JP3289154B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having a silver halide photosensitive layer on a support, and more particularly to a silver halide photographic material capable of obtaining a high contrast.

[0002]

2. Description of the Related Art Conventionally, a photomechanical process includes a process of converting a continuous tone original into a halftone image. In this step, an infectious development technique has been used as a photographic technique capable of reproducing a super-high contrast image.

A lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average particle diameter of 0.2 μm, a narrow particle distribution, a well-shaped particle, and a high silver chloride content (at least 50 mol. % Or more) silver chlorobromide emulsion. By processing this lithographic silver halide photographic material with an alkaline hydroquinone developing solution having a low sulfite ion concentration, a so-called lithographic developing solution, an image having high contrast, high sharpness and high resolution can be obtained.

However, since these squirrel-type developers are susceptible to air oxidation, they have extremely poor preservative properties.
It is difficult to keep development quality constant during continuous use. There has been known a method for quickly obtaining a high-contrast image without using the lith-type developer. For example, as described in JP-A-56-106244, a silver halide photographic light-sensitive material containing a hydrazine derivative is treated with an alkali developing solution. According to these methods, a high-contrast image can be obtained even by processing with a developing solution having good preservation properties and rapid processing.

[0005] In these techniques, the hydrazine derivative must be treated with a developer having a pH of 11.2 or more in order to sufficiently exhibit the high contrast. High pH developers with a pH of 11.2 or higher tend to oxidize the developing agent when exposed to air, and are more stable than squirrel developing solutions.However, due to the oxidation of the developing agent, sometimes very hard images cannot be obtained. .

To compensate for this disadvantage, Japanese Patent Application Laid-Open Nos. 63-29751, 1-179939, 1-179940 and U.S. Pat. A silver halide photographic light-sensitive material containing a hydrazine derivative that makes it harder and a nucleation accelerator is disclosed.

On the other hand, in a silver halide photographic light-sensitive material containing a hydrazine derivative, the unexposed portion peculiar to the light-sensitive material using the hydrazine derivative during storage, particularly during high-temperature storage, has a fine sand-like color called "black pot". There have been problems in that spots occur and sensitivity changes occur. When a fog inhibitor such as 1-phenyl-5-mercaptotetrazole is added as a compound known in the art to suppress the generation of black pots, the black pot suppression effect is insufficient or desensitization softening is caused. And the photographic performance changes over time.

[0008] The same problem also occurs in a silver halide photographic light-sensitive material containing a hydrazine derivative and a nucleation accelerator which hardens even in a developer having a relatively low pH as described above.

As described in JP-A-61-47945, benzimidazoles, indazoles and benzotriazoles can be added to a photosensitive material containing a hydrazine derivative to suppress black spots. It is known to add. As another technique which is effective for black potato, there is a method of adding adenines to a light-sensitive material as disclosed in JP-A-1-183648. U.S. Pat.
And JP-A-3-36540, there is a method of adding polyhydroxybenzenes to a photosensitive material.

However, at present, there is still a problem with silver halide photographic light-sensitive materials which are hardened with a developer having a pH of less than 11.2 as described above.

[0011]

It is an object of the present invention to provide a high sensitivity even in a developer having a pH of less than 11.2, and to reduce the rise of fog and the occurrence of "black spots" in an unexposed area during storage, especially during high temperature storage, and An object of the present invention is to provide a silver halide light-sensitive material having less fluctuation.

[0012]

The above object of the present invention is attained by the following constitutions.

(1) In a silver halide photographic material containing a hydrazine derivative in at least one silver halide emulsion layer and / or another hydrophilic colloid layer on a support, the silver halide emulsion layer and / or or other contain a hydrophilic colloid layer nucleation accelerator in, and in that it contains the above-mentioned general formula [5] and even without least that is represented by [6] one polyhydroxybenzene compound constituent layers Achieved by the characteristic silver halide photographic material .
In addition, general formulas [1] to [4] relating to Reference Examples are described below.
explain about.

[0014]

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[0015]

[0016]

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Wherein R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R
₃₃ , R ₄₁ and R _{42 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a substituted or unsubstituted amino group, an aryl group, a hydroxy group, Mercapto group,
Represents a carboxyl group or a salt thereof, or a halogen atom. R ₃₄ and R ₄₃ represent a phosphate group or an alkyl group having 1 to 8 carbon atoms which may be substituted. Below, specifically
explain.

The compound represented by the general formula [1] will be described.

In the general formula [1], the lower alkyl group represented by R ₁₁ may be linear or branched, and has 1 carbon atom.
To 8, for example, a methyl group, an ethyl group, an iso-propyl group, a butyl group and the like. The group represented by R ₁₁ is preferably a nitro group.

Specific representative examples of the compound represented by the general formula [1] are shown below.

(1-1) 5-nitroindazole (1-2) 6-nitroindazole (1-3) 5-methylindazole (1-4) 6-methylindazole (1-5) indazole (1-6) 5-chloroindazole (1-7) 5-methylbenzimidazole (1-8) 5-ethylbenzimidazole (1-9) 5-nitrobenzimidazole (1-10) 6-nitrobenzimidazole (1-11) 5 -Chlorobenzimidazole (1-12) Benzimidazole The compound represented by the general formula [1] is used in an amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide,
Particularly preferably, it is in the range of 1 × 10 ^{−4 to} 5 × 10 ⁻² mol.
This compound can be added by dissolving it in water or an organic solvent such as metatol or ethanol that is arbitrarily miscible with water, and then adding the compound to the constituents.

Next, general formulas [2], [3] and [4] will be described.

[0023]

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Where R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R
₃₃ , _R41 and _{R42 each} represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl, propyl, cyclohexyl, dodecyl, etc.), an alkenyl group (eg, allyl, 2-butenyl, etc.), alkoxy Groups (eg, methoxy, ethoxy, butoxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, etc.), amino groups (eg, amino, methylamino, benzylamino, anilino, 4-methoxyanilino, etc.), aryl Represents a group (eg, phenyl, naphthyl, etc.), a hydroxy group, a mercapto group, a carboxyl group or a salt thereof, or a halogen atom (eg, fluorine, chlorine, etc.).

Each of the above alkyl, alkenyl, alkoxy, alkoxycarbonyl and aryl groups is a substituent (for example, halogen, hydroxy, carboxy,
Alkyl, aryl, alkoxy, mercapto, alkoxycarbonyl, etc.).

R ₃₄ and R ₄₃ are a phosphate group or an optionally substituted alkyl group having 1 to 8 carbon atoms (eg, methyl, ethyl, hydroxymethyl, hydroxyethyl, etc.)
Represents

The following are specific examples of the general formula [2], but the present invention is not limited thereto.

[0028]

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[0029]

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The following are specific examples of the general formula [3] or [4], but the present invention is not limited thereto.

(3-1) 6-amino-purine riboside (3-2) 6-chloro-purine riboside (3-3) 6-hydroxy-purine riboside (3-4) 6-methylamino-purine riboside (3-5) 2 -Amino-6-hydroxy-purine riboside (3-6) 5'-phosphate-6-amino-purine riboside (3-7) 5'-phosphate-6-chloro-purine riboside (3-8) 5'-phosphate -6-Hydroxy-purine riboside (3-9) 5'-phosphate-6-methylamino-purine riboside (3-10) 5'-Hydroxymethyl-6-amino-purine riboside (3-11) 5'-methyl-6 -Amino-purine riboside The compounds represented by the general formulas [2], [3] and [4] are preferably used in an amount of 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide. And particularly preferably 1 × 10 ^-5
１1 × 10 ^-2 mol. This compound can be added by a usual method of adding an additive to a photographic emulsion. For example, a water-soluble compound can be used as an aqueous solution having a suitable concentration, and a compound insoluble or hardly soluble in water can be dissolved in a suitable organic solvent miscible with water and added to the emulsion as a solution.

The polyhydroxy benzene compounds of this invention are polyhydroxy benzene compound having two or more substituted or unsubstituted hydroxy group, is preferably selected from the following general formula [5] 及 beauty [6] At least one kind. The following general formula may be used.
The compound of [7] can be mentioned.

[0033]

[0034]

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[Wherein R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ ,
R ₅₆ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 23 carbon atoms, an alkoxy group having 1 to 23 carbon atoms, a carboxyl group, a carboxyl alkyl ester group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a sulfo group,
Represents an amidoalkyl group, an amidophenyl group, an imidoalkyl group and a nitrile group. ]

[0036]

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[Wherein R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ ,
R ₆₆ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 23 carbon atoms, an alkoxy group having 1 to 23 carbon atoms, a carboxyl group, a carboxylalkyl ester group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a sulfo group,
Represents an amidoalkyl group, an amidophenyl group, an imidoalkyl group and a nitrile group. ]

[0038]

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Wherein R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R ₇₅ and R ₇₆ are each a hydrogen atom, a chlorine atom, a fluorine atom, a sulfo group, an unsubstituted or substituted alkyl group, an alkylamino group, Aryl group, aralkyl group, heterocyclic group,-
It represents an O-R ₇₇ or -S-R _77. R ₇₇ represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group. Next, the general formula [5] will be described.

[0040]

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Where R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R
₅₆ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 23 carbon atoms, an alkoxy group having 1 to 23 carbon atoms, a carboxyl group,
Carboxylalkyl ester group, hydroxyalkyl group, hydroxyalkoxyalkyl group, sulfo group, amidoalkyl group, amidophenyl group, imidoalkyl group,
Represents a nitrile group.

Each of the above groups includes those having a substituent. For example, a fluorinated alkyl group, a sulfo group substituted with an alkali metal, and the like can be used.

R ₅₃ , R ₅₄ , R ₅₅ and R ₅₆ may form a ring with each other, or may form a dimer while forming a ring.

Next, the above general formula [5] used in the present invention.
Representative specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0045]

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Specific compounds other than those described above include compounds described in
There are compound examples 4-7 to 4-12 and 4-15 to 4-20 described in 3-36541, pages 311 (17) to 312 (18).

Next, the general formula [6] will be described.

[0048]

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Where R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ , R
₆₆ is a hydrogen atom, a halogen atom, an alkyl group having 1 to 23 carbon atoms, an alkoxy group having 1 to 23 carbon atoms, a carboxyl group,
Carboxylalkyl ester group, hydroxyalkyl group, hydroxyalkoxyalkyl group, sulfo group, amidoalkyl group, amidophenyl group, imidoalkyl group,
Represents a nitrile group.

Each of the above groups includes those having a substituent. For example, a fluorinated alkyl group, a sulfo group substituted with an alkali metal, and the like can be used.

Next, the above general formula [6] used in the present invention.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0052]

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Specific compounds other than those described above include compounds described in
There are compound examples 4-7 to 4-22 and 4-26 to 28 and 4-31 to 37 described in 2-310555, pages 363 (17) to 364 (18).

Next, the general formula [7] will be described.

[0055]

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In the formula, R ₇₁ , R ₇₂ , R ₇₃ , R ₇₄ , R ₇₅ and R ₇₆ each represent a hydrogen atom, a chlorine atom, a fluorine atom, a sulfo group, an unsubstituted or substituted alkyl group, an alkylamino group, an aryl group, respectively. Group, aralkyl group, heterocyclic group, -O
-R ₇₇ or an -S-R _77. R ₇₇ represents an alkyl group, an aryl group, an aralkyl group or a heterocyclic group.

Specific examples of the compound represented by the general formula [7] are shown below, but the present invention is not limited to these compounds.

[Exemplary Compounds] 7-1 Hydroquinone 7-2 2-Chloro-hydroquinone 7-3 2-Methoxyhydroquinone 7-4 2-n-octadecylhydroquinone Specific compounds other than those described above are described in JP-A-3-36540. 28
Compounds III-2 to 5-2 described on pages 5 (5) to 286 (6)
There are III-17, III-19 to III-23 and III-26 to III-39.
The amount of the compound of the general formula [5] or [6 ] contained in the silver halide photographic light-sensitive material of the present invention is 5 × 10 5 per mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. ^{-6 to} 5 × 10 ^-1 mol, particularly preferably 5 × 10 ^-1 mol.
It is preferred to be in the range of 10 ^-5 to 1 × 10 ^-2 mol. Ma
The same applies to the compound represented by the general formula [7].

[0059] The general formula [5] or compound <br/> of [6] of the present invention to allowed to contain in the hydrophilic colloid layer of the general formula in an appropriate water and / or organic solvents [5] or [6 Or a method in which a solution dissolved in an organic solvent is dispersed in a hydrophilic colloid matrix of gelatin or a gelatin derivative and then added, or a method in which the compound is dispersed in latex and added. Can be Also general
The same applies to the compound represented by the formula [7].

The compound represented by the general formula [ 5] or [6 ] may be added at any position in the emulsion production step, but is preferably added after grain formation and before coating. Also, represented by general formulas [1] to [4] and [7].
The same applies to compounds.

The compound of the general formula [1] is contained in any of the constituent layers, but is preferably contained in a silver halide emulsion layer and / or another hydrophilic layer.

The general formulas [2], [3], [4], [5],
The addition position of the compound of [6] or [7] is also determined by the general formula [1].
Is the same as

Examples of the nucleation accelerator used in the present invention include an amine compound, a hydrazine compound, a quaternary onium salt compound and a carbinol compound, and an amine compound and a carbinol compound are preferred. These nucleation accelerators include those described in JP-A-4-56749, JP-A-63-124045 and JP-A-62-187340. These compounds preferably have a diffusion resistance or a silver halide adsorption group in the molecule. Other specific examples include the compounds described in the following patents. Japanese Patent Application 3-29
Compounds described in the specifications of 5926, 3-293366, 3-286619 and 4-33451.

More specifically, the following nucleation accelerators can be mentioned, but the present invention is not limited to these.

Compounds described in JP-A-4-56949

[0066]

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[0067]

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[0068]

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And the like.

The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula [H].

[0071]

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In the present invention, among these, a compound represented by the following general formula [Hc] or [Hd] is preferable.

[0073]

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In the formula, A represents an aryl group having a substituent, or a heterocyclic group containing at least one sulfur atom or oxygen atom having a substituent, and n represents an integer of 1 or 2.
When n = 1, R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Or a heterocyclic oxy group, and R ₁₅ and R ₁₆ may form a ring together with the nitrogen atom. When n = 2, R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group,
Aryl group, saturated or unsaturated heterocyclic group, hydroxy group,
Represents an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group.
However, when n = 2, at least one of R ₁₅ and R ₁₆ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic oxy group. Represents a group. R ₁₇ represents an alkynyl group or a saturated heterocyclic group.

The compound represented by the general formula [Hc] or [Hd] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.

More specifically, A is an aryl group having a substituent (eg, phenyl, naphthyl, etc.) or a heterocyclic group having at least one sulfur atom or oxygen atom having a substituent (eg, thiophene, furan) , Benzothiophene, pyran, etc.).

R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl) Alkynyl groups (eg, propargyl, butynyl, pentynyl, etc.),
Aryl groups (eg, phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (eg, unsaturated heterocyclic groups such as pyridine, thiophene, furan and saturated heterocyclic groups such as tetrahydrofuran, sulfolane),
Hydroxy group, alkoxy group (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy group (eg, allyloxy, butenyloxy, etc.), alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), aryloxy group (eg, ,
Phenoxy, naphthyloxy, etc.) or a heterocyclic oxy group (eg, pyridyloxy, pyrimidyloxy, etc.), and when n = 1, R ₁₅ and R ₁₆ are rings together with a nitrogen atom (eg, piperidine, piperazine, morpholine, etc.) May be formed.

When n = 2, at least one of R ₁₅ and R ₁₆ is alkenyl, alkynyl, saturated heterocyclic, hydroxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy or heterooxy. It represents a ring oxy group.

Specific examples of the alkynyl group and the saturated heterocyclic group represented by R ₁₇ include those described above.

A substituent is introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of the substituent to be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group. , An acyl group, an amino group, an alkylamino group, an arylamino group, an acylamino group, a sulfonamide group, an arylaminothiocarbonylamino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, and a cyano group. Of these substituents, a sulfonamide group is preferred.

In each formula, A preferably contains at least one diffusion-resistant group or silver halide adsorption-promoting group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, and the like. Can be.

Examples of the silver halide adsorption promoting groups include groups described in US Pat. No. 4,385,108, such as a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.

-NH in the general formulas [Hc] and [Hd]
H of NH—, that is, the hydrogen atom of hydrazine is a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg, acetyl, trifluoroacetyl,
Ethoxycarbonyl) or an oxalyl group (eg, ethoxylyl, pyruvoyl, etc.), and the compounds represented by the general formulas [Hc] and [Hd] may be substituted with such substituents. Including.

More preferred compounds in the present invention are compounds of the general formula [Hc] when n = 2 and compounds of the general formula [Hd].

In the compound of the formula [Hc] where n = 2, R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, Or an alkoxy group, and R ₁₅
And at least one of R ₁₆ and R ₁₆ is more preferably a compound representing an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group.

Representative compounds represented by the above general formulas [Hc] and [Hd] include the following.
However, needless to say, specific compounds of the general formulas [Hc] and [Hd] which can be used in the present invention are not limited to these compounds.

Specific Compound Examples

[0088]

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[0089]

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[0090]

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[0091]

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Specific compounds other than those described above include compounds described in
Examples of compounds described on pages 542 (4) to 546 (8) of 2-841
There are (1) to (61) and (65) to (75).

The hydrazine derivative in the present invention is disclosed in
It can be synthesized by the method described on pages 546 (8) to 550 (12) of No. 2-841.

The nucleation accelerator of the present invention is added to the silver halide emulsion layer and / or the adjacent layer. The addition amount is preferably from 1 × 10 ^-6 to 1 mol per mol of silver, more preferably from 1 × 10 ^-5 mol to 1 × 10 ^-1 mol per mol of silver.

The addition position and amount of the hydrazine derivative of the present invention are the same as those of the nucleation accelerator of the present invention.

The silver halide emulsions (hereinafter referred to as silver halide emulsions or simply emulsions) used in the present invention include silver chloride, silver bromide, silver iodobromide, silver chloroiodobromide and chloroodor. Silver halide can be used, but silver chlorobromide, silver bromide, or silver iodobromide or silver chloroiodobromide containing 3 mol% or less of silver iodide is preferred.

(Standard deviation of particle size) / (Average value of particle size)
Monodisperse particles having a coefficient of variation of 15% or less represented by × 100 are preferred.

Various techniques and additives known in the art can be used for the silver halide emulsion of the present invention.

For example, in the silver halide photographic emulsion and the backing layer used in the present invention, various chemical sensitizers, color toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents,
A development inhibitor, an ultraviolet absorber, an antiirradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. The silver halide photographic emulsion and the backing layer of the present invention may contain a polymer latex.

The support which can be used in the silver halide photographic light-sensitive material of the present invention is coated with cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, and polyolefin. paper,
Glass, metal and the like can be mentioned. These supports are subjected to a base treatment as required.

These additives are described in more detail in Research Disclosure (RD), Vol. 176, Item / 7643 (1978).
December 1987) and Volume 187, Item / 8716 (November 1979), and the relevant locations are summarized below.

Additive Type RD / 7643 RD / 8716 Chemical sensitizer page 23 648 right column 2. Sensitivity increasing agent Same as above 3. 3. Spectral sensitizers, pages 23 to 24, right column, page 648 to supersensitizers, right column, page 649. Brightener page 24 5. 5. Antifoggants and stabilizers, pages 24 to 25, right column, page 649. 6. Light absorbers, filter dyes, pages 25 to 26, right column, page 649 to ultraviolet absorbers, left column, page 650 7. Stain inhibitor 25 pages right column 650 pages left to right column 8. Dye image stabilizer page 25 Hardening agent Page 26 651 Left column 10. Binder page 26 Same as above 11. Plasticizers and lubricants Page 27 Right column on page 650 12. Coating aids, surfactants 26-27 Same as above 13. Stakch inhibitor page 27 Ditto Development processing of the silver halide photographic light-sensitive material of the present invention is carried out, for example, by using the Theory of the Photographic Process, 4th Edition, by TH James (The Theory of Photographic Process).
the Photographic Process, Fourth Edition) 291-33
4 pages and Journal of the American Chemical Soci
ety), vol. 73, p. 3, 100 (1951), a developer can be effectively used in the present invention.

These developers may be used alone or in combination of two or more, but it is preferable to use two or more in combination.

The effect of the present invention is not impaired by using a preservative, for example, a sulfite such as sodium sulfite or potassium sulfite as a preservative in the developing solution used for developing the light-sensitive material of the present invention. Further, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, it can have a pH adjustment and buffer function with caustic alkali, alkali carbonate, amine or the like as used in general black and white developers. The developer used in the present invention has a pH of 9.5 to 11.2.
Are preferred. If the pH is lower than 9.5, the contrast is insufficient, and if the pH is higher than 11.2, black pot is greatly deteriorated.

In the developing solution, an inorganic development inhibitor such as bromkari and an organic development inhibitor such as 5-methylbenzotriazole, 5-methylbenzimidazole, 5-nitroindazole, adenine, guanine and 1-phenyl-5-mercaptotetrazole are used. Agents, metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol and polyalkylene oxide, sodium alkylaryl sulfonate, natural saponins, saccharides and surface activities such as alkyl esters of the above compounds Agent,
It is optional to add a hardening agent such as glutaraldehyde, formalin or glyoxal, or an ionic strength adjusting agent such as sodium sulfate.

The developer used in the present invention is described in JP-A-56-106.
No. 244, No. 61-267759, No. 61-230145, No. 62-211647
Alkanolamine compounds (for example, Nn-butyldiethanolamine, 3-diethylamino-1,2-propanediol, 1-diethylamino-1-) as described in JP-A-2-50150, JP-A-2-208652 and the like. Ethanol, 2-diethylamino-1-butanol, 3-diethylamino-1-propanol, N, N-di-n-butylethanolamine). Does not substantially contain
It is an amount of 0.01 mol / l or less.

The developer used in the present invention may contain glycols such as diethylene glycol and triethylene glycol as organic solvents.

[0108]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples.

Reference Example 1 (Preparation of silver halide photographic emulsion A) A silver chloroiodobromide emulsion (0.2 mol% of silver iodide and 65 mol% of silver chloride per mol of silver) was prepared by a double jet method. During this mixing, K ₂ IrCl ₆ was added to 8 × 10 ⁻⁷ mol per mol of silver and Na ₃ RhC
1 × 10 ⁻⁷ mol of ₁₆ was added. The resulting emulsion has an average particle size
This emulsion was composed of cubic monodispersity particles of 0.20 μm (coefficient of variation: 10%). After adding SD-1 at 8 mg / m ^2, it was washed with water and desalted by a conventional method. Then, compound [A] [B]
After adding the mixture of [C], gold-sulfur sensitization was performed to obtain Emulsion A.

[0110]

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(Preparation of silver halide photographic light-sensitive material) One side of a 100 μm-thick polyethylene terephthalate film having a 0.1 μm-thick undercoat layer on both sides (see Example 1 of JP-A-59-19941) on the undercoat layer, the following formulation (1) the amount of gelatin is 2.0 g / m ² of silver halide emulsion layers of the silver amount of 3.2 g / m ²
The emulsion protective layer of the following formula (2) is further coated thereon so that the amount of gelatin becomes 1.0 g / m ^2, and on the other undercoat layer on the opposite side. According to the following formula (3), a backing layer is coated so that the amount of gelatin becomes 2.4 g / m ^2, and a backing protective layer of the following formula (4) is further coated thereon so that the amount of gelatin becomes 1 g / m ² . To obtain a sample.

Formulation (1) (Silver halide emulsion layer composition) Gelatin Amount of 1.5 g / m ² as emulsion layer Silver halide emulsion A Silver amount 3.2 g / m ²

[0113]

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Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: Compound of the general formula [1] of the present invention 1 × 10 ^-4 mol / m ² 5-sodium sulfonate-2-mercaptobenzimidazole 5 mg / m ² Surfactant: saponin 0.1 g / m ²

[0115]

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[0116]

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Formulation (3) (backing layer composition)

[0118]

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Gelatin 2.4 g / m ² Surfactant: Saponin 0.1 g / m ² : S-1 6 mg / m ² Colloidal silica 100 mg / m ² Formula (4) [Backing protective layer composition] Gelatin 1 g / m ² matting agent average particle size: 3.5μm monodisperse polymethyl methacrylate a cleat 40 mg / m ² surfactant: ^S-2 10mg / m 2 hardener: glyoxal 35 mg / m ² [photographic performance and storage stability evaluation] the obtained sample Was heated at 55 ° C. and 48% RH for 3 days as a substitute for storage stability evaluation.
A wedge is adhered to the sample, and ^10-6
Automatic processing machine GR-26SR for rapid processing manufactured by Konica Corporation, which was given a second exposure and charged with a developer and a fixer of the following composition.
Was processed under the following conditions.

The density of the obtained sample was measured with an optical densitometer Konica PDA-65, and the sensitivity of Sample No. 1 at a density of 2.5 was 100%.
The gamma was indicated by the tangent between the densities 0.1 and 2.5. If the gamma value is less than 8.0, the contrast is insufficient and it can be used.

[Evaluation of Black Pots] The unexposed portions of the thus obtained samples containing the developing agent were visually evaluated using a 40-fold loupe. Those with no black spots are assigned the highest rank "5", and ranks "4", "3", "2", and "1" are sequentially reduced according to the degree of occurrence of black spots and evaluated. And Ranks “2” and “1” are levels that are not practically desirable.

[Developer Composition 1] Potassium sulfite 50.0 g Hydroquinone 20.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 1.0 g Ethylenediaminetetraacetic acid disodium salt 2.0 g Potassium carbonate 12.0 g Potassium bromide 5.0 g 5-methylbenzotriazole 0.3 g diethylene glycol 25.0 g 5-nitroindazole 0.1 g Compound (d) 0.1 g Water was added to make up to 1 liter, and the pH was adjusted to 10.4 with potassium hydroxide.

The structure of the compound (d) is shown below.

[0124]

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Fixer Formulation Ammonium thiosulfate (72.5% W / V aqueous solution) 200 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g Pure water (ion-exchanged water) 17 ml Sulfuric acid ( Aqueous solution of 50% W / V) 2.0 g Aluminum sulfate (aqueous solution having an equivalent content of 8.1% W / V in terms of Al ₂ O ₃ ) 8.5 g Finished to 1 liter when using a fixing solution. This fixer
The pH was adjusted to 4.8 with acetic acid.

(Development processing conditions) The time includes the time of wading.

[0127] Table 1 shows the results.

[0128]

[Table 1]

From the results shown in Table 1, it can be seen that the sample of the present invention did not decrease in sensitivity and gamma and the generation of black spots was suppressed.

Reference Example 2 The sensitizing dye SD-1 in the silver halide emulsion layer was prepared by the following SD-
3 to (amount 5 mg / m ^2), the reference example except compound instead of the [2] [3] or [4], was replaced by nucleation accelerator as shown in Table 2 of the compound [1] of the present invention A sample was obtained in the same manner as in Example 1. The obtained sample was evaluated in the same manner as in Reference Example 1 except that the sample was exposed to light using a HeNe laser instead of an Ar laser. Table 2 shows the results.

[0131]

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[0132]

[Table 2]

As is clear from Table 2, the examples of the present invention are superior to the comparative examples.

Example 3 A compound [5] [6] or [7] was used instead of the compound [1] of the present invention in a silver halide emulsion layer, and the nucleation accelerator was changed as shown in Table 3. A sample was obtained in the same manner as in Reference Example 1. The obtained sample was evaluated in the same manner as in Reference Example 1 except that the developer was changed to the following developer composition 2. Table 3 shows the results
Shown in

[0135]

[Table 3]

As is clear from Table 3, the examples of the present invention are superior to the comparative examples.

[Developer Composition 2] Potassium sulfite 70.0 g Hydroquinone 25.0 g 4-Methyl-4-hydroxymethyl-1phenyl-3-pyrazolidone 1.0 g Diethylenetriaminepentaacetic acid pentasodium salt 5.0 g Sodium carbonate 60.0 g Potassium bromide 5.0 g 5-methylbenzotriazole 0.2 g Diethylene glycol 25.0 g Compound d 0.1 g Water was added to 1 liter, and the pH was adjusted to 10.5 with potassium hydroxide.
Was adjusted.

[0138]

The silver halide light-sensitive material according to the present invention comprises:
Even a developer having a pH of less than 11.2 makes it possible to obtain a light-sensitive material which is hardened and hardly raises fog and "black spots" in unexposed areas during storage, particularly during high-temperature storage, and has little fluctuation in sensitivity.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 1/34 G03C 1/33 G03C 1/06

Claims (1)

(57) [Claims] 1. The method according to claim 1 , wherein at least one halogen is present on the support.
In the silver halide emulsion layer and / or other hydrophilic colloid layer,
For silver halide photographic materials containing drazine derivatives
The silver halide emulsion layer and / or other hydrophilic
Contains a nucleation promoting agent in the conductive colloid layer, and
At least one of the following general formulas [5] and [6]
Characterized by containing a polyhydroxybenzene compound
Silver halide photographic material. [G] (Wherein R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ and R ₅₆ are hydrogen
Atom, halogen atom, alkyl group having 1 to 23 carbon atoms, carbon
Alkoxy groups of 1 to 23, carboxyl group, carboxy
Alkyl ester group, hydroxyalkyl group, hydro
Xyalkoxyalkyl group, sulfo group, amidoalkyl
Group, amidophenyl group, imidoalkyl group, nitrile group
Represents ) [Formula H] (Wherein, R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ are hydrogen
Atom, halogen atom, alkyl group having 1 to 23 carbon atoms, carbon
Alkoxy groups of 1 to 23, carboxyl group, carboxy
Alkyl ester group, hydroxyalkyl group, hydro
Xyalkoxyalkyl group, sulfo group, amidoalkyl
Group, amidophenyl group, imidoalkyl group, nitrile group
Represents )