JP2670852B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material and a method for forming an ultra-high contrast negative image using the same, and particularly to a silver halide photographic material used in a photomechanical process. The present invention relates to a photosensitive material, and more particularly, to a super-high contrast negative type photographic material suitable for a light room photosensitive material.

(Prior Art) In the field of graphic arts, image formation showing photographic characteristics of ultra-high contrast (especially gamma of 10 or more) in order to improve reproduction of continuous tone images or halftone images by halftone dot images. System required.

U.S. Pat. Nos. 4,224,401 and 4,168,977 for obtaining high contrast photographic characteristics using a stable developer.
No. 4,166,742, No. 4,311,781, No. 4,272,60
No. 6, No. 4,221,857, No. 4,269,922, No. 4,650,746
No. 4,681,836 and the like, a method using a hydrazine derivative is known. According to this method, photographic characteristics with ultra-high contrast and high sensitivity are obtained, and the addition of a high concentration of sulfite to the developer is allowed. Dramatically improved.

However, although the above-mentioned image system is suitable for a remarkably high-sensitivity hardening system, it has been difficult to obtain a low-sensitivity light-sensitive material for a bright room which is widely used in the reversion process in the plate making process. A light-sensitive material for a bright room having a low contrast and having a high contrast using a stable processing solution is described in US Pat. No. 4,452,882. As a method for obtaining a low-sensitivity light-sensitive material for a bright room containing hydrazine, there is disclosed in JP-A-60-162246 and JP-A-60-14.
0338, 61-238049. However, these known examples are still insufficient in terms of low sensitivity or high contrast. Regarding silver halide emulsions containing a hydrazine compound and rhodium, U.S. Pat. Nos. 4,332,878 and 4,634,661.
No. 4,618,574, European Patent No. 138200A, etc., but it cannot be said to be a low-sensitivity bright room light-sensitive material.

Japanese Patent Application Nos. 62-65116, 62-133015, 62-204342
JP-A No. 1993-242242 describes a silver halide photographic light-sensitive material which obtains favorable characteristics by using hydrazine having an adsorption group in an emulsion containing a large amount of rhodium. However, the silver halide photographic light-sensitive material exhibits excellent performance in terms of high contrast, but there is a problem that fog increases during long-term storage (especially under high temperature and low humidity).

Methods for preventing fog increase due to long-term storage in silver halide emulsions are disclosed in JP-A-49-69124, JP-A-52-11029 and JP-A-52-11029.
53-137133, 58-194029, 59-191031, 60-1367
40, 62-55644, etc., but particularly in a hydrazine infectious development system, it leads to a decrease in γ.

Further, a method for preventing the increase of fog by using a nonionic surfactant and / or an anionic surfactant having a polyoxyethylene group in combination with an antifoggant is disclosed in JP-A-63-12.
8336, the antifoggant effect is insufficient for silver halide containing 90% or more of AgCl.

Therefore, even if it is stored for a long time without causing a decrease in γ,
A stable silver halide photographic light-sensitive material in which an increase in fog is sufficiently suppressed is desired.

The light-sensitive material for a bright room described in this patent refers to a light-sensitive material that does not contain an ultraviolet light component and has a wavelength of substantially 400 nm or more and can be safely used for a long time as safelight light.

(Object of the Invention) A first object of the present invention is to provide a bright room photographic light-sensitive material utilizing the contrast enhancement by a hydrazine compound.

A second object of the present invention is to provide a bright room photographic light-sensitive material which causes little increase in fog even after long-term storage (especially under high temperature and low humidity).

(Constitution of the Invention) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the emulsion layer is at least 1 per mol of silver.
× 10 ⁻⁶ mol of rhodium salt, silver chloride content of at least 90 mol% consisting of silver halide grains, a hydrazine derivative and a nitrogen-halogen bond in the molecule in the emulsion layer or other hydrophilic colloid layer. It was achieved by a super-hard tone negative-working silver halide photographic light-sensitive material characterized by containing at least one compound having

Typical compounds having a nitrogen-halogen bond in the molecule are compounds represented by the following general formula (I).

General formula (I) In the formula, X represents a halogen atom, A is R ¹ —CO—, R ¹
SO ₂ represents a hydrogen atom or an alkali metal, and B represents R ²
—CO—, R ² SO ₂ — represents an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group; R ¹ and R ² each represent an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group; May be linked to each other to form a nitrogen-containing heterocycle.

Here, among those represented by B, R ¹ and R ² , the alkyl group preferably has 1 to 20 carbon atoms and may be linear, branched or cyclic. The alkenyl group preferably has 2 to 20 carbon atoms and may be linear, branched or cyclic.

The aryl group preferably has 6 to 20 carbon atoms and may be either monocyclic or bicyclic.

The heterocyclic group preferably has 1 to 20 carbon atoms and may be either monocyclic or bicyclic.

The alkyl group, alkenyl group, annealed group and heterocyclic group represented by A, B, R ¹ and R ² may further have a substituent, and typical examples of the substituent include an alkyl group, an aralkyl group and an alkoxy group. Group, arylamino group, amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, arylkythio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, Examples thereof include a halogen atom, a cyano group, a sulfo group and a carboxyl group.

Further, among those represented by the general formula (I), particularly preferable ones are those represented by the general formulas (II) and (III).

General formula (II) In the formula, Z is an organic group composed of an atom selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom, and forms a 3- to 8-membered ring with the nitrogen atom. n is an integer of 1 to 3. X has the same meaning as in formula (I).

General formula (III) In the formula, R ³ is an alkyl group, an alkenyl group, an aryl group,
Alternatively, it represents a heterocyclic group, Y represents —CO—, —SO ₂ —, R ⁴ represents a halogen atom, a hydrogen atom or an alkali metal, and X has the same meaning as in formula (I).

Specific examples of the nitrogen-containing hetero ring formed by Z and a nitrogen atom in the general formula (II) include a succinimide ring, a phthalimide ring, a saccharin ring, a hydantoin ring, a barbitur ring, a valerolactam ring, a caprolactam ring, a piberidone ring, An oxazolidione ring, a thiazolidione ring, a piperidine ring, a benzotriazole ring, an oxazolidone ring, and the like, in which the nitrogen-containing heterocycle may have a substituent, and the substituent is the aforementioned A, B, R ¹ , R ² The same thing as what was demonstrated as a substituent is mentioned.

An alkyl group represented by R ³ in the general formula (III),
The alkenyl group, the aryl group and the heterocyclic group are the same as the above B,
It has the same meaning as the heterocycle of R ¹ and R ² .

The specific compounds represented by formula (I) are listed below, but the invention is not limited thereto.

The compound represented by formula (I) is disclosed in JP-A-49-45,718.
Most of them are commercially available and can be synthesized by the methods described in general literature.

In the present invention, the addition amount of the compound having a nitrogen-halogen bond in the molecule is 1 × 10 ⁻⁵ to 1 × per mol of silver halide.
10 ⁻² mol, particularly 5 × 10 ^{−5 to} 5 × 10 ⁻³ mol is preferable. The addition time is a time when the compound can be present in the constituent layer of the completed silver halide photographic light-sensitive material, and it is preferably added and used immediately before coating.

The compound having a nitrogen-halogen bond in the molecule can be added after being dissolved in water, methanol, ethanol, acetone, tetrahydrofuran, N, N, dimethylformamide, or the like.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (IV).

General formula (IV) In the formula, R ₁ represents an aliphatic group or an aromatic group, R ₂ represents 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, and G ₁ Carbonyl group, sulfonyl group, sulfoxy group, Or 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 a substituted or unsubstituted acyl Represents a group.

In the general formula (IV), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms.
Is a linear, branched or cyclic alkyl group. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. The alkyl group may have a substituent such as an aryl group, an alkoxy group, a sulfoxy group, a sulfonamide group, and a carbonamide group.

In the general formula (IV), the aromatic group represented by R ₁ 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.

For example, there are a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, and a benzothiazole ring.

Particularly preferred as R ₁ is an aryl group.

The aryl group or unsaturated heterocyclic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, and an acylamino group. 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,
Examples thereof include an acyloxy group, a carbonamido group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, and an imide group. Preferred substituents include a linear, branched, or cyclic alkyl group (preferably carbon A group of 1 to 20), an aralkyl group (preferably a monocyclic or bicyclic alkyl group having 1 to 3 carbon atoms), an alkoxy group (preferably having a carbon number of 1 to 20), a substituted amino group ( Preferably, an amino group substituted with an alkyl group having 1 to 20 carbon atoms, an acylamino group (preferably having 2 carbon atoms)
~ 30), sulfonamide group (preferably having 1 to 30 carbon atoms), ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms) Stuff).

The alkyl group represented by R ₂ in the general formula (IV) is preferably an alkyl group having 1 to 4 carbon atoms,
It may have a substituent such as a halogen atom, a cyano group, a carboxy group, a sulfo group, an alkoxy group, a phenyl group and a sulfonyl group.

As the aryl group, a monocyclic or bicyclic aryl group is preferable, and for example, those containing a benzene ring. The aryl group may be substituted with, for example, a halogen atom, an alkyl group, a cyano group, a carboxyl group, a sulfo group, a sulfonyl group, or the like.

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 a monocyclic one, and the substituent includes a halogen atom.

As the amino group, an unsubstituted amino group and a group having 1 to 10 carbon atoms
Are 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, and 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 having 1 to 10 carbon atoms or an aryloxycarbonyl group, 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 R ₂ , when G ₁ 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 (for example, o
-Hydroxybenzyl group), an aryl group (for example,
A phenyl group, a 3,5-dichlorophenyl group, an o-methanesulfonamidophenyl group, a 4-methanesulfonylphenyl group, etc., and a hydrogen atom is particularly preferable.

When G ₁ is a sulfonyl group, R ₂ represents an alkyl group (eg, a methyl group), an aralkyl group (eg, o
A hydroxyphenylmethyl group), an aryl group (e.g., a phenyl group) or a substituted amino group (e.g.,
And a dimethylamino group.

When G ₁ is a sulfoxy group, preferred R ₂ is a cyanobenzyl group, a methylthiobenzyl group or the like, and G ₁ is In the case of a methoxy group as R _2, an ethoxy group, a butoxy group, a phenoxy group, a phenyl group are preferred, in particular,
Phenoxy groups are preferred.

When G ₁ is an N-substituted or unsubstituted iminomethylene group,
Desirable R ₂ is a methyl group, an ethyl group, or a substituted or unsubstituted phenyl group.

As the substituent for R _2, the substituents listed for R ₁ can be applied.

A carbonyl group is most preferable as G in the general formula (IV).

R ₂ also splits the G ₁ -R ₂ moiety from the rest of the molecule, leaving -G _1-
A cyclization reaction that generates a cyclic structure containing an atom of the R ₂ moiety may be performed, and specifically, the cyclization reaction can be represented by the general formula (a).

In the general formula (a) -R ₃ -Z ₁ formula, Z ₁ is nucleophilically attacked to G _1, a group capable of -G ₁ -R ₃ -Z ₁ moiety disrupts the residual molecule, R ₃ is R _{2 with} one hydrogen atom removed, and Z ₁ nucleophilically attacks G ₁ .
A cyclic structure can be generated by G ₁ , R ₃ and Z ₁ .

More specifically, Z ₁ is easily prepared when the hydrazine compound of the general formula (I) produces the next reaction intermediate by oxidation or the like.
G ₁ and nucleophilic reaction with _{R 1 -N = N-G 1} -R 3 -Z 1 R 1 -N = N group is a group capable of splitting from G _1, in particular OH, SH or NHR ₄ (R ₄ is a hydrogen atom, an alkyl group, an aryl group, —COR ₅ , or —SO ₂ R ₅ , and R ₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, etc.), COOH, etc. It may be filed with a functional group which reacts directly with G ₁ to _{(wherein, OH, SH, NHR 4,} -COOH is be temporarily protected so as to generate these groups by hydrolysis such as an alkali Good) or (R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group) and react with G ₁ by reacting with a nucleophile such as a hydroxide ion or a sulfite ion. It may be a functional group capable of performing the above.

The ring formed by G ₁ , R ₃ and Z ₁ is preferably a 5- or 6-membered ring.

Among the compounds represented by the general formula (a), preferred are the compounds represented by the general formulas (b) and (c).

General formula (b) In the formula, ▲ R ¹ _b ▼ to ▲ R ⁴ _b ▼ are a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms), an aryl group (preferably Represents those having 6 to 12 carbon atoms), and may be the same or different. B is an atom necessary to complete a 5- or 6-membered ring which may have a substituent, and m and n are 0 or 1
And (n + m) is 1 or 2.

As the 5-membered or 6-membered ring formed by B, for example,
A cyclohexene ring, a cycloheptene ring, a benzene ring, a naphthalene ring, a pyridine ring, a quinoline ring and the like.

Z ₁ has the same meaning as in formula (a).

General formula (c) In the formula, ▲ R ¹ _c ▼ and ▲ R ² _c ▼ represent a hydrogen atom, an alkyl group,
Represents an alkenyl group, an aryl group or a halogen atom, and may be the same or different.

R ▲ ³ _c ▼ is hydrogen atom, an alkyl group, an alkenyl group or an aryl group.

 p represents 0 or 1, and q represents 1-4.

▲ R ¹ _c Ｒ, ＲR ² _cお よ び and ▲ R ³ _cよ い may combine with each other to form a ring as long as Z ₁ is capable of intramolecular nucleophilic attack on G ₁ .

_{^{▲ R 1 c ▼, ▲ R}} 2 c ▼ is preferably a hydrogen atom, a halogen atom or an alkyl group,, ▲ R ³ _c ▼ is preferably an alkyl group or an aryl group.

q preferably represents 1-3, p is 0 or 1 when q is 1, p is 0 or 1 when q is 2, p is 0 or 1 when q is 3, and q is 2 Or when ▲ CR ¹ _c
▼ ▲ R ² _c ▼ may be the same or different.

Z ₁ has the same meaning as in formula (a).

A ₁ and A _{2 each} represent a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably phenylsulfonyl group or phenylsulfonyl substituted such that the sum of the substituent constants of Hammett is -0.5 or more Group), 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; or a straight-chain, branched or cyclic unsubstituted group; Substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group). A ₁ and A ₂ are most preferably hydrogen atoms. preferable.

R ₁ or R _{2 in} the general formula (IV) may have a ballast group, which is commonly used in a non-moving photographic additive such as a coupler, incorporated thereinto. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose from.

R ₁ or R _{2 in} the general formula (IV) may have a group in which a group that enhances adsorption to the surface of the silver halide grain is incorporated. Examples of such adsorbing groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, triazole groups, and the like, U.S. Patent Nos. 4,385,108 and 4,459,347;
-195,233, 59-200,231, 59-201,045, 5
Nos. 9-201,046, 59-201,047, 59-201,048,
59-201,049, JP-A-61-170,733, JP-A-61-270,744
No. 62-948, Japanese Patent Application No. 62-67,508, No. 62-67,501
And the groups described in JP-A-62-67,510.

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

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item23516 (1983
November, p. 346) and references cited therein,
U.S. Pat.Nos. 4,080,207, 4,269,929, 4,276,364
No. 4,278,748, No. 4,385,108, No. 4,459,347,
4,560,638, 4,478,928, UK Patent 2,011,391B,
JP-A-60-179934, JP-A-62-270,948, JP-A-63-29,751
No., JP-A-61-170,733, JP-A-61-270,744, JP-A-62-94
No.8, EP217,310, Japanese Patent Application No. 61-175,234, 〃61-251,48
No. 2, 〃 61-268,249, 〃 61-276,283, 〃 62-67528
No., 〃 62-67,509, 〃 62-67,510, 〃 62-58,513
No., 〃 62-130,819, 〃 62-143,467, 〃 62-166,11
No. 7, or US Pat. No. 4,686,167, JP-A-62-178,246, JP-A-63-234,244, JP-A-63-234,245, JP-A-63-234,246.
No. 63-294,552, No. 63-306,438, Japanese Patent Application No. 62-16
No. 6,117, No. 62-247,478, No. 63-105,682, No. 63-1
No. 14,118, No. 63-110,051, No. 63-114,119, No. 63-
No. 116,239, No. 63-147,339, No. 63-179,760, No. 63
No. 229,163, Japanese Patent Application No. 1-18,377, No. 1-18,378,
〃1-18,379, 〃1-15,755, 〃1-16,814, 〃
Nos. 1-40,792, # 1-42,615 and # 1-42,616 can be used.

In the present invention, the above-mentioned hydrazine derivative is usually 10 ^{−6 to} 5 × 10 ⁻² mol, particularly 10 ⁻⁵ to 2 × 10 5 mol per mol of silver.
Used in the range of ^-2 moles. The hydrazine derivative is
You may use individually or in combination of 2 or more types. The hydrazine derivative may be added to the photosensitive material by dissolving it in methanol, ethanol, N, N, dimethylformamide or the like. Alternatively, it may be added by a method of containing it in the polymer fine particles (described in Japanese Patent Application No. 63-57303).

In addition to the silver halide emulsion layer, the light-sensitive material according to the present invention is preferably provided with an auxiliary layer such as a protective layer, an intermediate layer, a filter layer, an antihalation layer and a back layer.

The compound having a nitrogen-halogen bond in the molecule and the hydrazine derivative of the present invention can be added to any of the above layers and used. Above all, it is preferable to use it by adding it to a silver halide emulsion layer and an adjacent layer.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is a silver halide comprising 90 mol% or more, more preferably 95 mol% or more, and silver bromide of 0 mol% or more.
It is silver chlorobromide or silver chloroiodobromide containing about 10 mol%. If the proportion of silver bromide or silver iodide is increased, the safety of safelight in a bright room is deteriorated or γ is decreased, which is not preferable.

In order to contain a rhodium atom, a metal salt of an arbitrary form such as a single salt or a complex salt can be added at the time of preparing particles.

Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like, preferably a water-soluble trivalent rhodium halide complex compound such as hexachlororhodium (III) acid or a salt thereof. (Ammonium salt, sodium salt, potassium salt, etc.).

The addition amount of these water-soluble rhodium salts is 1
It is used in a range of 1.0 × 10 ⁻⁶ mol to 1.0 × 10 ⁻³ mol per mol. It is preferably 1.0 × 10 ⁻⁵ mol to 1.0 × 10 ⁻³ mol, and particularly preferably 5.0 × 10 ⁻⁵ mol to 5.0 × 10 ⁻⁴ mol.

If the rhodium salt is at least 10 ^-3 mol, it will not be possible to achieve a sufficiently high contrast. Conversely, if the amount is less than 10 ^-6 mol, it is impossible to reduce the sensitivity suitable for a light-sensitive material.

The silver halide used in the present invention is preferably a so-called core / shell type silver halide, and particularly preferably a core / shell type silver halide having a higher rhodium content in the shell than the core.

When the water-soluble silver salt and the water-soluble halide solution are mixed at the same time when the water-soluble rhodium salt is present in the silver halide grains by using the water-soluble rhodium salt, a method in which the water-soluble silver salt is added to the water-soluble silver salt or the halide solution is used. preferable. Alternatively, when a silver salt and a halide solution are simultaneously mixed, silver halide grains may be prepared as a third solution by a three-solution simultaneous mixing method.

The grain size of the silver halide emulsion of the present invention is preferably 0.15 μm or less, more preferably 0.12 μm or less.

In the present invention, silver halide fine particles are prepared by mixing at a reaction temperature of 50 ° C. or lower, preferably 40 ° C. or lower, more preferably 30 ° C. or lower, under conditions of sufficiently high stirring speed to uniformly mix. Good results can be obtained by adjusting the potential to 100 mV or more, preferably 150 mV to 400 mV, and the pH to 3 to 8, preferably 5 to 7. In the case of silver chloride fine particles, particle growth may occur even in the washing step and dispersion step due to its high solubility, and the temperature is 35 ° C or less, or nucleic acid, mercapto compound, tetrazaindene compound, etc. that suppress particle growth coexist Can be done.

The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein refers to a particle group in which at least 95% by weight or number of particles has a size within ± 40% of the average particle size, and more preferably ±
Within 20%.

The silver halide grains of the present invention preferably have regular crystals such as cubes and octahedrons, and particularly preferably cubes.

In addition to the rhodium salt, a cadmium salt, a lead salt, a thallium salt, and an iridium salt can be coexisted.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good.

Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium and iridium may be contained. Specific examples are described in US Pat. No. 2,448,060 and British Patent 618,061.

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

Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer.

The silver halide photographic light-sensitive material of the present invention may contain an organic desensitizer. The organic desensitizer preferably has at least one water-soluble group or alkali-dissociable group.

The organic desensitizer used in the present invention is defined by its polarographic half-wave potential, that is, the oxidation-reduction potential determined by polarography, and the sum of the polaro anodic potential and the cathodic potential becomes positive. A method of measuring the oxidation-reduction potential of a polarograph is described in, for example, US Pat. No. 3,501,307. Specific examples of the water-soluble group present in the organic desensitizer include a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, and the like. These groups include an organic base (for example, ammonia, pyridine, triethylamine, A salt may be formed with piperidine, morpholine and the like, or an alkali metal (eg, sodium and potassium).

The alkali dissociable group is defined as the pH of the processing solution (usually pH 9 to pH 1).
Although it is in the range of 3, there may be a treatment solution having a pH other than this. ) Also, it refers to a substituent that undergoes a deprotonation reaction at a pH below that and becomes anionic. Specifically, a substituted / unsubstituted sulfamoyl group, a substituted / unsubstituted carbamoyl group,
A substituent such as a sulfonamide group, an acylamino group, a substituted / unsubstituted ureido group, and the like, in which at least one hydrogen atom bonded to a nitrogen atom is present, and a hydroxyl group.

Further, a heterocyclic group having a hydrogen atom on a nitrogen atom constituting the hetero ring of the nitrogen-containing hetero ring is also included in the alkali-dissociable group.

These water-soluble groups and alkali-dissociable groups may be connected to any part of the organic desensitizer, or may have two or more kinds at the same time.

Preferred specific examples of the organic desensitizer used in the present invention,
It is described in Japanese Patent Application No. 61-209169, of which some examples are given below.

The organic desensitizer is contained in the silver halide emulsion layer in an amount of 1.0 × 10 ^{−8 to} 1.0
It is preferred to be present in an amount of × 10 ^-4 mol / m ² , particularly 1.0 × 10 ^{-7 to} 1.0 × 10 ^-5 mol / m ² .

In the emulsion layer of the present invention, or other hydrophilic colloid layer,
A water-soluble dye may be contained at the same time as the compound of the general formula (I) as a filter dye or for various purposes such as prevention of irradiation. As the filter dye, a dye for further reducing the photographic sensitivity, preferably,
A UV absorber that has a spectral absorption maximum in the intrinsic sensitivity region of silver halide and a safety light for safelight when handled as a bright-room light-sensitive material are mainly used.
A dye having substantial light absorption in the region of 0 nm to 600 nm is used.

Different by the molar extinction coefficient of the dye, but usually 10 ^-2 g / m ² ~
It is added in the range of 1 g / m ² . Preferably 10 mg-200 mm / m ²
It is.

Specific examples of dyes are described in detail in Japanese Patent Application No. 61-209169, some of which are as follows.

The dye is dissolved in an appropriate solvent [eg, water, alcohol (eg, methanol, ethanol, propanol, etc.), acetone, methyl cellosolve, etc., or a mixed solvent thereof] for the non-photosensitive hydrophilic colloid layer of the present invention. It is added to the coating solution.

As the support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate paper, baryta-coated paper, polyolefin-coated paper and the like can be used.

Examples of development accelerators suitable for use in the present invention or accelerators for developing nucleation transmission include JP-A-53-77616 and JP-A-54-77616.
7732, 53-137133, 60-140340, 60-1495
In addition to the compounds disclosed in No. 9, various compounds containing an N or S atom are effective.

 Next, specific examples are listed.

These accelerators have an optimal addition amount that varies depending on the type of the compound, but 1.0 × 10 ^{−3 to} 0.5 g / m ² , preferably 5.0 × 10 ^−3.
It is desirable to use it in the range of 0.1 g / m ² . These accelerators are dissolved in a suitable solvent (H ₂ O, alcohols such as methanol and ethanol, acetone, dimethylformamide, methylcellosolve, etc.) and added to the coating solution.

 A plurality of these additives may be used in combination.

The light-sensitive material used in the present invention includes a sensitizing dye (for example, a cyanine dye, which has an absorption maximum in the visible region described in JP-A-55-52050, pages 45 to 53, for the purpose of increasing sensitivity.
Merocyanine dye etc. ) Can be added,
It is preferable not to do it.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. With sensitizing dye,
A dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and which exhibits supersensitization may be contained in the emulsion.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Rese
arch Disclosure) Volume 176 17643 (Issued December 1978) No. 23
It is described in section J on page IV.

As a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates and the like; sugar derivatives such as sodium alginate and starch derivatives;
Polyvinyl alcohol, polyalcohol-containing acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylimidazole, etc. Can be used.

In addition to lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin as described in Bull. Soc. Sci. Phot. Japan, No. 16, P30 (1966) may be used. Products and enzymatic decomposition products can also be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxadrinethione; azeindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3.3a, 7) tetraazaindenes), pentaazaindenes; Many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, phosphoniums, oximes, aldoximes, etc. It can be added.

Among these, particularly preferred are benzotriazoles (eg 5-methylbenzotriazole) and nitroindazoles (eg 5-nitroindazoles). Further, these compounds may be contained in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacrylois-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s). -Triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.) and the like can be used alone or in combination.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic surfactants such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agents: alkyl carboxylates, alkyl sulfonates, alkyl benzene sulfonates Acid salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus Anionic surfactants containing acidic groups such as carboxylic acid groups, sulfo groups, phospho groups, sulfuric acid ester groups, phosphoric acid ester groups such as acid ester acids; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid Amphoteric surfactants such as esters, alkyl betaines, amine oxides; alkyl amine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

When polyalkylene oxides are used in the present invention, the polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412 are preferable.

In the photographic light-sensitive material used in the present invention, for the purpose of improving the dimensional stability of the photographic emulsion layer and other hydrophilic colloid layers,
It may include a dispersion of a water-insoluble or poorly soluble synthetic polymer. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth)
Acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate , A polymer having a combination of sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

The developing agent used in the developing solution used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes in that good halftone dot quality can be easily obtained. Combinations of pyrazolidones or combinations of dihydroxybenzenes and p-aminophenols may be used.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone,
Although there are 2,5-dimethylhydroquinone and the like, hydroquinone is particularly preferred.

The developing agents of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4 -Hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-p-aminophenyl-
4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-
4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone and the like.

Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. , 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-
P-aminophenol is preferred.

The developing agent is preferably used usually in an amount of 0.5 mol / to 0.8 mol /. Dihydroxybenzenes and 1
-When using a combination with phenyl-3-pyrazolidones or p-amino-phenols, the former is 0.05 mol /
It is preferred to use 0.5 mol / l and the latter in an amount of 0.06 mol / or less.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
The amount of bisulfate is preferably 0.3 mol / or more, more preferably 0.4 mol / or more. The upper limit is preferably up to 2.5 mol /, particularly up to 1.2.

Examples of the alkaline agent used for setting the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate, potassium tertiary phosphate, sodium silicate, and potassium silicate. Contains a buffer.

Additives other than the above components include compounds such as boric acid and borax, and development inhibitors such as sodium bromide, potassium bromide and potassium iodide: ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve , Hexylene glycol, ethanol, organic solvents such as methanol: 1-phenyl-5-mercaptotetrazole, mercapto-based compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole-based compounds such as 5-nitroindazole, An antifoggant or a black pepper inhibitor such as a benztriazole compound such as 5-methylbenztriazole may be contained, and if necessary, a toning agent, a surfactant, a defoaming agent, a curing and softening agent. , Hardener, JP-A-56-106244 And the amino compounds described in Japanese Patent Application No. 1-294185 may be included.

The developer used in the present invention contains a compound described in JP-A-56-24347 as a silver stain inhibitor, a compound described in JP-A-62-212,651 as a development unevenness inhibitor, and a dissolution aid as a dissolution aid. The compounds described in Japanese Patent Application No. 60-109743 can be used.

The developing solution used in the present invention has a buffer
Boric acid described in 61-28708, saccharides described in JP-A-60-93433 (for example, saccharose), oximes (for example, acetoxime), phenols (for example, 5-sulfosalicylic acid), and tertiary phosphate ( For example, sodium salt, potassium salt, etc. are used, and boric acid is preferably used.

The fixer is an aqueous solution containing a hardener (for example, a water-soluble aluminum compound), acetic acid, and a dibasic acid (for example, tartaric acid, citric acid, or a salt thereof), if necessary, in addition to the fixing agent. 8 or more, more preferably 4.0 to 5.5
Having.

Examples of the fixing agent include sodium thiolactate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent to be used can be appropriately changed, and is generally about 0.1 to about 5 mol /.

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 an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum.

Tartaric acid or a derivative thereof as the aforementioned dibasic acid,
Citric acid or a derivative thereof can be used alone or in combination of two or more. These compounds are used in Fixer 1
Is effective in containing 0.005 mol or more, particularly 0.01 mol / to 0.03 mol /.

Specifically, there are tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like.

Examples of citric acid or a derivative thereof effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like.

The fixing solution may further contain a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, boric acid), if desired.
It may contain a pH adjuster (eg, ammonia, sulfuric acid), an image preserving agent (eg, potassium iodide), and a chelating agent. Here, the pH buffer is 10 to 40 g /
, More preferably about 18 to 25 g / about.

Fixing temperature and time are the same as for development, about 20 ° C
Preferred is 10 seconds to 1 minute at ~ 50 ° C.

In addition, anti-mold agents (for example, compounds described in Horiguchi's "Chemistry of Antibacterial and Antifungal Chemistry", Japanese Patent Application No. 60-253807), washing accelerators (sulfites, etc.), chelating agents Etc. may be contained.

According to the above method, the developed and fixed photographic material is washed with water and dried. The washing with water is performed to almost completely remove the silver salt dissolved by the fixing, and it is preferable that the temperature is about 20 ° C. to about 50 ° C. for 10 seconds to 3 minutes. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions.
Usually, it may be about 5 seconds to 3 minutes 30 seconds.

US Patent No. 30 for roller transport type automatic developing machine
No. 25779, No. 3,554,971 and the like, and are simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. . Here, in the rinsing step, water can be saved by using a two- or three-stage countercurrent rinsing method.

The developer used in the present invention is preferably stored in a packaging material having a low oxygen permeability as described in Japanese Patent Application No. 59-196,200. The developer used in the present invention is disclosed in Japanese Patent Application No. 60-232,
The replenishment system described in No. 471 can be preferably used.

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

There is no particular limitation on the reducing liquid used in the present invention. For example, Mies, “The theory of the Photograph
ic Process, pp. 738-744 (1954, Macmillan),
In addition to written works such as Tetsuo Yano, "Theory and Practice of Photographic Processing," pp. 166-169 (Kyoritsu Shuppan, 1978), etc.
No. 3, No. 52-68429, No. 55-17123, No. 55-79444,
Those described in JP-A-57-10140, JP-A-57-142639, and Japanese Patent Application No. 59-182456 can be used. That is, as an oxidizing agent, permanganate, persulfate, ferric salt, cupric salt,
Cerium salts, red blood salts, dichromates, etc., alone or in combination, and if necessary, a reducer containing an inorganic acid such as sulfuric acid or alcohols, or a red blood salt or ethylenediaminetetraacetic acid Oxidizing agents such as ferrous salts, thiosulfates,
A silver halide solvent such as a rhodan salt, thiourea, or a derivative thereof, and a reducer containing an inorganic acid such as sulfuric acid as necessary are used.

Typical examples of the reducer used in the present invention are so-called Farmer reducer, ethylenediaminetetraacetic acid ferric salt, potassium permanganate, ammonium persulfate reducer (Kodak R-5), and cerium cerium. A reducing fluid may be mentioned.

Conditions for the reduction treatment are generally 10 ° C to 40 ° C, especially 15 ° C to 30 ° C.
It is preferable that the reaction can be completed at a temperature of ° C. within a period of several seconds to several tens of minutes, particularly within several minutes. If the photosensitive material for plate making of the present invention is used, a sufficiently wide reduction range can be obtained within the range of these conditions.

The reducer acts on the silver image formed in the emulsion layer through the non-photosensitive upper layer containing the compound of the present invention.

Specifically, there are various methods, for example, immersing the plate-making photosensitive material in a reducing fluid, stirring the liquid, or applying the reducing fluid to the surface of the plate-making photosensitive material with a brush, a roller, or the like. Method is available.

 Hereinafter, the present invention will be described in more detail with reference to Examples.

(Example) 5.0 x 10 per mol of silver in a gelatin aqueous solution kept at 40 ° C
-Synthetic aqueous solution of silver nitrate and aqueous solution of sodium chloride are simultaneously mixed in the presence of ^-6 mol of (NH ₄ ) ₃ RhCl ₆ and then soluble salts are removed by a method well known to those skilled in the art, and then gelatin is added to 2-methyl-4 as a stabilizer without aging
-Hydroxy-1,3,3a, 7-tetraazaindene was added. This emulsion was a cubic monodispersed emulsion having an average grain size of 0.15 μm.

Into this emulsion, polymer fine particles (compound No. and addition amount are shown in Table 1) of the present invention and polymer fine particles containing a hydrazine derivative compound example IV-30 (preparation method is described later) are prepared. -30 as 1.6 × 10 ^-3 mol / mol Ag, mercaptotetrazole derivative as 4.5 mg / m ² , dye, 110 mg / m ²
m ² , nucleation accelerator 20 mg / m ² , and polyethyl acrylate latex were added to the solid content of 30% by weight of gelatin,
1,3-Vinylsulfonyl-2-propanol was added as a hardener and coated on a polyester support at an Ag amount of 3.8 g / m ² . Gelatin was 1.8 g / m ² .

A protective layer containing 1.5 g / m ² of gelatin as a protective layer and the following surfactants as a coating aid, a stabilizer, and a matting agent was applied onto this and dried.

Surfactant Stabilizer thioctic acid 2.1mg / m ² Matting agent Polymethylmethacrylate (average particle size 2.5μ) 9.0mg / m ² Silica (average particle size 4.0μ) 9.0mg / m ² (Preparation method of polymer particles containing hydrazine derivative) Example of hydrazine derivative compound IV-30 25g, same IV-5 1
A solution consisting of 2.5 g, a melting point depressant 17.5 g, a t-butylacrylamide polymer 50 g, and ethyl acetate 250 ml was heated to 60 ° C.
After heating to complete dissolution, gelatin 100 g, preservative 0.3 g,
In addition to 1000 ml of an aqueous solution containing 7.2 g of a surfactant, a fine particle emulsified dispersion was obtained with an auto homomixer (manufactured by Tokushu Kika Kogyo). Ethyl acetate was removed from this emulsion by superheated vacuum distillation. Polymer fine particles containing a hydrazine derivative were obtained. This emulsion had an average particle size of 0.15μ.
(Nanosizer measurement).

Melting point depressant Preservative The sample thus obtained was exposed through a light wedge with a bright room printer P-627FM manufactured by Dainippon Screen Co., Ltd.
It was developed for 20 seconds, fixed, washed with water and dried. (Automatic developing machine FG-660F). The composition of the developer is as follows. As the fixing solution, GR-F1 manufactured by Fuji Photo Film Co., Ltd. was used.

Table-1 (Comparative compound) 1) Sensitivity; reciprocal of the exposure dose that gives a density of 1.5, sample 1 is 100
And

3) Preservation property with time: Each sample was left under conditions of 60 ° C. and 30% ^RH for 7 days, and then developed at 38 ° C. for 20 seconds, showing changes in fog immediately after coating. However, this change value is
Shows the change (increase) in the fog value when the sheets are stacked. …… (Δ
fog) As is clear from Table 1, Samples 2 to 11 of the present invention show little increase in fog (Δfog) in the storage stability test.

On the other hand, Comparative Samples 1 and 12 to 21 are inferior to the present invention in terms of increased fog or decreased γ.

Except that the compound of Example-1 was added to the protective layer,
Also with respect to the sample prepared in the same manner as in Example-1, the same result as in Example-1 was obtained in which the storability was improved. Therefore, the compound represented by the general formula [I] of the present invention has the same effect whether it is added to the silver halide emulsion layer or the protective layer.

From the above results, according to the present invention, the bright room light-sensitive material, which has excellent storability over time without impairing the photographic performance required,
Can be provided.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, said emulsion layer containing at least 1.times.10.sup.- ⁶ mol of rhodium salt per mol of silver. A silver halide grain having a silver chloride content of at least 90 mol%, and the emulsion layer or other hydrophilic colloid layer contains at least one hydrazine derivative and a compound having a nitrogen-halogen bond in the molecule. A characteristic silver halide photographic light-sensitive material.