JPH06258781A - Development processing method for black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the development processing method for the black-and-white silver halide photographic sensitive material capable of obtaining ultrahigh contrast photographic performance and preventing occurrence of black spots, without impairing sensitivity even in the case of using a developing solution of pH<10.7 and capable of ultrahigh contrast photographic performance without impairing sensitivity even in the case of processing by using a replenishing solution in an amount of <=200ml/m<2> of the photosensitive material in an automatic developing machine. CONSTITUTION:The black-and-white silver halide photographic sensitive material has at least one silver halide emulsion layer on a support and the emulsion layer and,/or another hydrophilic colloidal layer contains a hydrazine derivative, and this photosensitive material is processed with a developing solution having a pH of 9.5-10.7 and comprising (1) a dihydroxybenzene-based developing agent; (2) a 3-pyrazolidone-based or aminophenolic, developing agent; (3) a sulfite in a concentration of >=0.3mol/l; and (4) a carbonate in a concentration of >=0.2-0.9mol/l.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a black and white silver halide photographic light-sensitive material having a silver halide light-sensitive layer on a support, and more specifically, it has high contrast and black spots suppressed without impairing sensitivity. The present invention relates to a development processing method for a black and white silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art The photolithography process includes a process of converting a continuous-tone original into a halftone dot image. In this process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultra-high contrast.

The 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 and a well-shaped particle shape, and a high silver chloride content (at least 50 mol). % Or more) of silver chlorobromide emulsion.
By processing this lith-type silver halide photographic material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type developer, a high cost last,
Images with high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to aerial oxidation, their preservative properties are extremely poor.
It is difficult to keep the development quality constant during continuous use.

There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as can be seen in JP-A-56-106244, a silver halide photographic light-sensitive material contains a hydrazine derivative,
The processing is carried out with an alkali developing solution containing an amino compound. According to these methods, the homeostasis is good,
A high-contrast image can also be obtained by processing with a developer capable of rapid processing.

In these techniques, the hydrazine derivative had to be processed with a developing solution having a pH of more than 11.2 in order to fully exhibit the high contrast property. In a high pH developer having a pH of over 11.2, the developing agent is easily oxidized when exposed to air. It is more stable than the lith developer, but due to the oxidation of the developing agent, an ultrahigh contrast image may not be often obtained.

In order to make up for this drawback, Japanese Patent Laid-Open No. 63-29751 and European Patents 333,435 and 345,025 have comparatively low levels.
There is disclosed a silver halide photographic light-sensitive material containing a contrast-increasing agent that makes the contrast high even with a pH developer. However, when a silver halide photographic light-sensitive material containing such a contrast enhancer is treated with a developer having a low pH, the contrast is not sufficiently hardened, and when the pH is adjusted to a pH (10.8 to 11.0) that makes the tone sufficiently high, black spots appear. The current situation is that they tend to occur and satisfactory performance cannot be obtained. Further, since the pH is still higher than that of a normal developing solution, air oxidation is likely to occur, black spots are likely to occur, and a super-high contrast image cannot be obtained. In recent years, with the trend toward lower replenishment, this tendency has strengthened and satisfactory performance cannot be obtained.

[0008]

The object of the present invention is to provide a pH1
A method of developing black and white silver halide photographic light-sensitive materials, in which super-high contrast photographic characteristics are obtained without developing sensitivity with a developing solution of less than 0.7, and black spots are prevented. The replenishment amount is 200 per 1 m ² of photosensitive material.
It is an object of the present invention to provide a development processing method for a silver halide photographic light-sensitive material, which can obtain ultrahigh contrast photographic characteristics without deteriorating the sensitivity even when replenishing at a ratio of less than ml.

[0009]

The above object of the present invention is achieved by the following constitution (1), (2) or (3).

(1) Black-and-white silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the silver halide emulsion layer and / or other hydrophilic colloid layer. In a development processing method for processing a material, the developer contains the following components, and
A method for developing a black-and-white silver halide photographic light-sensitive material, which has a pH of 9.5 or more and less than 10.7.

Dihydroxybenzene type developing agent 3-pyrazolidone type or aminophenol type developing agent 0.3 mol or more per liter sulfite salt 0.2 mol or more and 0.9 mol or less carbonate per liter (2) The developing solution is substantially alkanolamine The method of developing a black-and-white silver halide photographic light-sensitive material according to claim 1, which contains no compound.

(3) The replenishment amount of the developing material is 1 m ² with the automatic developing machine.
The method for developing a black-and-white silver halide photographic light-sensitive material according to claim 2, wherein the replenishment rate is 200 ml or less per replenishment.

The present invention will be described in more detail below.

The dihydroxybenzene type developing agent used in the developing solution of the present invention includes, for example, hydroquinone, chlorohydroquinone, methylhydroquinone and the like, preferably hydroquinone.

Examples of 3-pyrazolidone developing agents 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-
Examples include tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone.

As aminophenol type developing agents, N-methyl-p-aminophenol, p-aminophenol, N- (β
-Hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc.
N-methyl-p-aminophenol is preferred.

The dihydroxybenzene type developing agent is usually 0.
It is preferably used in an amount of 05 mol / l to 2 mol / l. When a combination of dihydroxybenzenes and 3-pyrazolidones or aminophenols is used, it is preferable to use the former in an amount of 0.05 mol / l to 1.5 mol / l and the latter in an amount of 0.2 mol / l or less.

The carbonate used in the present invention is sodium carbonate, potassium carbonate, sodium bicarbonate or the like which is usually used in a developing solution, and the concentration range is 0.2 mol to 0.9 mol per liter, more preferably 0.3 mol. Mole or more 0.
It is 7 mol or less. The object of the present invention cannot be achieved outside this concentration range. The role of carbonate in the present invention is simply
It shows a high contrast effect rather than a pH buffer effect.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite. The sulfite is used in an amount of 0.3 mol / l or more, but if added in an excessively large amount, it precipitates in the developer and causes liquid contamination, so the upper limit is preferably 1.2 mol / l.

The pH value of the developer in the present invention is 9.5 to 1
If it is less than 0.7 and less than 9.5, a hard image cannot be obtained, and if it is 10.7 or more, black spots are likely to occur.

In the present invention, JP-A-56-106244 is used.
No. 61-267759, No. 61-230145, No. 62-211647, JP-A No. 2-50150, No. 2-208652, and the like alkanolamine compounds (for example, Nn-butyldiethanolamine, 3 -Diethylamino-1,2-propanediol, 1-diethylamino-1-ethanol, 2-diethylamino-1-butanol, 3-diethylamino-1-propanol,
(N, N-di-n-butylethanolamine, etc.) is substantially free. The term "substantially free from" means an amount of 0.01 mol / l or less.

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

[0023]

[Chemical 1]

Of these, compounds represented by the following general formula [Hc] or [Hd] are preferred in the present invention.

[0025]

[Chemical 2]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, 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, R ₁₅ and R
₁₆ may form a ring with a nitrogen atom. When 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, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or hetero. Represents a ring oxy group. However, when n = 2, R ₁₅ and R
_At least one of ₁₆ represents 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. 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 (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, and 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 of the general formulas, 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, mercaptoheterocyclic group and triazole group.

--NH in the general formulas [Hc] and [Hd]
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 [Hc] and [Hd] are such compounds. Also includes.

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

In the compound of the general formula [Hc] n = 2, 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.

Typical compounds represented by the above general formulas [Hc] and [Hd] are shown below.
However, as a matter of course, the specific compounds of the general formulas [Hc] and [Hd] that can be used in the present invention are not limited to these compounds.

Specific compound examples

[0040]

[Chemical 3]

[0041]

[Chemical 4]

[0042]

[Chemical 5]

[0043]

[Chemical 6]

Specific compounds other than the above are disclosed in JP-A
2-841 542 (4) to 546 (8) compound examples
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 in No. 2-841, pages 546 (8) to 550 (12). 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.

The silver halide emulsion (hereinafter referred to as a silver halide emulsion or simply an emulsion) used in the present invention includes, as silver halide, for example, silver bromide, silver iodobromide, silver iodochloride, chloroodor. Any silver halide, silver chloride, or any other silver halide emulsion can be used, but silver chlorobromide, silver iodochlorobromide or chloride containing 50 mol% or more of silver chloride is preferably used. It is silver.

Further, (standard deviation of particle size) / (average value of particle size)
Monodisperse particles represented by × 100 and having a coefficient of variation of 15% or less are preferable.

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

For example, for the silver halide photographic emulsion and backing layer used in the present invention, various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, slip 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 and the backing layer of the present invention.

As a support which can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate, polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, and polyolefin are coated. paper,
Examples thereof include glass and metal. These supports are subjected to a surface treatment if necessary.

More specifically, these additives are described in Research Disclosure Vol. 176 Item / 7643 (December 1978) and Vol. 187 Item / 8716 (November 1979),
The relevant parts are summarized below.

Additive Type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Anti-stuck agent page 27 Same as above Developing agents other than those of the present invention (pyrogallol, ascorbic acid, 1-aryl-3-pyrazolines (for example, 1- (p-hydroxyphenyl) -3-aminopyra) may be added to the developing solution if necessary. Zoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline, 1- (p-amino-3-M-methylphenyl) -3- Aminopyrazoline, etc.], solubilizers (eg polyethylene glycols, their esters), sensitizers (eg nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds etc.), surfactants, antifoggants Agents (eg,
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, diethylenetriamine pentaacetate, nitrilotriacetic acid salts, polyphosphate salts, etc.), development accelerators (eg US Patent No. 2,304,025
Nos. 3,047,456 and Japanese Patent Publication No. 47-45541), a hardener (eg, glutaraldehyde or a bisulfite adduct thereof), or an antifoaming agent can be added.

In the developer used in the present invention, silicate, borate, sodium hydroxide, potassium hydroxide and the like may be used in combination as an alkaline agent and a buffer agent.

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 others, 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 and the like can be added to the fixing solution.

The developer may be a mixture of solid components, an organic aqueous solution containing glycol, or a semi-kneaded viscous liquid having a high viscosity. Further, it may be diluted at the time of use, or may be used as it is. Preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, sulfuric acid), pH adjusting agents (eg, sulfuric acid), chelating agents having a water softening ability, and Japanese Patent Application No. 60-218562
The compounds described in US Pat.

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.

The black and white silver halide photographic light-sensitive material according to the present invention is preferably processed by using an automatic processor.
At that time, the processing is performed while replenishing a fixed amount of developing solution proportional to the area of the photosensitive material. The development replenishment amount is 200 ml or less per 1 m ² in order to reduce the amount of waste liquid. Preferably 1
It is 75 ml or more and 200 ml or less per m ² . If the developer replenishment amount is less than 75 ml per 1 m ^2, desensitization, softening, etc. cannot be obtained and satisfactory photographic performance cannot be obtained.

According to the present invention, the total processing time (Dry to Dry) from when the leading edge of the film is inserted into the automatic developing machine to when it comes out of the drying zone when the processing is carried out by using the automatic developing machine is demanded from the desire of shortening the developing time. It is preferably 20 to 60 seconds.
The total processing time referred to here includes all process times required for processing a black and white silver halide photographic light-sensitive material, and specifically includes, for example, development, fixing, bleaching, washing with water, stabilization processing and drying necessary for processing. The time including all process times, that is, Dr
It's y to Dry time. If the total processing time is less than 20 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 30 to 60 seconds.

At least one of the nucleation promoting compounds described in JP-A-4-98239, page 7, lower left column, line 1 to page 26, lower left column, line 11 is used as a halogen on a silver halide emulsion layer and / or a support. It is preferably contained in the non-photosensitive layer on the silver halide emulsion layer side.

Typical examples of the nucleation accelerator are shown below.

[0062]

[Chemical 7]

[0063]

[Chemical 8]

Still another specific example is JP-A-4-98239.
Compounds I-1 to I-26 described on page (8), Compounds II-1 to II described on pages (9) to (10)
-29, Compound II described on pages (10) to (11) of the same
Compounds IV described in I-1 to III-25, pages 84 to 90
-1 to IV-41, compounds described on pages (11) to (13) of the same, VI-1 to VI-27, described on pages (13) to (14) of the same Compounds V-II-1 to V-II-30, Compounds V-III-35 and (1) described in the same page (16).
Compounds VI-I-1 to V described on pages 8) to 20)
II-44, compounds described on pages (21) to (24) of the same, VI-II-1 to VI-II-68 and compounds described on pages (24) to (26) of the same There are other than the above-mentioned representative examples among VI-III-1 to VI-III-35.

The position of addition may be in any constituent layer,
It is preferably in the same layer as or adjacent to the hydrazine derivative. The addition amount is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver.

[0066]

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 photographic emulsion A) A silver iodochlorobromide emulsion (65 mol% of silver chloride per 1 mol of silver) was prepared by the simultaneous mixing method. During this mixing, K ₂ IrCl ₆ was added at 8 × 10 ^-7 per mol of silver.
Mol and Na ₂ RhCl ₆ were added at 1 × 10 ⁻⁷ mol. The resulting emulsion was an emulsion consisting of cubic monodisperse grains (coefficient of variation 9%) having an average grain size of 0.20 μm. After adding 8 mg / m ^{2 of} SD-1, it was washed with water and desalted by a conventional method. Thereafter, a mixture of the compounds [A], [B] and [C] was added, followed by gold sulfur sensitization to obtain an emulsion A.

[0068]

[Chemical 9]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate films having a 0.1 μm-thick undercoat layer (see Example 1 of JP-A-59-19941) on both sides On the undercoat layer, a silver halide emulsion layer having the following formulation (1) was used, in which the amount of gelatin was 1.5 g / m ² and the amount of silver was 3.2 g / m ²
And an emulsion protective layer of the following formulation (2) so that the amount of gelatin will be 1.0 g / m ^2, and on the other undercoat layer on the opposite side. Is a backing layer coated according to the following prescription (3) so that the amount of gelatin is 2.4 g / m ^2, and a backing protective layer of the following prescription (4) is further applied so that the amount of gelatin is 1 g / m ² . A sample was obtained by applying it to the.

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

[0071]

[Chemical 10]

Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: Adenine 10 mg / m ² 1-Phenyl-5-mercaptotetrazole 5 mg / m ² Surfactant: saponin 0.1g / m ²

[0073]

[Chemical 11]

[0074]

[Chemical 12]

Formulation (3) (backing layer composition)

[0076]

[Chemical 13]

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 prescription (4) [backing protective layer composition] gelatin 1 g / m ² matting agent: average particle size 3.5 μm monodisperse polymethyl methacrylate a cleat 40 mg / m ² surfactant: ^S-2 10mg / m 2 hardener: glyoxal ^{25mg / m 2: H-1} 35mg / m 2 [ evaluation of photographic performance] resulting wedge sample in close contact to provide a 10 ^-6 seconds exposure at HeNe laser, those subjected developer prepared in a reaction vessel after 10 days having the following composition and fixer were charged Konica K.K. rapid processing automatic processor GR-26SR was processed under the following conditions.

The concentration of the obtained sample was measured with an optical densitometer, Konica PDA-65, and the relative sensitivity was shown with the sensitivity of sample No. 2.5 at a density of 2.5 as 100. Was displayed. If the gamma value is less than 8.0, the contrast becomes insufficient and it can be used.

[Evaluation of black spots] The unexposed area of the sample containing the developing agent obtained above was visually evaluated using a 40-fold loupe. The highest rank is "5" when there are no black spots, and the rank is "4", "3", "2", and "1" according to the degree of occurrence of black spots. And Ranks "2" and "1" are levels that are not practically preferable.

The obtained sample was exposed with a HeNe laser for 10 ^-6 seconds to prepare a developing solution having the composition shown below, which was stored at room temperature for 3 days, and a fixer was added to Konica Corporation. 1m ^{2 under the following} conditions with GR-26SR automatic developer for rapid processing
The developing process was performed while replenishing 160 cc of the developing solution and 190 cc of the fixing solution.

Under these conditions, a work of developing 200 sheets of large size per day was carried out for 3 days, and then photographic performance and black spots were evaluated in the same manner as described above.

[Developer Composition 1] Potassium Sulfite Amount shown in Table 1 Hydroquinone 25.0 g 4-Methyl-4-hydroxymethyl-1-phenyl-3-pyrazolidone 800 mg Ethylenediaminetetraacetic acid disodium salt 2.0 g Potassium carbonate and comparative compound table Amount shown in 1 Potassium bromide 5.0 g 5-Methylbenzotriazole 0.3 g Diethylene glycol 25.0 g 1-Phenyl-5-mercaptotetrazole 30 mg Water was added to make 1 liter, and pH was adjusted to the amount shown in Table 1 with potassium hydroxide. .

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 exchange water) 17 ml Sulfuric acid ( Aqueous solution of 50% W / V) 2.0 g Aluminum sulphate (Aqueous solution containing 8.1% W / V in terms of Al ₂ O ₃ ) 8.5 g The fixing solution was finished to 1 liter and used. Of this fixer
The pH was adjusted to 4.8 with acetic acid.

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

[0085] The results are shown in Table 1.

[0086]

[Table 1]

From the results shown in Table 1, it can be seen that the samples of the present invention have no deterioration in sensitivity and gamma, and the generation of black spots is suppressed.

Further, it is excellent with almost no deterioration in photographic performance after running.

Claims (3)

[Claims] 1. A black and white silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the silver halide emulsion layer and / or other hydrophilic colloid layer. In the development processing method, the developer contains the following constituents, and
Is 9.5 or more and less than 10.7, and a development processing method of a black and white silver halide photographic light-sensitive material. Dihydroxybenzene type developing agent 3-pyrazolidone type or aminophenol type developing agent 0.3 mol or more per liter of sulfite 0.2 to 0.9 mol or less per liter carbonate 2. The development processing method for a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the developer contains substantially no alkanolamine compound. 3. The method of developing a black-and-white silver halide photographic light-sensitive material according to claim 2, wherein the replenishment amount is 200 ml or less per 1 m ^{2 of the} light-sensitive material with an automatic processor.