JPS62250439A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To rapidly form an ultrahigh contrast image with a processing soln. having high stability by forming at least one photosensitive silver halide emulsion layer on a support and incorporating a hydrazine deriv., an amine compound and a quat. onium salt compound into the emulsion layer and/or other constituent layer. CONSTITUTION:At least one silver halide emulsion layer is formed on a support and a hydrazine deriv., an amine compound and a quat. onium salt compound are incorporated into the emulsion layer and/or other hydrophilic colloidal layer. The amine compound used is preferably represented by formula I (where each of R<1> and R<2> is 1-30C alkyl, R<3> is 1-30C alkyl or the like, A is alkylene or the like, X is -O- or the like and n=0 or 1). The quat. onium salt used is a compound contg. nitrogen represented by formula II (where each of R1-R4 is optionally substituted alkyl, optionally substituted aryl, optionally substituted aralkyl, an optionally substituted hetero ring or amino, R1-R4 may bond to each other to form a ring, Z is an anion and n=1 or 2). The molar ratio of the amine compound to the quat. onium salt is 50-1. The hydrazine compound used may be a compound represented by formula III (where R1 is an aliphatic or aromatic group).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is applied to silver halide photographic materials (particularly negative materials) that are used in the field of photoengraving and are capable of rapidly forming ultra-high contrast images using a highly stable processing solution. (type).

(Prior Art) It is known that certain silver halides can be used to form extremely high contrast photographic images, and methods for forming such photographic images are used in the field of photolithography.

For example, silver chlorobromide (with a silver chloride content of at least 50%)
% or more) is processed with a hydroquinone developer containing an extremely low effective concentration of sulfite ions (usually 0.1 mol/l or less), which makes it possible to clearly distinguish between image and non-image areas. A method is known for obtaining line drawings or halftone dot images with high contrast and high blackening density. However, with this method, the concentration of sulfite in the developer is low, making the development extremely unstable against air oxidation.Currently, various efforts and innovations have been made to keep the solution activity stable. Met.

For this reason, the above development method (lith development system)
There is a need for an image forming system that eliminates the instability of image formation caused by the process, develops with a processing solution that has good storage stability, and obtains ultra-high contrast photographic characteristics, and the U.S. Patent No. 4.7
λ No., same gu, /≦? , No. 972, same number, 2 pieces/, 73
No. 7, same g.

Ko2<1.4tO1 No. 1, '1.24t3,739,
Same 4t, 272. ≦Og issue, same 4t, 3//,? As seen in No. ♂/, a surface latent image type silver halide photographic light-sensitive material to which a specific acylhydrazine compound is added, I)
H//, θ ~ 72.3 with sulfite preservative θ, /! Mol/
A system has been proposed for forming ultra-high contrast negative images in which r exceeds /θ by processing with a developer containing 1 or more and having good storage stability.

This new image forming system has the feature that it can also use silver iodobromide and silver chloroiodobromide, whereas conventional ultra-high contrast image formation could only use silver chlorobromide, which has a high silver chloride content. There is.

However, in general, in silver halide photographic light-sensitive materials, the image blackening density obtained per unit amount of developed silver increases as the size of the silver halide grains decreases, but the sensitivity of silver halide generally increases due to the size of the silver halide grains. The larger the value, the higher the value. Therefore, in order to obtain a light-sensitive material that provides high sensitivity and high blackening density, it is necessary to contain a larger amount of silver halide emulsion with a larger grain size per unit area. However, photosensitive materials containing a large amount of silver halide emulsion undergo fixing, washing, and washing during the development process.
As a result, it takes a long time to dry, which impairs rapid processability. Furthermore, since silver is expensive and its production and reserves are limited, it is required to produce photosensitive materials using as little silver as possible.

For this reason, research has been carried out for many years on silver halide photosensitive materials that have high image density and high sensitivity while using less silver.

However, with these silver halide photographic materials, sensitivity and
, or had the disadvantage that the maximum concentration was lowered.

Therefore, there has been a strong desire for a system that can stably obtain the high sensitivity and high contrast characteristics obtained by this new image forming system.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide photographic material that uses a stable developer and has extremely high sensitivity and high contrast photographic properties with a γ of over 10. be.

A second object of the present invention is to provide a silver halide photographic material that exhibits little decrease in sensitivity, γ, and maximum density (Dmax) even when the pH decreases or the bromide ion concentration increases due to processing of a large amount of film. It's about doing.

(Means for Solving the Problems) The above object of the present invention is to have at least one silver halide emulsion layer on a support, and in the emulsion layer or other hydrophilic colloid layer, a hydrazine derivative, an amine compound and This can be achieved using a silver halide photographic material containing a quaternary onium salt compound.

Changes in photographic properties due to fatigue of the developer can be improved to some extent by changing the content of the hydrazine derivative, but as the content increases, black spots are more likely to occur. This is not a preferable method. On the other hand, it is surprising that by using an amine compound and a quaternary onium salt compound in combination as in the present invention, the deterioration of photographic properties caused by fatigue of the developer can be significantly improved.

The amine compound used in the present invention is preferably of the following general formula (
This is a compound represented by 1).

General formula (I) In the formula, R1 and R2 are substituted or unsubstituted carbon atoms of ~3
0 alkyl group, which may be linear, branched or cyclic.

Furthermore, R1 and R2 may be connected to form a ring, in which seven or more heteroatoms (such as oxygen atoms,
sulfur atom, nitrogen atom, etc.), such as methyl group,
Examples include ethyl group, isOpropyl group, n-butyl group, n-octyl group, t-octyl group, cyclohexyl group, pyrrolidyl group, and morpholino group. Also R1
.

As the substituent for R2, an aryl group (preferably carbon number ~20), an alkoxy group (preferably carbon number/~--〇)
, sulfo group, sulfonamide group (preferably carbon number/~
an alkyl sulfonamide group having 0 to -0 carbon atoms), a carbonamide group (preferably an alkyl carbon amide group having 0 to 20 carbon atoms, an aryl carbon amide group having 7 to .2 θ carbon atoms) , a ureido group (preferably an alkylureido group having carbon number/~20,
(aryl ureido group having j-20 carbon atoms).

R3 is a substituted or unsubstituted alkyl group having up to 30 carbon atoms (e.g., methyl group, ethyl group, n-butyl group, n-octyl group, n-dodecyl group, n-hexadecyl group, t-butyl group, cyclohexyl group, etc.), Substituted or unsubstituted aryl group having t to 30 carbon atoms (e.g. phenyl group, naphthyl group, etc.), or substituted or unsubstituted heterocyclic group (1
Contains more than one nitrogen, oxygen, or sulfur atom! It is a membered ring, a two-membered ring, or a seven-membered heterocycle, and also includes those in which a fused ring is formed at an appropriate position on these heterocycles. For example, pyridine ring, pyrimidine ring, imidazole ring, quinoline ring, isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc.)
Substituents for R include halogen atoms (fluorine, chlorine, bromine), alkyl groups (preferably those with a carbon number of ~20),
Aryl group (preferably one with a carbon number of g-20), an alkoxy group (preferably one with a carbon number of ~20), an aryloxy group (preferably one with a carbon number of g-20), an alkylthio group (preferably one with a carbon number of g-20), 7 to 20 carbon atoms), arylthio group (preferably one with a carbon number of 5 to -0), an acyl group (preferably one with a carbon number of λ to 20), an acylamino group (preferably an alkanoyl group with a carbon number of 0 to 0) (amino group, benzoylamino group having 7 to 0 carbon atoms), nitro group, cyano group, oxycarbonyl group (preferably an alkoxycarbonyl group having 0 carbon atoms, an aryloxycarbonyl group having ≦ 0 carbon atoms) , hydroxy group, carboxy group, sulfo group, ureido group (preferably carbon number/~
- 〇alkylureido group, arylureido group having 6 to 20 carbon atoms), sulfonamide group (preferably
-0 alkylsulfonamide group, arylsulfonamide group having t to -0 carbon atoms), sulfamoyl group (preferably an alkylsulfamoyl group having 20 carbon atoms, arylsulfamoyl group having t - J o carbon atoms) group), carbamoyl group (preferably an alkylcarbamoyl group having 7 to 0 carbon atoms, arylcarbamoyl group having t to 20 carbon atoms), acyloxy group (preferably one having 7 to 0 carbon atoms), amine group (unsubstituted Amine, preferably carbon number/~2
o alkyl group, or a secondary or tertiary amino group substituted with an aryl group having 6 to -0 carbon atoms), carbonate group (preferably an alkyl carbonate group having carbon number/~λθ, carbon number g-1), 〇 aryl carbonate group), sulfone group (preferably an alkyl sulfone group with carbon number/~2°, aryl sulfone group with 6 to -0 carbon atoms), sulfinyl group (preferably C 7 to 0 carbon atoms) Examples include alkylsulfinyl groups and arylsulfinyl groups having up to 2Q carbon atoms. Here, these substituents may have λ or more, and when there are two or more substituents, they may be the same or different.

A is an optionally substituted alkylene group having up to 10 carbon atoms (
(e.g., methylene, dimethylene, trimethylene, tetramethylene, methylpropylene, etc.), examples of the substituents of A include aryl groups, alkoxy groups, hydroxy groups, halogen atoms, etc., and X is -CONR5-, -0CONR5- .

-NR5CONR5-, -NR5COO-, -COO-
, -0CO-.

-CO-, -NR5CO-, -8O2NR-5-, -N
R5SO2-.

-5o2-, -s-, or -〇- R5 represents a hydrogen atom or a lower alkyl group with carbon number /, j) n represents 0 or /.

Preferred amine compounds in the present invention are R1゜R, R
The total number of carbon atoms in and A is 20 or more.

Preferred specific examples of the amine compounds represented by the general formula (1) are shown below. However, the present invention is not limited to the following compounds.

I-2 ■-gusn α ■-70 ■-// 1-/co■-73 An amine compound that has a similar effect, although it is inferior to the amine with a palust group as in the above specific example. A specific example is shown below.

(1-/j) (■-/g) (■-/ri) (1-/r) (■-/ri) (■-22) (I-23) (I-29) (1--2 -t) ■ Ha (I-2g) (1-!7) (!-cor) (l-30) (I-j/) Next, among the amine compounds represented by general formula (I), preferred A specific example of compound synthesis will be shown.

Synthesis Example 1 Exemplified Compound 1-/Phenyl chloroformate 7,r, 3g (o, j mol) was dissolved in acetonitrile 2jOmlK, and j-(2,4t-cyamylphenoxy) was added to this solution under constant stirring at o'C. 32 g (0, ut mol) of propylamine i, 9. jml, and acetonitrile 23-OmJl
A mixed solution of was added dropwise over about 3 hours. After the dropwise addition, the reaction temperature was raised to ar0c, ice water 21 was added, and the mixture was extracted with chloroform. Chloroform was distilled off under reduced pressure and methanol was added to the oily residue for 10 minutes. t%J-(-2,4'-cyamylphenoxy)-7-fethoxycarbonylaminopropane/!
θg was obtained.

Next, this urethane compound/θ,, Hg (o, os! mol) and 3°3 g of 3-diethylaminopropylamine (0,
02jmol) was dissolved in ioml of dimethylacetamide, and the mixture was heated to 40°C and reacted for 7 hours with stirring.The reaction temperature was then returned to 2t'cK, and 10ml of water was added.This solution was extracted three times with 700ml of n-hexane. After that, n-
Hexane was distilled off under reduced pressure to obtain Exemplified Compound 1-/.

Yield q, rg (♂/%) Oil Synthesis Example Co-Exemplary Compound I-2 Diethylaminopropylamine (0°32 mol) was dissolved in acetonitrile/θOml and cooled and stirred (t
To 'c) was added 10/7 g (0.3 mol) of α-(co,nadiamylphenoxy)butyrylic acid chloride, and after reacting at room temperature for about an hour, 3θOml of water was poured. Next is concentrated hydrochloric acid! , after adding 3ml and 10θml of ethanol, n
- Extract 3 times with 300 ml hexane. Next, alkaline water dissolved in 2 ml of sodium hydroxide/l and 1 ml of water was added to this aqueous layer, followed by extraction with 300 ml of n-hexane. After washing the hexane layer three times with water and 20θml, activated carbon≦0ml was added, heated to reflux, cooled to room temperature, and n-hexane was distilled off under reduced pressure to obtain exemplified compound I.
−λ was obtained.

Yield i 172.2g (, r4.4t%) Melting point g/-
2°C Other amine compounds can also be easily synthesized according to the above synthesis method/2.

The content of the amine compound used in the present invention is preferably /x/θ-5 to /X/(7-
1 mol, more preferably /x10-4 to jX/θ-2 mol.

In the present invention, when an amine compound is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (e.g., a protective layer, an intermediate layer, a filter layer, It may be included in an antihalation layer, etc.). It is preferably used in the emulsion layer. Specifically, if the compound to be used is water-soluble, it can be used as an aqueous solution, or if it is poorly water-soluble, it can be used as an alcohol,
It may be added to the hydrophilic colloid solution as a solution of a water-miscible organic solvent such as esters or ketones. When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between after the end of chemical ripening and before coating. In particular, it is preferable to add it to a coating solution prepared for coating.

The quaternary onium salt used in combination with the amine compound in the present invention is preferably JP-A-Sho tθ-/4tos4to,
There are nitrogen-containing compounds represented by general formulas (If) and (III) or phosphoric acid-containing compounds represented by (IV) as disclosed in Japanese Patent Application No. 6O-934t7. Examples of compounds represented by general formulas (n), (m) and (IV) are shown below.

General Formula (II) In the general formula (n), the groups represented by R1, R2, R3 and R4 preferably have 7 to 30 carbon atoms.

The alkyl group represented by R1 to R4 is straight chain, branched,
The aryl group represented by R1 to R4 is preferably a phenyl group or a 7-tyl group, and the heterocycle represented by R1 to R4 is preferably a monocyclic or bicyclic ring. An aromatic heterocyclic group (preferably containing at least 7 types of N, '0.S, and the number of ring members is ! or B)! >, the aralkyl group represented by R1 to R4 preferably has a straight chain alkyl moiety,
It is branched or cyclic, and the aryl moiety is a phenyl group, a naphthyl group, or a monocyclic or bicyclic aromatic heterocyclic group (preferably containing at least 7 types of N, O, and S! or 6 member ring). Substituents for these groups include:
These include: That is, straight-chain, branched, or cyclic alkyl groups (preferably having 7 to 10 carbon atoms), aralkyl groups (preferably monocyclic or 2@, and the number of carbon atoms in the alkyl moiety is / to 3), alkoxy groups (preferably having 1 to 10 carbon atoms),/or a λ-substituted amino group (preferably an alkyl group, acyl group, alkyl or arylsulfonyl group having 1 to 20 carbon atoms; in the case of λ substitution, a substituent The total number of carbon atoms in the group is less than or equal to θ), / to 3-substituted or unsubstituted ureido group (preferably the number of carbon atoms / to 0), substituted or unsubstituted aryl group (preferably carbon a substituted or unsubstituted arylthio group (preferably 2 to λ9 carbon atoms), a substituted or unsubstituted alkylthio group (preferably 1 to 29 carbon atoms), Substituted or unsubstituted alkylsulfinyl group (preferably 1 to 29 carbon atoms), substituted or unsubstituted arylsulfinyl group (preferably monocyclic or bicyclic with 1 to 9 carbon atoms), substituted or unsubstituted Substituted alkylsulfonyl group (preferably carbon atoms/to co9), substituted or unsubstituted arylsulfonyl group (
Preferably, the number of carbon atoms is 5 to 9, monocyclic or 2fR
), aryloxy group (preferably having 1 to 29 carbon atoms, monocyclic or bicyclic), carbamoyl group (preferably having 1 to 29 carbon atoms), sulfamoyl group (preferably having 1 to 29 carbon atoms), 29), a hydroxy group, a halogen atom (for example, F, α, Br, I), a sulfonic acid group, or a carboxylic acid group. Among these substituents, those which may have further substituents may have the following substituents; namely, Al.

Kyl group (number of carbon atoms / to 20), aryl group (monocyclic or cocyclic ring having number of carbon atoms / to 20), alkoxy group (number of carbon atoms / to λθ), aryloxy group (
from 1 to 20 carbon atoms), alkylthio group (from 1 to some carbon atoms), arylthio group (from 6 to 20 carbon atoms), alkylsulfonyl group (from 7 to 2θ carbon atoms), arylsulfonyl group (from 7 to 2θ carbon atoms), 6 or
20), carbonamide group (number of carbon atoms/to coθ)
, sulfonamide group (number of carbon atoms: 0 to θ), carbamoyl group (number of carbon atoms/to 20), sulfamoyl group (number of carbon atoms: 7 to some), alkylsulfinyl group (number of carbon atoms/to θ), Arylsulfinyl group (7 to 0 carbon atoms), ester group (7 to λ0 carbon atoms), hydroxy group, -COOM or -
8o2M (M represents a hydrogen atom or an alkali metal atom, substituted or unsubstituted ammonium), trisubstituted ammonio group (-NRIR2R3・-Zn: f/:, riLRt
, R2.

Ra Oyohizba general formula (II) VC Okel Rt
, R2.

selected from the groups synonymous with R3 and 2; ), or a halogen atom (F, α, Br, I). More specifically, the group represented by 2 in general formula (II) is .

Ie), perchlorate ion, nitrate ion, sulfate ion, P
Inorganic anions such as F6e and OHe or acetate ions,
Represents organic acid ions such as benzoate ion, methanesulfonate ion, and paratoluenesulfonate ion. However, these organic sulfonic acid ions or carboxylic acid ions may form a part of the group represented by R1 to R4 to form an inner salt. Note that the number of Z and the number of negative charges are the numbers necessary to neutralize the hot water charges in the compound represented by the general formula (It).

Specific examples of the compound represented by the general formula (II) are shown below, but the scope of the present invention is not limited only by these.

(■)-2 Φ (CH3)3NCH2CH20CH3, Bre(II)
-Dan-C16H33N(CH3)3 Bre(II),
t e (n-C4H9)4Nα (nC4H9)4N (lJO4e (II)-7 e (nC3H7)4N 0H (If)-♂ (C2H5)4Nα04 (II)-ta (C2H6)4N FS (n)-// (II)-/CO(CHa)aCH2CH20H-C0(II)-/J (II)-/4' (It)-/j (II)-# n-Cl2H25=(CH3)3 Q!!e (It)-
/7 (II)-/♂ (If)-/9 (C2H5)3N-(CH2)8-N(C2H5)32
C1ee Φ (If)-CoO's e (n-C4Hg)3NCH2CH2N(n-C4Hg)
3 ・5O42-(n)-co/ (II)-coco(If)-,23 (I[)-24t (]II-JJ- (Il)-24 (n)-27 General formula (II[) here In, Xo represents an anion.

R1 is -Y-R3, -Y-COOR3, -Y-COOR
3, -Y/-COO-Y-COOR3, -Y/-0CO
-Y-COOR3, -Y/-Coo-Y-COOR3.

R2 is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkyl group, an oxycarbonyl group, an acyloxy group, an alkoxy group, an amino group, a substituted amino group, an acrylamide group, a sulfamide group, a carbamoyl group, R2 in R1, R2 It has at least 7 ester groups.

Specifically, there are the following compound examples.

(I[[-/) (III-J) (III-4) (III-1) (m-, <) (III-7) (I[[-/) (■-9) (III-7o) (III-//) (■-/ko) (l[-73) re ([[-/4t) (I[[-/J-) (■-/O) (I[I-/7) Brθ General formula (IV) Examples of groups represented by R1, R2, and R3 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 5eC-butyl group, tert-butyl group, and octyl group. , 2-ethylhexyl group, dodecyl group,
Straight chain or branched alkyl groups such as hexadecyl group and octadecyl group; cycloalkyl groups such as cyclopropyl group, cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, naphthyl group and phenanthryl group;
Allyl group, vinyl group! -hexenyl group, etc.; cycloalkenyl group such as cyclobontenyl group, cyclohexenyl group; pyridyl group, quinolyl group, furyl group, imidazolyl group, thiazolyl group, thiadiazolyl group, benzo) IJ azolyl group, benzothiazolyl group ,
Examples include heterocyclic residues such as morpholinyl group, pyrimidyl group, and pyrrolidyl group. Examples of substituents substituted on these bases include, in addition to the groups represented by R1, R2, and R3, halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom, nitro group, /, 2. Tertiary amine group, alkyl or aryl ether group, alkyl or aryl thioether group, carbonamide group, carbamoyl group,
Examples thereof include a sulfonamide group, a sulfamoyl group, a hydroxyl group, a sulfoxy group, a sulfonyl group, a carboxyl group, a sulfonic acid group, a cyano group, and a carbonyl group.

Examples of the group represented by R1, R2, and R3 include trimethylene group, tetramethylene group, hexamethylene group, ha/tamethylene group, octamethylene group,
Polymethylene groups such as dodecamethylene groups, covalent aromatic groups such as phenylene groups, biphenylene groups, and naphthylene groups,
Polyvalent aliphatic groups such as trimethylenemethyl group and tetramethylenemethyl group, phenylene-/, 3. r-tolyl group,
Phenylene/2. Examples include polyvalent aromatic groups such as 'l, if-tetrayl group.

Examples of the anion represented by
Carboxylate ions such as benzoate ions, p
- Sulfonate ions such as toluenesulfonate, methanesulfonate, butanesulfonate, benzenesulfonate, sulfate ions, perchlorate ions, carbonate ions,
Examples include nitrate ion.

Particularly preferred compounds among the compounds represented by the general formula (A) are those in which m represents an integer of 2, and L represents R1, R2.
, a group having 2θ or less carbon atoms among the groups synonymous with R3, or P
represents a divalent organic group having 20 or less carbon atoms bonded to an atom and its carbon atoms, n represents an integer from 7 to -, X represents a monovalent or covalent anion, and X represents L
It may be connected to

Many of the compounds represented by the general formula (A) of the present invention are known and commercially available as reagents. General synthesis methods include a method in which phosphite/acids are reacted with an alkylating agent such as an alkyl halide or a sulfonic acid ester; or a method in which the counter anion of a phosphonium salt is exchanged by a conventional method.

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

(IV)-/ (II/)-2 (N>-3 (If/)-ta (FV) -r (Pi>-g ■ (n-C4Hg)4P Bre (F/)-7 (IV) - / (IV)-9 (IV)-#7 (IV)-// CN)-/2 (■)-/J (IV)-/4t (IV)-/j (IV)-# Ph5P-(CH2 )4COOHBre(IV)-/7 NV)-// (n-C4H9)3P n-C16H33Bre(IV
)-/9 (■)-10(Fl/)-,21 (■)-2,2 (It/)-23 (n-C4Hg)3PCH2CH20HBre(IV)
-,2g(!I/)-Jj (■)-2g (F/)-,27 (n-C4Hg)3PCH3Ie (F/)-λr Φ (HoCH2)3PCH3eng e (IV)-19 (■ ) -30 In the present invention, the 9th class onium salt is used by being added to at least seven silver halide emulsion layers or other hydrophilic colloid layers of a photographic light-sensitive material. The preferred amount used is F)/×10-6 mol to IXIQ per mol of silver halide.
It is preferable to contain -1 mole, especially /xIQ-5 mole! The preferred addition amount is in the range of x70-2 moles.

When the 9th grade onium salt of the present invention is incorporated into a photographic light-sensitive material, it can be contained in an aqueous solution if it is water-soluble, or as an alcohol (e.g., methanol, ethanol) or an ester (e.g., ethyl acetate) if it is water-insoluble. It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as a ketone (for example, acetone).

Although the ratio of the amine compound and the onium salt used in the present invention cannot be unconditionally determined depending on the type of each compound used, the type of silver halide emulsion, and the type of hydrazine derivative, it is preferable to use the amine compound/grade onium salt. <Primary onium salt=j0~/(molar ratio).

Examples of the hydrazine derivatives used in the present invention include the hydrazine derivatives having a sulfinyl group described in US Patent No. 4t4t7!9.2 and compounds represented by the following general formula (V).

General formula (V) R□-M core 1'H-CHO In the formula, R1 represents an aliphatic group or an aromatic group.

In general formula (V), the aliphatic group represented by R1 preferably has carbon atoms/~30, particularly carbon atoms/~30.
20 straight chain, branched or cyclic alkyl groups. The branched alkyl group herein may be cyclized to form a saturated heterocycle containing seven or more heteroatoms therein. In addition, this alkyl group is an aryl group,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfo/amide group, or a carbonamide group.

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 (V), the aromatic group represented by R1 is a single
j! or an aryl group of a λ ring or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or λ-ring aryl 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 R1 is an aryl group.

The aryl group or aromatic group of R1 may have a substituent.

Typical substituents include straight-chain, branched or cyclic alkyl groups (preferably those with a carbon number of up to 20), aralkyl groups (preferably monocyclic or monocyclic ones with an alkyl moiety of up to 3 carbon atoms). ), an alkoxy group (preferably one with a carbon number of / to θ), a substituted amino group (preferably one with a carbon number of /
(amino group substituted with ~20 alkyl groups), acylamino group (preferably having a carbon number of 2 to 30), sulfonamide group (preferably having a carbon number/~30), ureido group (preferably carbon number/~30).

R1 in the general formula (V) may have a pallast group, which is commonly used in immobile photographic additives such as couplers, incorporated therein. Ballast base! It is a relatively inert group with respect to photography having the above carbon number, 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.

R1 in general formula (V) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Such adsorption groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, etc. as described in US Pat. , No. 10♂.

Synthesis methods for these compounds are described in JP-A-63-. No. 20927, No. j-3-209-2.2, No. 20927, Same! No. 3732 on 3-, same! 3-203/, No. f, etc.

In the present invention, when a hydrazine derivative is contained in a photographic light-sensitive material, it is preferably contained in a silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (e.g., a protective layer, an intermediate layer, a filter layer, It may be included in an antihalation layer, etc.). Specifically, when the compound used is water-soluble, it is prepared as an aqueous solution, and when it is poorly water-soluble, it is prepared as a solution of water-miscible organic solvents such as alcohols, esters, and ketones, and as a hydrophilic colloid solution. It can be added to. When added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added between after the end of chemical ripening and before coating. In particular, it is preferable to add it to a coating solution prepared for coating.

The content of the hydrazine derivative of the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, the type of anti-capri compound, etc. It is desirable to select the optimal amount accordingly, and testing methods for this selection are well known to those skilled in the art. Usually, it is preferably used in a range of 10-6 mol to /X10-1 mol, particularly 10-5 to 4tXio-2 mol, per mol of silver halide.

Specific examples of the compound represented by general formula (V) are shown below.

However, the present invention is not limited to the following compounds.

V-/ ■-2 y-3 ■−da -t V-≦ V-/ ■-70 V-／　／ 'l/-/λ ■-73 V-/G Mu ■-7! V-/to CH3 ■-72 CH2CH2CH25H ■-7? ■-79 ■-27 V-22 ■-23 ■-2! (Jt; M3 V-,2,< ■-27 ■-29 V-3θ ■-37 ■-32 ■-33 In addition, as described in U.S. Patent No. 4, &7/, and No. 9 and so on.

In the light-sensitive material of the present invention, the hydrazine derivative may be used in the same layer as the amine compound or the 9th class onium salt, or may be used in a different layer. It is preferably used in the same layer as the amine compound.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver iodochlorobromide, etc., but 70 molti or more, especially 9θ molti or more consists of silver bromide. Silver halide is preferred.

The content of silver iodide is less than 10 mole, especially less than 0. /~t morti is preferable.

The average grain size of the silver halide used in the present invention is preferably fine (for example, 0.7 μm or less), particularly 0.7 μm or less.
! It is preferably less than μ. There are basically no restrictions on the particle size distribution, but monodisperse distribution is preferable. Monodisperse here means at least 9 in terms of weight or number of particles! This means that the particle group is composed of a group of particles whose size is within 10% of the average particle size.

Silver halide grains in photographic emulsions may have regular crystals such as cubic or octahedral, or irregular crystals such as spherical or plate-like.
ular) crystals, or a composite form of these crystal forms.

The interior and surface layers of the silver halide grains may be composed of uniform phases or may be composed of different phases.

Two or more silver halide emulsions formed separately may be used in combination.

In the silver halide emulsion used in the present invention, cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or its complex salt, iridium salt or its complex salt, etc. are allowed to coexist in the silver halide grain formation or physical ripening process. Good too.

Silver halide particularly suitable for use in the present invention is prepared in the presence of 10-8 to 10-5 moles of iridium salt or complex salt thereof per 7 moles of silver, and has a silver iodide content on the grain surface of The silver iodide content is higher than that of silver iodide. By using an emulsion containing such silver haloiodide, photographic characteristics with higher sensitivity and higher gamma can be obtained.

The silver halide emulsion used in the method of the present invention does not need to be chemically sensitized, but may be chemically sensitized. Sulfur sensitization, reduction sensitization, and noble metal sensitization methods are known as methods for chemical sensitization of silver halide emulsions, and any of these methods can be used alone or in combination for chemical sensitization. Good too.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, noradium, and rhodium. A specific example is US Patent Co., 4t4t/
, 0 to 0, British patent per/r.

It is described in the oti issue etc.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

In the above, it is desirable to add the iridium salt in the above amount before the completion of physical ripening in the silver halide emulsion manufacturing process, particularly during grain formation.

The iridium salt used here is a water-soluble iridium salt or an iridium complex salt, such as iridium trichloride, iridium tetrachloride, potassium hexachloroiridate (I [I) acid, potassium hexachloroiridate (fV) acid, hexachloroiridate (Ill) acid Ammonium etc.

In the present invention, the silver halide emulsion layer is
It is preferable to include two types of monodisperse emulsions with different average particle sizes as disclosed in Japanese Patent Application Shobu 0-23207B, from the viewpoint of increasing the maximum density (Dmax), and small-sized monodisperse particles. is preferably chemically sensitized, and the most preferred chemical sensitization method is sulfur sensitization. Large size monodispersed emulsions do not need to be chemically sensitized, but
It may be chemically sensitized. Large-sized monodisperse particles generally tend to generate black spots, so chemical sensitization should not be performed.
When chemically sensitizing, it is particularly preferable to apply the chemical sensitization shallowly to the extent that black spots do not occur. Here, ``shallow application'' refers to applying chemical sensitization for a shorter time than chemical sensitization of small-sized particles, lowering the temperature, and reducing the amount of chemical sensitizer added. . There is no particular limit to the sensitivity difference between large-sized monodispersed emulsions and small-sized monodispersed emulsions, but Δflag E
as 0. /~/, 01 preferably 0.2~0゜7
Therefore, the higher the dog size monodisperse emulsion, the better.

Here, the sensitivity of each emulsion is determined by coating it on a support containing a hydrazine derivative and adding sulfite ions to 0. /! pH containing mol/1 or more H/θ,! This is obtained when processing using a developer of ~/2.3.

More specifically, it follows the evaluation method described in Examples.

The average grain size of the small size monodisperse grains is 90% or less of the average size of the large size silver halide monodisperse grains, preferably 10 inches or less.

The average grain size of the silver halide emulsion grains is preferably θ, 02μ to 0μ, preferably θ.

7μ～θ,! It is preferable that the average particle size of large size and small size monodisperse particles is included in this range.

In the present invention, when emulsions of 2'm or more with different sizes are used, the coating silver amount of the small size monodisperse emulsion is preferably <10 to 9 owt, more preferably to- It's rowc.

In the present invention, monodispersed emulsions having different grain sizes may be introduced into the same emulsion or may be introduced into separate layers.

When introduced in separate layers, it is preferred to have the dog size emulsion in the upper layer and the small size emulsion in the lower layer.

The total coating silver amount is preferably /g/m2 to ♂g/m2.

The photosensitive material used in the present invention includes Japanese Patent Application Laid-Open No. 61-320! for the purpose of increasing sensitivity. θ No. q! The sensitizing dyes (for example, cyanine dyes, merocyanine dyes, etc.) described on pages 3 to 3 can be added.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
erch Disclosure) / Volume 7 /
2≦4t3 (Published February 1997), page 13, Section 5.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing capri or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. Azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzos triazoles, etc.; mercaptopyrimidines; mercaptopyrimidines; thioketo compounds, e.g. A number of compounds known as anti-capri agents or stabilizers can be added, such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Among these, preferred are benzotriazoles (eg !-methyl-benzotriazole) and nitroindazoles (eg !-nitroindazole). Further, these compounds may be included in the treatment liquid.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde, etc.), N-methylol compounds (
dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (/, j, j-triacryloyl-hexahydro-5-) riazine, /, 3-vinylsulfonylruco furopanol, etc.), active halogen compounds (, z, 4t-dichloro-4-hydroxy-3
), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. can be used alone or in combination.

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, high contrast, 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 alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: alkyl carponate, alkyl sulfone ff1L alkylbenzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate acid, alkyl phosphate ester, N-acyl-N-alkyl taurine, sulfosuccinate ester, sulfonate Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as alkyl polyoxyethylene alkylphenyl ethers and polyoxyethylene alkyl phosphate esters. ;Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine oxides; alkyl amine salts;
Cationic surfactants such as aliphatic or aromatic 9th class ammonium salts, heterocyclic 9th class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

Particularly, the surfactant preferably used in the present invention has a molecular weight of 00 as described in Japanese Patent Publication No.
These are the above polyalkylene oxides. When used as an antistatic agent, a fluorine-containing surfactant (for details, see US Pat.
No.) is particularly preferred.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for purposes such as improving dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. is used. be able to.

It is preferable that the silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention contain a compound having an acid group. Compounds with acid groups include organic acids such as salicylic acid, acetic acid, ascorbic acid, acrylic acid, maleic acid,
Mention may be made of polymers or copolymers having acid monomers such as phthalic acid as repeating units. Regarding these compounds, patent application No. 779 and 6θ in Sho tθ-
-bu No. 2273, θ-/4376, and 40
-/91 to 15' can be referred to. Among these compounds, particularly preferred is ascorbic acid as a low-molecular compound, and as a high-molecular compound, an acid monomer such as acrylic acid and a crosslinking monomer having two or more unsaturated groups such as divinylbenzene are particularly preferred. It is a copolymer water-dispersible latex.

Binders or protective colloids used in photosensitive materials include:
It is advantageous to use gelatin, but other hydrophilic synthetic polymers can also be used. As the gelatin, lime-treated gelatin, acid-treated gelatin, derivative gelatin, etc. can also be used. Specifically, research
Disclosure (RESEARCH DISCLO8
URE) Volume 776, A/7bu4t3 (/p7♂year/ko month), section ■.

In order to obtain ultra-high contrast and high sensitivity photographic properties using the silver halide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or the pH/J described in U.S. Patent No. 4T/9.97J. It is not necessary to use a similar highly alkaline developer, and a stable developer can be used.

That is, the silver halide photosensitive material of the present invention contains sulfite ions as a preservative at a concentration of 0. l! Contains mol/1 or more, I)
H/o, t~/ko, 3, especially p Hi/, θ~/
2. With the developer of Q, a sufficiently ultra-high contrast negative image can be obtained.

Although there are no particular restrictions on the developing agent used in the developer used in the present invention, it is preferable to include dihydroxybenzenes, since it is easy to obtain good halftone dot quality. A combination of 3-pyrazolidones or a combination of dihydroxybenzenes and p-aminephenols may also be used.

Examples of dihydroxybenzene developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2. j-
Dichlorohydroquinone, 2,3-dibromohydroquinone, λ,! -dimethylhydroquinone, etc., and hydroquinone is particularly preferred.

The developing agent for /-phenyl-3-pyrazolidone or its derivative used in the present invention is /-phenyl-3-pyrazolidone, l-phenyl-X, 4t-dimethyl-3-
Bira/IJ ton, l-phenyl-gumethyl-q-hydroxymethyl-3-pyrazolidone, l-phenyl-4
1,4t-dihydroxymethyl-3-pyrazolidone, /
-Phenyl-! -Methyl-3-pyrazolidone, 1-p-
Examples include aminophenyl rug, 4t-dimethyl-3-pyrazolidone, /-p-) IJ lua, and 4t-dimethyl-3-pyrazolidone.

Examples of the p-aminephenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4t-hydroxyphenyl)glycine. , λ-methyl-p-aminephenol, p-benzylaminophenol, among others, N-methyl-p-
Aminophenols are preferred.

The developing agent is preferably used in an amount of usually 0.0 t mol/l to O0♂ mol/it. In addition, when using a combination of dihydroxybenzenes and 7-phenyl-3-pyrazolidones or p-amine-phenols, the former is reduced to 0.
．． 0tmol/11-0°! mol/l, the latter preferably in an amount of up to 0.01 mol/l.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. Sulfites are 0. <1 mol/1 or more, especially 0. jmol/! The above is preferable. Also, the upper limit is 10! Preferably up to mol/no.

Alkaline agents used to set pH include sodium hydroxide, potassium oxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulators and buffers.

Additives used in addition to the above ingredients include compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, and methylseron. Organic solvents such as l-phenyl, hexylene glycol, ethanol, and methanol: l-phenyl-! -Mercaptotetrazole, Komerkabutobenzimidazole! -Mercapto compounds such as sulfonic acid sodium salts, indazole compounds such as j-nitroindazole,! - An antifoggant or a black pepper inhibitor such as a penztriazole compound such as methylpenztriazole, and may further include a color toning agent, a surfactant, an antifoaming agent, a water softener, It may also contain a hardening agent, such as an amino compound described in JP-A-74-104-4T4.

The fixing solution is an aqueous solution containing thiosulfate, a water-soluble aluminum compound, acetic acid, and a dibasic acid (such as tartaric acid, citric acid, or a salt thereof), and has a pH of 4 or more, preferably 4 t.
, 4t, j, θ.

The fixing agent includes ammonium thiosulfate, ammonium thiosulfate, and the like, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and is generally about 0. /~about! Mol/l.

The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is generally a compound known as a hardening agent for acidic hardening fixing solutions, such as aluminum chloride, aluminum sulfate, and potassium alum.

Since the silver halide photographic material of the present invention provides a high I)max, it maintains a high density even if the halftone dot area is reduced when subjected to a power reduction treatment after image formation.

(Example) The present invention will be explained in detail below with reference to Examples.

Example/ Emulsions CA: ] and (B:l were prepared as shown below.

[Emulsion A]

! a x 1 per 7 moles of silver in an aqueous gelatin solution maintained at θ0C
In the presence of o-7 moles of iridium tetrachloride and ammonia, an aqueous solution of silver nitrate, potassium iodide, and aqueous potassium bromide were simultaneously added over a period of 60 minutes, during which time the pAg was 7. A cubic monodispersed emulsion having an average grain size of 0.3 .mu.m and an average silver iodide content of 1 mol was prepared by maintaining the emulsion at 0.3 μm, and desalting was carried out by the 70° curing method.

[Emulsion B]

The amounts of potassium iodide and ammonia were adjusted in the same manner as in Emulsion A to obtain an average grain size θ of 22μ and an average silver iodide content of 0.
After preparing a 7 mol cubic monodisperse emulsion, it was desalted by the 70 curation method.

The sample was desalted and hyposensitized with sulfur sensitization.

As a sensitizing dye in these silver iodobromide emulsions! .

! '-Dichloro-9-ethyl-3. Sodium salt of 3'-bis(3-sulfoprobyl)oxacarbocyanine, guhydroxy-6-methyl-/ as a stabilizer, 3.
After adding 3&,7-tetrazaindene, ascorbic acid, a dispersion of polyethyl acrylate, /,3-divinylsulfonyl-copropanol, emulsions A and B were prepared in terms of silver halide weight ratios as shown in Table 1. The amine compound (1) of the present invention and the quaternary onic 1! Compounds (II) to (IV) and hydrazine derivatives (
V-9) was added as shown in Table/1c silver amount on the polyethylene terephthalate film together with the protective layer. ,4tg
/m2. Each sample was exposed and developed and the photographic properties were compared.

Photographic properties were determined using FG-ttoF automatic processor (manufactured by Fuji Photo Film Co., Ltd.) using developer A with the following formulation.
This is the result of processing for 0CjO seconds. Photographic characteristic 2 is
This is the result of processing 200 sheets of 100% blackened Fujiris orthofilm Go-10Q full size (jθ, a'cmXj/am) in the same manner as photographic properties/.

As is clear from Table 1, A/, 9 of the present invention.

/4t has higher sensitivity γ, maximum concentration (Dma
x) decrease is small.

Developer A Hydroquinone at, ogN・Methyl p・Aminophenol//λ Sulfate 0.2g Sodium hydroxide 72.0g Potassium hydroxide
jj, θg!・Sulfosalicylic acid
4tj, 0g boric acid
21, 0g potassium sulfite //θ,
θg Ethylenediaminetetraacetic acid disodium salt /, 0g Potassium bromide A, Og! Methylbenzotriazole 0. agn, butyl, jetanolamine /! , θg water added / 1 (pH=//,
) Examples! In the presence of potassium iridium (III) hexachloride and ammonia of 1 mol of Ag/θ-7 mol to an aqueous gelatin solution maintained at 00C, a nitrate aqueous solution and potassium iodide and potassium bromide aqueous solutions were added simultaneously for 0 minutes, p between
Ag 2. By keeping it ♂, the average particle size is 0.2! ；μ、
Cubic monodisperse emulsions with an average silver iodide content of 1 molty were prepared, and these silver iodobromide emulsions were used as sensitizing dyes! ,!
'-dichloro-9-ethyl-3.3'-bis(3-sulfoprovir)oxacarbocyanine sodium salt,
3. Guhydroxy-methyl-/ as a stabilizer; j
a, 7-tetrazaindene, polyethyl acrylate dispersion, aqueous latex represented by the following structural formula (a
), polyethylene glycol, /, 3-dipinylsulfonyl-copropanol, the compound of the general formula (1) of the present invention and the quaternary onium salt compound, and the hydrazine derivative (V)-3/ as shown in the table. The amount of silver j is added to the polyethylene terephthalate film along with the protective layer.
, 4 tg/m2.

Aqueous latex (a) H3 +C-CH2+ H3 Each sample was exposed and developed in the same manner as in Example/1, and the photographic properties were compared. As is clear from Table a, 4/4 of the present invention
For t to -r, the decrease in sensitivity, r, and I) max is smaller than that of the comparative sample. Among amine compounds, amines having a ballast group are better.

Example 3 In Example 3, ya e! ', 9. /41. /! When the same procedure as in Example C was carried out except that compound ■-27 was used in place of compound ■-70 in t, good "photographic properties λ" were obtained.

Example G In Example G, flattened 10. Compound ■-instead of //, /bu, /2 [1-r or m-? The procedure was carried out in the same manner as in Example 1, except for using
"was gotten.

Example! In Example 1, Al1. /3. Example λ except that ■-t is used instead of compound 11/-/ in /r and /9.
When the same procedure as above was carried out, good "photographic characteristics" were obtained.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Letter, July 1988 [I. Director General of the Patent Office, Form 1, Indication of Case, 1988 Patent Application No. 2aOj No. 2, Title of Invention Silver Halide Photographic Light-sensitive Material 4 , Subject of amendment The description in column 5 of the "Detailed Description of the Invention" in the specification and the section of "Detailed Description of the Invention" in the Contents of the Amendment A are amended as follows.

(1) From page 3, line 70 Up to the 7th line of Hirosada Delete.

(2) Page 3, line 1 “Second purpose” “λth purpose” and correct it.

(3) Page 37, line 2 r(A)J "(■)" and correct it.

(4) Page 37, line 17 r(A)J r(W)J and correct it.

(5) 3rd page Hirokime r(A)J r(MN and correct it.

(6) Page 72, line it "Potassium oxide" "Potassium hydroxide" and correct it.

Claims (1)

[Claims] It is characterized by having at least one photosensitive silver halide emulsion layer on a support, and containing a hydrazine derivative, an amine compound and a quaternary onium salt compound in the emulsion layer and/or other constituent layers. A silver halide photographic light-sensitive material.