JPH02306236A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the contrast and blackening density of a sensitive material and to reduce black spots by using silver halide particles each having a higher iridium content in the shell than in the core and adding specified hydrazine deriv. CONSTITUTION:The emulsion layer of this sensitive material is made of an emulsion contg. an Ir salt such as K3(IrCl6) by >=1x10<-8> mol per 1 mol silver and >=60% of Ir contained in all the silver halide particles in the emulsion is contained in the surface parts of the particles corresponding to 50% of the total volume of the particles. The emulsion layer or other hydrophilic colloidal layer contains a hydrazine deriv. represented by formula I (where R1 is an aliphat. or arom. group, etc., R2 is H, alkyl, etc., and each of A1 and A2 is H or one of them is H and the other is alkylsulfonyl, etc.). A compd. represented by formula III may be used as the deriv. represented by the formula I.

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) In order to improve the reproduction of continuous tone images or line images using halftone images in the field of photoengraving,
There is a need for an imaging system that exhibits the photographic properties of carbide 11 (particularly gamma greater than or equal to 10).

Traditionally, a special developer called a Lith developer has been used for this purpose. Lith developer contains only hydroquinone as a developing agent, and uses sulfite as a preservative in the form of an adduct with formaldehyde so as not to inhibit its infectious development properties, and the concentration of free sulfite ions is kept extremely low (usually 0). Therefore, the Lith developer has the serious drawback that it is extremely susceptible to air oxidation and cannot be stored for more than 3 days.

As a method for obtaining high contrast photographic properties using a stable developer, US Pat.
, No. 168,977, No. 4. No. 166.742, No. 4.311,781, No. 4.272.606,
There is a method using hydrazine derivatives described in 4,221,857, 4,243,739, 4,269,929, and the like. According to this method, photographic characteristics with ultra-high contrast and high sensitivity can be obtained, and since it is allowed to add a highly sensitive sulfite to the developer, the stability against air oxidation of the developer is better than that of the lithium developer. A dramatic improvement in comparison.

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 photosensitive material that provides high sensitivity and high blackening density, it is necessary to contain more per unit area of a silver halide emulsion with a large grain size.However, a large amount Photosensitive materials containing silver halide emulsions undergo fixing, washing, and
As a result, it takes a long time to dry, which impairs rapid processability. Furthermore, since silver is expensive and the amount of 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.

On the other hand, with this new high-contrast negative image system, if you try to increase the maximum density by changing the amount of hydrazine derivative added, you can increase the maximum density and achieve a remarkable high-contrast contrast.
per), which is a problem in the photolithography process.

A black spot is a black spot made of minute developed silver that occurs in an unexposed, non-image area.

Black spots occur frequently due to a decrease in sulfite ions, which are generally used in developing solutions as preservatives, and an increase in the pH value, and significantly reduce the commercial value of photolithographic materials. Although much effort has been made to improve black spots, improvements in black spots are often limited to sensitivity and gamma (r).
), there has been a strong desire for a system that maintains high contrast and improves black outs. As one such method, Japanese Patent Application Laid-open No. 77274/1983 describes particle size 0.
．． A silver halide photographic light-sensitive material containing two types of monodispersed opal and a hydrazine derivative with a size of 5 μm or less is disclosed.

(Problems to be Solved by the Present Invention) The object of the present invention is to provide a silver halide photographic material capable of obtaining high sensitivity, high contrast (for example, T of 10 or more), and high black density with few black spots. An object of the present invention is to provide an image forming method.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support.
a silver halide emulsion containing at least 1 x 10-'' mole of iridium salt per mole, the iridium content of the outer shell of the silver halide grains of the silver halide emulsion being greater than that of the inner core; This can be achieved using a silver halide photographic material characterized by containing a hydrazine derivative represented by the following general formula (I) in the emulsion layer or other hydrophilic colloid layer.

I At formula, R1 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R is a hydrogen atom, an alkyl group, an aryl group,
It represents an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarbonyl group, and G1 is a carbonyl group, a sulfonyl group, a sulfoxy group, a -P- group, or an iminomethylene R group.

represents a group, where A, , A are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. represents a group.

(Detailed Description of the Invention) The hydrazine derivative used in the present invention has the following general formula (
Preference is given to compounds represented by r).

General formula (I) % formula % In the formula, R represents an aliphatic group or an aromatic group, and R2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, or an oxycarbonyl group. Gl represents a carbonyl group, sulfonyl group, sulfoxy group, -P- group, or iminomethylene group, R8 A, and At are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkyl group. It represents a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

In the general formula (I), the aliphatic group represented by R 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, and the alkyl group may be an aryl group,
It may have a substituent such as an alkoxy group, a sulfoxy group, a sulfonamide group, or a carbonamide group.

The aromatic group represented by R1 in general formula (I) is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group.

Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group.

Examples include benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring, quinoline ring,
Among the isoquinoline ring, benzimidazole ring, thiazole ring, benzothiazole ring, etc., those containing a benzene ring are preferred.

Particularly preferred as R is an aryl group.

The aryl group or unsaturated heterocyclic group of R8 may be substituted, and typical substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, Acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamide group, sulfonamide group or carboxyl group, phosphoric acid amide group, diacylamino group,
Examples of substituents include imide groups, and preferred substituents include linear, branched, or cyclic alkyl groups (preferably 1 to 1 carbon atoms).
20 carbon atoms), aralkyl groups (preferably monocyclic or bicyclic alkyl groups with 1 to 3 carbon atoms), alkoxy groups (preferably carbon atoms with 1 to 20 carbon atoms), substituted amino groups (preferably carbon atoms (amino group substituted with 1 to 20 alkyl groups), acylamino group (preferably 2 to 3 carbon atoms)
0), sulfonamide group (preferably has 1 to 30 carbon atoms), ureido group (preferably has 1 to 30 carbon atoms), phosphoric acid amide group (preferably has 1 to 30 carbon atoms) things) etc.

The alkyl group represented by R8 in general formula (I) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, cyano group, carboxy group, sulfo group, alkoxy group, phenyl group, or sulfonyl group.

The aryl group is preferably a monocyclic or bicyclic aryl group, such as one containing a benzene ring. This aryl group is, for example, a halogen atom, an alkyl group, a cyano group,
It may be substituted with a carboxyl group, a sulfo group, a sulfonyl group, etc.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

The aryloxy group is preferably monocyclic, and the substituent includes a halogen atom.

The amino group includes an unsubstituted amino group and a carbon number of 1 to 10.
An alkylamino group or an arylamino group is preferred, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, a carboxy group, or the like.

The carbamoyl group is preferably an unsubstituted carbamoyl group, an alkylcarbamoyl group having 1 to 10 carbon atoms, or an arylcarbamoyl group, which may be substituted with an alkyl group, a halogen atom, a cyano group, a carboxy group, or the like.

The oxycarbonyl group is preferably an alkoxycarbonyl group or an aryloxycarbonyl group having 1 to 10 carbon atoms, and may be substituted with an alkyl group, a halogen atom, a cyano group, a nitro group, or the like.

Among the groups represented by R2, preferred is G.

is a carbonyl group, a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group, a 3-hydroxypropyl group, a 3-methanesulfonamidopropyl group,
phenylsulfonylmethyl group, etc.), aralkyl group (e.g., 0-hydroxybenzyl group, etc.), aryl group (e.g., 0-hydroxybenzyl group, etc.),
For example, phenyl group, 3゜5-dichlorophenyl group, 0
-methanesulfonamidopropyl group, 4-methanesulfonylphenyl group, etc.), and a hydrogen atom is particularly preferred.

Furthermore, when G is a sulfonyl group, R2 is an alkyl group (e.g., methyl group, etc.), an aralkyl group (e.g., 0
-hydroxyphenylmethyl group), aryl group (e.g. phenyl group) or substituted amino group (e.g.
dimethylamino group, etc.) are preferred.

When G is a sulfoxy group, preferred Rt is a cyanobenzyl group, a methylthiobenzyl group, etc., a methoxy group,
An ethoxy group, a butoxy group, a phenoxy group, and a phenyl group are preferred, and a phenoxy group is particularly preferred.

When G1 is an N-substituted or unsubstituted iminomethylene group,
Preferred R2 is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R1, the substituents listed for R3 can be applied.

G in general formula (I) is most preferably a carbonyl group.

Also, Rt splits the G+ Ri part from the remaining molecules,
-G+ It may be one that causes a cyclization reaction to produce a cyclic structure containing an atom of the R1 portion, and specifically, one that can be represented by general formula (a).

General formula (a) Rs L In the formula, Z+ nucleophilically attacks G, -R3-
21 moiety can be split from the remaining molecule, R1 is R1 with one hydrogen atom removed, Z, makes a nucleophilic attack on G, and G, Ih.

A cyclic structure can be formed with Z+.

More specifically, when the hydrazine compound of the general formula (I) generates the next reaction intermediate by oxidation, Zl easily undergoes an abstraction reaction with G, R, -N, -G, -R, - Z.

R1-N-N is a group capable of splitting from G+, specifically 0) ISSH or NHRa (Ra is a hydrogen atom, an alkyl group, a naryl group, -COR, or -
3OxRs, where R2 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), or may be a functional group that directly reacts with G, such as C0OR (here, OH, SH, NHR ,, -COOH is temporarily protected so that these groups are generated by hydrolysis with alkali etc. (R,,R, is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group). It may also be a functional group that can react with G by reacting with a nucleophilic side such as a hydroxyl ion or a sulfite ion, as shown in (representing G).

Furthermore, the ring formed by G, R3, and Z is preferably a 5- or 6-membered ring.

Among those represented by general formula (a), preferred are those represented by general formulas (b) and (C).

General formula (b) In the formula, R5-R5 is a hydrogen atom, an alkyl group (preferably one having 1 to 12 carbon atoms), an alkenyl group (preferably one having 2 to 12 carbon atoms), or an aryl group (preferably one having 2 to 12 carbon atoms). 6 to 12), which may be the same or different, B is an atom necessary to complete a 5- or 6-membered ring that may have one substituent, and m and n are 0 or 1, and (n+m) is 1 or 2.

Examples of the 5J or 6-membered ring formed by B include a cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, and a quinoline ring.

Zl has the same meaning as in general formula (a).

General formula (C) Rc " fN? 7-eCRcR,? -Z.

In the formula, Rc and Rc represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a halogen atom, or the like, and may be the same or different.

Rc represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

p represents O or 1, and q represents 1-4.

RcSR and Rc may be bonded to each other to form a ring as long as the structure allows Zl to make an intramolecular nucleophilic attack on G.

Rc and Rc are preferably a hydrogen atom, a halogen atom, or an alkyl group, and Rc is preferably an alkyl group or an aryl group.

q preferably represents 1 to 3; when q is 1, p represents 0 or 1; when q is 2, p represents O or 1; when q is 3, p represents O or 1; when q is 2, p represents O or 1; Or CRゎR when 3
c may be the same or different.

Z is synonymous with -temple (a).

AI and Ax are hydrogen atoms, alkylsulfonyl groups and arylsulfonyl groups having 20 or less carbon atoms (preferably phenylsulfonyl groups, or Hammett's sum of substituent constants is -0).
, 5 or more), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) group, or linear, branched, or cyclic unsubstituted and substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, and sulfonic acid groups) )) Hydrogen atoms are most preferable as AI and Ax.

R or R2 in the general formula (I) may have a ballast group commonly used in immobile photographic additives such as couplers incorporated therein.

The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group,
It can be selected from alkylphenoxy groups, etc.

R5 or R1 in the general formula (7) may have a group incorporated therein that enhances adsorption to the silver halide grain surface. Examples of such adsorption groups include a thiourea group, ? j
[U.S. Pat. No. 4,385.108, U.S. Pat.
No. 59,347, JP-A No. 59-195,233, No. 5
9-200゜231, 59-201.045, 59-201.046, 59-201,047,
59-2OL, 048, 59-201,049, JP-A-61-170.733, JP-A-61-270,7
No. 44, No. 62-948, Patent Application No. 62-67.508
No. 62-67.501 and No. 62-67.510.

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

zHs CHg CHt Cfh SH I-17) N"-N I-22) 0l-
25) OCN 1-21>I-30> I-44) [-45) r-46) In addition to the above, the hydrazine derivatives used in the present invention include RES[1ARCHDISCLOSURE
I tea23516 (November 1983 issue, P,
346) and the references cited therein, as well as U.S. Pat.
No. 080.207, No. 4,269,929, No. 4.
276,. No. 364, No. 4,278,748.

No. 4,385,108, No. 4,459,347, No. 4,560,638, No. 4,478.928, British Patent No. 2,011,391B, JP-A-60-179734
No. 62-270,948, No. 63-29,751
No., JP-A-61-170.733, JP-A No. 61-270,
No. 744, No. 62-948, EP No. 217,310,
Patent Application No. 61-175.234, No. 61-251,48
No. 2, No. 61-268.249, No. 61-276゜2
No. 83, No. 62-67528, No. 62-67゜509
No. 62-67.510, No. 62-58.513, No. 62-130,819, No. 62-143,467
No. 62-166.117, or US 4,686
, No. 167, JP-A No. 62-178, 246, JP-A No. 6
No. 3-234,244, No. 63-234,245, No. 63-234.246, No. 63-294,552,
No. 63-306,438, patent application No. 62-166゜11
No. 7, No. 62-247,478, No. 63-105.6
No. 82, No. 63-114, 118, No. 63-110,
No. 051, No. 63-114, 119, No. 63-116
, No. 239, No. 63-147.339, No. 63-17
No. 9,760, No. 63-229,163, Patent Application No. 1-
No. 18,377, No. 1-18,378, No. 1-18,
No. 379, No. 1-15,755, No. 1-16,814
No. 1-40,792, No. 1-42,615, and No. 1-42,616 can be used.

In the present invention, when the hydrazine derivative represented by general formula (I) 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 included as a water-soluble compound, or if it is poorly water-soluble, it may be included in alcohols, esters, etc. It can be added to a hydrophilic colloid solution as a solution of water-miscible aqueous solvents such as ketones.When added to a silver halide emulsion layer, it can be added at any time from the start of chemical ripening to before coating. However, it is preferable to add it between the end of chemical ripening and before coating, and it is particularly preferable to add it to the coating liquid prepared for coating.

In the present invention, the hydrazine derivative represented by the general formula (I) is preferably contained in an amount of 1 x 10-'' mol to 1 x 10-' mol per 1 mol of silver halide.
Preferably, the content is from 10-' to 4X10-' moles.

The present invention is characterized by the distribution of iridium in the silver halide grains. That is, 60% or more, preferably 80%, of the total iridium content in all particles is contained in the area from the particle surface to a portion corresponding to 50% of the particle volume within the total volume of the particles.
The above lies in the existence of this.

That is, it is characterized by the presence of a large amount of iridium in a portion closer to the particle surface than in the interior of the particle.

In particular, it is preferable that 60% or more of the total iridium content in all the particles exists in a portion corresponding to 30% of the total particle volume from the particle surface, and it is particularly preferable that the iridium content is localized in the particle surface portion.

Regarding itadium content, the silver halide grains of the present invention may have a multiple structure with a double structure or more, or may have a structure in which the content changes continuously, but a double structure is preferable.

In the case of a double structure, the itadium content in the inner core, which is closer to the center of the particle, is lower than that in the outer shell, which is a layer closer to the particle surface, and itadium is localized in the outer shell. Preferably.

In addition, in the case of a multilayer structure, it is preferable that the layer closest to the particle surface has the highest iridium content, and in the case of a continuously changing structure, the iridium content in the layer closest to the particle surface should be 20% of the total particle volume. Preferably, there is a portion of the volume with the highest iridium content.

Such silver halide grains in which iridium distribution is considered in the grains are disclosed in JP-A-56-147142 and JP-A-58-58-1.
No. 221839, No. 59-152438, No. 61-4
No. 7941, etc., the present invention provides a silver halide photographic light-sensitive material that can be used in combination with a hydrazine derivative to provide high sensitivity, high contrast (for example, T of 10 or more), and high blackening density with few black spots. There are no examples, and examples of using silver halide grains containing iridium in combination with hydrazine derivatives are disclosed in JP-A-61-29837, JP-A-61-47942, JP-A-61-201233, etc. However, there is no description of iridium distribution in these silver halide grains.

In order to incorporate iridium salt into the grains, it is desirable to add the iridium salt 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(II), potassium hexachloroiridate(IV),
Ammonium hexachloroiridate (III) and the like.

The amount of these water-soluble iridium salts added is at least 1.0x10-' mole per mole of silver oxide, preferably 1x10-'mole-1x10-' halogen used in the present invention. The silver emulsion may have any composition such as silver chloride, silver chlorobromide, silver iodochlorobromide, silver iodochlorobromide, etc., but the composition is 70 mol%.
Above all, silver halide containing 90 mol% or more of silver bromine is particularly preferred.

The content of silver iodide is 10 mol% or less, especially 0. It is preferably 1 to 5 mol%.

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 composites 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, a cadmium salt, sulfite, lead salt, thallium salt, rhodium salt or a complex salt thereof may be present in the silver halide grain formation or physical ripening process.

Silver halides suitable for use in the present invention are silver halide iodides in which the silver iodide content on the grain surface is higher than the silver iodide content on the grain average. When an emulsion containing such silver haloiodide is used, photographic characteristics with even higher sensitivity and high comma can be obtained.

The silver halide emulsion used in the method of the present invention may not 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 may be used alone or in combination for chemical sensitization. good.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses gold compounds, mainly total complex salts. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum, palladium, and rhodium. A specific example is U.S. Patent No. 2,448,060
No. 618, British Patent No. 618.

It is described in No. 061, etc.

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

In the present invention, the silver halide emulsion layer is
It is preferable to include two types of monodispersed emulsions having different average particle sizes as disclosed in No. 3734 and No. 62-90646 from the viewpoint of increasing the maximum density (Dmax).
The small-sized monodisperse particles are preferably chemically sensitized, and the most preferred chemical sensitization method is sulfur sensitization. Large size monodisperse emulsions may not be chemically sensitized (although they may be chemically sensitized).Large size monodisperse grains are more likely to produce black spots, so chemical aggravation should not be performed or When deterioration occurs, it is particularly preferable to apply the chemical sensitization shallowly to the extent that black spots do not occur.Here, “applying shallowly” means shortening the chemical sensitization time compared to chemical sensitization of small-sized particles,
This can be done by lowering the temperature or 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 Δj! 0 as ogE.

1-1. It is more preferably 0.2 to 0.7 than Ol, and the higher it is in large size monodispersed emulsions.

The sensitivity of each emulsion is obtained when it is coated on a support containing a hydrazine derivative and processed using a developer with a pH of 10.5 to 12.3 containing 0.15 mol/1 or more of sulfite ions. It is something that can be done.

More specifically, the evaluation method described in Example 1 was followed.

The average grain size of the small monodisperse grains is 90% or less, preferably 80% or less, of the average grain size of the large monodisperse silver halide grains.

The average grain size of the silver halide emulsion grains is preferably 0.02μ to 1.0μ, more preferably 0.1μ to 0.5μ.
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 two or more types of emulsions of different sizes are used, the coating amount of small-sized monodisperse emulsions is preferably 40 to 90 wt%, more preferably 50 to 80 wt%, based on the total coated silver amount. .

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 that the large emulsion be in the upper layer and the small emulsion in the lower layer.

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.
There is basically no limit to the zero particle size distribution, which is preferably 5 μm or less, but it is preferably monodisperse. Monodisperse herein refers to a group of particles of which at least 95% by weight or number of particles has a size within ±40% of the average particle size, more preferably within ±20%.

When the silver halide has a double structure, the average grain size of the silver halide constituting the core with a low iridium content of the present invention is 0.03 to 0.45μ, preferably 0.1 to 0.
．． 35μ, deviation of particle size from average particle size is ±40%
Particles with a narrow distribution of less than ±20%, preferably less than ±20%, are preferred.

The final average particle diameter after the outer shell portion with a high iridium content of the present invention is laminated on the core portion is preferably 0.5μ or less, more preferably 0.2μ to 0.5μ. It is 4μ.

The distribution of iridium in silver halide is determined by the concentration of (
It can be determined by sequentially etching the NHt)t'SOOs solution several times, quantifying the amounts of silver and iridium in each solution, and converting them into particle volumes. Quantification can be performed by atomic absorption method or the like.

When the silver halide has a double structure, the iridium content in the inner core is 0 to 5X10-'' mol 1 mole silver, and the iridium content in the outer shell is 1.0XIQ-1 to 1.0X.
Preferably it is 10-' mole silver.

The composition of the core portion with less iridium content and the shell portion with more iridium content can be arbitrarily selected in a volume ratio of 1:too to 100:1, but preferably in the range of 1:1O to 10:1.

In order to make the above-mentioned water-soluble iridium salt exist in silver halide grains, it is preferable to add it to the water-soluble silver salt or to the halide solution when simultaneously mixing the water-soluble root mass and the water-soluble halide solution.

Alternatively, when silver salt and halide solutions are mixed simultaneously, silver halide grains may be extracted as a third solution by a three-liquid time mixing method, or during or immediately after grain formation or during physical heat formation. A necessary amount of an aqueous solution of iridium salt may be added to the reaction vessel during or at the end of the reaction.

Incidentally, the total amount of coated silver is preferably Ig/po to 8 g/bo.

The photosensitive material used in the present invention includes Japanese Patent Application Publication No. Sho! j-rJθj0 No. 4tj page~! The sensitizing dyes described on page 3 (for example, cyanine dyes, merocyanine dyes, etc.) 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 76/7
t<t3 (Published in July, 2007), page 23, item 5.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines; mercaptotriazines: thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetrazaindenes (especially g-hydroxy substituted (/, 3. J &, 7) tetrazaindenes) ), hantaazaindenes, etc. Many compounds known as anti-capri agents or stabilizers can be added, such as benzenethiosulfonate, benzenesulfinic acid, benzenesulfonamide, 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-S -) riazine, /, 3-
vinylsulfonyl coufropanol, etc.), active halogen compounds (s, 4t-dichloro-6-hydroxy-3
-triazine, etc.), 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 alkyl ethers, etc.) ) alkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Ionic surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfate acids, alkyl phosphoric esters, N-acyl-N-alkyl taurines, sulfosuccinic acid Anions containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkylbeciins, amine oxides; alkylamine salts,
Cationic surfactants such as aliphatic or aromatic secondary ammonium salts, heterocyclic 9th class ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

In particular, the surfactant preferably used in the present invention is Tokko Sho! ! - Molecule xtoo described in Publication No. 94t/2
These are the above polyalkylene oxides. When used as an antistatic agent, fluorine-containing surfactants (for details, see US Pat. preferable.

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 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 repeat units. Regarding these compounds, Japanese Patent Application No. 20-44/79 and O
-6♂♂No.23, same 0-7≦3♂! and 60
-/ri! ≦! You can refer to the description in the specification. 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.

The binder or protective colloid used in the photosensitive material button is as follows:
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 DISCLOS)
URE) Volume 72g, Boiled/2t<t3(/y7.r Year 7
February).

In order to obtain ultra-high contrast and high-sensitivity photographic properties using the Rogge/Silver Cide photosensitive material of the present invention, it is necessary to use a conventional infectious developer or the pH 13 described in U.S. Pat. It is not necessary to use a similar high-potassium 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. /! Contains mol/1 or more, pH
10, r~/2.3, especially I)H//, θ~/2.0, a sufficiently 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 that it contains dihydroxybenzenes, since it is easy to obtain good halftone dot quality. A combination of nyl-3-pyrazolidones or a combination of dihydroxybenzenes and p-aminephenols may also be used.

Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, inpropylhydroquinone, methylhydroquinone, co, 3-dichlorohydroquinone, co,! −
Examples include dichlorohydroquinone, 2,3-sifuromehydroquinone, u, J'-dimethylhydroquinone, and hydroquinone is particularly preferred.

The developing agent for /-phenyl-3-pyrazolidone or its derivative used in the present invention is /-phenyl-3-pyrazolidone, /-phenyl-g, 4t-dimethyl-3-
Pyrazolidone, /-phenyl-gumethyl-guhydroxymethyl-3-pyrazolidone, /-phenyl-g, 4
t-dihydroxymethy/l/-3-hylaso! J ton, /-phenyl-r-methyl-3-pyrazolidone, /-
p-aminophenyl-g, 4t-dimethyl-3-pyrazolidone, /-p-tolyl-g, 4t-dimethyl-3
-Pyrazolidone, etc.

Examples of the p-aminephenol developing agent used in the present invention include N-methyl-p-aminephenol, p-aminephenol, N-(β-hydroxyethyl)-p-aminephenol, and N-(4t-hydroxyphenyl)glycine. , 2-methyl-p-aminophenol, p-benzylaminophenol, etc. Among them, N-methyl-p-
Aminophenols are preferred.

The developing agent is usually 0. θ! Mol/l~0. Preferably it is used in an amount of r mol/l. Further, when using a combination of dihydroxybenzenes and/-phenyl-3-pyrazolidones or p-amine-phenols, the former is 0.
0tmol/l-0゜! mol/l, the latter is θ, θg mol/l
It is preferable to use it in an amount of 1 or less.

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. Gumoru/1 or more! ￥fKo, rmol/1 or more is preferable. Also, the upper limit is ko! Preferably up to mol/l.

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 methyl cellosolve. , aqueous solvents such as hexylene glycol, ethanol, and methanol; mercapto compounds such as 1-phenyl-5-mercaptotetrazole and 2-mercaptobenzimidazole-5-sulfonic acid sodium salt; indazole compounds such as 5-nitroindazole; It may also contain an antifoggant or a black pepper inhibitor such as a benztriazole compound such as 5-methylbenztriazole, and if necessary, a color toning agent, a surfactant, an antifoaming agent,
It may also contain a water softener, a hardening agent, an amino compound described in JP-A No. 56-106244, Japanese Patent Application No. 1-29418, and the like.

The fixing solution is an aqueous solution containing thiosulfate, a water-soluble aluminum compound, acetic acid, and a dibasic acid (for example, tartaric acid, citric acid, or a salt thereof), and has a pH of 4 or more, preferably 4.4.
~5.0.

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 varied as appropriate, and is generally about 0.1 to about 5 mol/l.

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

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

(Example) 'In the examples, developers A and B were used with the following formulations.

C was used.

Developer A At this time, add potassium hydroxide to adjust the pH to 11°7.

At this time, add potassium hydroxide to adjust the pH to 11°7.

Add potassium hydroxide to the developer and adjust to p)[=11°7.

(Example 1) Emulsion (A) (B) (C) CD) (E
) (F) (G) (H) were prepared.

[Emulsion A]

A monodisperse silver iodobromide emulsion (average grain (size: 0.26μ, silver iodide content: 2 mol%) was prepared.

This emulsion was washed with water in a conventional manner to remove soluble salts, and then chemically enhanced by adding sodium thiosulfate. Further, by adding potassium iodide to the emulsion to convert the grain surface, a silver iodobromide emulsion having a grain average silver iodide content/silver iodide content on the grain surface=1/3 was obtained. Proxel was added thereto as a preservative at a rate of 70 ml/mol.

This emulsion was designated as A.

[Emulsion B]

Potassium iodide and potassium iodide containing potassium hexachloroiridate (If) corresponding to 4 x 10-' mol per 1 mol of silver nitrate in an aqueous gelatin solution kept at 50 °C. 6 aqueous solutions at the same time
A monodisperse silver iodobromide emulsion having an average grain size of 0.26 μm and a uniform iridium content of 2 mol % silver iodide was prepared by adding it for 0 minutes and maintaining the PAg at 7°5. .

This emulsion was washed with water in the same manner as Emulsion A, subjected to chemical aggravation, potassium iodide was added, and a preservative was added.

Emulsion B was thus prepared.

[Emulsion C]

Silver nitrate dissolved in gelatin solution kept at 50°C? At night, an aqueous solution of potassium iodide and potassium bromide containing 7X10-' moles of potassium hexachloroiridate(III) per mole of mention was added simultaneously over 30 minutes, during which time P
Average particle size 0.20 by keeping Ag at 7.5
Monodisperse silver iodobromide core grains having a silver iodide content of 2 mol% were prepared. After that, add 1 mol of silver nitrate to 1 mol of silver nitrate solution.
X 10-, 'mol of hexachloroiridium (I[[
) By simultaneously adding a halogen salt aqueous solution containing potassium acid for 30 minutes and maintaining PAg at 7.5 during that time, iridium was produced with an average grain size of 0.26μ, a silver iodide content of 2 mol%, and a total iridium of 14 x 10-' mol. Monodisperse silver iodobromide with a double structure was prepared in terms of content.

This emulsion was washed with water in the same manner as Emulsion A, and subjected to chemical amplification. Potassium iodide and preservatives were added. The emulsion thus made is C
And so.

[Emulsion D]

Silver nitrate aqueous solution and Sl in gelatin aqueous solution kept at 50℃
An aqueous solution of potassium iodide and potassium bromide containing 1 x 10-' mol of potassium hexachloroiridium ([[
Average particle size 0.20μ by keeping g at 7.5
, monodispersed silver iodobromide core grains having a silver iodide content of 2 mol % were prepared. Then add silver nitrate aqueous solution and 7X10 per mole of silver.
-' mol of potassium hexachloroiridate(I[I) in an aqueous halogen salt solution is simultaneously added over 30 minutes;
During this period, by keeping PAg at 7.5, the average grain size is 0.26μ, the silver iodide content is mol%, and the total iridium ft4 is
A double-structured, monodisperse silver iodobromide was prepared for iridium content with X10-' moles of silver.

This emulsion was washed with water in the same manner as Emulsion A, subjected to chemical agitation, and potassium iodide and preservatives were added. The emulsion thus produced was designated as D.

[Emulsion E]

Silver nitrate aqueous solution, potassium iodide, and potassium bromide aqueous solution were simultaneously added to a gelatin aqueous solution kept at 50°C for 30 minutes, and the PAg was maintained at 7.5 during that time, resulting in an average particle size of 0.20μ and silver iodide. Monodisperse silver iodobromide core grains containing 2 mol % of N and no iridium were prepared. Thereafter, an aqueous solution of silver nitrate and an aqueous halogen salt solution containing 8 x 10-' mol of potassium hexachloroiridate(III) per mol were simultaneously added for 30 minutes, during which time the PA
By keeping g at 7.5, the average size is 0.26μ, the silver iodide content is 2 mol%, and the total iridium content is 4Xlo-'mol 1.
A monodisperse silver iodobromide with a double structure was prepared with respect to iridium content.

This emulsion was washed with water in the same manner as Emulsion A, subjected to chemical agitation, and potassium iodide and preservatives were added. The emulsion thus made is
And so.

[Emulsion F] A silver nitrate aqueous solution, potassium iodide, and potassium bromide aqueous solutions were simultaneously added to an aqueous gelatin solution kept at 50° C. over a period of 60 minutes, during which PAg was maintained at 7.5. Then, 6 minutes after the start of addition, an aqueous solution of potassium hexachloroiridate(III) corresponding to 4×10-' mol per 1 mol of total grains was added, and the average grain size was 0.26μ, the silver iodide content was 2 mol%, A silver iodobromide emulsion was prepared in which iridium was localized at a position of 10% of the total grain volume from the grain center.

This emulsion was washed with water in the same manner as Emulsion A, subjected to chemical sensitization, potassium iodide was added, and a preservative was added.

The emulsion thus produced was designated as F.

[Emulsion G]

Emulsion F except that an aqueous solution of potassium hexachloroiridate(III) corresponding to 4×10-' mol per mol of silver in the finished emulsion was added 54 minutes after the start of addition of the aqueous solution of silver nitrate, potassium iodide, and potassium bromide. A silver iodobromide emulsion was prepared in the same manner, washed with water, chemically sensitized, potassium iodide and a preservative were added, and iridium was localized at a position of 90% of the total grain volume from the center of the grain.

[Emulsion H]

When mixing a silver nitrate aqueous solution, potassium iodide, and potassium bromide aqueous solution in a gelatin aqueous solution kept at 50 °C for 60 minutes, at the same time, a potassium hexachloroiridate (II) aqueous solution was added as a third solution at a certain rate. At the start,
The addition is increased linearly from 0 to a total iridium content of 4×10 −′ moles per mole of silver over 60 minutes. Thus, the average grain size is 0.26μ, the silver iodide content is 2 mol%, and the total iridium content is 4X1 per mole of silver.
A silver iodobromide emulsion was prepared in which the iridium content increased from the grain center to the grain surface at 0-' molar.

This emulsion was washed with water and chemically sensitized in the same manner as Emulsion A, and after addition of potassium iodide, a preservative was added. The emulsion thus produced was designated as H.

Table 1 summarizes the iridium content of emulsions A to H, the structure of the content, the location of the content, and the content.

Each of these emulsions A to H contains 4-hydroxy-6-
Methyl-1,3,3a,7-titrazyden, a dispersion of polyethyl acrylate, polyethylene glycol (molecular weight 600), and 1,3-vinylsulfonyl-2-probanol were processed, and then the general formula of the present invention shown in Table 2 ( I
) was added as shown in Table 2 per mole of silver, and then coated on a cellulose triacetate film at a coated silver amount of 4 g/rrf.

After exposing the film thus obtained through a sensitometric exposure wedge, it was exposed to light using developer A at 38°C.
Developed for seconds, stopped, fixed, washed with water, and dried.

The results are shown in Table 2, where: O relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of 1.5, and the sensitivity of film sample 1 is set to 100.

O-Kurobo is a grade of 5, which is obtained by observing the unexposed areas of the film using a microscope, with ``5'' representing the best quality and ``1'' representing the best quality.
'' represents the worst quality, 4 or higher is suitable for practical use, 3 is inferior but somehow usable, and 2 or lower is not practical. Also, the black areas are the result of 40 seconds of 3B'C development.

As is clear from Table 2, compared to the comparative sample of the present invention, the sensitivity, T, and maximum density Dmax are higher, and the black spots are also better.

(Example 2) Each of Samples 1 to 12 used in Example 1 was carried out in the same manner as in Example 1, except that developer B was used instead of developer A. Good "photographic properties" similar to those obtained were obtained.

(Example 3) Each of Samples 1 to 12 used in Example 1 was treated in the same manner as in Example 1, except that developer C was used instead of developer A. Similar good "photographic properties" were obtained.

Patent applicant: Fuji Photo Film Co., Ltd. 1999//Monday/ρDate 1, Case indication: 1999 Patent Application No. 1 Cor.RJts No. 2, Title of invention: Silver halide photographic light-sensitive material 3, Amendment person's case Relationship with Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. Contact address 2 Nishi-Azabu, Minato-ku, Tokyo 106
1-Item 26 No. 30 No. 4, Subject of amendment: Column 5 of "Detailed description of the invention" in the description. Contents of amendment The description in the "Detailed description of the invention" section of the description is amended as follows.

1) Page 3, line 9 “Easy to accept” "Easy to accept" and correct it.

2) Page 4, line 10 "per unit area of emulsion" "More emulsion per unit area" and correct it.

3) Page 5, line 7 “The J that has become "It's becoming" and correct it.

4) The iridium content of the outer shell of F on page 6, lines 14-15 is higher than that of the inner core, Particles containing iridium of 60% or more of the iridium content in all particles are corrected as j.

5) 6th line from the bottom of No. 8 after "especially" "Preferably" Insert.

6) Page 9, line 11 Before “among others” "but," Insert.

7) Page 12, line 16 "Methanesulfone" "Methanesulfone" and correct it.

8) 15th true line 20th "by reacting to" "by reacting to" and correct it.

9) Page 15, line 2 After “general formula (I)” "of" Insert.

10) Page 18, line 18 "It can be mentioned.))" "It can be mentioned.)) etc." and correct it.

11) Change the chemical structure of 1-24 on page 25 to C! Hs” and correct it.

12) The chemical structural formula of page 25, 1-25) and correct it.

13) The chemical structural formula of page 26 l-28) and correct it.

14) Page 36, line 20 "Itadium" "iridium" and correct it.

15) Page 37, line 5 "total" 1st layer” and correct it.

16) Page 37, line 5 "Itadium J" "iridium" and correct it.

17) Page 37, line 9 "Iridium" "iridium" and correct it.

18) Page 37, line 14 “Wo J. "of" and correct it.

19) Page 38, line 8 "Itadium" "iridium" and correct it.

20) Page 39, line 12 “Setsumono” "What you have" and correct it.

21) Page 43, line 19 "many" "expensive" and correct it.

22) Page 44, line 4 '(NHZ) gszo3J “(NHa)zszos J and correct it.

23) Page 44, line 19 "S Seal" "Silver Salt" and correct it.

24) Page 45, line 4 "Raku" Delete.

25) Page 45, line 6 "Itadium" "iridium" and correct it.

26) Page 46, line 3 "etc.)" r, etc.) and correct it.

27) Page 51, line 17 "Contains organic acid" "Organic acids and" and correct it.

28) Page 52, lines 1-3 [Patent Application No. 60-66179, Same No. 60-68873, No. 60-163856, and No. 60-195655” “Unexamined Japanese Patent Publication No. 61-223,834, Same 61-228. No. 437, No. 62-25,745, and Same 62-55. No. 642”.

29) Page 55, line 6 "p-amino phenol" [p-aminophenol] and correct it.

30) Page 55, line 18 "Potassium oxide" "Potassium hydroxide" and correct it.

31) Page 56, line 12 "triazole etc." "Triazole etc." and correct it.

32) Page 56, line 13 "Kurobot" “Kurobo.

and correct it.

33) Page 57, lines 2 to 4, “Ammonium thiosulfate, ammonium thiosulfate, etc.
It contains thiosulfate ion and ammonium ion as essential components, and ``ammonium thiosulfate, sodium thiosulfate, ammonium thiocyanate, etc.'' is corrected to ``.

34) Page 58, line 13 "Sulfonic acid J "Sulfonic acid" and correct it.

35) Page 59, line 15 "Sulfonic acid" "Sulfonic acid" and correct it.

36) Page 60, line 19 [Sulfonic acid J "Sulfonic acid" and correct it.

37) Page 62, line 11 "Potassium iodide and odor potassium" "Potassium Bromide" and correct it.

38) Page 64, line 9 "Silver iodide" "Silver iodide" and correct it.

39) Page 65, line 19 "Aqueous solution and addition" "Add aqueous solution" and correct it.

40) Page 66, line 3 “With this emulsion” “This emulsion.” and correct it.

41) The entire statement on page 68 is amended as shown in the attached sheet.

42) Page 70, line 4 "of the present invention" "The sample of the present invention is" and correct it.

43) Page 72, line 2 "1~12J "1-20" and correct it.

Procedural amendment

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the emulsion layer contains silver 1
It consists of a silver halide emulsion containing at least 1 x 10^-^8 moles of iridium salt per mole, and the silver halide grains of the silver halide emulsion extend from the grain surface to a portion corresponding to 50% of the total grain volume. Particles containing iridium in an iridium content of 60% or more of the total iridium content, and characterized in that the emulsion layer or other hydrophilic colloid layer contains a hydrazine derivative represented by the following general formula (I). Silver halide photographic material. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aliphatic group, aromatic group, or heterocyclic group, and R_2 is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, amino group, carbamoyl group or oxycarbonyl group, G_1 is carbonyl group, sulfonyl group, sulfoxy group, ▲ formula,
There are chemical formulas, tables, etc. ▼ group, or iminomethylene group, where A_1 and A_2 are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, Or represents a substituted or unsubstituted acyl group.