JP2824715B2 - Processing method of black and white silver halide photographic material - Google Patents

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 developing machine, wherein the replenishment of a developing solution and a fixing solution per unit area of the light-sensitive material can be reduced. 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 after exposure by the steps of developing, fixing, washing and drying. Recently, most of them are processed using an automatic developing machine (hereinafter abbreviated as an automatic developing machine). At this time, the developing process is usually performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photosensitive material. It has been desired that stable photographic performance can be obtained when such development processing is performed. Further, it has been desired to obtain stable photographic performance and stable fixing by reducing the amount of replenisher per unit area. Conventionally, a developing replenisher and a fixing replenisher are used in an amount of 250 ml or more, especially 3 m ^2, for 1 m ² of a so-called sheet-like photographic material such as X-ray photograph or graphic arts photographic material.
It was common to supplement more than 30 ml. However, photographic waste and fixing wastes have high chemical oxygen demands (so-called COD) or biological demands (so-called BOO).
D), the development waste solution and the fixing waste solution are subjected to chemical or biological treatment or the like to render them harmless, and then the waste solution is discharged. Since a great economic burden is imposed on the treatment of these waste liquids, a processing method with a small amount of a developing replenisher and a small amount of a fixing replenisher has been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a processing method for processing a transmission type black-and-white silver halide photographic light-sensitive material using an automatic developing machine, in which the amount of a developing replenisher and the amount of a fixing replenisher per unit processing area are small. Is to provide. Another object of the present invention is to provide a processing method capable of obtaining a stable photographic characteristic even if the amounts of the developing replenisher and the fixing replenisher are small.

[0004]

According to the present invention, in a method for processing a transmission-type black-and-white silver halide photographic material in an automatic processor, 70 mol% or more of all cations in a developing solution are sodium ions and a pH of 9.8. The following developer has an average particle size of 0.1 to 0.4 μm, a (100) face / (111) face ratio of 5 or more, and a silver chloride content of 90 mol% or more per m ² of a photosensitive material. The replenishment of the developing solution and the fixing solution at a rate of 150 ml or less was achieved by the feature and processing method. More preferably, the developer contains a benztriazole derivative and / or a nitroindazole compound. More preferably, the fixer contains at least 0.8 mol / liter of thiosulfate ions.

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).
Silver chlorobromide, silver iodochloride, silver iodochlorobromide or silver chloride. The silver iodide content is preferably at most 1 mol%. 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 silver bromide content is relatively higher than that of a substrate in silver halide grains.

A preferred example of such a localized structure is one having a localized phase on or near the surface of a silver halide grain, and particularly in an edge portion, a corner portion, or a crystal face of the crystal surface of the grain. Those having a localized phase in the form of projections are preferred. The halogen composition in the localized phase may be from 10 mol% to 95 mol% in terms of silver bromide content.
It is preferable that the content is not less than mol% and not more than 90 mol%. Further, it is preferably from 20 mol% to 60 mol%, and most preferably from 30 mol% to 60 mol%. The remaining silver halide in the localized phase consists of silver chloride, but preferably also contains traces of silver iodide. However, as described above, it is not preferable that the amount exceeds 1 mol% based on the total amount of silver halide. Further, these localized phases preferably account for 0.03 mol% or more and 10 mol% or less, and more preferably 0.1 mol% or more and 10 mol% or less of the silver halide constituting all silver halide grains of the emulsion. Preferably, it accounts for less than mol%.

The localized phase does not need to be composed of a single halogen composition, and may have two or more localized phases having distinctly different silver bromide contents, and may have other than the localized phase. It may be one in which the interface with the phase is formed while continuously changing in the halogen composition. In order to form the above-described silver bromide localized phase, 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. And convert a portion of the silver chloride or high silver chloride grains that have already been formed into a silver bromide-rich phase using a so-called halogen conversion method, or silver chloride or high silver chloride grains. It can also be formed by adding fine particles of silver bromide or silver bromide, or other hardly soluble silver salts, and crystallizing the surface of silver chloride or silver chloride particles 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 an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis”, Maruzen) or an XPS method (for example, “Surface Analysis,-
IMA, Application of Auger electron and photoelectron spectroscopy-"Kodansha,
) Can be analyzed. Further, the localized phase of silver bromide can be known by observation with an electron microscope or the method described in the aforementioned European Patent Application Publication No. 0,273,430A2.

Among such methods, a method of forming a 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. This is preferable in that high sensitivity and low fog can be obtained.

In the silver halide grains used in the present invention, metal ions other than silver ions (for example, a metal ion of Group VIII, a transition metal ion of Group II, a lead ion of Group IV, a Group I ion) Metal ions, copper ions, etc.) or complex ions thereof are preferred in order to better exhibit the effects of the present invention under various conditions. These metal ions or complex ions thereof may be contained in the whole silver halide grains, in the above-mentioned silver bromide localized phase, or in other phases. Among the above-mentioned metal ions or their complex ions, 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 together with the desired photographic properties rather than used alone, especially by changing the type and amount of added ions between the localized phase and other parts of the particles. Is preferred. In particular, it is preferable that iridium ions and rhodium ions are contained in the localized phase.

In order for the metal ions or complex ions to be contained in the localized phase of the silver halide grains and / or in other parts of the grains, the metal ions or complex ions are added before, during or during the formation of the silver halide grains. It may be added directly to the reaction vessel during the subsequent physical ripening, or may be added in advance to a solution containing a water-soluble halogen salt or a water-soluble silver salt. When the localized phase is formed of fine grains of silver bromide or high silver chloride, it is contained in the fine grains of silver bromide or high silver chloride in the same manner as described above, and the silver halide or high silver chloride emulsion is prepared. May be added. In addition, a metal ion may be contained while forming a localized phase by adding a relatively insoluble bromide of the above-mentioned metal ion other than a silver salt 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, more preferably
It is preferable that the content be 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, more preferably 0.3 μm or less. This is because the smaller the particles, the higher the covering power can be obtained.
This is desirable in that the binder ratio can be reduced.

Although the size distribution of the silver halide grains may be wide or narrow, the so-called monodisperse emulsion is better in photographic characteristics such as latent image stability and pressure resistance and processing stability such as developer pH dependency. preferable. The value S / d obtained by dividing the standard deviation S of the diameter distribution when the projected area of the 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 preferably a P.I. Glafkides, "Chemistry and Physics of Photography" (Paul Montell,
1967); F. "The Chemistry of Photographic Emulsions" by Duffin (Focal Press, 1966),
V. L. "Preparation and coating of photographic emulsions" by Zelikman et al. (Focal Press, 1964)
Can be prepared by applying the method described in the above.
That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, but an acidic method and a neutral method are particularly preferable in the present invention in terms of reducing fog. In order to obtain a silver halide emulsion by reacting a soluble silver salt and a soluble halogen salt, any of a so-called single-side mixing method, a double-side mixing method, and a combination thereof may be used. A so-called back-mixing method in which grains are formed under conditions of excess silver ions can also be used. In order to obtain an emulsion of monodisperse grains which is preferable for the present invention, it is preferable to use a double jet method. As one form of the double jet method, it is more preferable to use a method of maintaining a constant silver ion concentration in a liquid phase in which silver halide is formed, 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 having a regular silver halide crystal shape and a narrow grain size distribution.

In the course of such silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, or an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt as described above. Alternatively, a complex salt thereof may coexist. During or after grain formation, a silver halide solvent (for example, ammonia, thiocyanate, U.S. Pat.
No. 57, JP-A-51-12360, JP-A-53-82
408, JP-A-53-144319 and JP-A-54-143319.
Thioethers and thione compounds described in JP-A-100717 or JP-A-54-155828, etc., and when used in combination with the above-mentioned method, the silver halide crystals of the present invention have a regular shape and a narrow grain size distribution. A preferred silver halide emulsion can be obtained.

To remove the soluble salt from the emulsion after physical ripening, it is possible to use Nudel washing, flocculation sedimentation method, ultrafiltration method or the like. 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 (eg, thiosulfate, thiourea compound, mercapto compound, rhodanine compound, etc.), a reducing substance (eg, stannous salt) Sensitization using amines, amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, etc .; and metal compounds (for example, the above-mentioned gold complex salts, platinum, iridium, palladium, rhodium, iron, etc., periodic table group VIII) , Or a complex salt thereof) can be used alone or in combination. In the emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used, and it is preferable to use gold sensitization in combination with these sensitizations. In addition, in the case of these chemical sensitizations, the presence of a hydroxyazaindene compound or a nucleic acid is preferable for controlling sensitivity and gradation.

The sensitizing dye used in the present invention is described in JP-A-3-11.
336, JP-A-64-40939, and Japanese Patent Application No. 2-26.
No. 6934, No. 3-121798, No. 3-22874
Nos. 1, 3-266959 and 3-31498
And the like. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Research Disclosure).
sure) 176, 17643 (issued in December 1978), page 23, IV, J, or the aforementioned Japanese Patent Publication No. 49-2550
0, 43-4933, JP-A-59-19032, 5
9-192242. The content of the sensitizing dye having a diameter of 600 nm or more preferably used in the present invention includes 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 an optimal amount according to the type of the inhibitory compound and the like, and a test method for the selection is well known to those skilled in the art. Usually, it is preferably used in an amount of from 10 ^-7 to 1 × 10 ^-2 mol, particularly from 10 ^-6 to 5 × 10 ^-3 mol, per mol of silver halide.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during its existence or during photographic processing, or for stabilizing photographic performance. Azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitro Benzotriazoles, etc .; 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 benzenesulfonamide; Many compounds can be added. Among these, preferably benzotriazole (for example,
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 the development described in JP-A-62-30243 can be contained for the purpose of a stabilizer.

The photographic light-sensitive material of the present invention can 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 (chrome 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, etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid) And the like can be used alone or in combination.

The black-and-white photographic light-sensitive material prepared according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye 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. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

As the support of the photographic light-sensitive material of the present invention,
It is necessary to have a thickness of 150 to 250 μm. This is indispensable from the viewpoint of handleability when observing on a medical shakasten. The material is preferably a polyethylene terephthalate film, particularly preferably colored blue. The surface of the support is preferably subjected to a corona discharge treatment, a glow discharge treatment, or an ultraviolet irradiation treatment in order to improve the adhesion to the hydrocolloid layer. Alternatively, an undercoat layer made of styrene-butadiene latex, vinylidene chloride latex or the like may be provided, and a gelatin layer may be further provided thereon. Further, 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 to the hydrocolloid layer can be further improved.

The total coating amount of gelatin on the silver halide emulsion layer side with respect to 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, it is preferably 3.0 g / m ² . Further, the amount of coated Ag per side of the silver halide emulsion of the present invention was 2.6 g / m ^2.
Or less, preferably 2.3 g / m ² or less, 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 rapid processing suitability. When the ratio of silver and gelatin in the silver halide emulsion layer is increased, when processed with an automatic processor,
The above-described emulsion pick-off occurs in that the silver halide photographic light-sensitive material is peeled off by the projections of the roller, making the image 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 for various additives used in the photographic light-sensitive material of the present invention, those described in the following applicable places can be used.

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

2) Antifoggant, stable JP-A-2-68539, page 10, lower left column, line 17 to the same, page 11 upper left column, line 7 and page 3, lower left column, second line to line 4, The lower left column of the page.

3) Color tone improver JP-A-62-276439, 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 the eye on page 11, line 19 in the upper right column.

4) Surfactant, antistatic From page 11, upper left column, line 14 of JP-A-2-68539 from the stopping agent to page 12, upper left column, line 9;

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

6) Hydrophilic colloid From page 11, upper right column, line 11 to lower left column, line 16 of JP-A-2-68539.

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

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

9) Layer Configuration JP-A-3-19841.

The developing agent preferably used in the developing solution of the present invention is a dihydroxybenzene developing agent. Hydroquinone, dihydroxybenzene-based developing agents
Chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3
-Dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone hydroquinone monosulfonic acid, etc., with hydroquinone being particularly preferred. The developing agent is preferably used in an amount of usually 0.05 mol / l to 0.8 mol / l. In the present invention, in particular, 1-phenyl-3 is used together with the above-mentioned dihydroxybenzene-based developing agent.
-It is preferred to use pyrazolidones or p-aminophenols in combination.

The 1-phenyl-3-pyrazolidones include 1-phenyl-3-pyrazolidone, 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone and the like. As p-aminophenols,
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-based developing agent is used in combination with an auxiliary developing agent such as 1-phenyl-3-pyrazolidone or p-aminophenol, the former is used in an amount of 0.05 mol / l to 0.5 mol / l. Liter, the latter being 0.001 to 0.06 mol / liter (particularly 0.0
It is preferably used in an amount of from 0.3 to 0.06 mol / liter).

Examples of the sulfite include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite,
Examples include sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The amount of sulfite is preferably 0.10 mol / L or more, particularly preferably 0.20 mol / L or more. The upper limit is preferably up to 2.5 mol / l, especially up to 1.2 mol / l.
The developer used in the present invention may contain an amino compound for promoting development. In particular, JP-A-56-106244
JP-A-61-267759, 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.
8 or less. As the alkali agent used for setting the pH value, a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide or sodium carbonate) can be used. The replenisher for development of the present invention may further include a pH buffer such as boric acid, borax, sodium phosphate dibasic, potassium phosphate dibasic, sodium phosphate monobasic, and potassium phosphate monobasic. No. 60-93433; development inhibitors such as potassium bromide and potassium iodide; dimethylformamide, methyl cellosolve,
Organic solvents such as hexylene glycol, ethanol and methanol; as the benztriazole derivatives, 5-methylbenztriazole, 5-bromobenztriazole,
5-Chlorobenztriazole, 5-butylbenztriazole, benzotriazole and the like, among which 5-methylbenztriazole is particularly preferred as nitroindazole, such as 5-nitroindazole, 6-nitroindazole,
There are 4-nitroindazole, 7-nitroindazole, 3-cyano-5-nitroindazole and the like, but 5-nitroindazole is particularly preferable. In particular, when using a compound such as 5-nitroindazole, dissolve it in a portion different from the portion containing the dihydroxybenzene-based developing agent and the sulfite preservative in advance, mix both portions at the time of use, and add water. Is common. Further, if the portion where 5-nitroindazole is dissolved is made alkaline, it is colored yellow and is convenient for handling. Further, if necessary, a toning agent,
Surfactants, water softeners, hardeners and the like may be included.

As the chelating agent in the developer, the following compounds may be mentioned. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanol tetraacetic acid, triethylenetetramine hexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol ether diaminetetraacetic 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. Particularly preferred are, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and 1,3.
-Diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylethylenediaminetriacetic 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 developing solution of the present invention, for the purpose of silver contamination, Japanese Patent Publication No. 62-4702, Japanese Patent Publication No. 62-4703, Japanese Patent Application No. 63-24123, Japanese Patent Application No. 3-94955, and Japanese Patent Application No. 3-94955.
112275 and the compounds described in 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, maleic dialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α -N-butoxyglutaraldehyde, α, α-dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α-diethylsuccindialdehyde, butylmaleic dialdehyde, and bisulfite adducts thereof. The dialdehyde compound is used in such an amount that the sensitivity of the photographic layer to be processed is not suppressed and the drying time is not significantly increased. Specifically, 1 to 50 g, preferably 3 to 1 g per liter of the developing solution
0 g. Among them, glutaraldehyde or its bisulfite adduct is most commonly used.

When a bisulfite adduct of a dialdehyde hardener is used, the bisulfite of this adduct is also calculated as a sulfite in the developer. In addition, L.
F. A. Mason, Photographic Processing Chemistry, Focal Press (1966)
226-229, U.S. Pat. No. 2,193,01.
5, No. 2,592,364, JP-A-48-649.
The additives described in No. 33 and the like may be used.

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 in the range of 50 ml to 150 ml per 1 m ² of the light-sensitive material. As the developer to be injected into the developing tank of the automatic developing machine at the beginning of the development, a liquid having the same composition as the above-described developer or a liquid having a partially changed composition may be used.

The fixing solution used in the present invention is an aqueous solution containing a thiosulfate, and has a pH of 3.8 or more, preferably 4.2 to 4.2.
6.0. Sodium thiosulfate as fixing agent,
And ammonium thiosulfate. The amount of the fixing agent to be used can be appropriately changed, and is generally about 0.1 to about 3 mol / l. The fixing solution may contain a water-soluble aluminum salt acting as a hardener, and examples thereof include aluminum chloride, aluminum sulfate, potassium alum and the like.

In the fixing solution, tartaric acid, citric acid, gluconic acid or derivatives thereof can be used alone or in combination of two or more. It is effective that these compounds contain 0.005 mol or more per liter of the fixing solution, and in particular, they contain 0.1 mol.
01 mol / l to 0.03 mol / l is particularly effective.

The fixing solution may optionally contain a preservative (for example, sulfite or bisulfite), a pH buffer (for example, acetic acid or boric acid), a pH adjuster (for example, sulfuric acid), a chelating agent capable of softening water. And the 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 machine used in the present invention, various types such as a roller transport type and a belt transport type can be used, but a roller transport type automatic machine is preferable. Japanese Patent Application Laid-Open No. 1-166040 and Japanese Patent Application No. 63-18631
By using an automatic developing machine with a small opening ratio as described in the above paragraph, air oxidation and evaporation are small, stable operation in the processing environment is possible, and the replenishment amount can be further reduced. As a method for reducing the replenishing amount of the washing water, a multi-stage countercurrent method (for example, two-stage, three-stage, or the like) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing is gradually processed in a clean direction, that is, a processing solution that is not stained with the fixing solution is sequentially contacted.
Further efficient water washing is performed. In the water-saving treatment or the non-pipe treatment, it is preferable to apply a means for preventing the washing water or the stabilizing solution.

As a means for preventing rusting, JP-A-60-263
No. 939, No. 60-26394.
Method using magnetic field described in No. 0, 61-13163
No. 2, a method of making pure water using an ion exchange resin, JP-A Nos. 61-115154 and 62-15395.
No. 2, Japanese Patent Application No. 61-63030 and No. 61-51396
Can be used.
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), RDDeega
n, “Phot Processing Wash Water Biocides” J. Imagi
ng Tech 10, No. 6 (1984) and
No. 8542, No. 57-58143, No. 58-1051
No. 45, No. 57-132146, No. 58-18631
, An antibacterial agent, a surfactant and the like described in JP-A-57-97530, JP-A-57-157244 and the like.

Further, a washing bath or a stabilizing bath may include RT.
Kreiman, J.Image.Tech 10, (6) p. 242 (198
The isothiazoline compound described in 4), Research
Disclosure Vol. 205, No. 20526 (May 1981), isothiazoline-based compounds described in Id.
28, No. 22845 (April 1983), isothiazoline compounds disclosed in Japanese Patent Application No. 61-51396.
And the like can be used in combination as a bacteriostatic agent (Microbiocide). In addition, "The Chemistry of Bactericidal and Fungicide" by Hiroshi Horiguchi, Sankyo Publishing (Showa 57), "Bacterial and Fungicide Technical Handbook", Japan Society of Bactericidal and Fungicide, Hakuhodo (Showa 61)
May be included.

In the method of the present invention, when washing with a small amount of washing water, it is more preferable to provide a squeeze roller washing tank described in JP-A-63-18350. Also,
It is preferable to adopt a configuration of a washing step as disclosed in JP-A-63-143548. Further, part or all of the overflow from the washing or stabilizing bath caused by replenishment of the water subjected to the means for preventing the washing or stabilizing bath by the method of the present invention according to the treatment is described 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 the preceding processing step.

In the present invention, the term "development step time" or "development time" refers to the time from when the leading end of the photosensitive material to be processed is immersed in the developing tank solution of the automatic developing machine until it is immersed in the next fixing solution. "Fixing time" is the time from immersion in the fixing tank solution to immersion in the next washing tank solution (stabilizing solution),
"Washing time" refers to the time of immersion in the washing tank liquid. The “drying time” is usually 35 ° C.
A drying zone to which hot air of 100 ° C., preferably 40 ° C. to 80 ° C. is blown is provided, and it refers to a time in the drying zone. In the development processing in the present invention,
The development time is 5 seconds to 1 minute, preferably 8 seconds to 30 seconds, and the development 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
8 ° C to about 50 ° C, preferably 5 seconds to 1 minute, 20 ° C to 40 ° C
C. for 30 seconds is more preferable. Within this range, sufficient fixing can be performed, and the sensitizing dye can be eluted to such an extent that no residual color is generated. The temperature and time in the water washing (or stabilizing bath) are preferably 0 to 50 ° C. and 6 seconds to 1 minute, and 15 ° C.
6 to 30 seconds at -40 ° C is more preferable.

According to the method of the present invention, the photosensitive material which has been developed, fixed and washed (or stabilized) is squeezed with washing water, that is, dried through a squeeze roller. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time may be appropriately changed depending on the surrounding conditions, but is usually about 5 seconds to 1 minute, particularly preferably 40 to 80 ° C. for about 5 seconds to 30 minutes.
Seconds. Dry to Dry with the photosensitive material / processing system of the present invention
When the development processing is performed for 100 seconds or less in JP-A-63-15194 in order to prevent development unevenness peculiar to rapid processing.
Japanese Patent Application Laid-Open Publication No. Sho 6 (1994) discloses the use of a rubber roller as described in
As described in JP-A-3-151944, the discharge flow rate for stirring the developer in the developer tank is set to 10 m / min or more.
As described in Japanese Patent Application Laid-Open Publication No. H10-207, it is more preferable to perform stronger stirring at least during development processing than during standby. For more rapid processing, the configuration of the roller in the fixing liquid tank is more preferably an opposing roller in order to increase the fixing speed. By using the opposing rollers, the number of rollers can be reduced, and the processing tank can be reduced. That is, it is possible to make the self-developing machine more compact.

[0053]

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

Embodiment 1 1. Preparation of silver halide emulsion A 32 g of gelatin was added to 900 ml of distilled water, and
After dissolution, the pH was adjusted to 3.8 with sulfuric acid, and sodium chloride was added.
3.3 g were added. 32 g of silver nitrate in 200 ml of distilled water
Dissolved solution and sodium chloride 11g, K_TwoIrCl₆0.0
A solution obtained by dissolving 2 mg in 200 ml was mixed at 40 ° C. for 2 minutes.
The mixture was added to and mixed with the above solution. Distill further 64g of silver nitrate
A solution dissolved in 280 ml of water and 21.6 g of sodium chloride
Apply the solution dissolved in 275 ml for 5 minutes at 40 ° C.
And mixed. Subsequently, 64 g of silver nitrate was added to 28 parts of distilled water.
Solution dissolved in 0 ml, sodium chloride 22.4 g, K_FourFe (C
N) ₆・ 3H_TwoA solution prepared by dissolving 0.04 g of O in 285 ml
The mixture was further added and mixed at 40 ° C. for 5 minutes. Profit
Observation of the resulting emulsion with an electron microscope revealed that
1μm average side length and particle size distribution variation coefficient
An emulsion consisting of cubic grains having a value of 9.8%.
Was. Adjustment of silver halide emulsions B, C and D Sodium chloride for forming emulsion of silver halide emulsion A
To sodium chloride and potassium bromide
The halogen composition shown in Table 1 was changed by changing the grain formation temperature.
Emulsion was obtained.

[0055]

[Table 1]

After desalting these emulsions, gelatin 72
g, 2.6 g of phenoxyethanol, pH6.
7. Chemical sensitization was performed at 58 ° C. in the following procedure according to pAg 7.9 with NaCl. First, an average particle size of 0.05
A monodispersed silver bromide emulsion having a particle size of 1 μm was added thereto in an amount corresponding to 1 mol% of silver halide, and then 7.2 mg of compound (1) and 9.2 m
g, 1.3 mg of triethylthiourea, selenium sensitizer (A)
Add 0.72 mg, 0.29 g of nucleic acid and finally add 4
Then, 162 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, and the mixture was quenched and solidified to obtain emulsions A, B, C, and D, respectively.

Compound (1)

[0058]

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Selenium sensitizer (A)

[0060]

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[0061] 2. Preparation of Emulsion Coating Solution An emulsion coating solution was prepared by adding the following chemicals to Emulsion A per mole of silver halide.

(Formulation of emulsion coating solution)

B. Spectral sensitizing dye [2] 5.5 × 10 ^-5 mol b. Supersensitizer [3] 3.3 × 10 ^-4 mol c. Polyacrylamide (molecular weight: 40,000) 9.2 g d. Trimethylolpropane 1.4 g e. Latex of poly (ethyl acrylate / methacrylic acid) 22 g Spectral sensitizing dye [2]

[0064]

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Supersensitizer [3]

[0066]

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3. Preparation of Coating Solution for Surface Protective Layer of Emulsion Layer A container was heated to 40 ° C., and the following chemicals were added to obtain a coating solution. I. Gelatin 100g b. Polyacrylamide (molecular weight: 40,000) 12.3 g c. Sodium polystyrene sulfonate (molecular weight: 600,000) 0.6 g d. 2.7 g of polymethyl methacrylate fine particles (average particle size: 2.5 μm) 3.7 g of sodium polyacrylate f. Sodium t-octylphenoxyethoxyethanesulfonate 1.5 g g. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.3 g h. C ₈ F ₁₇ SO ₃ K 84mg 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. Methanol 78cc III. 1,2-Bis (vinylsulfonylacetamide) ethane Prepared so as to be 2.5% by weight based on the total gelatin content of the emulsion layer and the surface protective layer. W. Compound (5) 52mg

[0068]

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4. Preparation of coating solution for back layer

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

[0071]

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

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

[0074]

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H. Oligomers of Dye (C) described in JP-A-62-275639 Surfactant dispersion Dye itself (46 mg) Dye (C)

[0076]

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5. Preparation of coating solution for back surface protective layer

The container was heated to 40 ° C., and the following chemicals were added to obtain a coating solution.

B. Gelatin 100g b. Sodium polystyrene sulfonate 0.3 g c. Polymethyl methacrylate fine particles (average particle size: 3.5 μm) 4.3 g d. sodium t-octylphenoxyethoxyethanesulfonate 1.8 g e. 1.7 g of sodium polyacrylate f. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.6g bets. C ₈ F ₁₇ SO ₃ K 268mg Ji. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 45mg Li. NaOH 0.3 g 131 ml of methanol. 1,2-bis (vinylsulfonylacetamide) Ethane Prepared to be 2.2% of the total amount of gelatin in the backing layer and surface protective layer.ヲ. Compound (5) 45mg

6. Preparation of Photographic Material The above-mentioned back layer coating solution and the back layer surface protective layer coating solution were coated on one side of a blue-colored polyethylene terephthalate support with a back layer gelatin coating amount of 2.6.
9 g / m ² , and the amount of gelatin applied to the surface protective layer of the back 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 Coating was performed so that the gelatin coating amount of the surface protective layer was 1.23 g / m ² . Thus, a photographic material was produced.

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: A solution obtained by adding 0.20 g of 5-methylbenztriazole to 1 liter of developer A.

Developer C A solution obtained by adding 0.15 g of 5-nitroindazole to 1 liter of developer A.

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

Developing solution E A solution obtained by changing 25.0 g of sodium carbonate (monohydrate) in developing solution D to 27.8 g of equimolar potassium carbonate.

Developer F: A solution prepared by adding sodium hydroxide to 1 liter of developer A to adjust pH to 10.5. The fixing solution was prepared by adding 158 g (1.0 mol) of sodium thiosulfate, 30 g of sodium bisulfite, 0.025 g of disodium ethylenediaminetetraacetate dihydrate, 40.0 g of diethylene glycol, and adjusting the pH to 5.50 with 1 liter of sodium hydroxide.

As an automatic developing machine, a washing tank of FPM2000 manufactured by Fuji Photo Film Co., Ltd. was modified to have three tanks. The washing water supplied to the washing tank and overflowing therefrom was sequentially supplied to the washing tank on the front side. Further, the drive shaft of the automatic machine was modified so that the transport speed was 45 seconds from the time of film insertion to the location of the drying outlet. The washing water used contained 0.2 g of ethylenediaminetetraacetic acid disodium dihydrate and 0.04 g of glutaraldehyde per liter of water. Each of the developing solution film daily 4m ² treated fixer, washing water 400
A running test was carried out for 3 weeks while replenishing each ml (100 ml / m ² ). Table 2 shows the obtained results. Here, the sensitivity refers to a reciprocal of an exposure amount that gives an optical density of fog plus 1.0 with a new solution of the developing solution A as 100, and fog indicated as a relative value indicates an optical density including a support at an unexposed portion.

[0088]

[Table 2]

The fixing failure was evaluated on a five-point scale. 5
Indicates a state in which no residual silver is present, 4 indicates a color developed as silver sulfide when immersed in a sodium sulfide solution, and some residual silver is present, but practically acceptable 3 is a state in which the residual silver is slightly observed visually. Levels 2 and 1, which are not practically acceptable, sequentially indicate that the fixing failure state is bad.

As is clear from the results in Table 2, the developer A,
In B, C, D, and E, the sensitivity was stable without change even after 3 weeks, and such a result was obtained even with a small replenishment amount of 100 ml per 1 m ² . Conventionally, a replenishing amount of 650 ml per m ² is used with a developer such as a developer F having a pH of 10.50, and the photographic properties can be stably used with little change in photographic properties even after three weeks of running. Effect of the present invention is 1 m ² per 10
This is a remarkable progress, because the sensitivity can be stably used for a long period of time with a small replenisher amount of 0 ml without any change in sensitivity. Regarding the fixation nuclei, the emulsions A and B of the present invention show good fixation nuclei even in the running solution after 3 weeks, provided that the comparative developer E contains 56% of sodium ions in all cations in the developer. After three weeks of running, the developer is brought into the fixing solution by the film processing, so that the degree of deterioration of the fixing drop is increased.

Example 2 A developer formulation, a washing water formulation, an automatic processor humidity time, and an emulsion were all the same as in Example 1 and only the fixer formulation was as follows. Fixer formulation Sodium thiosulfate 118.5 g (0.75 mol) Sodium bisulfite 30.0 g Disodium ethylenediaminetetraacetate dihydrate 0.025 g Diethylene glycol 40.0 g Add water to 1 liter and adjust to pH 5.50 with sodium hydroxide. Combine. Table 3 shows the obtained results. The sensitivity and fog are the same as those in Table 2 of Example 1, but the fixation loss is as follows:
B is a practically acceptable level for the running solution after 3 weeks, but in the case of the comparative developing solution E in which the sodium ion in the total cations in the developing solution is 56%, the deterioration of fixation drop is worse after 3 weeks of running. The degree is getting bigger.

[0092]

[Table 3]

[0093]

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

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ identification symbol FI G03C 5/38 G03C 5/38 5/395 5/395 (58) Investigated field (Int.Cl. ⁶ , DB name) G03C 5 / 29 G03C 1/035 G03C 5/305 G03C 5/31 G03C 5/38 G03C 5/395

Claims (3)

(57) [Claims] 1. A method for processing a transmission-type black-and-white silver halide photographic material using an automatic developing machine, wherein pH 9.8 wherein 70 mol% or more of all cations in a developer is sodium ion.
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) plane / (111) plane ratio of 5 or more and a silver chloride content of 90 mol% or more. when processing a light-sensitive material, processing method characterized by supplementing the replenisher for developer and fixer in an amount of less than the silver halide photographic light-sensitive material 1 m ² per 150 ml. 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 ions.