JPH05257240A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a method for processing a photographic sensitive material free from the deterioration of photographic property such as the lowering of sensitivity and the lowering of gamma. CONSTITUTION:In the silver halide photographic sensitive material having >=2 and <=4.5 gamma and containing a hydrazine compound, total processing time is <=90 seconds (preferably <=50 seconds) under the condition that the replenishing quantity of a developer is 100-350ml/m<2> at the time of processing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more specifically, a silver halide photographic light-sensitive material excellent in development stability even if the developer replenishment amount is reduced for environmental protection. The present invention relates to the developing treatment method.

[0002]

BACKGROUND OF THE INVENTION When a silver halide photographic light-sensitive material after exposure is processed by an automatic processor, the processing solution is generally replenished according to the processing amount, and usually the developing solution replenishing amount is processed. It is 400 ml to 600 ml per 1 m ^{2 of the} light-sensitive material.

In recent years, in the field of development processing of photographic light-sensitive materials, there is an increasing demand for reduction of processing waste liquid as much as possible in view of environmental protection.

However, for example, as one means for reducing waste liquid, if the developer replenishment amount is decreased, the developing agent in the developer is consumed more, and at the same time, the accumulation due to elution from the silver halide photographic light-sensitive material increases, In the present situation, this cannot be easily realized despite the strong demand for reduction of the replenisher because the developing ability will be reduced.

On the other hand, recently, there is a strong demand for rapid processability of silver halide photographic light-sensitive materials. For example, in the medical field, there is an increasing demand for rapid process because of the quickness of diagnosis and urgency. .. However, it goes without saying that one of the problems associated with the speeding up of the development process is that the deterioration of the developing ability (reduction of sensitivity, decrease of gamma) due to the shortening of the development time becomes large. As a means for suppressing a decrease in developing ability, many techniques have been proposed in the past. For example, a means for stabilizing by maintaining a pH by supplementing a high pH replenisher to suppress a decrease in pH due to development processing. Or
In addition, it is common to use a pH buffering agent for the developer itself.

However, none of these conventional techniques is sufficient when the replenishment amount of the developing solution is reduced and rapid processing is performed by an automatic processor, and a new technique has been desired. ..

[0007]

SUMMARY OF THE INVENTION The present invention solves the above problems and does not provide a method for processing a silver halide photographic light-sensitive material, which is free from deterioration in photographic performance such as sensitivity reduction and gamma reduction. It is what

[0008]

The above object is to provide a method for processing a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. Its gamma is 2 or more and 4.5 or less, it contains a hydrazine compound, and the replenishing amount of the developing solution when the silver halide photographic light-sensitive material is processed is 100 to 35.
It was achieved by a processing method of a silver halide photographic light-sensitive material characterized in that the total processing time is 90 seconds or less (preferably 50 seconds or less) under the condition of 0 ml / m ² .

The present invention will be described in detail below. In this specification, gamma (γ) means optical density (D) and exposure dose (log).
In the characteristic curve on the Cartesian coordinate system with the same unit length of the coordinate axis in E), it indicates the gradient of the straight line connecting the points of optical density 0.5 and 2.0, and expresses the tone hardness of the photosensitive material numerically. It was done.

Generally, in an image with high gamma and high contrast, the sharpness of the characteristic curve is steep, so the sharpness is good.
There is a drawback that the amount of information in the low-exposure portion is poor. On the other hand, in the case of a low-gamma and soft-tone image, the amount of information in the low-exposure portion is abundant, but on the other hand, it has the drawback that the sharpness is poor and image diagnosis is difficult.

For example, in the case of the medical light-sensitive material, the average density of the diagnostic site in the medical light-sensitive material is around 1.0, and the low density area (low exposure amount area) centered around 1.0 is measured. Gamma (γ) over the density area (medium exposure amount area) is important. That is, the gamma (γ) in the density range from about 0.5 to about 2.0 is 2.0 or more and 4.5 or less, so that the image is sharp, the information amount is sufficient, and the diagnostic ability is high. The photosensitive material for X-ray is obtained.

Obtaining this gamma is easy in the art, and for example, X-ray photosensitive materials are generally in this region.

As means for obtaining this gamma, specifically, means for mixing particles having different sensitivities or means for using particles having a wide particle size distribution can be adopted. Further, a means of using particles having a distribution in the manner of chemical sensitization can be adopted.

Next, the light-sensitive material to be processed contains a hydrazine compound, and a preferable hydrazine compound is represented by the following general formula [I].

[Chemical 1]

In the formula, R ¹ represents an alkyl group, an aryl group or a heterocyclic group, and R ² represents a hydrogen atom or a block group. Ar represents an arylene group or a heterocyclic group, and ^one of A ¹ and A ² represents a hydrogen atom and the other represents a hydrogen atom, an acyl group, a sulfonyl group or an oxalyl group.

The general formula [I] will be described in more detail. R ¹ is an alkyl group (eg, a group such as octyl, t-octyl, decyl, dodecyltetradecyl), an aryl group (eg, a group such as phenyl, p-propylphenyl, octyl), a heterocyclic group (eg, pyridyl, tetrazoline). , Oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl and the like). R
Preferred as the alkyl group of ^{1 is} a group having 6 to 20 carbon atoms. The preferred aryl group for R ¹ is represented by the following formula.

[Chemical 2]

X is a substituted or unsubstituted alkyl group (for example, a group such as methyl, ethyl, methoxy, i-propyl), acylamino (for example, a group such as octanamide, tetradecanamide), ureide (for example, hexylureido, δ-). (Groups such as 2,4-di-t-acylphenoxy) butylureido), hydrazinocarbonylamino (for example, 2,2-dibutylhydrazinocarbonylamino, 2-
Groups such as phenyl-2-methylhydrazinocarbonylamino), sulfonamides (eg, groups such as hexadecanesulfonamide, 4-butoxybenzenesulfonamide, morpholinosulfonamide), aminosulfonamides (eg, N, N-dibutylsulfamoyl) Amino, N, N-
Groups such as dimethylsulfamoylamino), oxycarbonylamino (eg octyloxycarbonylamino,
Groups such as benzyloxycarbonyl amino), - s-carbonylamino (e.g., _{C 8 H 17 SCONH-, C 6} H 5
Group such as SCONH-) or a group represented by the following formula.

[Chemical 3]

R ₃ and R ₄ are each a hydrogen atom, alkyl (for example, groups such as methyl, ethyl, propyl, butyl, cyclohexyl, etc.), aryl (for example, groups such as phenyl, naphthyl, etc.), heterocycle (for example, pyridyl, thienyl, Groups such as piperidino and morpholino), and R ₃ and R ₄ may form a ring (eg, ring such as piperidino, piperazino, morpholino) together with a nitrogen atom, and a group represented by the following formula It may be formed.

[Chemical 4]

R ₆ and R ₇ are each a hydrogen atom or a substitutable group (for example, a group such as alkyl, aryl or heterocycle), and a ring (for example, cyclohexane, thiazole,
Ring such as oxazole or benzothiazole) may be formed.

R ₅ represents a hydrogen atom, an aryl group (for example, a group such as phenyl or naphthyl), or a heterocycle group (for example, a group such as piperidino, morpholino, tetrahydropyranyl, pyridyl, thienyl).

Z ₁ is a substitutable group (eg, alkyl,
Aryl, heterocycle, hydroxy, alkoxy, amino,
Acylamino, ureido, hydrazinocarbonylamino, sulfonamide, aminosulfonamide, oxycarbonylamino, -s-carbonylamino, carbamoyl, sulfamoyl, halogen or a group represented by the following formula).

[Chemical 5]

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl (for example, a group such as acetyl or trifluoroacetyl), a sulfonyl (for example, a group such as metasulfonyl or toluenesulfonyl), an oxalyl (for example, Groups such as ethoxalyl) are represented by A ₁ and A
Most preferably, both ₂ are hydrogen atoms.

R ² is a hydrogen atom, and alkyl as a blocking group (eg, methyl, ethyl, benzyl,
Methoxymethyl, trifluoromethyl, phenoxymethyl, hydroxymethyl, methylthiomethyl, phenylthiomethyl, etc.), aryl (eg, phenyl, chlorophenyl, etc.), heterocycle (eg, pyridyl, thienyl, furyl, etc.), Alternatively, a group represented by the following formula is preferable.

[Chemical 6]

R ₈ and R ₉ are hydrogen atoms, alkyl (eg, groups such as methyl, ethyl, benzyl, etc.), alkenyl (eg, groups such as allyl, butenyl), alkynyl (eg, groups such as propargyl, butynyl), aryl (eg, groups). Groups such as phenyl and naphthyl), heterocycles (eg 2, 2, 6,
Groups such as 6-tetramethylpiperidinyl, N-ethyl-N'-ethylpyrazolidinyl, pyridinyl), hydroxy, alkoxy (for example, groups such as methoxy and ethoxy),
It represents each group of amino (for example, a group such as amino and methylamino), and R ₈ and R ₉ may form a ring (for example, a ring such as piperidino and morpholino) together with a nitrogen atom. R ₁₀ is a hydrogen atom, alkyl (eg, a group such as methyl, ethyl, hydroxyethyl, etc.), alkenyl (eg, a group such as allyl, butenyl), alkynyl (eg, a group such as propargyl, butynyl), aryl (eg, phenyl, naphthyl, etc.). Group) and a heterocycle (for example, groups such as 2,2,6,6-tetramethylpiperidinyl, N-methylpiperidinyl and .lysyl).

Next, preferable specific examples of the hydrazine compound will be shown.

[Chemical 7]

[Chemical 8]

[Chemical 9]

[Chemical 10]

The above compounds can be synthesized by known methods, for example European Patent 330,109.
Can be obtained by the synthetic method described in No. 1 or a method analogous thereto.

When the above-mentioned compound is used in the silver halide emulsion or the hydrophilic colloid layer of the present invention, it may be added after being dissolved in water or a hydrophilic solvent such as methanol.

In the case of a silver halide emulsion, it may be added in an appropriate step from the end of chemical ripening to immediately before coating, preferably before coating.

The amount of these compounds added may be within a wide range, but is 6 to 2000 m for silver halide emulsions.
g / mol AgX, more preferably 30 to 1500 mg
/ Mol AgX.

When it is added to a layer other than the silver halide emulsion layer, it is added in an amount of 10 to 2500 mg / m ² , and preferably 5
It is 0 to 2000 mg / m ² .

The method of developing a silver halide light-sensitive material of the present invention comprises 90 steps from development to drying when processed by an automatic processor including the steps of development, fixing, washing (or stabilizing) and drying. It is to be completed within seconds.

That is, from the time when the tip of the photosensitive material starts to be dipped in the developing solution to the time when the tip comes out of the drying zone after the processing step (so-called Dry to Dry).
Is less than 90 seconds, and more preferably, this Dry to Dry time is less than 50 seconds.

In the rapid processing, the developing time is preferably within 20 seconds, preferably within 15 seconds, and the developing temperature is 25.
-50 degreeC is preferable and 30-40 degreeC is more preferable.

The drying temperature is usually preferably 35 to 100.
The automatic developing machine may be provided with a drying zone in which hot air at 40 ° C., more preferably 40 to 80 ° C. is blown or a heating means by far infrared rays is provided.

The developer used in the present invention is generally preferably based on a developer containing 1,4-dihydroxybenzenes as a developer or, if necessary, a p-aminophenol-based developer and / or pyrazolidone. Becomes

As the 1,4-dihydroxybenzene developing agent, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone,
There are 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone and the like, but hydroquinone is particularly preferable. As the p-aminophenol-based developing agent, N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl There are -p-aminophenol, p-benzylaminophenol and the like, among which N-methyl-p-aminophenol is preferable.

Examples of the pyrazolidone compound that can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-ethyl-3-pyrazolidone. ,
1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxy Methyl-3-
Pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4 -Dimethyl-
3-pyrazolidone, 1- (2-benzothiazolyl) -3
-Pyrazolidone, 3-acetoxy-1-phenyl-3-
Pyrazolidone compounds such as pyrazolidone may be mentioned.

The developer used in the present invention may contain a hardening agent which strengthens the physical properties of the film by undergoing a hardening reaction with gelatin in the light-sensitive material during the development process. Examples of the hardener include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde, α, α-dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaleindialdehyde, or a bisulfite adduct thereof is used. ..

In the developer used in the present invention, a sulfite (for example, sodium sulfite or potassium sulfite) can be used as a preservative of the developing agent. In addition, as additives used in addition to the above components, development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol and the like. An organic solvent or 1-phenyl-5-mercaptotetrazole, a mercapto-based compound such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, an antifoggant such as a benztriazole-based compound such as 5-methylbenztriazole may be contained. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a water softener, etc. may be contained.

Generally preferred pH of the developer is 9.0 to
It may be 12, and more preferably in the range of 9.0 to 11.5. The alkaline agent or buffer used for setting the pH includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

The replenishment amount of the developing solution in the present invention is not uniform depending on the type of automatic developing machine used, but is within the range of 100 ml to 350 ml per 1 m ^{2 of} the light-sensitive material.

The fixing solution may use sodium thiosulfate, ammonium thiosulfate, etc. as a fixing agent, and ammonium thiosulfate is preferable from the viewpoint of fixing speed.

Water-soluble aluminum such as aluminum chloride, aluminum sulfate or potassium alum may be used as a hardening agent in the fixing solution. Further, tartaric acid, citric acid, gluconic acid or their derivatives may be used alone or in combination in the fixing solution.

Further, a preservative such as sulfite or bisulfite, a pH adjuster such as sulfuric acid, and a water softener such as a chelating agent may be used. P of the fixing solution of the present invention
H is 3.8 or more, preferably 4.2 to 7.0, and more preferably 4.2 to 5.5.

The fixer replenisher used in the present invention generally has the same fixer composition as described above.
Depending on the case, you may use what contains other components.

The fixer replenisher may be prepared as a concentrated solution by mixing, for example, two or more agents at the time of use.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be any silver halide such as silver iodobromide, silver iodochloride and silver iodochlorobromide, but particularly high sensitivity is preferred. From the viewpoint that it can be obtained, silver iodobromide is preferable.

The silver halide grains in the photographic emulsion are all isotropically grown such as cubes, octahedra and tetrahedra, or are polyhedral crystals such as spheres, and are dihedral with plane defects. It may be composed of crystals or a mixed type or a composite type thereof. The grain size of these silver halide grains may be from fine grains of 0.1 μm or less to large grains of 20 μm.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643
(December 1978) pages 22-23, 1 emulsion manufacturing method (E
mulsion preparation and
types) and the same (RD) No. 18716 (197
It can be prepared by the method described on page 648 (November 9th).

A preferred embodiment of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. The monodisperse emulsion referred to herein means at least 9 in terms of number of particles or weight when the average particle diameter is measured by a conventional method.
5% of the grains are silver halide grains having an average grain size within ± 40%, preferably within ± 30%. The grain size distribution of silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution.

The crystal structure of silver halide may have a silver halide composition in which the inside and the outside are different.

The emulsion as a preferred embodiment of the present invention is a core / shell type monodisperse emulsion having a definite two-layer structure comprising a high iodine core portion and a low iodine shell layer.

The preferable silver iodide content in the high iodine portion is 20 to 4
It is 0 mol%, particularly preferably 20 to 30 mol%.

The method for producing such a monodisperse emulsion is known, and is described in, for example, J. Photo. Sic. 12.242-251 (1963), JP-A-48-36890, 52-1.
6364, 55-142329, 58-499.
38, British Patent 1,413,748, US Patent 3,
Nos. 574,628 and 3,655,394.

As the above monodisperse emulsion, seed crystals are used,
An emulsion in which grains are grown by supplying silver ions and halide ions using this seed crystal as a growth nucleus is particularly preferable. As a method for obtaining a core / shell emulsion, for example, British Patent 1,027,146 and US Pat.
5,068, 4,444,877, JP-A-60-
It is described in detail in publications such as 14331.

The silver halide emulsion used in the present invention is
It may be a tabular grain emulsion having an aspect ratio of 5 or more.

The advantages of such tabular grains are that the spectral sensitization efficiency can be improved and the graininess and sharpness of images can be improved. For example, British Patent 2,112,157 and US Pat. 520, 4,433,048,
Nos. 4,414,310 and 4,434,226 are known, and the emulsion can be prepared by the methods described in these publications.

The above-mentioned emulsion is either a surface latent image type emulsion forming a latent image on the grain surface, an internal latent image type emulsion forming a latent image inside the grain, or a type emulsion forming a latent image on the surface and inside. You may. These emulsions may use a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a Noudel water washing method or a flocculation sedimentation method in order to remove soluble salts. A preferable washing method is, for example, Japanese Examined Patent Publication No. 35-16086.
A particularly preferable desalting method is a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-A No. 1988-2000, or a method using G3 or G8, which is an aggregation polymer agent exemplified in JP-A-63-158644.

The emulsion used in the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure No. 17643 (19
December 1978) and the same No. 18716 (1979, 1)
The compound described in January) is mentioned. The following table lists the types of compounds and the locations where they are described in these two Research Disclosures.

Additive RD-17643 RD-18716 Page classification Page classification Chemical sensitizer 23 III 648-Upper right sensitizing dye 23 IV 648 Right-649 Left Development accelerator 29 XXI 648-Upper right antifoggant 24 VI 649-Right Lower stabilizer 24 VI Color stain inhibitor 25 VII 650 Left-right Image stabilizer 25 VII UV absorber 25-26 VIII 649 Right-650 left Filter dye 25-26 VIII Whitening agent 24 V Curing agent 26 X 651 Left coating Auxiliary 26-27 XI 650 Right Surfactant 26-27 XI 650 Right Plasticizer 27 XII 650 Right Sliding Agent 27 Antistatic Agent 27 XII 650 Right Matting Agent 28 XVI 650 Right Binder 26 IX 651 Left

Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD-17643-2.
8 and RD-18716, page 647, left column.

A suitable support is a plastic film or the like, and the surface of these supports may generally be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer. .. Then, the emulsion according to the present invention can be coated on one side or both sides of the support thus treated.

The present invention can be applied to all silver halide photographic light-sensitive materials, but is particularly suitable for high-sensitivity black-and-white light-sensitive materials.

When the present invention is applied to medical X-ray radiography, for example, a fluorescent intensifying screen whose main component is a phosphor that emits near-ultraviolet light or visible light upon exposure to penetrating radiation is used. It is desirable that the emulsion is brought into close contact with both sides of a light-sensitive material prepared by coating the emulsion of the present invention on both sides and exposed.

[0065]

EXAMPLES Next, examples of the present invention will be described. However, as a matter of course, the present invention is not limited to the following examples.

Example 1 Preparation of coating sample Silver iodide 2 having an average grain size of 0.3 μm by the double jet method while controlling 60 ° C., pAg = 8 and pH = 2.0.
A monodisperse cubic emulsion of silver iodobromide (A) containing mol% was obtained. The number of twins in this emulsion was 1% or less from the electron micrograph. Using this emulsion (A) as seed crystals,
It was grown as follows.

That is, the seed crystal (A) was dissolved in 8.5 liters of a solution containing protected gelatin and ammonia as needed at 40 ° C., and the pH was adjusted with acetic acid.

Using this solution as a mother liquor, a 3.2N aqueous ammoniacal silver ion solution was added by the double jet method.

That is, pAg was controlled to 7.3 and pH was controlled to 9.7 to form a layer having a silver iodide content of 30 mol%. Next, the pH was converted from 9 to 8.2 and the pAg was maintained at 9.0 to grow up to 95% of the particle size. Then, a potassium bromide solution was added through a nozzle over 8 minutes, pAg was dropped to 11.0, and mixing was completed 3 minutes after the addition of the potassium bromide was completed. This emulsion has an average grain size of 0.7 μm and the silver iodide content of the entire grain is about 2.0 mol%.

Next, a desalting step was carried out in order to remove an excessive soluble salt in this reaction solution. That is, the reaction solution was kept at 40 ° C., and the compound (I) described below was added at 5 g / AgX1 mol and MgS.
O ₄ was added 8 g / AgX1 mol, and stirred for 5 minutes then allowed to stand. Then, the supernatant was discharged to a liquid volume of 200 cc per mol of AgX. Then, pure water at 40 ° C. was added to 1.8 liter / Ag × 1 mol, and the mixture was stirred for 5 minutes. Then MgSO ₄ 20 g / AgX1 mol was added, similarly to the above stirred standing, eliminating the supernatant was desalted.

The solution was then stirred and post-gelatin was added to redisperse the AgX.

The obtained emulsion was kept at 55 ° C., the following sensitizing dyes (1) and (2) were added, and then ammonium thiocyanate, chloroauric acid and hypo were added to carry out gold / sulfur sensitization. After completion of sensitization, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added.

[Chemical 11]

A hydrazine compound was added to these emulsions as shown in Tables 1 and 2. In addition, t-butyl-catechol 400 per 1 mol of AgX as an additive
mg, polyvinylpyrrolidone (molecular weight 10,000)
1.0 g, styrene-maleic anhydride copolymer 2.5
g, trimethylolpropane 10 g, diethylene glycol 5 g, nitrophenyl-triphenylphosphonium chloride 50 mg, 1,3-dihydroxybenzene-4-sulfonic acid ammonium 4 g, 2-mercaptobenzimidazole-5-sodium sulfonate 15 mg

[Chemical 12]

1,1-Dimethylol-1-bromo-1-
10 mg of nitromethane was added to prepare an emulsion coating solution.

Further, the following compounds were added as protective layer additives. (The added amount is shown as an amount per 1 g of gelatin.)

[Chemical 13]

7 mg of a matting agent made of polymethylmethacrylate having an average particle diameter of 5 μm, 70 mg of colloidal silica having an average particle diameter of 0.013 μm, (CHO) ₂ 8 mg, HC
6 mg of HO was added to obtain a coating liquid for protective layer.

Each of the obtained coating solutions was mixed with 50 wt% of glycidyl methacrylate and 10 wt of methyl acrylate.
%, Butyl methacrylate 40 wt%, a copolymer consisting of three types of monomers was diluted so as to have a concentration of 10 wt%, and the thickness was 1 obtained by undercoating with an aqueous copolymer dispersion.
It was coated on an 80 μm polyethylene terephthalate blue base.

That is, two layers of an emulsion layer and a protective layer were simultaneously coated in layers from the support on both sides of the base and dried to obtain a sample, which was then left in an atmosphere of 23 ° C. and 55% RH for 3 days to harden it. After stabilizing the film, the next development experiment was performed.

The coated silver amount of each sample was 4 g / m ^{2 on} both sides.
The coating solution for the protective layer was a 3% gelatin solution, and the coating gelatin amount including the emulsion layer protective layer was 6.5 g / m on both sides.
It is applied so that it becomes ² .

Preparation of Processing Solution A developing solution and a fixing solution having the following compositions were prepared. <Developer> Potassium sulfite 55 g Hydroquinone 25 g 1-Phenyl-3-pyrazolidone 1.2 g Boric acid 10.0 g Sodium hydroxide 21.0 g Triethylene glycol 17.5 g 5-Nitrobenzimidazole 0.10 g Glutaraldehyde bisulfite 5 0.0 g Glacial acetic acid 16.0 g Potassium bromide 4.0 g Triethylenetetramine 6-acetic acid 2.5 g Water was adjusted to 900 ml and pH was adjusted to 10.50 with acetic acid.

<Fixer> Ammonium thiosulfate 130.0 g Anhydrous sodium sulfite 7.3 g Boric acid 7.0 g Acetic acid (90 wt%) 15.0 g Sodium acetate trihydrate 25.8 g Aluminum sulfate 18 hydrate 14.6 g Sulfuric acid (50 wt) %) 6.77 g Make up to 1 liter with water, and adjust the pH to 4.40 with sodium hydroxide.

(Processing method) Next, these developing solutions and fixing solutions were used. To the developing (mother liquor) solution, 3 g / liter of potassium bromide as a starter and 4 ml / liter of glacial acetic acid were added, and an automatic developing machine was used. SRX501 (Konica Corporation)
Manufactured) was used to change the developer replenishment amount as shown in Table 1, and the line speed was changed to change the total processing time, and the following items were evaluated. The replenishing amount of the fixing solution at this time was 380 ml / m ² . (However, developer temperature 35 ° C, fixer temperature 33 ° C, wash water volume 3
Liter / min)

(Evaluation of Stability) The prepared sample was exposed to a blackening density of 1.0 and treated by each of the above-mentioned treatment methods until the treatment level became stable (about 100 m ² ) and the initial level and a stable level. Sensitometry was performed for each sample to determine the sensitivity and gamma of each sample.

(Sensitometry) The standard light B described in "New Edition, Data Book for Illumination" is used as the light source, and the exposure time is 0.
Both sides of the film were exposed to the same amount of light for 1 second and 3.2 cms with no filter. For the sensitivity, the reciprocal of the amount of light required to increase the blackening density by 1.0 is obtained, and Table 1
The relative sensitivity was expressed with the initial sensitivity of Sample 1 of 100 as 100.

[Table 1]

As can be seen from Table 1, the samples processed by the method of the present invention have stable sensitivity and gamma even when the replenishment amounts of the developing solution and the fixing solution are reduced and the processing time is shortened. I understand.

Example 2 Two kinds of grains having different average particle sizes (0.4 μm, 1.2 μm, silver iodide content is 2.0 mol%) were prepared, and the grains obtained in Example 1 were used. 0.4 μm: 1.2 μm: 0.7
A coating sample was prepared in the same manner as in Example 1 except that the mixture was performed at a ratio of μm = 20: 10: 70. Next, Example 1
The same treatment as above was performed and stability was evaluated.

[Table 2]

As can be seen from Table 2, the sample treated by the method of the present invention has excellent graininess even when the gamma is high.

[0088]

According to the present invention, it is possible to provide a processing method of a silver halide photographic light-sensitive material which does not cause deterioration of photographic performance such as reduction of sensitivity and reduction of gamma.

Claims (1)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the gamma of the silver halide photographic light-sensitive material being 2 or more.
5 or less, a hydrazine compound is contained, and a developer replenishing amount when processing the silver halide photographic light-sensitive material is 100 to 350 ml / m ² ,
A method for processing a silver halide photographic light-sensitive material, characterized in that the total processing time is 90 seconds or less.