JPH0619068A - Processing method for black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a developing method for a transmission type black-and- white silver halide photographic sensitive material in which the amt. of the replenisher for a developer is small per unit processing area. CONSTITUTION:In the developing method of transmission type black-and-white silver halide photographic sensitive material by using an automatic developing machine, the developer used contains sodium ion by >=70mol% of the whole cation in the liquid and has <pH9.8. The developer and fixing liquid are replenished by the amt. of <=150ml per 1m<2> photosensitive material which contains >90mol% silver chloride having 0.1-0.4mum average particle size, and satisfying the ratio of (100) plane/(111) plane >= 5.

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 black-and-white silver halide photographic light-sensitive material using an automatic processor, which can reduce the replenishment amount of the developing solution and the fixing solution per unit area of the light-sensitive material. In addition, the present invention relates to a processing method capable of obtaining stable photographic performance.

[0002]

2. Description of the Related Art A black-and-white silver halide photographic light-sensitive material is generally processed in the steps of developing, fixing, washing with water and drying after exposure. Recently, most of them are processed by using an automatic processor (hereinafter, abbreviated as an automatic processor). Then, at that time, it is usual to carry out the development process while replenishing a fixed amount of developing solution and fixing solution proportional to the area of the light-sensitive material. It has been desired that stable photographic performance be obtained when such development processing is performed. Further, it has been desired that the amount of replenishing liquid per unit area be reduced to obtain stable photographic performance and fixing loss. Conventionally, for each so-called sheet-shaped photographic material 1 m ² such as X-ray photography or graphic arts photographic material, 250 ml or more of a developing replenisher and a fixing replenisher, particularly 3
It was common to replenish 30 ml or more. However, photographic developer waste and fixing waste liquid have high chemical oxygen demand (so-called COD) or biological demand (so-called BO).
Due to the presence of D), the developing waste liquid and the fixing waste liquid are subjected to chemical or biological treatment or the like to be rendered harmless before being discharged. Since a large economic burden is imposed on the treatment of these waste liquids, a treatment method in which the developer replenisher amount and the fixing replenisher amount are small has been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to process a transmission type black-and-white silver halide photographic light-sensitive material using an automatic processor in which the amount of developing replenisher and the amount of fixing replenisher per unit processing area are small. To provide. Another object of the present invention is to provide a processing method capable of obtaining a photographic property with good stability even when the amount of developing replenisher and fixing replenisher is small.

[0004]

The present invention is a method of processing a transmission type black-and-white silver halide photographic light-sensitive material with an automatic processor, wherein 70 mol% or more of all cations in the developer are sodium ions and have a pH of 9.8. With respect to 1 m ² of a light-sensitive material having an average particle size of 0.1 to 0.4 μ, a (100) face / (111) face ratio of 5 or more and a silver chloride content of 90 mol% or more in the following developing solutions: It was achieved by the processing method characterized in that the developing solution and the fixing solution were replenished at a rate of 150 ml or less. More preferably, the developing solution contains a benztriazole derivative and / or a nitroindazole compound, and further preferably the fixing solution contains at least 0.8 mol / liter of thiosulfate ion.

The high silver chloride content in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is 90 mol% or more (average value).
And silver chlorobromide, silver iodochloride, silver iodochlorobromide, or silver chloride. The silver iodide content is preferably 1 mol% or less. Particularly preferred is silver chlorobromide or silver chloride containing 96 mol% or more (average value) of silver chloride. The high silver chloride emulsion used in the present invention preferably has a silver bromide localized layer in which the silver bromide content is relatively higher than that of the substrate in the silver halide grains.

A preferred example of such a localized structure is one having a localized phase on the surface of the silver halide grain or in the interior close to the surface, and particularly in the edge portion or corner portion of the crystal surface of the grain, or the crystal plane. Those having a localized phase in the form of protrusions are preferable. The halogen composition in the localized phase may have a silver bromide content of 10 mol% or more and 95 mol% or less.
It is preferably in the range of mol% to 90 mol%. Further, it is preferably 20 mol% or more and 60 mol% or less, and most preferably 30 mol% or more and 60 mol% or less. The remaining silver halide in the localized phase consists of silver chloride, but it is also preferred to include traces of silver iodide. However, as described above, it is not preferable to exceed 1 mol% with respect to the total amount of silver halide. Further, these localized phases preferably account for 0.03 mol% or more and 35 mol% or less of the silver halide constituting all silver halide grains of the emulsion, and more preferably 0.1 mol% or more and 25 mol% or more. It is preferable to occupy mol% or less.

The localized phase does not have to consist of a single halogen composition, and may have two or more localized phases having distinctly different silver bromide contents, and other than the localized phase. It may be such that the interface with the phase is formed while continuously changing the halogen composition. In order to form a silver bromide localized phase as described above, a water-soluble silver salt and a water-soluble halogen salt containing a water-soluble bromide are simultaneously mixed with an emulsion containing silver chloride or high silver chloride grains already formed. Or deposit a portion of the already formed silver chloride or high silver chloride grains into a silver bromide-rich phase using the so-called halogen conversion method, or silver chloride or high silver chloride grains. It can also be formed by adding fine grained silver bromide or high silver bromide grains or other sparingly soluble silver salt to crystallize the surface of silver chloride or high silver chloride grains by recrystallization. For such a manufacturing method,
For example, it is described in European Patent Application Publication No. 0,273,430A2.

The silver bromide content of the localized phase can be determined by the X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis” Maruzen) or XPS method (for example, “Surface analysis, −
IMA, Application of Auger electron and photoelectron spectroscopy- "Kodansha,
, Etc.) and the like. The silver bromide localized phase can also be known by electron microscope observation or the method described in the above-mentioned European Patent Application Publication No. 0,273,430A2.

Of these methods, the method of forming a high silver bromide layer particularly useful in the present invention is a method of forming silver bromide and / or silver chlorobromide on the surface of a high silver chloride emulsion during chemical ripening. And is preferable in that high sensitivity and low fog can be obtained.

The silver halide grains used in the present invention include metal ions other than silver ions (for example, metal ions of Group VIII of the periodic table, transition metal ions of Group II, lead ions of Group IV and Group I). It is preferable that the effect of the present invention be better exhibited under various conditions. The metal ions or complex ions thereof may be contained in the entire silver halide grains, the above-described silver bromide localized phase, or any other phase. Among the above metal ions or complex ions thereof, those selected from iridium ion, palladium ion, rhodium ion, zinc ion, iron ion, platinum ion, gold ion, copper ion and the like are particularly useful. It is often the case that these metal ions or complex ions are used in combination, rather than being used alone, to obtain desirable photographic properties. In particular, it is necessary to change the added ionic species and the added amount between the localized phase and other parts of the particle. Is preferred. In particular, iridium ions and rhodium ions are preferably contained in the localized phase.

In order to incorporate a metal ion or a complex ion in the localized phase of the silver halide grain and / or the other portion of the grain, the metal ion or the complex ion is formed before, during or after the formation of the silver halide grain. It may be added directly to the reaction vessel during the subsequent physical ripening, or may be added in advance in the addition solution of the water-soluble halogen salt or water-soluble silver salt. When the localized phase is formed of fine grains of silver bromide or high silver chloride, it is contained in fine grains of silver bromide or high silver chloride by the same method as described above, and then it is added to a silver chloride or high silver chloride emulsion. May be added to. In addition, a metal ion may be contained while forming a localized phase by adding a bromide other than a silver salt, which is relatively insoluble in metal ions as described above, as a solid or powder.

The silver halide emulsion of the present invention contains 50% by weight or more of silver halide grains having a (100) face / (111) face ratio of 5 or more, preferably 10 or more, and more preferably
The content is preferably 60 wt% or more, particularly 80 wt% or more.

The size of the silver halide grains used in the present invention is not larger than 0.4 μm, preferably 0.35 μm.
m or less, more preferably 0.3 μm or less. This is because the smaller particles have higher covering power, so silver /
It is desirable in that the binder ratio can be reduced.

The size distribution of silver halide grains may be wide or narrow, but so-called monodisperse emulsions are better in terms of photographic characteristics such as latent image stability and pressure resistance and processing stability such as pH dependency of developing solution. preferable. The value S / d obtained by dividing the standard deviation S of the diameter distribution when the projected area of silver halide grains is converted into a circle by the average diameter is preferably 20% or less, more preferably 15% or less. The silver chloride, silver chlorobromide or silver chloroiodobromide emulsion used in the present invention is described in P.I. "The Chemistry and Physics of Photography" by Glafkides (Paul Montel,
1967), G. F. Duffin, "Chemistry of Photographic Emulsions" (Focal Press, 1966),
V. L. "Preparation and coating of photographic emulsions" by Zelikman et al. (Focal Press, 1964)
It can be prepared by applying the method described in et al.
That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, but the acidic method and the neutral method are particularly preferable in the present invention in terms of reducing fog. To obtain a silver halide emulsion by reacting a soluble silver salt with a soluble halogen salt, any one of so-called one-side mixing method, simultaneous mixing method or a combination thereof may be used. It is also possible to use a so-called reverse mixing method in which grains are formed under the condition of excess silver ions. In order to obtain the monodisperse grain emulsion preferred in the present invention, it is preferable to use the simultaneous mixing method. As one form of the simultaneous mixing method, it is more preferable to use a method of keeping the silver ion concentration in the liquid phase where silver halide is produced constant, that is, a so-called controlled double jet method. By using this method, it is possible to obtain a silver halide emulsion suitable for the present invention, which has a regular silver halide crystal shape and a narrow grain size distribution.

In the course of such grain formation or physical ripening of silver halide, a cadmium salt, a zinc salt, a lead salt, a thallium salt, or the above-mentioned iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt. Alternatively, its complex salt may coexist. During or after grain formation silver halide solvents (eg, as known, ammonia, thiocyanates, U.S. Pat. No. 3,271,1).
57, JP-A-51-12360, JP-A-53-82.
408, JP-A-53-144319, JP-A-54-
No. 100717 or thioethers and thione compounds described in JP-A No. 54-155828, etc. may be used. When used in combination with the above-mentioned method, the present invention has a regular silver halide crystal shape and a narrow grain size distribution. A preferable silver halide emulsion can be obtained.

In order to remove the soluble salt from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method or the like can be used. The emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc., alone or in combination. That is, a sulfur sensitization method using active gelatin or a compound containing a sulfur compound capable of reacting with silver ions (for example, thiosulfate, thiourea compound, mercapto compound, rhodanine compound, etc.) or a reducing substance (for example, stannous salt) , Amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, etc.), and metal compounds (such as the above-mentioned gold complex salts, platinum, iridium, palladium, rhodium, iron, etc.) Noble metal sensitization method using a metal salt or complex salt thereof, etc.) can be used alone or in combination. In the emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used, and gold sensitization is preferably used in combination with these. In addition, it is preferable that a hydroxyazaindene compound or a nucleic acid is present in the chemical sensitization in order to control sensitivity and gradation.

The sensitizing dye having a wavelength of 600 nm or more used in the present invention is disclosed in JP-A-3-11336 and JP-A-64-40939.
No. 2, Japanese Patent Application No. 2-266934, No. 3-121798.
Nos. 3,228,741, 3,266,959 and 3,311498 can be preferably used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.
A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Research Di
sclosure) 176, 17643 (issued in December 1978), page 23, IV, paragraph J, or the aforementioned Japanese Patent Publication No. 49-2.
5500, 43-4933, JP-A-59-1903.
2, 59-192242 and the like. The content of the sensitizing dye of 600 nm or more in the present invention is the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relation between the layer containing the compound and the silver halide emulsion, and the antifoggant compound. It is desirable to select the optimum amount according to the type and the like, and the test method is well known to those skilled in the art for the selection. Usually preferably silver halide 1
It is used in a range of 10 ⁻⁷ to 1 × 10 ⁻² mol, especially 10 ⁻⁶ to 5 × 10 ⁻³ mol per mol.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during production process of the light-sensitive material, presence thereof or photographic processing or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro. Benzotriazoles and the like; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4
-Hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes and the like; benzenethiosulfonic acid, benzenesulfinic acid; known as antifoggants or stabilizers such as benzenesulfonic acid amide Many compounds can be added. Among these, preferably benzotriazole (eg,
5-methyl-benzotriazole) and nitroindazoles (eg 5-nitroindazole). Further, these compounds may be contained in the treatment liquid. Further, a compound capable of releasing an inhibitor during development described in JP-A No. 62-30243 may be contained for the purpose of a stabilizer.

The photographic light-sensitive material of the present invention may contain a developing agent such as a hydroquinone derivative or a phenidone derivative for various purposes such as a stabilizer and an accelerator. The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (1,3,3).
5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol and the like), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalogen acids (mucochloric acid) Etc.), etc. can be used alone or in combination.

The black and white photographic light-sensitive material produced by the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

As the support of the photographic light-sensitive material of the present invention,
It must have a thickness of 150-250 μm. This is essential from the viewpoint of handleability when observing on a medical Schaukasten. Further, the material is preferably a polyethylene terephthalate film, and particularly preferably colored blue. The support is preferably subjected to a corona discharge treatment, a glow discharge treatment, or an ultraviolet irradiation treatment for improving the adhesion to the hydrocolloid layer. Alternatively, an undercoat layer made of styrene butadiene-based latex, vinylidene chloride-based latex or the like may be provided, and a gelatin layer may be further provided on the undercoat layer. An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrocolloid layer can be further improved.

The total coating amount of gelatin on the silver halide emulsion layer side of the support of the present invention is preferably 3.5 g / m ² or less, more preferably 3.3 g / m ² or less,
Further, 3.0 g / m ² is preferable. The coated Ag amount per one side of the silver halide emulsion of the present invention is 2.6 g / m ^2.
Or less, preferably 2.3 g / m ² or less, and more preferably 2.0 g / m ² or less. Further, the weight ratio of silver to gelatin in the silver halide emulsion layer is also an important factor from the viewpoint of suitability for rapid processing. Increasing the ratio of silver and gelatin in the silver halide emulsion layer, when processed by an automatic processor,
The above-mentioned emulsion pick-off occurs in which the silver halide photographic light-sensitive material is peeled off by the protrusions of the roller and the image becomes difficult to see. From this viewpoint, the weight ratio of silver to gelatin in the silver halide emulsion layer is preferably 1.4 or less, more preferably 1.2 or less, and further preferably 1.1 or less.

As various additives and the like used in the photographic light-sensitive material of the present invention, those described in the following relevant parts can be used.

Item 1) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16, Japanese Patent Application No. 3-105035.

2) Antifoggant, Stabilization JP-A-2-68539, page 10, lower left column, line 17 to agent, page 11 upper left column, line 7 and page 3, lower left column, line 2 to fourth Lower left column of the page.

3) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94249, page 6, lower left column, line 15 From page 11, page 11, upper right column, line 19

4) Surfactants and Antistatics JP-A-2-68539, page 11, upper left column, line 14 From inhibitor to page 12, upper left column, line 9

5) Matting agent, slipping agent, JP-A-2-68539, page 12, upper left column, line 10 From plasticizer, same upper right column, line 10; page 14, lower left column, line 10 to lower right column First line.

6) Hydrophilic Colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16

7) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6

8) Polyhydroxy ester JP-A-3-39948, page 11, upper left column to the same, genus, page 12, lower left column, EP Patent No. 452772A.

9) Layer Structure JP-A-3-198041.

The developing agent preferably used in the developing solution of the present invention is a dihydroxybenzene type developing agent. As the dihydroxybenzene type developing agent, hydroquinone,
Chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3
-Dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone hydroquinone monosulfonic acid, etc., but hydroquinone is particularly preferable. The developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. Particularly in the present invention, 1-phenyl-3 is used together with the above-mentioned dihydroxybenzene type developing agent.
-Pyrazolidones or p-aminophenols are preferably used in combination.

Examples of 1-phenyl-3-pyrazolidones include 1-phenyl-3-pyrazolidone and 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Examples include pyrazolidone and 1-phenyl-5-methyl-3-pyrazolidone. As p-aminophenols,
There are N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like. However, among them, N-methyl-p-aminophenol is preferable.

When a dihydroxybenzene type developing agent and an auxiliary developing agent such as 1-phenyl-3-pyrazolidone or p-aminophenol are used in combination, the former is 0.05 mol / liter to 0.5 mol / Liter, the latter 0.001 to 0.06 mol / liter (especially 0.0
It is preferably used in an amount of 03-0.06 mol / liter).

As the sulfite, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite,
Examples include sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably 0.10 mol / liter or more, particularly preferably 0.20 mol / liter or more. The upper limit is preferably 2.5 mol / liter, particularly preferably 1.2 mol / liter.
The developer used in the present invention may contain an amino compound for promoting development. In particular, JP-A-56-106244
No. 6-267759, Japanese Patent Application No. 1-2941
The amino compound described in No. 8 may be used.

The pH value of the developer used in the present invention is 9.
It is 8 or less. As the alkali agent used for setting the pH value, a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, sodium carbonate) can be used. In addition to the above, the developing replenisher of the present invention may further include a pH buffering agent such as boric acid, borax, sodium diphosphate, potassium diphosphate, sodium monophosphate and potassium monophosphate. The pH buffering agents described in 60-93433 can be used; development inhibitors such as potassium bromide and potassium iodide; dimethylformamide, methyl cellosolve,
Organic solvents such as hexylene glycol, ethanol and methanol; 5-methylbenztriazol, 5-bromobenztriazole as benztriazole derivatives,
There are 5-chlorobenztriazole, 5-butylbenztriazole, benztriazole and the like, and 5-methylbenztriazole is particularly preferable as nitroindazole, 5 nitroindazole, 6 nitroindazole,
There are 4 nitroindazole, 7 nitroindazole, 3 cyano-5-nitroindazole and the like, but 5-nitroindazole is particularly preferable. Particularly when a compound such as 5-nitroindazole is used, it is dissolved in advance in a part different from the part containing the dihydroxybenzene type developing agent or the sulfite preservative, and both parts are mixed and water is added at the time of use. Is common. Further, if the portion of 5-nitroindazole to be dissolved is made alkaline, it is colored yellow, which is convenient for handling. Furthermore, if necessary, toning agent,
A surfactant, a water softener, a hardener, etc. may be included.

Examples of the chelating agent in the developing solution include the following compounds. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropane tetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2 Phosphonobutane -
1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,3,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate,
Examples thereof include sodium tetrapolyphosphate and sodium hexametaphosphate, and particularly preferable examples include diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and 1,3.
-Diaminopropanol tetraacetic acid, glycol ether diamine tetraacetic acid, hydroxyethylethylenediamine triacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphone Acid, diethylenetriaminepentaphosphonic acid,
1-hydroxypropylidene-1,1-diphosphonic acid,
There are 1-aminoethylidene-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

In the developer of the present invention, for the purpose of silver stain, JP-B-62-4702, JP-B-62-4703, JP-A-63-24123, JP-A-3-94955, and JP-A-3-94955.
The compounds described in 112275 and Japanese Patent Application No. 3-233718 can be used.

In addition, the developer of the present invention may contain a dialdehyde hardener or a bisulfite adduct thereof. Specific examples thereof include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α. Examples include -n-butoxyglutaraldehyde, α, α-dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaleindialdehyde, and bisulfite adducts thereof. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed cannot be suppressed and that the drying time is not significantly lengthened. Specifically, 1 to 50 g, preferably 3 to 1 per liter of the developing solution.
It is 0 g. Of these, glutaraldehyde or its bisulfite adduct is most commonly used.

Of course, when a bisulfite adduct of a dialdehyde hardener is used, the bisulfite of this adduct is also calculated as the sulfite in the developer. In addition, L.
F. A. Mason, "Photographic Processing Chemistry," published by Focal Press (1966)
226-229, U.S. Pat. No. 2,193,01
5, No. 2,592,364, JP-A-48-649.
You may use the additive as described in No. 33.

In the present invention, the developing process is carried out while replenishing the above-mentioned developing solution in an amount of 150 ml or less, particularly 50 ml to 150 ml per 1 m ² of the light-sensitive material. As the developing solution to be injected into the developing tank of the developing machine at the beginning of development, a solution having the same composition as the above developing solution may be used, or a solution having a part of the composition changed may be used.

The fixer used in the present invention is an aqueous solution containing thiosulfate, and has a pH of 3.8 or higher, preferably 4.2 to 4.2.
Has 6.0. Sodium thiosulfate as a fixing agent,
Examples include ammonium thiosulfate. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 3 mol / liter. The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and they include, for example, aluminum chloride, aluminum sulfate and potassium alum.

For the fixing solution, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per 1 liter of the fixing solution, and particularly, it is preferable that the content of the compound is 0.005.
01 mol / liter to 0.03 mol / liter is particularly effective.

Preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having a water softening ability may be included in the fixing solution, if desired. And compounds described in JP-A-62-78551. In the processing method of the present invention,
After the development and fixing steps, the film is treated with washing water or a stabilizing solution and then dried.

As the automatic developing machine used in the present invention, various types such as a roller carrying type and a belt carrying type can be used, but a roller carrying type developing machine is preferable. Further, JP-A-1-166040 and Japanese Patent Application No. 63-18631.
By using the developing machine of the developing tank having a small opening ratio as described in No. 3, it is possible to perform stable operation in the processing environment with less air oxidation and evaporation and further reduce the replenishment amount. As a method of reducing the replenishment amount of washing water, a multi-stage countercurrent system (for example, two-stage, three-stage, etc.) has long been known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the clean direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed,
Further efficient water washing is performed. In the above water-saving treatment or pipe-less treatment, it is preferable to apply antifouling means to the washing water or the stabilizing solution.

As an anti-fungus means, Japanese Patent Laid-Open No. 60-263
UV irradiation method described in No. 939, 60-26394
Method using magnetic field described in No. 0, Ibid.
A method for producing pure water using an ion exchange resin described in JP-A No. 61-115154 and JP-A No. 62-15395.
No. 2, Japanese Patent Application Nos. 61-63030 and 61-51396.
It is possible to use the method using the antibacterial agent described in No.
Furthermore, LFWest, “Water Quality Criteria” Phot
o.Sci. & Eng.Vol.9 No.6 (1965), MWBeach, "W
icrobiological Growths in Motion-picture Processin
g "SMPTE Journal Vol.85, (1976), RD Deega
n, “Phot Processing Wash Water Biocides“ J.Imagi
ng Tech 10, No. 6 (1984) and JP-A-57-
No. 8542, No. 57-58143, No. 58-1051
45, 57-132146, 58-18631.
No. 57-97530, No. 57-157244, etc., antibacterial agents, antifungal agents, surfactants and the like can also be used in combination.

Further, the washing bath or stabilizing bath should be RT
Kreiman, J. Image.Tech 10, (6) 242 (198).
4) isothiazoline compounds described in Research
Disclosure Vol. 205, No. 20526 (May, 1981), isothiazoline compounds, No. 2
28, No. 22845 (April 1983), isothiazoline compounds, Japanese Patent Application No. 61-51396.
It is also possible to use the compounds described in the above item as a bacteriostatic agent (Microbiocide). Others, "The Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Sankyo Publishing (Showa 57), "Handbook of Antibacterial and Antifungal Technology" Japan Antibacterial and Antifungal Society, Hakuhodo (Showa 61)
May include compounds such as those described in.

When washing with a small amount of washing water in the method of the present invention, it is more preferable to provide a squeeze roller washing tank described in JP-A-63-18350. Also,
It is preferable to adopt the constitution of the water washing step as disclosed in JP-A-63-143548. Further, some or all of the overflow from the washing or stabilizing bath caused by supplementing the washing or stabilizing bath with anti-fouling water according to the method of the present invention is disclosed in JP-A-60-23513.
As described in No. 3, it can also be used for a processing solution having a fixing ability which is a processing step before that.

In the present invention, the "development process time" or "development time" means the time from the dipping of the tip of the photosensitive material to be processed in the developing tank solution of the developing machine to the dipping of the next fixing solution. "Fixing time" is the time from immersion in the fixing tank liquid to immersion in the next washing tank liquid (stabilizing liquid),
"Washing time" means the time of immersion in the washing tank liquid. In addition, "drying time" is usually 35 ° C to
A drying zone in which hot air of 100 ° C., preferably 40 ° C. to 80 ° C. is blown is installed, and it means the time during which the drying zone is entered. In the development processing of the present invention,
The developing time is 5 seconds to 1 minute, preferably 8 seconds to 30 seconds, and the developing temperature is preferably 18 ° C to 50 ° C, more preferably 20 ° C to 40 ° C.

According to the present invention, the fixing temperature and time are about 1
5 seconds to 1 minute at 8 ° C to about 50 ° C is preferable, and 20 ° C to 40 ° C.
More preferably, the temperature is 6 seconds to 30 seconds. Within this range, sufficient fixing can be performed and the sensitizing dye can be eluted to the extent that residual color is not generated. The temperature and time for washing with water (or stabilizing bath) are preferably 0 to 50 ° C and 6 seconds to 1 minute, and 15 ° C.
More preferably at -40 ° C for 6 seconds to 30 seconds.

According to the method of the present invention, the light-sensitive material which has been developed, fixed and washed (or stabilized) is squeezed out of washing water, that is, dried through a squeeze roller. The drying is carried out at about 40 ° C. to about 100 ° C., and the drying time may be appropriately changed depending on the ambient conditions, but it is usually about 5 seconds to 1 minute, and particularly preferably 40 to 80 ° C. for about 5 seconds to 30 minutes.
Seconds. Dry to Dry with the sensitive material / processing system of the present invention
In order to prevent development unevenness peculiar to rapid processing when developing is carried out for 100 seconds or less in JP-A-63-15194.
A roller made of a rubber material as described in Japanese Unexamined Patent Application Publication No. 3-3200 is applied to the roller at the outlet of the developing tank,
As described in JP-A-3-151944, the discharge flow rate for stirring the developing solution in the developing solution tank is set to 10 m / min or more, and further, JP-A-63-264758.
As described in the publication, it is more preferable to stir more strongly than during standby at least during the developing process. For more rapid processing, it is more preferable that the rollers of the fixing solution tank are opposed rollers in order to increase the fixing speed. By configuring with opposed rollers, it is possible to reduce the number of rollers and the processing tank. That is, the automatic processing machine can be made more compact.

[0053]

EXAMPLES Examples will be shown below, but the present invention is not limited to these examples.

Example 1 1. Preparation of silver halide emulsion A 32 g of gelatin was added to 900 ml of distilled water and the mixture was added at 40 ° C.
After dissolution, adjust the pH to 3.8 with sulfuric acid and add sodium chloride.
3.3 g was added. 32 g of silver nitrate in 200 ml of distilled water
Dissolved liquid and sodium chloride 11g, K₂IrCl₆To 0.0
2mg dissolved in 200ml and 2 minutes under the condition of 40 ℃
In the meantime, the above liquid was added and mixed. Distill 64g of silver nitrate
A solution dissolved in 280 ml of water and 21.6 g of sodium chloride
The solution dissolved in 275 ml is applied at 40 ° C for 5 minutes.
Were added and mixed. Subsequently, 64 g of silver nitrate was added to distilled water 28
Liquid dissolved in 0 ml and sodium chloride 22.4 g, K_FourFe (C
N) ₆・ 3H₂A solution of 0.04 g of O 2 dissolved in 285 ml
The mixture was added and mixed at 40 ° C. for another 5 minutes. Profit
When the obtained emulsion was observed with an electron microscope, it was about 0.2.
As an average side length of 1 μm and coefficient of variation of particle size distribution
An emulsion consisting of cubic grains having a value of 9.8%
It was Preparation of silver halide emulsions B, C and D Sodium chloride when forming emulsion of silver halide emulsion A
Sodium chloride and potassium bromide to adjust the amount appropriately
And the halogen composition shown in Table 1 by changing the grain formation temperature.
An emulsion of was obtained.

[0055]

[Table 1]

After desalting these emulsions, gelatin 72
g, 2.6 g of phenoxyethanol, and pH of 6.
7. Chemical sensitization was carried out at 58 ° C. according to the following procedure according to pAg of 7.9 with NaCl. First, average particle size 0.05
A monodisperse silver bromide emulsion having a thickness of 1 μm was added in an amount of 1 mol% with silver halide, and then 7.2 mg of the compound (1) and 9.2 m of chloroauric acid were added.
g, triethylthiourea 1.3 mg, selenium sensitizer (A)
Add 0.72 mg and 0.29 g of nucleic acid, and finally add 4
162 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added and rapidly solidified to give Emulsions A, B, C and D, respectively.

Compound (1)

[0058]

[Chemical 1]

Selenium sensitizer (A)

[0060]

[Chemical 2]

2. Preparation of Emulsion Coating Solution The following chemicals were added to Emulsion A per mol of silver halide to prepare an emulsion coating solution.

(Formulation of emulsion coating solution)

B. Spectral sensitizing dye [2] 5.5 × 10 ⁻⁵ mol. Supersensitizer [3] 3.3 × 10 ⁻⁴ mol c. Polyacrylamide (molecular weight 40,000) 9.2 g d. Trimethylolpropane 1.4 g e. Poly (ethyl acrylate / methacrylic acid) latex 22g Spectral sensitizing dye [2]

[0064]

[Chemical 3]

Supersensitizer [3]

[0066]

[Chemical 4]

3. Preparation of Coating Solution for Surface Protecting Layer of Emulsion Layer The container was heated to 40 ° C., and the following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12.3 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 2.7 g e. Sodium polyacrylate 3.7 g f. t-octylphenoxyethoxyethanesulfonic acid sodium salt 1.5 g. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.3 g h. C ₈ F ₁₇ SO ₃ K 84 mg li. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 84mg j. NaOH 0.2 g ru. Methanol 78cc. 1,2-Bis (vinylsulfonylacetamide) ethane Prepared to be 2.5% by weight based on the total gelatin amount in the emulsion layer and the surface protective layer. Wa. Compound (5) 52mg

[0068]

[Chemical 5]

4. Preparation of back layer coating liquid

The container was heated to 40 ° C. and the following chemicals were added to prepare a back layer coating solution. I. Gelatin amount 100 g b. Dye (A) 2.38g

[0071]

[Chemical 6]

C. Sodium polystyrene sulfonate 1.1 g d. Phosphoric acid 0.55 g E. Poly (ethyl acrylate / methacrylic acid) latex 2.9 g f. Compound (5) 46mg

G. Oil dispersion of dye (B) described in JP-A-61-285445 246 mg as dye itself Dye (B)

[0074]

[Chemical 7]

H. Dye (C) oligomer described in JP-A-62-275639 Surfactant dispersion 46 mg as dye itself Dye (C)

[0076]

[Chemical 8]

5. Preparation of back surface protective layer coating liquid

The container was heated to 40 ° C., and the chemicals shown below were added to prepare a coating solution.

B. Gelatin 100 g b. Sodium polystyrene sulfonate 0.3 g c. Polymethylmethacrylate fine particles (average particle size 3.5 μm) 4.3 g d. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g e. Sodium polyacrylate 1.7 g f. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.6 g g. C ₈ F ₁₇ SO ₃ K 268 mg Chi. C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) _4- SO ₃ Na 45 mg. NaOH 0.3 g Nu. 131 ml of methanol 1,2-Bis (vinylsulfonylacetamide) Prepared to be 2.2% of the total gelatin amount in the ethane back layer and surface protective layer. Wo. Compound (5) 45mg

6. Preparation of Photographic Material The coating solution for the back layer together with the coating solution for the surface protective layer for the back layer was coated on one side of a polyethylene terephthalate support colored in blue, and the gelatin coating amount for the back layer was 2.6.
The coating amount was 9 g / m ² , and the coating amount of the back surface protective layer was 1.13 g / m ² . Followed by the opposite side of the support and the emulsion coating solution and surface protective layer coating solution described above which, and the gelatin coating amount of the emulsion layer coating amount Ag is 1.85 g / m ² is at 1.6 g / m ² The surface protective layer was coated such that the coating amount of gelatin was 1.23 g / m ² . Thus, a photographic material was prepared.

Developer A Hydroquinone 20.0 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g Sodium sulfite 35.0 g Sodium carbonate (monohydrate) 25.0 g Diethylenetriaminepentaacetic acid 2.0 g Diethylene glycol 20.0 g Boric acid 9.0 g Potassium bromide 0.6 g (0.005 mol) Potassium hydroxide 2.0 g Water is added to adjust to 1 liter pH = 9.50.

Developer B Developer A A obtained by adding 0.20 g of 5-methylbenztriazole to 1 liter of developer A.

Developer C A developer A containing 0.15 g of 5-nitroindazole per 1 liter of developer A.

Developer D Developer A A 0.11 g of 5-methylbenztriazolyl and 2-mercaptoimidazole-5 per liter of developer A
-0.10 g of sulfonic acid and 2,3,5,6,7,
Added with 0.10 g of 8-hexahydro-2-thioxo-4- (1H) -quinazolinone.

Developer E A solution obtained by replacing 25.0 g of sodium carbonate (monohydrate) in Developer D with 27.8 g of equimolar potassium carbonate.

Developer F A pH of 10.5 was obtained by adding sodium hydroxide to 1 liter of developer A. As a fixer formulation, sodium thiosulfate 158 g (1.0 mol) sodium bisulfite 30 g ethylenediaminetetraacetic acid disodium dihydrate 0.025 g diethylene glycol 40.0 g water is added and the pH is adjusted to 5.50 with 1 liter sodium hydroxide.

As the automatic processor, the washing tank of FPM2000 manufactured by Fuji Photo Film Co., Ltd. was remodeled into three tanks, and the three-stage countercurrent method, which has been known for a long time, was used. The wash water that was supplied to the water wash tank and overflowed was sequentially replenished to the front water wash tank. Further, the drive shaft of the automatic machine was modified so that the conveying speed was 45 seconds from the film insertion to the drying outlet. As washing water, water containing 0.2 g of disodium ethylenediaminetetraacetic acid dihydrate and 0.04 g of glutaraldehyde per 1 liter of water was used. The film is processed for 4 m ² every day, and each developer, fixer and wash water are 400
A running test was performed for 3 weeks while supplementing each with 100 ml (100 ml / m ² ). The obtained results are shown in Table 2. Here, the sensitivity is a relative value with the reciprocal of the exposure amount that gives an optical density of fogging plus 1.0 in the new developer A as 100, and the fogging is an optical density including the support in the unexposed area.

[0088]

[Table 2]

The fixing loss was evaluated on a 5-point scale. 5
Indicates that there is no residual silver, and 4 indicates that when immersed in a sodium sulfide solution, it develops color as silver sulfide, and there is some residual silver, but practically acceptable one is 3 where slight residual silver is visually observed. Levels 2 and 1, which are practically unacceptable, indicate that the state of sequentially missing fixing is poor.

As is clear from the results of Table 2, the developer A,
With B, C, D, and E, the sensitivity was stable even after 3 weeks, and such results were obtained even with a small replenishing amount of 100 ml per m ² . Conventionally, a developer F having a pH of 10.50 was used with a replenishing amount of 650 ml per 1 m ² , and it can be stably used with little change in photographic properties even after running for 3 weeks. The effect of the present invention is 10 per 1 m ^2.
This is a remarkable advance because it enables stable use for a long period of time with a small replenisher volume of 0 ml without any change in sensitivity. Regarding the fixing loss, the emulsions A and B of the present invention had good fixing loss also in the running solution after 3 weeks, provided that Comparative Developer E in which sodium ion in all cations in the developing solution was 56% In three weeks after running, the developing solution is brought into the fixing solution by the film processing, so that the extent of the fixing loss becomes large.

Example 2 The developing solution formulation, washing water formulation, automatic developing machine humidity time, and emulsion were all set under the same conditions as in Example 1, and only the fixing solution formulation was prepared as follows. Fixer formulation sodium thiosulfate 118.5 g (0.75 mol) sodium bisulfite 30.0 g ethylenediaminetetraacetic acid disodium dihydrate 0.025 g diethylene glycol 40.0 g water added to 1 liter to pH 5.50 with sodium hydroxide Can match. The results obtained are shown in Table 3. The sensitivity and the fog are the same as those in Table 2 of Example 1, but the fixing loss is the emulsion A of the present invention,
Regarding B, the running solution after 3 weeks had an acceptable level for practical use, but in the case of the comparative developer E in which 56% of sodium ions in all cations in the developing solution were used, the fixing loss was deteriorated after 3 weeks of running. The degree is increasing.

[0092]

[Table 3]

[0093]

According to the present invention, the replenishing amount of the processing solution per unit processing area of the light-sensitive material can be reduced.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 26, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction content]

A preferred example of such a localized structure is one having a localized phase on the surface of the silver halide grain or in the interior close to the surface, and particularly in the edge portion or corner portion of the crystal surface of the grain, or the crystal plane. Those having a localized phase in the form of protrusions are preferable. The halogen composition in the localized phase may have a silver bromide content of 10 mol% or more and 95 mol% or less.
It is preferably in the range of mol% to 90 mol%. Further, it is preferably 20 mol% or more and 60 mol% or less, and most preferably 30 mol% or more and 60 mol% or less. The remaining silver halide in the localized phase consists of silver chloride, but it is also preferred to include traces of silver iodide. However, as described above, it is not preferable to exceed 1 mol% with respect to the total amount of silver halide. Further, these localized phases preferably account for 0.03 mol% or more and 10 mol% or less, more preferably 0.1 mol% or more and 10 mol% or less of the silver halide constituting all the silver halide grains of the emulsion. It is preferable to occupy mol% or less.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

The sensitizing dye used in the present invention is disclosed in JP-A-3-11.
336, JP-A-64-40939, Japanese Patent Application No. 2-26
No. 6934, No. 3-121798, No. 3-22874
No. 1, No. 3-266959 and No. 3-311498.
The sensitizing dyes having a wavelength of 600 nm or more described in JP-A No. 1989-242 can be preferably used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure.
sure) 176, 17643 (issued in December 1978), page 23, item IV, J, or the aforementioned Japanese Examined Patent Publication No. 49-2550.
0, 43-4933, JP-A-59-19032, 5
9-192242 and the like. The content of the sensitizing dye of 600 nm or more preferably used in the present invention is the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion, and the fog. It is desirable to select the optimum amount depending on the kind of the preventive compound, and the test method is well known to those skilled in the art for the selection. Usually, it is preferably used in the range of 10 ^-7 to 1 × 10 ^-2 mol, particularly 10 ^-6 to 5 × 10 ^-3 mol per mol of silver halide.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

As the automatic developing machine used in the present invention, various types such as a roller carrying type and a belt carrying type can be used, but a roller carrying type automatic developing machine is preferable. Further, JP-A-1-166040 and Japanese Patent Application No. 63-18631.
By using the developing machine of the developing tank having a small opening ratio as described in No. 3, it is possible to perform stable operation in the processing environment with less air oxidation and evaporation and further reduce the replenishment amount. As a method of reducing the replenishment amount of washing water, a multi-stage countercurrent system (for example, two-stage, three-stage, etc.) has long been known. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in the clean direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed,
Further efficient water washing is performed. In the above water-saving treatment or pipe-less treatment, it is preferable to apply antifouling means to the washing water or the stabilizing solution.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

Developer D Developer A A 0.11 g of 5-methylbenztriazole and 2-mercaptoimidazole-5 per 1 liter of developer A
-0.10 g of sulfonic acid and 2,3,5,6,7,
Added with 0.10 g of 8-hexahydro-2-thioxo-4- (1H) -quinazolinone.

Claims (3)

[Claims] 1. A method of processing a transmission type black-and-white silver halide photographic light-sensitive material with an automatic processor, wherein sodium cations account for 70 mol% or more of all cations in the developer.
The following developer has an average particle size of 0.1 to 0.4 μm,
A silver halide photograph having a composition of silver chlorobromide or silver chloroiodide or silver chloroiodobromide having a (100) face / (111) face ratio of 5 or more and a silver chloride content of 90 mol% or more. A processing method characterized in that, when processing a light-sensitive material, a replenisher for a developing solution and a fixing solution is replenished at a ratio of 150 ml or less per 1 m ^{2 of a} silver halide photographic light-sensitive material. 2. The processing method according to claim 1, wherein the developer contains a benztriazole derivative and / or nitroindazole. 3. The processing method according to claim 1, wherein the fixing solution contains at least 0.8 mol / liter of thiosulfate ion.