following compounds.

■-1) ■-2) ■-3) ■-4) ■-5) ■-6) ■-7) ■-8) ■-9) IV-10) IV-11) fV-12) rV- 13) IV-14) rV-15) TV-16) IV-17) IV-18) rv-19) IV-20) IV-21) rV-23) rV-24) IV-25) rV-26) TV-27) IV-28) [+/-29) rV-30) ○ IV-31) In addition to the above-mentioned hydrazine derivatives used in the present invention, RESEARCHDISCLO3URE
I tea23516 (November 1983 issue, P, 3
46) and the documents cited therein, as well as U.S. Pat.
No. 76.364, No. 4,278,748, No. 4,38
No. 5,108, No. 4,459,347, No. 4,560
, No. 638, No. 4,478,928, British Patent No. 2,0
11,391B, and those described in JP-A-60-179734 can be used.

Others, patent application No. 62-67508, No. 62-67509
A nucleating agent disclosed in , No. 62-67510 can be used.

For the hydrophilic colloid layer (referred to as intermediate layer 1) which does not substantially contain the compound represented by the general formula (I) of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids may also be used. Can be done.

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, and cellulose sulfate esters, W derivatives such as sodium alginate and starch derivatives, and polyvinyl alcohol. , polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

The intermediate layer has a thickness of 0.1 to 5.0 μ, preferably 0°2 to 2
．． The intermediate layer, which is preferably used at a thickness of 0 μm, may contain various additives such as development accelerators, polymer latexes, water-soluble dyes, stabilizers, crosslinking agents, and coating aids as described below. can.

Substantially not containing the compound represented by the general formula (I) means that even if it is contained in a small amount, it will have a substantial effect on the gradation of the emulsion layer (for example, the γ value will be lowered to 10 or less). It means not to cause any harm (such as putting it away).

The silver halide emulsion that can be used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver iodochlorobromide.

The silver halide grains in the photographic emulsion layer are cubic, octahedral,
Regular shapes such as 14-hedron and rhombic-12-hedron
), or may have irregular crystal forms such as spherical or plate-like, or may have a composite form of these crystal forms. It may be composed of a mixture of particles or may have an epitaxial structure.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

It may also be a grain in which the latent image is mainly formed on the surface (for example, a negative emulsion), or a grain in which the latent image is mainly formed inside the grain (for example, an internal latent image emulsion, a pre-fogged direct reversal emulsion). ).

The halogenated particle size is generally 0. The range of O1μ to 4°0μ is good, especially for graphic materials.
0.02-0.4μ, preferably 0.2-3.0μ for general photographic light-sensitive materials and X-ray films, and particularly preferably 0.15μ or less in the present invention.

The photographic emulsion used in the present invention is P.
, Glafkides), Chis+ie er Ph
ysiquePhotogroheque) (Ballmontel, 1967), G.F. Duffin (
G., F. Duffin), Photographic Emulsion Chemistry
Bsulsion Chemistry (Focal Press, 1966), Bouy El Zelikman (
Making and Coating Photographic Emulsions (V., L. Zelkman) et al.
It can be prepared using the method described in Graphic Emulsion (Focal Libres, 1964).

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Silver halide emulsions may or may not be chemically sensitized. For chemical sensitization, for example, H, Friesel (H, F
r1eser)
Photography Proze
sse muSilberhalogeniden)
(Academische Verlagsgeserschacht 1
968) The method described on pages 675 to 734 can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, Reduction sensitization using noble metal compounds (e.g., total complex salts,
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as pt, Ir, and Pd can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitrointazoles, triazoles, penztriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles. , mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo; Compounds such as oxazolinthione, azaindenes such as tetraazaindene! W
(especially 4-hydroxy-substituted (I,3,3a,7)tetraazaindene If); benzenethiosulfonic acids.

Many compounds known as anti-capri agents or stabilizers can be added, such as benzenesulfinic acid; and the like.

The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

That is, it may contain a compound that can develop color by oxidative coupling with an aromatic primary amine developer (e.g., phenylene diamine derivative, aminophenol derivative, etc.) in color development treatment. For example, as a magenta coupler, 5-pyrazolone There are couplers such as pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers include: These include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive ones that have a hydrophobic group called a ballast group in the molecule.Couplers can be either 4-equivalent or 2-equivalent to silver ions, and colored couplers that have a color correction effect are preferred. , or a coupler that releases a development inhibitor upon development (so-called DI
R coupler).

In addition to the DIR coupler, the coupling reaction product may include a colorless DIR coupling compound which is colorless and releases a development inhibitor.

The light-sensitive material of the present invention may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, and ureides for the purpose of increasing sensitivity, increasing contrast, or accelerating development. It may also contain derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, hydroquinone or its derivatives, and the like.

The silver halide photographic emulsion of the present invention may contain known water-soluble dyes other than the dyes disclosed in the present invention (for example, oxonol dyes, hemioxonol dyes, and merocyanine dyes) as filter dyes or for various purposes such as preventing irradiation. dyes and benzylidene dyes), or may be used in combination with known cyanine dyes, merocyanine dyes, and hemicyanine dyes other than the dyes shown in the present invention as spectral sensitizers.

In addition, the photosensitive material of the present invention contains antifading agents, antifogging agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, as described in Research Disclosure vO1,176 (I978, Xn). RD-176
43, etc.

Further, in graphic materials, particularly photographic materials for bright room use, an organic desensitizer may be included. Particularly preferred organic desensitizers are those having at least one water-soluble group or alkali-dissociable group.

A specific example is described in Japanese Patent Application No. 61-205603.

In addition, in the case of a photosensitive material using the hydrazine derivative of the present invention, JP-A-53-77-616,
54-37,732, 53-137,133, 6
0-140,340, 60-14,959, patent application 1977
1-205603, 61-271.113, 61-
It is preferable to use the compounds shown in 2.528.461 and 61-280.998.

The photographic light-sensitive material of the present invention includes JP-A No. 60-76743;
Nitrones and derivatives thereof as described in JP-A No. 60-87322, mercapto compounds as described in JP-A-60-80839, heterocyclic compounds as described in JP-A-57-164735, and heterocyclic compounds and silver complex salts (for example, silver 1-phenyl-5-mercaptotetrazole) can be preferably used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene oxide adducts of silicones), alkyl esters of sugars. Nonionic surfactants such as; alkyl sulfonic acids, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl Anionic surfactants such as phenyl ethers; amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines; cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts, and imidazolium salts. be able to.

Among these, saponin, dodecylbenzenesulfone 1i1N
a salt, di-2-ethylhexyl α-sulfosuccinate Na
Anions such as salts, p-octylphenoxyethoxyethoxyethoxyethanesulfonic acid Na salt, dodecyl sulfate Na salt, triisopropylnaphthalene sulfonic acid Na salt, N-methyl-O, leoyl taurine Na salt, dodecyltrimethylammonium chloride, N-oleoyl -N', N
', N'-Trimethylammoniodiaminopropane bromide, cations such as dodecylpyridium chloride, betaines such as N-dodecyl-N, N-dimethylcarboxybetaine, N-oleyl-N, N-dimethylsul, and butylbetaine, (Average degree of polymerization n=10) Oxyethylene cetyl ether, poly(n=25) Oxyethylene p-nonylphenol ether, Bis(I-
Poly (n=15)oxyethylene-oxy-2,4-
Nonions such as di-t-pentylphenyl)ethane can be particularly preferably used.

As an antistatic agent, perfluorooctanesulfonic acid salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly (n=3)
Oxyethylene butanesulfonic acid Na salt, N-perfluorooctanesulfonyl-N',N',N'-trimethylammophodiaminopropane chloride, N-perfluorodecanoylaminoprobyl-N,N'-dimethyl-N Fluorine-containing surfactants such as '-carboxybetaine, nonionic surfactants described in JP-A-60-80848, JP-A-61-112144, JP-A-61-13398, JP-A-61-16056, etc. Alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides obtained by doping these with antimony or the like can be preferably used.

The surface layer of the photographic light-sensitive material of the present invention contains silicone compounds described in U.S. Pat. No. 3,489,576 and U.S. Pat. In addition, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention. Furthermore, the hydrophilic colloid layer of the photographic material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. Polymers include homopolymers of alkyl esters of acrylic acid or copolymers with acrylic acid, styrene-
Butadiene copolymers, polymers or copolymers consisting of monomers having active methylene groups can be preferably used.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, the active vinyl compounds (I,3,5-)lyacryloyl-hexahydro-5-)riazine, bis(vinylsulfonyl)methyl ether, N,N'-methylene bis[
β-(vinylsulfonyl)propionamide], etc.),
active halogen compounds (such as 2,4-dichloro-6-hydroxy-5-lyazine), mucohalogen acids (such as mucochloric acid), N-carbamoylpyridinium salts ((
I-morpholy, carbonyl-3-pyridinio) methanesulfonate, etc.), haloamidinium salts (I-(I-
Chloro-1-pyridinomethylene)pyrrolidinium, 2-
(such as naphthalene sulfonate) can be used alone or in combination. Among them, JP-A-53-41220
, 53-57257, 59-162546, 60
Preferred are the active vinyl compounds described in US Pat. No. 3,325,287 and the active vinyl compounds described in US Pat.

The finished emulsion can be prepared on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film,
Applied on other plastic bases or glass plates.

The silver halide photographic light-sensitive materials of the present invention include photographic light-sensitive materials for plate making (for example, tui+ films, return films, duplex films, etc.), color reversal papers and films, light-sensitive materials for color diffusion transfer processes, and silver salts. Examples include light-sensitive materials for diffusion transfer and light-sensitive materials for heat development.

Exposure to obtain photographic images may be carried out using conventional methods: natural light (sunlight), halogen lamps, tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode rays. Any of a variety of known light sources can be used, such as tube flying spots.

Exposure times range from 1/1000 seconds to 1 second, which is normally used with cameras, as well as exposure times shorter than 1/1000 seconds, such as 1/1 using xenon flash lamps and cathode ray tubes.
Exposures of 0' to 1/10' seconds can also be used;
Exposures longer than seconds can also be used, and the spectral composition of the light used for exposure can be adjusted with color filters if desired. Laser light can also be used for exposure.

Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, T-rays, α-rays, or the like.

For photographic processing of light-sensitive materials made using the present invention, Research Disclosure (Research Disclosure)
Losure) No. 176, pp. 28-30 (I978
Any of the known methods and known treatment liquids, such as those described in (December 2013), can be applied. Depending on the purpose, this photo processing can be used to form a silver image (
black-and-white photographic processing) or a photographic process that forms a dye image (
The p of the developer may be any color photographic processing).
Although H cannot be unconditionally defined depending on the difference between black and white developer and color developer, the type of developing agent, and the type of photosensitive material to be processed, it is usually in the pH range of 9 to 12.5, and the processing temperature is usually 18. and 50℃, but 1
The temperature may be lower than 8°C or higher than 50°C.

In particular, U.S. Pat. No. 4,224,401 and U.S. Pat.
The sulfite ion described in No. 4166742, etc.
．． 15 mol/I! Containing pH 11.0 to 12.3 or more
The developer disclosed in JP-A No. 60-258537 and U.S. Pat. No. 4,269,929 can be preferably used.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 (Preparation of Emulsion A) A silver nitrate aqueous solution and a sodium chloride aqueous solution containing 2.5 x 10-' mol of ammonium hexachloride rhodium (Ill) per mol of silver were mixed in a gelatin solution at 35°C by a double jet method. ) was mixed while controlling the ratio to be 2.3 to prepare a monodisperse silver chloride emulsion with an average grain size of 0.1 micron.

After particle formation, soluble salts are removed by flocculation methods known in the art and stabilizers such as 4-hydroxy-6-methyl-1,3°3a, 7-titraazaindene and l-phenyl are added. -5-Mercaptotetrazole was added. The gelatin contained in 1 klr of the emulsion was 55 g, and 1 silver was 105 kg. (Emulsion A) (Preparation of light-sensitive material) A nucleating agent represented by the following formula was added to the emulsion A. 20■/111
g and 2/111 g of an organic desensitizer were added, and 2,4-dichloro-6-hydroxy 1.3.5-triazine sodium salt was added as a hardening agent. te, I1
1? A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the amount of silver per layer was 3.5 g, and gelatin (0.8 g
/rrr) and polyethyl acrylate latex (0,
19 g/rrr), and on top of that the compound of the invention! -6 (0.1 g/rrf), gelatin (0
, 7g/rd) and as a matting agent with an average particle size of 2
μ polymethyl methacrylate (0,07g/rrr)
A protective layer containing the following was applied and dried (Sample 1).

For Compound 1-6, a gelatin dispersion was prepared and coated using the following procedure; a solution of 194.9 g of the compound dissolved in 39 mjl of methyl ethyl ketone was added to 260 g of a 5.0% (by weight) gelatin aqueous solution. , and mixed with stirring at 45° C. to obtain a slightly emulsified dispersion.

Comparative Example-1 A sample was prepared in Example-1 except for the intermediate layer (Sample A).

(Evaluation of performance) (I) The above two samples were exposed through an optical wedge using a Meishuku printer P-607 manufactured by Dainippon Screen Co., Ltd., and developed with the following developer at 38°C for 20 seconds. It was fixed using the following method, washed with water, and dried.

Sample 8 and the top sample were also completely decolored.

As shown in Table 1, the obtained photographic characteristics are as follows: Compared to comparative sample A, sample 1 has a higher f [
Dmax) is also higher, preferably 1゜Table-1 Hydroquinone 35.0g N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 18.0g 5-sulfosalicylic acid 75.0g Potassium sulfite
110.0g Ethylenediaminetetraacetic acid tetrasodium salt 1.0g Potassium bromide 6.0g 2-mercaptobenraimidazole 5-sulfonic acid 0.3g Sodium 3-(5-mercaptotetrazole)benzenesulfonate 0.1g 3-diethylamino-1゜2- Propanediol 15.0g Add water
11 (pH = 11.6) The sensitivity in the table is based on the sensitivity of sample 1 and represents the difference from it. When <n photometer, take log E,
(Displayed as the difference).

Sensitivity is the logarithm of the exposure (IogE) that gives a density of 1.5
It is expressed as

Dmax: From the sensitivity point, log! ! The value represents the density value at a point that is underexposed by 0.5.

Gradation (T): This is the slope of the straight line connecting the point of density 0.3 and the point of density 3.0 on the characteristic curve. The larger the straight line, the higher the contrast.

(2) Comparative sample A and sample I were forced to age under high temperature and high humidity, and then exposed in the same manner as in ([)].
Developed.

Forced aging conditions were 3 days at 50°C, 65% RH, and 50°C.
Each was tested at 75% RH for 3 days.

The results are shown in Table 2. It can be seen that Sample 1 of the present invention exhibits less change in sensitivity due to forced aging than Comparative Sample A. Fr indicates a sample without forced aging.

Table-2 Sample top 0 +0.01
The +0.05 rate sensitivity is based on the sensitivity of Fr on the sample, and the difference therebetween is expressed as an IogE value.

Example 2 (Preparation of Emulsion B) A silver nitrate aqueous solution and a sodium chloride aqueous solution containing ammonium hexachloride rhodium (Ill) at 1.0xlO-' mol per mol of silver were adjusted to pH in a gelatin solution at 38°C by a double jet method. A monodisperse silver chloride emulsion with an average grain size of 0.08 microns was prepared by mixing the grains while controlling the grain size to be 5.8 microns.

After particle formation, soluble salts were removed by flocculation methods well known in the art, and stabilizers 4-hydroxy-6-methyl-■, 3°3a, 7-titraazaindene, and 1-phenyl-5 were added. -Mercaptotetrazole was added. 1 kg of emulsion contained 55 g of gelatin and 105 g of silver. (Emulsion B) (Preparation of photosensitive material) Two types of nucleating agents represented by the following formula were added to the emulsion B, and polyethyl acrylate latex (0°UsN
a The following development accelerator, 20 μ/n (further addition of 2,4-dichloro-6-hydroxy 1.3.5-) riazine sodium salt as a hardening agent, In
? A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the amount of silver per layer was 3.5 g, and gelatin (0,8
g/rrr) and polyethyl acrylate latex (0
, 19 g/rrr), the following development accelerator, a hydrazine compound and 55 ■/rd 71 If/rtt A layer containing thioctic acid (6 ■/rd) is coated, and on top of that, the compound 1-6 of the present invention is applied. (0,1 g/d), gelatin (0,7 g/nf) and polymethyl methacrylate (0,07 g
/nf) was applied and dried (sample 2).
).

The following three types of surfactants were used as coating aids.

Cm F +yS Ox N CHt COOK5Hq (Evaluation of performance) As a result of examining the photographic characteristics and the sensitivity change with forced aging in the same manner as in Example 1, it was found that the sample had a high T value and D as in Sample 1.
max, and the change in sensitivity during forced aging was also small.

Example 3 In Example 2, instead of Compound 1 of the invention in the protective layer,
I-1, I'-4, l-11, l-15, summer-18, l
Samples 3-1 to 3-6 were prepared using -20, and photographic properties and forced aging tests were conducted in the same manner as in Example 2.

As a result, similar to Example 2, high γ and Dmax values and high forced aging stability were shown.

Preferred embodiments of the invention are as follows.

1. A light-sensitive material according to the claims, characterized in that the compound of general formula (I) is contained in a surface protective layer or an antihalation layer existing between a support and an emulsion layer.

2. The light-sensitive material according to the claims, characterized in that a gelatin intermediate layer is present between the layer containing the compound of general formula (I) and the photosensitive emulsion layer containing the hydrazine derivative.

3. The compound represented by general formula (I) is represented by general formula (II)
A photosensitive material according to claim 1 or 2 above, which is a compound represented by:

4. The compound represented by the general formula (r) has the general formula (II[
) The above-mentioned photosensitive material 3 is characterized by being represented by:

5. The photosensitive material described in 1 to 4 above, wherein the hydrazine derivative is represented by the general formula (IV).

6. The sensitive material described in 5 above, wherein the hydrazine derivative has diffusion resistance or a silver halide adsorption group.

7. A hydrazine derivative is contained in the photosensitive emulsion layer,
6. The photosensitive material described in 6 above, wherein the compound of general formula (I) is contained in the surface protective layer or in a layer between the support and the emulsion layer.

8. Silver halide grains have an average of 0. The photosensitive materials described in items 1 to 7 above are characterized by having fine particles of 2 μm or less.

9. After image exposure of the photosensitive materials 1 to 8 above, remove sulfite ions to 0.
．． A method for forming an ultra-high contrast image, characterized by developing with a developer containing 15 mol/1 or more and having a pH of 11°0-12.3.

Shit'kozHs tHs CI! IG5＼ しF3 しcalculated zns Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment 1, case indication: Showa era 1 year patent application No. 1330/4
A No. 2, Title of invention: Silver halide photographic material 3,
Relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address 2-26-30-4 Nishiazabu, Minato-ku, Tokyo 106 Subject of amendment Detailed description of the invention in Book A '' column 5, the description in the ``Detailed Description of the Invention'' section of the Statement of Contents of the Amendment is amended as follows.

l) tth line from the bottom of the second page "Z is an oxygen atom" "X is an oxygen atom" and correct it.

2) Page 3j, line J "Oxonol" "Oxonol" and correct it.

3) No. 3! Insert "hydrazine compound having a sulfinyl group and other compounds used in the present invention" after "compound represented by general formula (fV)" on page 1, line j.

≠) Page 77, line r After “nucleating agent represented by the following formula” "(Compound Example IV-J O) J Insert.

j) 1st/page hiroki "straight line" "value" and correct it.

6) Insert "(Compound Example ■ and Compound Example IV-J O) J" after "Two types of nucleating agents" on page r3, line j.

7) 1st≠page 10th line K after “hydrazine compound” "(Compound Example IV-j O) J Insert.

Claims (1)

[Scope of Claims] A support having at least one silver halide emulsion layer and a hydrophilic colloid layer containing a compound represented by general formula (I), wherein the at least one silver halide emulsion layer and having a hydrophilic colloid layer containing substantially no compound represented by the general formula (I) between the hydrophilic colloid layer containing the compound represented by the general formula (I);
A silver halide photographic light-sensitive material characterized in that at least one of these hydrophilic colloid layers or other hydrophilic colloid layers contains a hydrazine derivative. General formula [I] PWR-(Time)-_2LA In the formula, PWR represents a group that releases (Time)-_2LA upon reduction. Time represents a group that is released from PWR as (Time)-_2LA and then releases LA through a subsequent reaction. represents an integer of 0 or 1. LA represents a group having a light absorption maximum at 310 nm or more.