JPH0667368A - Method for developing black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce a development replenishing solution to a very small amount and to stabilize photographic performance by replenishing a developing solution specified in composition at a specified feed rate per a unit area of the photosensitive material to develop it. CONSTITUTION:This transmission type black-and-white silver halide photographic sensitive material is processed in an automatic developing machine with a developing solution of pH of 9.8 or lower and containing a compound represented by formula I at a replenishing solution feed rate of 200ml/m<2> or lower of the photosensitive material. In formula I, each of Y and Z is CR<2>; R<2> is H, optionally substituted alkyl or aryl; R<1> is an alkyl or aryl substituted by at least one sulfo, carboxy, or hydroxy or in the case of 2 or more substituents, each may be same or different; and M is H, or an alkali metal, a quaternary ammonium or a group convertible into H or an alkali metal under an alkaline condition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a black-and-white silver halide photographic light-sensitive material using an automatic processor, which can reduce the amount of development replenisher per unit area of the light-sensitive material and can provide stable photographic images The present invention relates to a developing method capable of obtaining 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). At that time, the developing process is usually carried out while replenishing a fixed amount of developing solution proportional to the area of the photosensitive 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. Conventionally, a developing replenisher is added to 250 m of so-called sheet-shaped photographic material 1 m ² such as X-ray photography or graphic arts sensitive material.
It was common to replenish more than ml, especially more than 330 ml. However, photographic developer wastes have a high chemical oxygen demand (so-called COD) or biological oxygen demand (so-called B.O.D.).
O. Due to the fact that it has D), it is performed that the developing waste liquid is subjected to chemical or biological treatment to be rendered harmless and then discharged. Since a large economic burden is imposed on the treatment of these waste liquids, a developing method with a small amount of developing replenisher has been desired.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a development processing method in which the amount of development replenisher per unit processing area is small in the development processing of a transmission type black-and-white silver halide photographic light-sensitive material using an automatic processor. Especially. It is another object of the present invention to provide a development processing method capable of obtaining a development replenisher having a small amount and exhibiting stable photographic characteristics even in the development processing.

[0004]

The present invention relates to a method of developing a transmission type black-and-white silver halide photographic light-sensitive material with an automatic processor, which contains a compound represented by the following general formula (I) and has a pH of 9.8. It was achieved by a developing method characterized in that replenishment was carried out with the following developing solution at a ratio of 200 ml or less per 1 m ² of the light-sensitive material. General formula (I)

[0005]

[Chemical 2]

In the formula, Y and Z are N or CR ² (R ² represents a hydrogen atom and a substituted or unsubstituted alkyl group or aryl group), R ¹ is at least one or more sulfo group, carboxy group or It represents an alkyl group or an aryl group substituted with a hydroxy group. When two or more of these substituents are present, they may be the same or different.
M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions.

More specifically, R ¹ is a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted with one or more sulfo group, carboxy group or hydroxy group (for example, methyl group, ethyl group, propyl group). , Hexyl group, dodecyl group, isopropyl group, etc.), C1-C20 cycloalkyl group (for example, cyclopropyl group, cyclohexyl group, etc.), or C6-C20 aryl group (for example, phenyl group, naphthyl group, etc.) Represents

The alkyl group (straight chain, branched alkyl group, cycloalkyl group) and aryl group may be further substituted, and specifically, a halogen atom (F, Cl, Br etc.), an alkyl group (methyl group). , Ethyl groups, etc.), aryl groups (phenyl groups, etc.), alkoxy groups (methoxy groups,
Ethoxy group), aryloxy group (phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (unsubstituted carbamoyl group, diethylcarbamoyl group, etc.), amide group (acetamide group, benzamide group) Groups), alkoxycarbonylamino groups (methoxycarbonylamino groups, etc.), allyloxycarbonylamino groups (phenoxycarbonylamino groups, etc.), alkoxycarbonyl groups (methoxycarbonyl groups, etc.), aryloxycarbonyl groups (phenoxycarbonyl groups, etc.), Cyano group, niloto group, amino group (unsubstituted amino group, dimethylamino group, etc.), alkylsulfinyl group (methylsulfinyl group, etc.), arylsulfinyl group (phenylsulfinyl group, etc.), alkylthio (Such as a methylthio group), and (like phenylthio) arylthio group may be mentioned. The alkyl group and aryl group represented by R ² have the same meanings as R ¹ , and the substituents are the same as those of R ¹ . Particularly preferred as R ¹ is a phenyl group substituted with one or more sulfo groups, carboxy groups or hydroxy groups, and particularly preferred as R ² is a hydrogen atom. M is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), a quaternary ammonium group (eg, trimethylammonium group, dimethylammonium group, tributylammonium group, etc.) and M becomes a hydrogen atom or an alkali metal under alkaline conditions. Group (eg, acetyl group, cyanoethyl group, methanesulfonyl group, etc.).

Specific examples of the compound represented by formula (I) used in the present invention are shown below, but the scope of the present invention is not limited to this compound.

[0010]

[Chemical 3]

[0011]

[Chemical 4]

[0012]

[Chemical 5]

[0013]

[Chemical 6]

[0014]

[Chemical 7]

The compound represented by the general formula (I) can be easily synthesized by a method using isothiocyanate as a starting material, as is well known. The patents and literature examples in which the synthetic method is described as reference are shown below. U.S. Pat. No. 2,585,388,
No. 2,541,924, Japanese Patent Publication No. 42-21842,
U.S. Pat. No. 3,266,897, JP-A-53-5016
No. 9, gazettes, US Pat. No. 1,275,701,
DABerges et all, "Journal of Heterocyclic chemis
try "Vol. 15, No. 981 (1978)," The chemist
ry of Heterocyclic chemistry "Imidazole and Derivat
ives part I. pp. 336-339, chemical Abatract
58, 7921 (1963), p. 394; E. Hoggarth.
"Journal of chemical Society" 1949 Volume 1160
Pp. 1167 and SR Sandler, W. Karo, "Organic F"
unctional Group Preparation "Academic Press, 1
968, pages 312-315, M. Chamdon et al. Bu.
ll.Soc.Chim.Fr., 723 (1954), DA Shirley,
DW Alley J. Amer. Chem. So., 79, 4922 (19)
57), A. Wohl, W. Marck wald, Journal of the German Chemical Society (Be
r) Volume 22, page 568 (1889). The above general formula (I)
The concentration of the compound of the formula (1) in the developing solution (working solution) is preferably 0.01 mmol to 50 mmol / liter, more preferably 0.05 mmol to 10 mmol / liter, and particularly preferably 0.1 mmol to 5 mmol / liter. It Further, since the developer is replenished with a small amount of developing solution of 200 ml or less per 1 m ^{2 of the} light-sensitive material, the exchange rate of the new solution in the developing tank becomes slow, and the developing solution is easily oxidized by air, which makes it difficult to maintain the initial photographic performance. become. Therefore, in order to suppress air oxidation of the developer, the pH of the developer is 9.8 or less.
0 or more is preferable.

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 inside the grain 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.

The localized phase does not have to consist of a single halogen composition, 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, 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 into the localized phase of the silver halide grain and / or other portions of the grain, the metal ion or the complex ion is added 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 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 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. 1994-202 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. 600 of the present invention
The content of the sensitizing dye of not less than nm depends on 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, the type of antifoggant compound, etc. It is desirable to select the optimum amount accordingly, and the method of testing is well known to those skilled in the art for the selection. Usually, it is preferably 10 ^-7 to 1 × 10 ^-2 mol, particularly 10 ^-6 to 5 mol per mol of silver halide.
It is used in the range of × 10 ^-3 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,
Emulsion pick-off occurs, in which the silver halide photographic light-sensitive material is peeled off by the projections 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 the 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, Stability 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 4 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, left lower 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 stop 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 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) Polyhydroxybe 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,
Hydroquinone monosulfonic acid, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,4-dimethylhydroquinone, but especially hydroquinone Is preferred. The developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. In the present invention, it is particularly preferable to use 1-phenyl-3-pyrazolidones or p-aminophenols together with the above-mentioned dihydroxybenzene type developing agent.

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-pyrazolidones or p-aminophenols are used in combination, the former amount 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 developing solution 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, but 5-methylbenztriazole is particularly preferable. As nitroindazole, 5 nitroindazole, 6 nitroindazole, 4 nitroindazole, 7 nitroindazole, 3
There are 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. Further, if necessary, a color tone agent, a surfactant, a water softener, a hardener and the like may be contained.

Specific examples of the chelating agent in the developer 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
Phosphonobtan-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,3,3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, hexametaphosphoric acid Sodium is mentioned, and particularly preferably, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, 2-phosphonobutane-1,2,4.
-Tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-
There are diphosphonic acid, 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 to this, L. F. A. Mason, "Photographic Processing Chemistry," Focal Press (1966), pages 226-229, U.S. Pat. Nos. 2,193,015, 2,592,36.
No. 4, the additives described in JP-A-48-64933 and the like may be used.

In the present invention, the developing treatment is carried out while replenishing the above-mentioned developing solution in an amount of 200 ml or less, particularly 50 ml to 200 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 fixing solution 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, sulfites, bisulfites), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having the ability to soften water by water are 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 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.

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 the stabilizing bath should have an 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 5 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 5 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.

[0062]

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

After desalting this emulsion, 72 g of gelatin,
2.6g of phenoxyethanol was added, pH 6.7, Na
In accordance with pAg of 7.9 with Cl, the chemical sensitization was performed by the following procedure.
It was carried out at 8 ° C. First, 1 mol% of silver halide was added to a monodispersed silver bromide emulsion having an average grain size of 0.05 μm, and then 7.2 mg of compound (A) and 9.2 mg of chloroauric acid were added.
Triethylthiourea 1.3mg, Selenium sensitizer 0.72m
g, further 0.29 g of nucleic acid, and finally 162 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added and rapidly solidified to give Emulsion A.

Compound (A)

[0066]

[Chemical 8]

Selenium sensitizer

[0068]

[Chemical 9]

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 5.5 × 10 ⁻⁵ mol. Supersensitizer 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

[0072]

[Chemical 10]

Supersensitizer

[0074]

[Chemical 11]

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 of the emulsion layer and the surface protective layer. Wa. Compound (B) 52 mg

[0076]

[Chemical 12]

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

[0079]

[Chemical 13]

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 (B) 46 mg

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

[0082]

[Chemical 14]

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

[0084]

[Chemical 15]

5. Preparation of back surface protective layer coating liquid

The container was heated to 40 ° C. and the following chemicals 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% with respect to the total gelatin amount in the ethane back layer and surface protective layer. Wo. Compound (2) 45mg

6. Preparation of Photographic Material The coating solution for the back layer and the coating solution for the surface protective layer of the back layer were coated on one side of polyethylene terephthalate colored blue, and the gelatin coating amount of 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 potassium carbonate 25.0 g diethylenetriaminepentaacetic acid 2.0 g diethylene glycol 20.0 g boro Acid 9.0 g Potassium bromide 0.6 g (0.005 mol) Add water and adjust to pH = 9.50 with 1 liter potassium hydroxide. Developer B Developer A A 1 liter, compound (3) 0.3
g added developer solution C developer solution A to 1 liter of the compound (5) 0.2
Compound (16) was added to 1 liter of Developer D.
28 g was added Developer E Developer A 1 liter of Compound (25) was added to 0.1 liter.
21 g Developer solution F Developer B 1 liter of 2-mercaptoimidazole-5-sulfonic acid 0.10 g and 2,3,3
5,6,7,8-hexahydro-2-thioxo-4-
(1H) -Quinazolinone 0.10 g was added Developer G Developer A A 1 liter was added with compound (A) 0.1
8g added Compound (A)

[0090]

[Chemical 16]

Developing solution H To 1 liter of developing solution A, 0.2 parts of compound (B) was added.
Compound (B) added with 9 g

[0092]

[Chemical 17]

Developer I Developer A A 1 liter of potassium hydroxide was added to adjust the pH to 10.50. Next, the formulation of the fixer is shown: sodium thiosulfate 185 g ethylenediaminetetraacetic acid disodium dihydrate. 025 g Sodium metabisulfite 22 g Water was added to 1000 ml (pH adjusted to 5.50 with sodium hydroxide) As an automatic processor, Fuji Photo Film Co., Ltd. FPM
-The 2000 drive shaft was improved so that the conveying speed was 30 seconds from the film insertion to the drying outlet. The film is processed for 2 m ² every day and 260 ml of each developer (1
A running test was performed for 3 weeks while replenishing each 30 ml / 1 m ² ). The results obtained are shown in Table 1. Here, the sensitivity is shown as a relative value with the reciprocal of the exposure amount giving a fog plus 1.0 optical density in the new developer A as 100. Fog is the optical density including the support in the unexposed area. Dm represents the maximum density. As is clear from the results shown in Table 1, with the developers B, C, D, E, and F of the present invention, the fog value was low, and the photographic performance was stable even after 3 weeks with a small replenishing amount of 130 ml per m ^2. I was able to get On the other hand, in the developer A containing no compound of the present invention, the sensitivity and Dm after 3 weeks are lowered. Further, in the developing solutions G and H containing compounds other than the present invention, the fog value in the new solution is high and the sensitivity D is high.
The m is lowered, and the sensitivity after 3 weeks is further lowered. Further, in the case of the developing solution I in which the pH of the developing solution is 10.50, the sensitivity of the new solution is high, but the sensitivity change after 3 weeks is very large and unstable.

[0094]

[Table 1]

Example 2 The following experiment was conducted using the coated sample of Example 1, the developing solutions A, B, E, G and the fixing solution. For automatic machines,
A rinsing tank and a rinsing roller (2 pairs) were installed between the developing tank and the fixing tank and between the fixing tank and the water washing tank according to the configuration of FIG. In FIG. 1, S represents a light-sensitive material. W is a rinsing tank that represents washing water, and water is previously put in the rinsing tank so that a fixed amount of water is supplied every time the photosensitive material is processed.
The processing speed was Dry to Dry for 30 seconds, and when the same processing as in Example 1 was performed, the same results as in Example 1 were shown. The process of 30 seconds processing in the above Dry to Dry is shown in Table 2.
As shown in.

[0096]

[Table 2]

[0097]

According to the present invention, stable photographic performance can be obtained for a long period of time even with a dry-to-dry treatment for 30 seconds with a small replenishing amount of 130 ml per 1 m ² .

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing a configuration example of an automatic developing machine used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Automatic developing machine 11 Development tank 12 Fixing tank 13 Water washing tank 61,71 Rinse roller 65,75 Rinse tank

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

[Procedure amendment]

[Submission date] November 9, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction content]

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a development processing method in which the amount of development replenisher per unit processing area is small in the development processing of a transmission type black-and-white silver halide photographic light-sensitive material using an automatic processor. Especially. It is another object of the present invention to provide a development processing method capable of obtaining a development replenisher having a small amount and good stability of photographic characteristics even in the development processing.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0043

[Correction method] Change

[Correction content]

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,
Hydroquinone monosulfonic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,4-dimethylhydroquinone, etc. Hydroquinone is preferred. The developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. In the present invention, it is particularly preferable to use 1-phenyl-3-pyrazolidones or p-aminophenols together with the above-mentioned dihydroxybenzene type developing agent.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

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 Patent Laid-Open No. 4 is applied to the roller at the outlet of the developing tank, and Japanese Patent Laid-Open No.
As described in Japanese Patent Laid-Open No. 3-151943, 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.

[Procedure amendment]

[Submission date] June 1, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

[Correction content]

Developer A hydroquinone 20.0 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.0 g sodium sulfite 35.0 g potassium carbonate 25.0 g diethylenetriaminepentaacetic acid 2.0 g diethylene glycol 20.0 g boro Acid 9.0 g Potassium bromide 0.6 g (0.005 mol) Add water and adjust to pH = 9.50 with 1 liter potassium hydroxide. Developer B Developer A A 1 liter, compound (3) 0.3
g added developer solution C developer solution A to 1 liter of the compound (5) 0.2
Compound (16) was added to 1 liter of Developer D.
28 g was added Developer E Developer A 1 liter of Compound (25) was added to 0.1 liter.
21 g was added Developer F Developer B 1 liter, 2-mercaptobenzimidazole-5-sulfonic acid 0.10 g and 2,
3,5,6,7,8-hexahydro-2-thioxo-4
-(1H) -quinazolinone 0.10 g was added Developer G Developer A A 1 liter, compound (A) 0.1
8g added Compound (A)

Claims (2)

[Claims] 1. A method of developing a transmission type black-and-white silver halide photographic light-sensitive material with an automatic processor, which contains a compound represented by the following general formula (I) and has a pH of 9.8.
A developing method comprising replenishing the following developing solution at a ratio of 200 ml or less per 1 m ² of a light-sensitive material. General formula (I) In the formula, Y and Z are N or CR ² (R ² represents a hydrogen atom and a substituted or unsubstituted alkyl group or aryl group), R ¹ is at least one or more sulfo group, carboxy group or hydroxy group. Represents a substituted alkyl group or aryl group. When two or more of these substituents are present, they may be the same or different. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium or a group in which M can be a hydrogen atom or an alkali metal under alkaline conditions. 2. A composition of silver chlorobromide, silver chloroiodide or silver chloroiodobromide having an average grain size of 0.1 to 0.4 μm and a silver chloride content of 90 mol% or more. 150μm layer of silver halide emulsion spectrally sensitized to 600nm or more
2. The developing method according to claim 1, wherein the photographic light-sensitive material having the above thickness on the transparent support is used.