JPH06347954A - Image forming method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To restrain occurrence of silver sludge and to enable an ultrahigh contrast image free from desensitization and drop of contrast to be formed in the method for processing the photographic sensitive material containing a hydrazine and a nucleation promoter by incorporating a specified N-containing heterocyclic compound in a developing solution containing a sulfite high in concentration. CONSTITUTION:The developing solution to be used is controlled to a pH of 9.5-12.3 and contains the following compounds (a)-(d): (a) a dihydroxybenzene type developing agent, (b) a 3-pyrazolidone or aminophenol type developing agent, (c) a sulfite in a connectration of >=0.3mol/l, and (d) the N-containing heterocyclic compound represented by formulae I-III and in formula I, each of R31-R34 is H, -SM31, hydroxy, optionally substituted alkyl, alkoxy, amino, aryl, -SO2M32, or -COM32, and at least one of R31-R34 is -SM31; and each of M31-M33 is an H or alkali metal atom or ammonium group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the processing of a photographic light-sensitive material used in a photoengraving process for reproducing a super-high contrast image for converting a continuous tone original into a halftone image.

[0002]

2. Description of the Related Art It is well known that a photographic image having an extremely high contrast can be formed by using a certain type of silver halide, and such a photographic image forming method is used in the field of photoengraving. . For example, lith-type silver halide light-sensitive materials composed of silver chlorobromide (silver chloride content of 50% or more) and their processing are well known. However, since the concentration of sulfurous acid in the developer cannot be increased, air oxidation is not possible. On the other hand, it had the drawback of being unstable.

For this reason, the instability of the image forming method by the developing method (lith development system) as described above is eliminated, and the image is developed with a processing solution having good storage stability, and an image having super high contrast photographic characteristics can be obtained. Forming system required, US patent
4,166,742, 4,168,977, 4,221,857, 4,22
4,401, 4,243,739, 4,272,606, 4,311,781
Surface latent image type silver halide photographic light-sensitive material added with a specific hydrazine compound as shown in No.
Then, treat with a developer containing 0.15 mol / L or more of a sulfite preservative,
A system for forming a super-high contrast negative image with γ exceeding 10 has been proposed.

However, even in this new image forming system, since the pH of the developing solution is high, it is easily affected by air oxidation and is much more stable than the lith developer, but due to the oxidation of the developing agent, an image having a very high contrast is often obtained. Was not obtained.

In order to make up for such drawbacks, JP-A-63-2 is used.
9751, JP-A-1-179939, JP-A 1-1
No. 79940 and US Pat. No. 4,975,354,
There has been disclosed a silver halide photographic light-sensitive material containing a hydrazine compound and a nucleation accelerator that cause a high contrast even in a developer having a relatively low pH.

On the other hand, when a large amount of processing is carried out with a developer containing a high concentration of sulfite, the silver halide is dissolved by sulfite ions, and silver ions are gradually accumulated in the developer and reduced by the developer. There is a problem that silver is generated as so-called silver sludge which deposits on the wall of the processing container or the surface of the photographic light-sensitive material.

[0007]

The object of the present invention is to suppress the generation of silver sludge in a photographic light-sensitive material containing a hydrazine compound and a nucleation accelerator even in a developer containing a high concentration of sulfite. Another object of the present invention is to provide a processing method for forming an ultrahigh contrast image without desensitization and softening.

[0008]

The above object of the present invention has been achieved by the following constitution.

That is, at least one silver halide emulsion layer is provided on a support, and the hydrazine derivative represented by the following general formula [H] is contained in the silver halide emulsion layer and / or other hydrophilic colloid layer. And the following general formulas [IV] and [V]
A method for processing a silver halide photographic light-sensitive material containing a compound represented by the following formula, characterized in that it is processed with a developer containing the following items and having a pH of 9.5 to 12.3: Method of processing photosensitive material.

Dihydroxybenzene-based developing agent 3-pyrazolidone-based or aminophenol-based developing agent 0.3 mol or more sulfite per liter Nitrogen-containing heterocyclic compound represented by the following general formula [I], [II] or [III]

[0011]

[Chemical 7]

In the formula, R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ are each a hydrogen atom, --SM ₃₁ , a hydroxyl group, a substituted or unsubstituted alkyl group, an alkoxy group, an amino group, an aryl group, --SO ₃ M ₃₂ , or -COOM ₃₃ group,
At least one of R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ is -SM _31.
Represents a group. M ₃₁ , M ₃₂ and M ₃₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different.

[0013]

[Chemical 8]

In the formula, R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ are each a hydrogen atom, --SM ₄₁ , a hydroxyl group, a substituted or unsubstituted alkyl group, an alkoxy group, an amino group, an aryl group, --SO ₃ M ₄₂ , or -COOM ₄₃ group,
At least one of R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ is -SM _31.
Represents a group. M ₄₁ , M ₄₂ and M ₄₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group and may be the same or different.

[0015]

[Chemical 9]

In the formula, R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ are each a hydrogen atom, --SM ₅₁ , a hydroxyl group, a substituted or unsubstituted alkyl group, an alkoxy group, an amino group, an aryl group, --SO ₃ M ₅₂ , or -COOM ₅₃ group,
At least one of R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ is —SM _51.
Represents a group. M ₅₁ , M ₅₂ and M ₅₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different.

[0017]

[Chemical 10]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and G represents-.
(CO) n-group, sulfonyl group, sulfoxy group, -P
A (= O) (R ₁ )-group or an iminomethylene group,
n represents 1 or 2, both A ₁ and A ₂ represent a hydrogen atom or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group, R represents a hydrogen atom, An alkyl group, an aryl group, a heterocyclic group, an amino group or an —OR ₂ group, R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a saturated heterocyclic group or an —OR ₃ group, R ₂ and R ₃
Each represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a saturated heterocyclic group.

[0019]

[Chemical 11]

In the formula, R ₇₁ , R ₇₂ and R ₇₃ represent a hydrogen atom or a substituent. R ₇₁ , R ₇₂ , and R ₇₃ may combine with each other to form a ring. _Examples of the substituent represented by R ₇₁ , R ₇₂ and R ₇₃ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group. R ₇₁ , R ₇₂ , R
₇₃ may be linked to each other to form a ring, for example, piperidine, morpholine, piperazine, pyridine ring and the like.

[0021]

[Chemical 12]

In the formula, R ₉₁ and R ₉₂ represent a hydrogen atom or a substituent. _{Examples of} the substituent represented by R ₉₁ and R ₉₂ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group. R ₉₁ and R ₉₂ may be linked to each other to form a ring, for example, piperidine, morpholine, piperazine, pyridine ring and the like.

In the above general formulas [I], [II] and [III], R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₄₁ , R ₄₂ , R ₄₃ ,
As the alkyl group and the alkoxy group represented by R ₄₄ , R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ , a lower alkyl group and a lower alkoxy group having 1 to 5 carbon atoms are preferable, and an alkyl group, an alkoxy group, an acylamino group and The carbamoyl group may be substituted with a halogen atom, an aryl group, a carbonyl group, a sulfoxy group, a sulfonamide group, a carboxamide group or the like.

R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₄₁ , R ₄₂ , R
_The aryl group represented by ₄₃ , R ₄₄ , R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ is a monocyclic or bicyclic aryl group or a conjugated unsaturated heterocycle. Here, the conjugated unsaturated heterocycle may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. Examples thereof include a benzene ring, a naphthalene ring, a pyridine ring and a quinoline ring. The substituent of the aromatic group may be substituted with an alkyl group, an alkoxy group, an acylamino group, a carbamoyl group, a halogen atom, an aryl group, a carbonyl group, a sulfoxy group, a sulfonamide group, a carbonamido group, an amino group or the like. .

M ₃₁ , M ₃₂ , M ₃₃ , M ₄₁ , M ₄₂ , M ₄₃ , M
_The ammonium group represented by ₅₁ , M ₅₂ and M ₅₃ is a substituted or unsubstituted ammonium group, preferably an unsubstituted ammonium group.

In the above general formulas [IV] and [V], R
₇₁ , R ₇₂ , R ₇₃ , R ₉₁ and an alkyl group represented by R ₉₂ ,
The alkenyl group, alkynyl group, aryl group and heterocyclic group may further have a substituent, which may be substituted with a halogen atom, an aryl group, a carbonyl group, a sulfoxy group, a sulfonamide group, a carboxamide group or the like. May be.

The general formulas [I], [II] and [III] are shown below.
Specific examples of the compound represented by are shown below, but the present invention is not limited thereto.

[0028]

[Chemical 13]

[0029]

[Chemical 14]

[0030]

[Chemical 15]

Among the hydrazine compounds represented by the general formula [H], the compounds represented by the following general formula [Ha] or [Hb] are preferable.

[0032]

[Chemical 16]

In the formula, A and n have the same meanings as in the general formula [H], and 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 or an alkoxy group. Represents a 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 a nitrogen atom. 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 is preferable. R ₁₇ is preferably an alkynyl group or a saturated heterocyclic group.

The compounds represented by the general formula [Ha] or [Hb] include those in which at least one H of -NHNH- in the formula is substituted with a substituent.

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

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). Etc.), an alkynyl group (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 together with the nitrogen atom form a ring (eg, piperidine, piperazine, morpholine, etc.) May be formed.

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

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

Various substituents can be 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 that can 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, a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples thereof include a hydroxy group, a carboxy group, a sulfo group, a nitro group and a cyano group. Of these substituents, the sulfonamide group is preferred.

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

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

-NH in the general formulas [Ha-] and [H-b]
H of NH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (for example, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg acetyl, trifluoroacetyl,
Ethoxycarbonyl, etc.), an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.) and the like, and the compounds represented by the general formulas [Ha] and [Hb] are such compounds. Also includes.

More preferable compounds in the present invention are the compounds of the general formula [Ha] when n = 2, and the compounds of the general formula [Hb].

In the compound of n = 2 of the general formula [Ha], R ₁₅ and R ₁₆ are hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, saturated or unsaturated heterocyclic group, hydroxy group, Or an alkoxy group, and R ₃₁
Further, a compound in which at least one of R ₃₂ and R ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group is more preferable.

The following are specific examples of the compound represented by the above general formula [H]. However, as a matter of course, the specific compound of the general formula [H] that can be used in the present invention is not limited to these compounds.

Specific compound examples

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

The addition position of the hydrazine derivative of the present invention is the silver halide emulsion layer and / or the adjacent layer. The addition amount is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol per mol of silver.

When [H-a] or [H-b] is contained as a hydrazine derivative, it is described in JP-A-4-98239, page (7), lower left column, line 1 to page (26), lower left column, line 11. It is preferred that at least one of the nucleation promoting compounds is contained in the silver halide emulsion layer and / or the non-photosensitive layer on the side of the silver halide emulsion layer on the support.

In the nucleation accelerator represented by the above general formulas [IV] and [V] of the present invention, an alkyl group, an alkenyl group represented by R ₇₁ , R ₇₂ , R ₇₃ , R ₉₁ and R ₉₂ , The alkynyl group is preferably an alkyl group having 6 or more carbon atoms,
An alkenyl group, an alkynyl group such as an octyl group,
A decyl group, a dodecyl group, an octadecyl group, etc., and the aryl group includes, for example, a phenyl group, a tolyl group, a t-butylphenyl group, a 2,4-di-t-amylphenyl group, a naphthyl group, and a heterocyclic group. Are, for example, piperidine, morpholine, piperazine, pyridine ring and the like, and these groups may further have a substituent, and the substituent may be a halogen atom, an aryl group, a carbonyl group, a sulfoxy group, a sulfonamide group, a carboxamide. It may be substituted with a group or the like.

These nucleation accelerators are disclosed in JP-A-4-56749.
And JP-A-63-124045 and 62-187340. These compounds preferably have a diffusion resistance or a silver halide adsorption group in the molecule.
Specific examples of the nucleation accelerator represented by the general formulas [IV] and [V] are shown below, but the invention is not limited thereto.

[0058]

[Chemical formula 24]

[0059]

[Chemical 25]

[0060]

[Chemical formula 26]

[0061]

[Chemical 27]

[0062]

[Chemical 28]

[0063]

[Chemical 29]

[0064]

[Chemical 30]

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

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

When the compound of the general formula according to the present invention is added to the hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used. These hydrophilic binders are preferably coated on both sides of the support at 10 g / m ² or less.

Examples of the support usable in the practice of the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, and polyester film such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic light-sensitive material.

Examples of the dihydroxybenzene type developing agent used in the developing solution in the present invention include hydroquinone, chlorohydroquinone, promhydroquinone, 2,
3-dichlorohydroquinone, methylhydroquinone, isopropylhydroquinone 2,5-dimethylhydroquinone and the like.

Examples of the 3-pyrazolidone-based developing agent that can be used in the present invention in combination with the above-mentioned dihydroxybenzene-based developing agent include 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-3- Pyrazolidone, 1-
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4
-Ethyl-3-virazolidone, 1-phenyl-5-methyl-3-pyrazolidone and the like, as the aminophenol-based developing agent, for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, Examples include M-methyl-p-aminophenol and 2,4-diaminophenol.

The sulfite which can be used in the developing solution in the present invention is, for example, potassium sulfite, sodium sulfite, ammonium sulfite or the like.

If necessary, the developer may contain an alkali agent (alkali metal hydroxide compound) and a pH buffering agent (eg,
Carbonates, borates, boric acid, acetic acid, citric acid, alkanolamines, etc.), solubilizers (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg non-containing polyoxyethylenes). Ionic surfactants, quaternary ammonium compounds, etc., surfactants, antifoaming agents, antifoggants (for example, silver halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, Benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphate salts, etc.), development accelerators (eg US Pat. -45541 compounds, etc.), hardeners If the example such as glutaraldehyde), or it can be added, such as anti-foaming agent.

The pH of the developer is preferably adjusted to 9.5-12.3.

As the fixing liquid, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and other additives, and the pH is usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur compounds capable of forming a soluble stable silver complex salt. A known fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum or the like can be added to the fixing solution.

The developer may be an aqueous solution of a solid component, an organic aqueous solution containing glycol or amine, or a viscous liquid with a high viscosity in a semi-kneaded state. Further, it may be diluted at the time of use, or may be used as it is.

In the development processing of the present invention, the development temperature is
It can be set to a normal temperature range of 20-30 ° C,
It can also be set to a high temperature treatment range of 30 to 40 ° C.

[0078]

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

Example 1 (Preparation of Silver Halide Emulsion A) A silver chloroiodobromide emulsion consisting of 70 mol% of silver chloride, 0.2 mol% of silver iodide and the rest of silver bromide was prepared by the simultaneous mixing method. . At the time of simultaneous mixing, K ₃ RhBr ₆ was added at 8.1 × 10 ^-8 mol per mol of silver. The resulting emulsion was a cubic, monodisperse grain (coefficient of variation 9) with an average grain size of 0.20 μm.
%) Emulsion. Then, the emulsion was desalted by adding the modified gelatin described in JP-A-2-280139 (a gelatin having an amino group substituted with a phenylcarbamyl group, for example, G-8 in JP-A-2-280139). EAg after desalting is 50 ℃
It was 190 mv.

The emulsion thus obtained was adjusted to pH 5.58 and EAg123 mV, and the temperature was adjusted to 60 ° C., and chloroauric acid was added per mol of silver.
After 2.2 × 10 ^-5 mol was added and stirred for 2 minutes, 2.9 × 10 ^-6 mol of S ₈ was added per 1 mol of silver, and chemical ripening was further performed for 78 minutes. At the end of ripening, the following was added per mol of silver.

4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 7.5 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole 3.5 × 10 ^-4 mol and gelatin 28.4 g This was added to give Emulsion A.

(Preparation of silver halide photographic light-sensitive material) On one undercoat layer of a polyethylene terephthalate film having a thickness of 100 μm and subjected to the antistatic treatment described in Example 1 of JP-A-3-92175, the following formulation The silver halide emulsion of No. 1 was coated so that the silver amount was 3.3 g / m ² and the gelatin amount was 2.6 g / m ² . Further, a coating solution of the following formulation 2 was applied as a protective layer on the upper layer so that the amount of gelatin was 1 g / m ² . On the opposite undercoat layer, a backing layer of the following formulation 3 is coated so that the amount of gelatin is 2.7 g / m ^2, and a protective layer of the following formulation 4 is 1 g / m ^{2 of} gelatin on the upper layer. Thus, 16 kinds of samples shown in Table 1 were obtained.

Formulation 1 (Silver halide emulsion layer composition) Gelatin 2.6 g / m ² Silver halide emulsion A Silver amount 3.3 g / m ²

[0084]

[Chemical 31]

Hydrazine Compound According to the Present Invention Shown in Table 1 Amount Shown in Table 1 Nucleation Accelerator Shown in Table 1 Amount Shown in Table 1 Formulation 2 (Emulsion Protective Layer Composition) Gelatin 1.0 g / m ² Surfactant: S -1 12mg / m ² Matting agent: Monodisperse silica with average particle size 3.5μm 22mg / m ² Hardening agent: 1,3-Vinylsulfonyl-2-propanol 40mg / m ²

[0086]

[Chemical 32]

Formulation 3 (Backing layer composition) Gelatin 2.7 g / m ² Surfactant: saponin 133 mg / m ² Surfactant: S-1 6 mg / m ² Matting agent: colloidal silica 100 mg / m ²

[0088]

[Chemical 33]

Formulation 4 (Backing protective layer composition) Gelatin 1.0 g / m ² Matting agent: Monodisperse polymethylmethacrylate 50 mg / m ^{2 with an} average particle size of 5.0 μm Surfactant: Sodium-di- (2-ethylhexyl) -sulfo Succinate 10 mg / m ² Hardener: Glyoxal 5 mg / m ² Evaluation of silver sludge (silver stain) The obtained sample was exposed with a HeNe laser for 10 ^-6 seconds, and the developing solution and fixing solution having the composition shown below were used. The developing process was carried out by using Konica Corporation's rapid developing automatic developing solution GR-26SR under the following conditions while replenishing 160 cc of the developing solution and 190 cc of the fixing solution per m ² .

Under these conditions, the work of developing 200 sheets of large size paper per day was carried out for 3 days, and then the unexposed large size film was processed by an automatic developing machine to remove silver stains on the surface of the film, which could be seen in the form of roller stripes. It was evaluated visually. Also, after processing for 3 days as described above, stop the automatic processor and
After a lapse of time, the black silver stain in the developer tank of the automatic processor was visually evaluated.

5th rank: No silver stain occurred 4th rank: Slightly generated 3rd rank: Slightly generated 2nd rank: Silver stains frequently occurred 1st rank: Large amount occurred 2nd rank or less is a practically problematic level.

Evaluation of Photographic Performance A wedge was adhered to the obtained sample, exposed for 10 ⁻⁶ seconds through an interference filter having a 633 nm fading as a substitute property of HeNe laser light, and a developer having the composition shown below was prepared.
After 10 days, processing was carried out under the following conditions with an automatic processor GR-26SR for rapid processing manufactured by Konica Co., Ltd. into which the fixing solution was added.

The density of the obtained sample was measured with an optical densitometer, Konica PDA-65, and the relative sensitivity was shown assuming that the sensitivity of Sample No. 1 at a density of 3.0 was 100. Gamma is displayed with a tangent. If the gamma value is less than 8.0, the contrast becomes insufficient and it cannot be used.

(Developer formulation) Sodium sulfite 55 g / liter Potassium carbonate 40 g / liter Hydroquinone 24 g / liter 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 0.9 g / liter Potassium bromide 5 g / liter 5- Methylbenzotriazole 0.13 g / liter Heterocyclic compound according to the present invention shown in Table 0.02 g / liter Boric acid 2.2 g / liter Diethylene glycol 40 g / liter Water and sodium hydroxide are added to make 1 liter and pH 11.5.

(Fixing solution formulation) Ammonium thiosulfate (72.5% W / V aqueous solution) 240 ml Sodium sulfite 17g Sodium acetate ・ 3hydrate 6.5g Boric acid 6.0g Sodium citrate ・ 2hydrate 2.0g (Composition B) Pure water (ion) Exchanged water) 17 ml Sulfuric acid (50% W / V aqueous solution) 4.7 g Aluminum sulphate (Al ₂ O ₃ equivalent content is 8.1% W / V aqueous solution) 26.5 g When using the fixer, the above composition A and composition in 500 ml of water are used. They were melted in the order of B and finished to 1 liter before use. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) Step Temperature Time Development 35 ° C. 30 seconds Fixing 33 ° C. 20 seconds Washing with water Room temperature 20 seconds Drying 40 ° C. 40 seconds Results are shown in Tables 1 and 2.

[0097]

[Table 1]

[0098]

[Table 2]

From the results shown in Tables 1 and 2, it can be seen that the samples of the present invention have no deterioration in sensitivity and gamma, and have less contamination of silver sludge.

[0100]

In the processing method of a photographic light-sensitive material containing a hydrazine compound and a nucleation accelerator, a developer containing a high concentration of sulfite has the general formula [I], [II] or [II].
By containing the nitrogen-containing heterocyclic compound represented by the formula [I], it was possible to provide a processing method in which generation of silver sludge was suppressed and a super-high contrast image without desensitization and softening was formed.

Claims (1)

[Claims] 1. A hydrazine derivative represented by the following general formula [H] in which at least one silver halide emulsion layer is provided on a support, and in the silver halide emulsion layer and / or other hydrophilic colloid layer. And a method for processing a silver halide photographic light-sensitive material containing the compounds represented by the following general formulas [IV] and [V], the following are contained and the pH is 9.5.
A method for processing a silver halide photographic light-sensitive material, which comprises processing with a developing solution of about 12.3. Dihydroxybenzene-based developing agent 3-pyrazolidone-based or aminophenol-based developing agent 0.3 mol or more sulfite per liter Nitrogen-containing heterocyclic compound represented by the following general formula [I], [II] or [III] ] [In the formula, R ₃₁ , R ₃₂ , R _33, and R ₃₄ are each a hydrogen atom,
SM ₃₁ , hydroxyl group, substituted or unsubstituted alkyl group, alkoxy group, amino group, aryl group, -SO ₃
M ₃₂ or —COOM ₃₃ group is represented, and R ₃₁ , R ₃₂ , and R ₃₃ are represented.
At least one of R ₃₄ and R ₃₄ represents a —SM ₃₁ group. M ₃₁ ,
M ₃₂ and M ₃₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different. ] [Chemical 2] [In the formula, R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ are each a hydrogen atom,
SM ₄₁ , hydroxyl group, substituted or unsubstituted alkyl group, alkoxy group, amino group, aryl group, -SO ₃
M ₄₂ or —COOM ₄₃ group is represented, and R ₄₁ , R ₄₂ and R ₄₃ are represented.
At least one of R ₄₄ and R ₄₄ represents a —SM ₃₁ group. M ₄₁ ,
M ₄₂ and M ₄₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different. ] [Chemical 3] [In the formula, R ₅₁ , R ₅₂ , R ₅₃ and R ₅₄ are each a hydrogen atom,
SM ₅₁ , hydroxyl group, substituted or unsubstituted alkyl group, alkoxy group, amino group, aryl group, -SO ₃
M ₅₂ or —COOM ₅₃ group is represented, and R ₅₁ , R ₅₂ , and R ₅₃ are represented.
And at least one of R ₅₄ represents a —SM ₅₁ group. M ₅₁ ,
M ₅₂ and M ₅₃ each represent a hydrogen atom, an alkali metal atom or an ammonium group, and may be the same or different. ] [Chemical 4] [In the formula, A represents an aryl group or a heterocyclic group containing at least one of a sulfur atom or an oxygen atom, and G represents-(CO) n-.
Group, sulfonyl group, sulfoxy group, -P (= O) (R
₁ ) -group or iminomethylene group, n is 1 or 2
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 acyl group, and R is a hydrogen atom, an alkyl group or an aryl group. , A heterocyclic group, an amino group or an —OR ₂ group, R ₁ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a saturated heterocyclic group or an —OR ₃ group, and R ₂ and R ₃ are each an alkyl group. Represents a group, an alkenyl group, an alkynyl group, an aryl group or a saturated heterocyclic group. ] [Chemical 5] [In the formula, R ₇₁ , R ₇₂ , and R ₇₃ represent a hydrogen atom or a substituent. R ₇₁ , R ₇₂ , and R ₇₃ may combine with each other to form a ring. ] [Chemical 6] [In the formula, R ₉₁ and R ₉₂ represent a hydrogen atom or a substituent. ]