JPH04194929A - Method for processing silver halide photographic sensitive material subjectible to ultrarapid processing - Google Patents

Abstract

PURPOSE:To enhance stability in development processing even in the case of lowering an amount of development processing solution to be replenished, by processing the specified silver halide photographic sensitive material with a developing solution containing a silver halide solvent and replenishing the developing solution in a specified amount. CONSTITUTION:At least one of the photosensitive material has a swelling rate of 150 - 250% in the developing solution, and a film thickness after the swelling is controlled to <=25mmu, and this silver halide photographic sensitive material is processed with the developing solution containing at least one kind of silver halide solvent. The developing solution is replenished in an amount of <=300, preferably, 250 - 150, especially, 220 - 180ml/m<2> of the photosensitive material to be processed, thus permitting development processing stability to be enhanced even when an amount of development processing solution to be replenished is reduced for the purpose of environmental pollution control.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an ultra-rapid processing method for silver halide photographic materials, and more particularly to a low-pollution and highly stable processing method.

[Background of the invention]

In the optical photography industry, speeding up, stabilizing, and reducing pollution are important issues, and many studies have been carried out in the past.

In recent years, especially in the photography industry, efforts have been made to prevent pollution problems.
Techniques have been developed to reduce the amount of various waste solutions generated in the development process of silver halide photosensitive materials.

As a method for reducing washing water, for example, JP-A-57
No. 8542 describes a method for significantly reducing the amount of washing water using a water solution containing a specific antifungal agent, JP-A No. 57-8543.
No. 57-1 describes a method of reducing the amount of washing water by adopting a multi-stage counter-current system and specifying the amount of replenishment.
．． No. 5724 discloses a method for reducing the amount of washing water by providing a preliminary washing step between a processing bath having a fixing ability and a washing bath.

On the other hand, the amount of replenishment of the developing processing solution has so far been about 700 m<+ per 1 m2 of photosensitive material, and it is desired to reduce this amount as well. However, simply reducing the amount of development processing causes problems such as (1) decrease in sensitivity and softening of the image, and it is difficult to simply reduce the amount of liquid. Furthermore, when the amount of replenishment of the developing solution is reduced, the developing solution exhibits a certain equilibrium state depending on the composition of the film and the composition of the replenisher. Therefore, the amount of replenishment has a very significant effect on the composition of the processing solution. This equilibrium state can be estimated from chemical engineering calculations. However, it is difficult to accurately know the amount of additives released from the film into the processing solution and the amount of adsorption of the processing solution composition to the film. It is difficult to accurately understand the composition of the composition, and it is difficult to know the correct equilibrium state. When the amount of replenishment is reduced, either there is a means to increase the concentration of the developing agent in order to maintain development stability, or simply increasing the amount of the developing agent in the processing solution causes the problem that the image quality deteriorates.

[Purpose of the invention]

In order to solve the above-mentioned problems, an object of the present invention is to provide a method for processing silver halide photographic materials that has high development processing stability and low pollution even when the amount of replenishment of a processing solution is reduced. .

[Structure of the invention]

The above object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer with a developer, in which the swelling ratio of at least one layer of the light-sensitive material in the developer is 150 to 150. A silver halide photographic light-sensitive material with a film thickness of 250% and a film thickness of 25 μm or less after swelling is added at a replenishment amount of a developing processing solution of 300 mQ per 1 m2 of the light-sensitive material.
This can be achieved by a method for processing a silver halide photographic material, which is as follows and is characterized in that it contains at least one of the developer and a silver halide solvent.

The present invention will be explained in detail below.

In the processing method of the present invention, the replenishment amount of the developing processing solution is 300 m1 or less per 1 m2 of photosensitive material to be processed, preferably 250 m71 to 150 m4. It is particularly preferably carried out at 220 mff-180 mN+. The developing solution is characterized in that a developing solution containing the silver halide solvent of the present invention is used.

Any fixer can be used as appropriate depending on the photosensitive material. Any fixer can be used, and for example, a fixer having the composition used in the Examples described later can be preferably used.

In the present invention, the swelling rate in the developer is 150 to 250.
%, and when a silver halide photographic light-sensitive material with a film thickness of 25 μm or less after swelling is processed using this processing method, development stability is maintained despite low replenishment, and the development replenishment specified in the present invention is maintained. The amount showed sufficient development stability performance.

When the swelling ratio exceeds 250%, problems such as insufficient drying occur, and for example, in processing with an automatic processor, drying defects or passage defects are likely to occur. In order to solve these problems, it may be possible to use a fixer containing a curing agent, for example.
In this case, the amount of curing agent used in ordinary hardening fixers cannot solve the problem, and unless a large amount of curing agent is used, good drying properties cannot be obtained. However, if this is done, problems such as precipitation of the hardening agent occur, which contaminates the photographic material after processing.

Moreover, if the swelling ratio is less than 150%, uneven development will occur during development, which is not preferable.

Also, the thickness of the hydrophilic colloid layer after swelling is 25 m
If it is below, the effect of the swelling rate specified above will be noticeable.

In the present invention, the swelling rate refers to a layer that swells in a developer,
It usually refers to the degree to which the hydrophilic colloid layer of a silver halide photographic light-sensitive material swells in a solution.The difference between the film thickness after swelling in a developer and the film thickness before swelling is calculated. It is divided by the film thickness and multiplied by 100.

Specifically, the swelling rate in the present invention is determined by the following steps ■, @
, O.

■Measure the thickness of the hydrophilic colloid layer in the silver halide photographic light-sensitive material, and add the O-nuclear silver halide photographic light-sensitive material to 1 liter of distilled water at 25°C.
Soak for 1 minute and compare with the layer thickness measured in step ○ to determine the percentage change in layer thickness.

Therefore, the swelling ratio in the present invention refers to the total amount of all the hydrophilic colloid layers (for example, silver halide emulsion layer, surface protective layer, intermediate layer) present on the side of the support where the silver halide emulsion layer is located. It can be said that the film thickness is the swelling ratio expressed as a percentage after being immersed in distilled water at 25°C for 1 minute.

In addition, when the photosensitive material of the present invention has a backing layer consisting of a hydrophilic colloid layer, the swelling ratio of the backing layer is also 1.
It is preferable that it is 50 to 250%.

In the light-sensitive material of the present invention, it is advantageous to use gelatin as the hydrophilic colloid binder used in the emulsion layer and the hydrophilic colloid layers such as the surface protective layer and the banking layer.

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, or silver iodochlorobromide, but one with particularly high sensitivity can be obtained. From this point of view, silver iodobromide is preferred.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
A crystal type that is entirely isotropically grown such as a tetrahedron, a polyhedral crystal type such as a spherical shape, a crystal type that is composed of twin crystals with planar defects, or a mixed or composite type thereof. Good too. The grain size of these silver halide grains may range from fine grains of 0.111 m or less to large grains of up to 20% m.

The emulsion used in the silver halide photographic material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 17643 (197
(December 2008), pages 22-23, 1, Emulsion manufacturing method (Emu
lsionPreparation and type
es) and RD No. 18716 (November 1979), page 648.

The emulsion of the silver halide photographic light-sensitive material according to the present invention is, for example, described in "The theory" by T. H. James.
of thephotographic processes
s” 4th edition, published by Macmillan (1977)
Method described on pages 38-104, G, F, Dauf f
in “Photographic Emulsion Chemistry J” Photography
ic emulsion Chemistry”, Fo
Cal Press (1966), P. Glaf
“Physics and Chemistry of Photography” by kids, Chimie eI
physique photograhique”P
aul Monte1 (1967), V, L, Z
e! “Manufacture and Coating of Photographic Emulsion” by ikman et al.
king and coating photogra
It is prepared by the method described in "Phicemulsion" published by Focal press (1964).

That is, solution conditions such as neutral method, acidic method, and ammonia method,
Can it be manufactured using mixing conditions such as forward mixing method, back mixing method, double jet I method, Chondral double jet method, particle preparation conditions such as conversion method, core/shell method, and combination methods of these methods? can.

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 particles in number or weight when measured by a conventional method, for example, the average particle diameter.
5% of the grains are silver halide grains within ±40%, preferably within ±30% of the average grain size. The grain size distribution of silver halide may be either a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

The crystal structure of silver halide may have different silver halide compositions inside and outside.

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

The silver iodide content of the high iodide portion is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

Methods for producing such monodisperse emulsions are known, for example, J. Ph.
ot, Sic, pp. 12.242-251 (1963)
, JP-A-48-36890, JP-A-52-16364,
No. 55-142329, No. 58-49938, British Patent No. 1,413,748, U.S. Patent No. 3,574,628
No. 3,655,394, etc.

The monodispersed emulsion mentioned above is particularly preferably an emulsion in which grains are grown by using seed crystals and supplying silver ions and halide ions using the seed crystals as growth nuclei. In addition, as a method for obtaining a core/shell emulsion, for example, British Patent 1
．． No. 027,146, U.S. Pat. No. 3,505,068
No. 4,444.877, JP-A-60-14331
It is described in detail in the issue.

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

The advantages of such tabular grains include improved spectral sensitization efficiency and improved image graininess and sharpness, as described in British Patent No. 2,112,157, US Patent No. 4,439, No. 520, No. 4,433,048, No. 4,414,310, No. 4,434.226, etc.

The above-mentioned emulsion may be a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside the grain. Good too. These emulsions may contain cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. in the stage of physical ripening or grain preparation. . In order to remove soluble salts, the emulsion may be subjected to water washing methods such as Tardel water washing method and flocculation sedimentation method. Preferred water washing methods include, for example, the method using an aromatic hydrocarbon aldehyde resin containing a sulfo group as described in Japanese Patent Publication No. 35-16086, or
Agglomerated polymer agent example G 3 described in No. 3-158644,
A particularly preferred desalting method is a method using G8.

Various photographic additives can be used in the emulsion according to the present invention in the steps before and after physical ripening or chemical ripening.

Known additives include, for example, the compounds described in Research Disclosure No. 17643 (December 1978) and Research Disclosure No. 18716 (November 1979). Compound types and notes shown in these two research disclosures = 12- Additive RD-17643R, D-1
Page 8716 Classification Page Classification Chemical Sensitizer 2311 [648-Upper Right Sensitizer Dye 23 ■ 6
48 Right-649 Left Development Accelerator 29 XXI 64
8-Top right blade anti-blur agent 24VI649-Bottom right stabilizer // 11 Color stain prevention agent 25 ■ 650 Left-Right image stabilizer 25
■ Ultraviolet absorber 25-26 ■ 649 right-650 left filter dye // // Brightening agent 24 V hard
Curing agent 26X651 left coating
Auxiliary agent 26-27 XI 650 right surfactant 26-27 n 650 right plasticizer 27 III t
t Slip agent 〃Static inhibitor 27 XI[//MAN 1・
Agent 28
-18716, page 647 left-.

Suitable supports include plastic films, and the surfaces of these supports may generally be provided with an undercoat layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve adhesion of the coating layer. The emulsion according to the present invention can also be coated on one or both sides of the support thus treated.

Silver halide photographic materials to which the sterilization and anti-mold method of the present invention can be applied include black and white photographic materials and various color photographic materials.

For example, X-ray photographic materials (direct and indirect medical use, industrial use), photographic materials for squirrels, general black and white negative film and photographic paper, micro-use, color negative film and color photographic paper, color reversal film and photographic paper, thermal It can be applied to hydrophilic colloids such as developable photosensitive materials and diffusion transfer photosensitive materials.

When the present invention is applied to color photosensitive materials, -14=Various couplers can be used. The coupler is one that forms a dye by campling with the oxidized product of an aromatic primary amine developing agent. Typical examples include naphthol or phenol uncoupler, pyrazolone or pyrazole macenta. couplers and acylacetamide-based yellow couplers, and specific examples of these couplers include Research Disclosure No.
, 17643 (December 1978)■-D Section, No.
, 1871.7 (November 1979) can be preferably used.

The photosensitive material of the present invention preferably has a melting time of 10 minutes to 90 minutes.

The melting time is more preferably in the range of 15 minutes to 80 minutes, most preferably 20 minutes to 70 minutes.

Melting time can be determined, for example, by immersing a sample cut into 1 cm x 2 cm in a 15% caustic soda aqueous solution kept at 50°C without stirring and measuring the time until the emulsion layer dissolves. .

In order to obtain the desired melting time, adjusting means using a hardening agent can be used.

For this purpose, all conventionally known hardeners can be used, either alone or in admixture.

An example is chromium salt (chromium salt, chromium acetate, etc.)
, aldehydes (formaldehyde, glyoxal,
geltaraldehyde), N-methylol compounds (
dimethylol urea, methylol dimethylhytantoin, etc.), dioxane derivatives (2,3-dihydroquine dioxane, etc.), active vinyl compounds (1,3,5-1-lyacryloyl-hexahydro-2-triazine, 1. 3-
vinylsulfonyl-2-furopanol), active halogen compounds (2,4-dichlor-6-hydroquine-3
- triazine), mucohalokenic acids (such as mucochloric acid and mucophenoxychloric acid), and the like can be used.

Preferred hardeners are aldehyde compounds, such as formaldehyde, glyoxal, S-1 to riazine compounds, such as 2-hydroquine-4,6-one chlorotriazine sodium salt, vinyl sulfone compounds, and the like.

The amount of hardening agent used is influenced by the presence of a hardening agent, hardening agent, etc., but is preferably in the range of 1X10-' mol/g gelatin to IX 10-2 mol/g gelatin. used in More preferably 5 x 10
-5 mol/g Seratin to 5 x 1 O-3 mol/g Gelatin.

The processing method of the present invention includes at least all steps of processing the photosensitive material of the present invention with a developer. In this case, the developer contains
At least one type of silver halide solvent is contained.

Hereinafter, such a developer (hereinafter referred to as "developer of the present invention")
).

That is, the developer used in the processing method of the present invention contains at least one type of silver halide solvent, or the silver halide solvent used in the developer of the present invention may include the following: .

That is, (a) U.S. Pat. No. 3,271,1.57, U.S. Pat. No. 3,531
．． No. 289, No. 3.574,628, Japanese Unexamined Patent Publication No. 1983-1
No. 019, No. 54-158917, No. 62-8523
Organic thioethers described in No. 9 and Japanese Patent Publication No. 58-30571, (b) Japanese Patent Application Publication Nos. 53-82408 and 55-77737
(C) A compound having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319, (d) ) imidasoles described in JP-A-54-100717; (e) sulfites; (f) hydroxyalkyl-substituted ethylenecyamines as described in JP-A-57-196228; (g) JP-A-57-196228; Substituted mercaptotetrazoles described in JP-A-57-202531, (h) pensimidazole derivatives described in JP-A-58-54333, and (1) thioneanate salts can be mentioned.

Next, specific examples of silver halide solvents of groups (a) to (1) that can be preferably used in the present invention will be given.

(a) Group (a-1) (a-2) (a-3) HO(CH2)2S (CH2)2S (CH2)
20H(a-4) H00CCH2CHCH2-5-CH2CH2-5-C
H CHCH2COOH0H0H (a-5) (a-6) CH2-NHCO-CH2CH2CH2CH3H CH2-5-CH2CH2SC2H5 (a-7) CH2-NHCO-CH2CH2CH3CH2-3-C
I+2CH2SCH2CH2COOH (a -8) (b) Group (b-1) (b-2) (+) -3)
(b -4)2O- (c) group (c-]) (c-2) (d) group (d-]) (a-2) (a-3) and H
3 (d-4) (d-5) (e) Group (e -1) K2S01 (f) Group (f-1) =21= (r-2) OHOH 0H0H (f -3) (f-4) OHOH ■ OHOH (g) Group (g-1) (g-2) (g-3)
(g-4) (g-5) ■ H3 (1) Group (h -1) (h-2) (h-3) (
1) Group (1-1) (i-2) (i 3)K
SCN Na5CN NH,SC
N When carrying out the processing method of the present invention, any technique can be applied except that a silver halide solvent is included in the developer. That is, in photographic processing embodying the light-sensitive material of the present invention, for example, Research Disclosure 17
Any of various methods and various treatment liquids as described in No. 6, pp. 25-30 (RD-17643) can be applied. This photographic processing may be either a photographic processing for forming a silver image (black and white photographic processing) or a photographic processing for forming a dye image (color photographic processing), depending on the purpose.

The processing temperature is usually chosen between 18°C and 50°C,
The temperature may be lower than 18°C or higher than 50°C.

Further, various other developing methods may be used depending on the case.

For example, the developer used in black and white photographic processing can contain known developing agents.

As the developing agent, dihydroxy/benzenes (eg, hydroquinone), 3-birasolitons (eg, 1-phenyl-3-birasoliton), and aminephenols (eg, N-methyl-p-aminophenol) are used alone. Or they can be used in combination. The developing solution generally contains various other preservatives, alkaline agents, pH buffering agents, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain a water softener, a hardening agent, a viscosity agent, and the like.

As a special form of development processing, in the photosensitive material as a developing agent,
For example, a method may be used in which the photosensitive material is contained in an emulsion layer and developed by processing the photosensitive material in an aqueous alkaline solution. Among the developing agents, hydrophobic ones are described in Research Disclosure No. 169 (RD-16928), U.S. Patent No. 2,739,8.
No. 90, British Patent No. 813.253 or West German Patent No. 1,5
They can be incorporated into the emulsion layer by various methods such as those described in No. 47.763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known for their effectiveness as fixing agents can be used. The fixer may contain a water-soluble aluminum salt as a hardening agent.

When the processing method of the present invention is applied to color development processing, the color developer generally consists of an alkaline aqueous solution containing a color developing agent. Color developing agents include various primary aromatic amine developers, such as phenylenediamines (e.g.
-amino-N,N-diethylaniline, 3-methyl-4
-amino-N, N-diethylaniline, 4-amino-N
-ethyl-N-β-hydroquine ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroquine ethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfamide ethylaniline, 4-amino-3-methyl-N-ethyl-N-β-me-1-quinethylaniline, etc.) can be used.

In addition, F.A. Mason, Photographic Processing Chemistry
cProcessing Chemist, Foc
al Press, 1966, P, 226-229.
, U.S. Patent No. 2,193,015, U.S. Patent No. 2,592.36
No. 4, JP-A No. 48-64933, etc. may be used.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or antifoggants such as bromides, iodides, and organic antifoggants. and may include. Also, if necessary, water softeners, preservatives such as hydroxylamine,
Organic solvents such as Hensyl alcohol, Schedlen gellicol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium borosonolide, auxiliary developers such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents, It may also contain antioxidants and the like.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleaching agent, for example, iron (1), co/
Compounds of polyvalent metals such as \ruto(I), chromium (Vl), and copper (II), peracids, quinones, and nitroso compounds are used.

For example, ferrinan compounds, dichromate, iron (m
) or organic complex salts of cobalt (ITI), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, di[-lilotriacetic acid, 1゜3-diamino-2-propatoltetraacetic acid, or citric acid, tartaric acid, apple Complex salts of organic acids with acids, persulfates: permancanates; nitrosophenols, etc. can be used. Among these, potassium ferrinanide, sodium ethylenecyaminetetraacetate iron (III), and ammonium ethylenediaminetetraacetate iron (TH) are particularly useful. Iron(III) ethylenediaminetetraacetate
Complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

〔Example〕

Examples of the present invention will be described in detail below. It should be noted that, as a matter of course, the present invention is not limited to the embodiments described below.

Example-1 Silver iodobromide containing 20 mol% of silver iodide with an average grain size of 0.20 μm was prepared using the tuple jet method while controlling the conditions at 60°C, pAg=8.0, and pH=2.0. A monodisperse cubic emulsion was obtained. A portion of this emulsion was used as a core and grown as follows. That is, the solution containing core particles and gelatin was heated to 40°C.
, pAg9. o, p) At 19.0, an ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added by a double jet method to form a first coating layer containing 30 mol % of silver iodide. and further p/Ig-9,0, pH-9,
A second coating layer was formed by adding an ammoniacal silver nitrate solution and a potassium bromide solution using a double jet method to prepare a tetrahedral monodispersed silver iodobromide emulsion with an average grain size of 0.50 μm. -1. The average silver iodide content of this emulsion was 2.2 mol%.

Emulsion E-2 having the same composition as E-1 and an average grain size of 0.65 μm was prepared in the same manner as E-1 by changing the addition time and flow rate of the ammoniacal silver nitrate solution and the halide solution.
Average silver iodide content: 2.0 mol%, average grain size: 1.0 μ
Prepare emulsion E-3 of m and l.

Furthermore, polydisperse emulsion E-4 was prepared by a forward mixing method. This was prepared using the following solutions A and B.

Solution B was poured into a reaction vessel for emulsion preparation, stirred with a propeller type stirrer at a rotation speed of 300 rpm, and the reaction temperature was adjusted to 65°C.
I kept it. Next, the solution A was divided into 1 volume and 2 volumes, and one of them, LOOMC, was added over a period of 1 minute. 3
After continuing stirring for 0 minutes, the remaining 2 volumes of solution A, 200
mff was added over 60 minutes, and stirring was continued for an additional 60 minutes.

The resulting emulsion contained 2.07% silver iodide and had disc-shaped grains. The average particle size of the disk-shaped particles (1.00 μm,
The thickness is 0.12 μ■ and the aspect ratio is 8.3.
child.

For E-1, E-2, E-3, and E-4, chlorauric acid salt, sodium thiosulfate, and ammonium thionate were added to optimally gold-sulfur sensitize, and the sensitizing dyes were as follows. Add the indicated amount and further add 4-hydroxy/-6-methyl-1,3,3a,7-tetrazaindene 2x sensitizing dye No. 1 Sensitizing dye No. 2 C2H5C2115 Amount of sensitizing dye added Prior to chemical sensitization, each emulsion was desalted by a conventional aggregation method. That is, the temperature was maintained at 40° C., and an aqueous solution of a formalin condensate of sodium naphthalene sulfonate and magunium sulfate was added to cause coagulation. After removing the supernatant, further heat at 40°C.
Add pure water, add magnonium sulfate aqueous solution again to cause flocculation, and remove the supernatant liquid.

Samples were prepared as follows using monodisperse emulsions E-1 to E-3 and polydisperse emulsion E-4 prepared as described above.

First, sample N081, which is a comparative sample, will be described. Sample No. I was prepared as follows.

That is, monodispersed emulsions E-1 to E-3 after chemical sensitization were mixed in a ratio (weight) of E-1:E-2:E-3, or 30.50:20. The following additives were added to prepare an emulsion for coating. A protective film solution was also prepared as described below.

A hardening agent was added to the emulsion solution and the protective film solution so that the swelling ratio would be the value shown in Table 1.

The emulsion layer additives contained in the emulsion solution are as follows: That is, t-butylcatecholbolyhinylpyrrolidone (molecular weight 10,000) 1.0 per mole of silver halide
g Styrene/maleic anhydride copolymer 2.5g polyethyl acrylate (molecular weight 250,000) 2.5
g Tritylolpropane 10g Diethylene glycol 5g Nitrophenyl-triphenylphosphonium chloride 50mg 1,3-
Ammonium dihydroxybenzene-4-sulfonate
4g Sodium 2-mercaptobenzimidazole-5-sulfonate 1
5mg 2-mercaptobenzthiazole IO
1 mg, IO mg of 1-dimethylol-1-bromo-1-nitromethane, etc. were added.

Along with the above emulsion, a protective layer prepared as described below was applied to both sides of a polyester film support that had been undercoated by a slide hopper method in an amount equal to the amount of gelatin, and silver halide emulsion layers ( A sample was obtained by simultaneously applying two layers of a protective layer (viscosity: 11 cp, surface tension: 35 dyn/cm) and a protective layer (viscosity: 11 cp, surface tension: 25 dyn/cm) at a coating speed of 60 m/min.

A protective layer solution was prepared by adding the following additives.

That is, per 1 g of gelatin, - :, lll - ■ 5O3Na C9F+ 9-O-f-CH, CH20-! TOCH2
CH20H2m gC8FI7SO3K
3mg average particle size 5μm
Matting agent made of polymethyl methacrylate
7 mg average particle size 0,0], 3 μm colloidal force 70 mg, etc. were added.

Samples No. 1 were created as described above. The degree of swelling of this sample in the developer is as shown in Table 1.

In addition, samples No. 2 to No. 16 shown in Table 1 were similarly prepared and exposed so that the degree of swelling in the developer reached the values shown in Table 1.

(Processing process) The obtained samples were developed with the following developer containing the silver halide solvent shown in Table 1, with the developer replenishment amount (drainage amount) shown in Table 1. Sensitivity and graininess were determined.

Incidentally, the development was carried out using an SRχ-501 automatic developing machine (manufactured by Konica Corporation) in a 45 second processing mode. The temperature of the developing tank was 32.0°C, and the temperature of the fixing tank was 33.0°C.

The developer and fixer used were as follows.

<Developer> Potassium sulfite 70g Hydroquine ethylethylenediamine triacetic acid trisodium 8g 1.4-dihydroquinebenzene 28g Boric acid
10g-; 6-5-methylbenzotriazole 0.04g1
-Phenyl-5-mercaptotitrasol Solulium metabisulfite 5g acetic acid (
90%) 13gl-lyethylene glycol 15gl-phenyl-3-pyrazolidone 1.2g 5-nitroindazole □ 0.2g geltaraldehyde 4g ethylenediaminetetraacetic acid 2
Sodium 2g Potassium Bromide
4g5-nitrobenzimidazole
1g Silver halide solvent described in Table-1 Make an aqueous solution of 1 and 4 in the amount described in Table-1, and add sodium hydroxide to pH 10 and 5.
0 liquid.

<Fixer> Sodium thiosulfate pentahydrate 45g Distrium ethylenediaminetetraacetate 0.5g Ammonium thiosulfate 150g Anhydrous sodium sulfite 8g Potassium acetate
16g aluminum sulfate 10-18 hydrate 27g sulfuric acid (50wt%)
6g citric acid
1g boric acid
7g glacial acetic acid 5g1
A was made into an aqueous solution, and glacial acetic acid was added to make a solution with pH 4.0.

(Method of evaluating sensitivity) The method of evaluating sensitivity is to
After sandwiching with O-250 (manufactured by Konica Corporation) and irradiating with X-rays through a Petrometer B type (manufactured by Konica Medical Corporation), continuous development treatment was performed using the processing solution as shown in Table 1. From the characteristic curve obtained for the sample, determine the exposure amount at the base density and the fog density +1.0, and
The sensitivity at the start of continuous processing with the new processing solution No. 1 was set as 100, and the evaluation was made in terms of relative sensitivity.

(Evaluation method of graininess) Graininess was evaluated as follows. For samples processed using a roller conveyance type automatic developing machine under the above processing conditions,
The degree of roughness of developed silver particles at the density of 1.0 is
Visual evaluation was performed. ■ Expressed on a 5-level scale from (poor) to 5 (excellent). Is there any problem with 3 to 5?] to 2 are not practical.

From the results in Table 1, it can be seen that the samples of the present invention maintain good graininess even when the replenishment amount is low, and remain stable even when the number of processed sheets increases.

〔Effect of the invention〕

According to the present invention, it has been possible to provide a method for processing a silver halide photographic light-sensitive material that has excellent development processing stability even when the replenishment amount of a processing solution is reduced as a pollution control measure.

Claims (1)

[Claims] In a method of processing a silver halide photographic material having at least one silver halide emulsion layer with a developer,
The swelling ratio of at least one layer of the photosensitive material in the developer is 15.
A silver halide photographic light-sensitive material having a film thickness of 0 to 250% and a film thickness after swelling of 25 μm or less, the replenishment amount of a developing processing solution is 300 ml or less per 1 m^2 of the light-sensitive material, and the developing solution is A method for processing a silver halide photographic material, the method comprising at least one silver halide solvent.