JPH07120895A - Method for processing black-and-white silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a black-and-white photosensitive material processing method less in loads of COD and BOD and using a fixer good in property not to miss fixation. CONSTITUTION:A black-and-white silver halide photographic sensitive material is processed with a fixer contg. 0.3-0.5mol/l of a thiosulfate and a mesoionic compd. shown by the formula. In the formula, Z is an atom group necessary to form at 5 to 6-membered ring and is selected from among carbon atom, nitrogen atom, oxygen atom, sulfur atom or selenium atom, X<-> is -O<->, -S<-> or -N-R-, and R is an alkyl, cycloalkyl, alkenyl, alkinyl, aralkyl, aryl or heterocyclic ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixing method for a black and white silver halide photographic light-sensitive material, and more particularly to a processing method with reduced environmental load.

[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 using an automatic developing machine (hereinafter abbreviated as an automatic processor). It has been desired that the amount of replenishing liquid per unit area when the above treatment is performed be further reduced to obtain fixing voids. Further, since the fixing waste liquid has a high chemical oxygen demand (so-called COD) or a biological oxygen demand (so-called BOD), the fixing waste liquid is chemically or biologically It is performed to detoxify it by treating it and then drain it. Since a great economic burden is imposed on the treatment of these waste liquids, C.I. O. D. Or B. O.
D. There has been a demand for a processing method of a fixing solution having a low load.

[0003]

The object of the present invention is to process C.I. O. D. And B. O. D. It is an object of the present invention to provide a processing method of a fixing solution having a small load. It is another object of the present invention to provide a processing method capable of obtaining a toner having a good fixing loss even if the amount of the fixing replenisher is small.

[0004]

The present invention relates to a method of processing a black and white silver halide photographic light-sensitive material, wherein the concentration of thiosulfate in the fixing solution is 0.3 mol / liter or more and less than 0.5 mol / liter. This is achieved by a method of processing a black-and-white silver halide light-sensitive material, which comprises processing with a fixing solution containing a compound represented by the following general formula (I).

[0005]

[Chemical 2]

In the formula, Z represents an atomic group necessary for forming a 5- or 6-membered ring and is selected from carbon atom, nitrogen atom, oxygen atom, sulfur atom or selenium atom. X ^- is ^-O -, -S ^- it represents or -N-R. R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. The mesoionic compound represented by the general formula (I), even when used alone, acts as a solvent for silver halide and has a fixing action, but the complex salt of silver and mesoion is an emulsion film as compared with the complex salt of silver and thiosulfate ion. It has the disadvantage that the diffusion speed inside is slow and it remains as residual silver in the emulsion film. In addition, the mesoionic compound has a longer clearing time in fixing (time until the photosensitive material becomes transparent in the fixing solution) when used alone, and is inferior to thiosulfate as compared with thiosulfate. The present inventor has found that the C. O. D. Or B. O.
D. As a result of diligent examination of a fixing solution having a low load, it was confirmed that the thiosulfate concentration should be less than 0.5 mol / liter. O.
D. Or B. O. D. It has been found that although it is effective in reducing the load, it has a drawback that fixing time is prolonged, but the fixing speed is unexpectedly increased by using a mesoionic compound together. However, when the thiosulfate concentration is less than 0.3 mol / liter, fixing is very slow, that is, the thiosulfate concentration is 0.3 mol / liter or more and less than 0.5 mol / liter, more preferably 0.35 mol / liter or less.
It has been found that the fixing speed is remarkably high by adding a small amount of the mesoionic compound at a concentration of 0.45 mol / liter. Among the compounds represented by the general formula (I) of the present invention, the compound represented by the general formula (II) is particularly preferable.

[0007]

[Chemical 3]

In the formula, R ₁ and R ₂ represent an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. However, R ₂ may be a hydrogen atom. Y is -O-, -S-, -N-
(R ₃₎ - represents, R ₃ is an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, a sulfonamido group, a ureido group or a sulfamoylamino group Represent. R ₁ and R ₂ , and R ₂ and R ₃ may be bonded to each other to form a ring. Further, the general formula (I) and the general formula (I
Details regarding I) are as described in JP-A-4-229860. Specific examples of the compound of the present invention are shown below, but the present invention is not limited thereto.

[0009]

[Chemical 4]

[0010]

[Chemical 5]

In the fixing solution of the present invention, if desired, a hardening agent (for example, a water-soluble aluminum compound), a preservative (for example, sulfite, bisulfite), a pH buffer (for example, acetic acid, boric acid), and a pH. Modifiers (eg ammonia, sulfuric acid), chelating agents, surfactants, wetting agents, fixing accelerators can be included. Examples of the surfactant include anionic surfactants such as sulfates and sulfonates, polyethylene surfactants, and amphoteric surfactants described in JP-A-57-6840. Further, a known antifoaming agent may be added. Examples of the wetting agent include alkanolamine and alkylene glycol.
As the fixing accelerator, for example, JP-B-45-35754
Nos. 58-122535 and 58-122536, thiourea derivatives described therein, alcohols having a triple bond in the molecule, and thioether compounds described in US Pat. No. 4,126,459. As the pH buffering agent, for example, organic acids such as acetic acid, malic acid, succinic acid, tartaric acid and citric acid, and inorganic buffering agents such as boric acid, phosphate and sulfite can be used. It is preferable to use an inorganic buffering agent from the viewpoint of suppressing odor and rusting of equipment materials. Here, the pH buffer is used for the purpose of preventing the pH rise of the fixing solution due to the carry-in of the developing solution, and is used in an amount of 0.1 to 1.0 mol / liter, more preferably 0.2 to 0.6 mol / liter. .

As the hardening agent in the fixing solution of the present invention, there are water-soluble aluminum salts and chromium salts. A preferred compound is a water-soluble aluminum salt, such as aluminum chloride, aluminum sulfate, potassium alum. The fixing temperature and time are preferably about 20 ° C. to about 50 ° C. and 5 seconds to 1 minute. The effect of the present invention becomes remarkable when the replenishing amount of the fixing solution is 350 ml / m ² or less.

The developer used in the development processing of the light-sensitive material of the present invention may contain additives usually used (eg, developing agent, alkaline agent, pH buffering agent, preservative, chelating agent). . Any known method can be used for the development processing of the present invention, and a known development processing solution can be used. The developing agent used in the developing solution used in the present invention is not particularly limited, but preferably contains dihydroxybenzenes and ascorbic acids,
Further, from the viewpoint of developing ability, a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or a combination of dihydroxybenzenes and p-aminophenols or ascorbic acids and 1-phenyl-3-pyrazolidones is preferable. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinones being particularly preferable. 1-Phenyl-3-pyrazolidone, 1- as a developing agent for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention
Phenyl-4,4-dimethyl-3-pyrazolidone, 1-
Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. Among them, N-methyl-p-aminophenol is preferable. The dihydroxybenzene type developing agent is usually 0.05 mol / liter to 0.8.
It is preferably used in an amount of mol / l. When a combination of 1-phenyl-3-pyrazolidones or p-aminophenols with dihydroxybenzenes or ascorbic acids is used, the former is 0.05 mol / liter to 0.5 mol / liter and the latter is 0.06 mol / liter. It is preferably used in an amount of not more than mol / liter.

Examples of preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite.
Sulfite is 0.05 mol / liter or more, especially 0.15
It is used in an amount of more than 1 mol / l, but if added in an excessively large amount, it precipitates in the developer and causes liquid contamination, so the upper limit is preferably 1.2 mol / l. The alkaline agent used for setting the pH is a usual water-soluble inorganic alkali metal salt (for example, sodium hydroxide, potassium hydroxide,
Sodium carbonate, potassium carbonate) can be used. As additives used other than the above, development inhibitors such as sodium bromide and potassium bromide; organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide; alkanolamines such as diethanolamine and triethanolamine, Development accelerator of imidazole or a derivative thereof; mercapto compounds such as 1-phenyl-5-mercaptotetrazole, indazole compounds such as 5-nitroindazole, benzotriazole compounds are antifoggants or black pepper inhibitors. In addition, a color tone agent, a surfactant, a defoaming agent, a water softening agent, a hardener, etc. may be contained as necessary. Further, the compound described in JP-A-62-212651 can be used as the development unevenness preventing agent, and the compound described in JP-A-61-267759 can be used as the dissolution aid.

In the developer used in the present invention, a boric acid described in JP-A-62-186259, a saccharide (eg saccharose) and an oxime (eg acetoxime) described in JP-A-60-93433 are used as a buffer. , Phenols (eg 5-sulfosalicylic acid), tertiary phosphates (eg sodium salt, potassium salt) and the like are used. For the purpose of transportation cost of the treatment liquid, packaging material cost, space saving, etc., it is preferable to concentrate the treatment liquid and dilute it before use. In order to concentrate the developer, it is effective to potassium salt the salt component contained in the developer.

The photosensitive material which has been developed and fixed is then washed with water or stabilized. The washing or stabilizing treatment may be carried out with a replenishing amount of 3 liters or less (including 0, that is, washing with water) per 1 m ^{2 of the} silver halide light-sensitive material. That is, not only is it possible to save water,
It is possible to eliminate the need for piping for the automatic processor. When the washing with water is carried out with a small amount of water, JP-A-63-18350 and JP-A-6-18350.
A squeeze roller as described in No. 2-287252,
It is more preferable to provide a cleaning tank for the crossover roller. In addition, various oxidants may be added or filter filtration may be combined in order to reduce the pollution load which becomes a problem when washing with a small amount of water. Further, a part or all of the overflow liquid from the washing or stabilizing bath produced by supplementing the washing or stabilizing bath with antifungal means by the method of the present invention depending on the treatment is disclosed in JP-A-60- As described in No. 235133, it can also be used for a processing solution having a fixing ability which is a processing step before that. Further, a water-soluble surfactant or an antifoaming agent may be added in order to prevent water bubble unevenness that tends to occur when washing with a small amount of water and / or to prevent the processing agent component attached to the squeeze roller from being transferred to the processed film. Good. Further, a dye adsorbent described in JP-A-63-163456 may be installed in a water washing tank to prevent contamination by dyes eluted from the light-sensitive material.

There is also a case where a stabilizing treatment is carried out subsequent to the water washing treatment, and as an example, there is JP-A-2-201357.
The baths containing the compounds described in JP-A Nos. 2-132435, 1-1022553, and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, ammonium compounds, metal compounds such as Bi and Al, fluorescent whitening agents, various chelating agents, film pH adjusting agents, film hardening agents, bactericides, fungicides, alkanolamines and surface active agents can also be used in this stabilizing bath. Agents can also be added. Water used in the washing or stabilization process includes tap water, deionized water, halogen, water sterilized with ultraviolet germicidal lamps and various oxidizers (ozone, hydrogen peroxide, chlorate, etc.). Preference is given to using.

In the developing treatment of the present invention, the developing time is 25 seconds or less, preferably 6 to 15 seconds, and the developing temperature is 25 ° C.
-50 degreeC is preferable and 30 degreeC-40 degreeC is more preferable.
The fixing temperature and time are preferably about 20 ° C. to about 50 ° C. and 19 seconds or less, more preferably 30 ° C. to 40 ° C. and 6 seconds to 15 seconds. The temperature and time for washing or stabilizing bath are more preferably 0 to 50 ° C. According to the method of the present invention, a photographic material that has been developed, fixed and washed (or stabilized) is squeezed out of the washing.
That is, it is dried after passing through a squeeze roller. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time can be appropriately changed depending on the ambient conditions.

The silver halide emulsion used in the light-sensitive material of the present invention contains, as silver halide, a conventional halogenated silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide or the like. Any silver emulsion can be used, and as a negative type silver halide emulsion, silver chlorobromide containing 60 mol% or more of silver chloride or positive type silver halide of 60 mol% or more can be used. Silver chlorobromide, silver bromide, and silver iodobromide containing silver.
The silver halide grains may be obtained by any of the acidic method, the neutral method and the ammonia method. The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain or a core / shell grain having a different silver halide composition between the inside and the surface layer of the grain, and the latent image is mainly on the surface. The particles may be particles that are formed inside the particles, or particles that are mainly formed inside the particles. The silver halide grains according to the present invention may have any shape. One example is a cube with {100} faces as the crystal surface. US Pat. No. 4,183,75
6, No. 4,225,666, JP-A-55-2658.
No. 9, Japanese Patent Publication No. 55-42737, etc., and The Journal of Photographic Science ((J.Photgr.
Sci.), 21-39 (1973), and the like, particles having a shape such as an octahedron, a tetrahedron, and a dodecahedron can be prepared and used. Furthermore,
You may use the grain which has a twin plane. In particular, tabular grains having an aspect ratio of 4 or more may be used. The silver halide grain according to the present invention may be a grain having a single shape, or may be a mixture of grains having various shapes.

The silver halide grains used in the emulsion of the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or complex salt in the course of forming grains and / or in the process of growing. , An iron salt or a complex salt may be used to add a metal ion so that the metal ion can be included inside the particle and / or on the particle surface. The photographic emulsion used in the present invention may be used in combination with sulfur sensitization, gold / sulfur sensitization, reduction sensitization using a reducing substance: noble metal sensitization using a noble metal compound, and the like. As the photosensitive emulsion, the above emulsions may be used alone, or two or more kinds of emulsions may be mixed. In the practice of the present invention, after completion of the chemical sensitization as described above, for example, 4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene, 5-mercapto-1
Various stabilizers can be used including phenyltetrazole and 2-mercaptobenzothiazole. Further, if necessary, a silver halide solvent such as thioether, or a crystal habit controlling agent such as a mercapto group-containing compound or a sensitizing dye may be used. In the present invention, particularly in the case of a photosensitive material for printing, a preferable effect is exhibited for a photosensitive material to which a so-called contrast-increasing agent such as a tetrazolium compound, a hydrazine compound or a polyalkylene oxide compound is added.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion may be spectrally sensitized with blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. These sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used especially for the purpose of supersensitization. The silver halide photographic light-sensitive material 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 and halation. 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. Specific examples of dyes that can be used are West German Patent 616,00.
7, British Patent 584,609, 1,117,42
No. 9, Japanese Patent Publication No. 26-7777, No. 39-22069
No. 54-38129, JP-A-48-85130.
No. 49-99620, No. 49-114420,
49-129537, PB Report 4175, Photographic Abstract (Photo.Abstr.) 1
28 ( ^'21 ) and the like. In particular, it is preferable to use these dyes in a bright room reversal light-sensitive material. In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like. Various compounds can be added to the above photographic emulsion in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. Further, a technique of incorporating a polymer latex into a silver halide emulsion layer or a backing layer to improve dimensional stability can also be used. These techniques are disclosed, for example, in Japanese Examined Patent Publication Nos. 39-4272 and 39-17702.
No. 43-13482, etc. Gelatin is used as the binder of the light-sensitive material used in the present invention. Examples include gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, and single or copolymers. A hydrophilic colloid such as a synthetic hydrophilic polymer substance can also be used in combination.

Various additives may be further used in the light-sensitive material of the present invention depending on the purpose. These additives are described in more detail in Research Disclosure No. 17
Volume 6 Item 17643 (December 1978) and 18
Volume 7 Item 18716 (November 1979), the relevant parts are summarized as follows. Additive type R17643 RD18716 1. Chemical sensitizer page 23 page 648 right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggant, pages 24 to 25, page 649, right column, and stabilizer 6. Light absorbers, filters Pages 25-26 649 Right column-Dyes, UV absorbers 650 Left column 7. Anti-staining agent, page 25, right column, page 650, left to right column 8. Dye image stabilizer, page 25 9. Hardener, page 26, page 651, left column 10. Binder, page 26, same as above 11. Plasticizer, lubricant, page 27, 650, right column 12. Coating aids / surfactants, pages 26-27, same as above 13. Antistatic agent, page 27 Same as above

The processing liquid used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The roller-conveying type automatic developing machine is described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and is herein simply referred to as a roller-conveying type processor. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. .

[0024]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 Preparation of Emulsion A In a gelatin aqueous solution kept at 40 ° C., an aqueous silver nitrate solution and 3 × 10 ⁻⁸ mol of K ₃ IrCl ₄ and 3 × 10 ⁻⁷ mol of (NH ₄ ) ₃ RhCl were added per 1 mol of silver. A monodispersed silver chlorobromide emulsion having an average grain size of 0.15 μm was prepared by simultaneously adding an aqueous solution of sodium chloride and sodium bromide containing ₆ for 30 minutes and maintaining the potential at 200 mV during that period. To this emulsion, 0.1 mol% potassium iodide aqueous solution was added per mol of silver for conversion, followed by desalting by flocculation method and dispersion in gelatin to prepare Emulsion A. (AgCl _69.9 Br ₃₀ I _0.1 , dispersion coefficient 10
%), To this emulsion, hypo and N, N dimethylselenourea were added and kept at 60 ° C. for chemical ripening, and then 4-hydroxy-6-methyl-1,3,3a, as a stabilizer.
A 1% solution of 7-tetrazaindene was added at 3 per mole of silver.
0 ml was added.

To 1 kg of these emulsions, a compound of the following structural formula was used as an infrared sensitizing dye, and 60 ml of a 0.05% solution thereof was added to carry out infrared sensitization. For the purpose of supersensitization and stabilization of the emulsion, 0,4'-bis- [4,6-di (naphthoxy-pyrimidin-2-ylamino] -stilbene-2,2'-disulfonic acid disodium salt was added to the emulsion. .5
% Methanol solution (50 ml), 2,5-dimethyl-3-aryl-benzothiazole iodo salt (0.5 ml) in methanol (90 ml) and potassium bromide (1% in water) (15 ml).

Further, hydroquinone 100 mg / m ² , polyethyl acrylate as a polymer latex 25% gelatin binder ratio, and 2-bis (vinylsulfonylacetamide) ethane as a hardener were added, and 2.5 g of silver / g on a PET support. It was applied so as to be m ² . The gelatin was 1.3 g / m ² . 0.6g of gelatin on this
m ² , polymethylmethacrylate 60 mg / m ² having a particle size of 3 to 4 μ as a matting agent, colloidal silica 40 mg / m ² having a particle size of 10 to ²⁰ μm, silicone oil 100 mg / m ² , dye 20 mg / m ^{2 having} the following structural formula, Dye 10 mg / m ² was added, and dodecylbenzene sulfonic acid sodium salt as a coating aid, a fluorine-containing surfactant of the following structural formula was added to the protective layer and the back surface of the support: 0.7 g / m ² , gelatin; acrylate latex 225 mg / m ^2, average particle diameter polymethyl methacrylate 40 mg / m ² of 5μ dye having the structural formula shown below 70 mg / m ^2, and as a matting agent, and sodium dodecyl benzene sulfonate salt as a coating aid and 2mg / A back layer containing m ² was simultaneously applied to prepare a light-sensitive material.

[0027]

[Chemical 6]

The light-sensitive material thus produced was processed using the following developing solution, fixing solution and developing machine without exposing it to light. The fixing liquid tank and washing water tank of the automatic developing machine are of the same type, and the number of opposed rollers is 7. The size of the photosensitive material is 20 × 24
Inches were used.

(Developer) Potassium sulfite 30.0 g Diethylenetriaminepentaacetic acid 2.4 g Sodium isoascorbate 55.0 g Diethylene glycol 10.0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.0 g 5- Methylbenzotriazole 0.06 g 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) quinazolinone 0.20 g 2-mercaptobenzimidazole-5-sulfonic acid 0.30 g 1000 ml pH = 10.30

(Fixer) Ammonium thiosulfate Addition amount shown in Table 1 Compound of the present invention (compound of Chemical formula 4 and 1) The addition amount is shown in Table 1 Acetic acid 15.0 g Sodium bisulfite 15.0 g Disodium ethylenediaminetetraacetate Dihydrate 0.025g Add water and adjust to pH = 5.50 with 1000ml sodium hydroxide

(Processing conditions of developing machine) Development temperature 35 ° C. Fixing temperature 35 ° C. Fixing time 16 seconds Fixing processing results are shown in Table 1.

[0032]

[Table 1]

The evaluation of the fixing gap was made in the sample of 20 × 24 inch size ..... Fixing was good.

C. O. D. The fixing solution prepared in Table 1 was diluted 100-fold according to JIS K 0102, and the C.I. O. D. (Chemical oxygen demand) was measured. What is a running liquid? Photosensitive material 1
This is the result of running processing of 50 m ² of light-sensitive material while replenishing 320 ml of fixing solution per m ² . As shown in the result of Table 1, the experiment numbers 6, 7, 8, 10, 1 of the present invention are shown.
In the case of 1, 12, 22, 23, 24, 26, 27, 28, C.I. O. D. Despite the low value, good fixing loss can be obtained.

Example 2 Preparation of tabular grains 4.5 g potassium bromide and 2 gelatin in 1 liter of water.
0.6 g, 5 of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
% Aqueous solution (2.5 cc) and agitated into a container kept at 60 ° C. while stirring, a double jet of 33 cc of an aqueous solution of silver nitrate 37 ° C. (3.43 g of silver nitrate), 2.97 g of potassium bromide and 0.363 g of potassium iodide. Method for 37 seconds. Next, an aqueous solution of 0.9 g of potassium bromide was added, and then the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (silver nitrate 4.
90 g) was added over 13 minutes. Here, 15 cc of 25% aqueous ammonia solution was added, and 14 cc of 100% acetic acid solution physically aged for 20 minutes at the same temperature was added.
Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the pAg at 8.5. Next, 10 cc of 2N potassium thiocyanate solution and AgI having a diameter of 0.07 μm.
Fine particles were added in an amount of 0.44 mol% based on the total amount of silver. 5
After physically aging at the same temperature for 3 minutes, the temperature was lowered to 35 ° C. Thus, the total silver iodide content is 0.70 mol%,
Average projected area diameter 1.10 μm, thickness 0.165 μm,
Monodisperse tabular grains having a diameter variation coefficient of 18.5% were obtained.
After this, the soluble salts were removed by the sedimentation method. 40 again
The temperature was raised to 0 ° C., 20 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 5.90 and pAg was 8.25 with caustic soda and silver nitrate solution.

Preparation of coating sample The following chemicals were added to 1 mol of silver halide to prepare a coating liquid.・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg ・ Gelatin The total coating amount with gelatin used in the surface protective layer described later was 2. 58 g / m ² was added ・ Trimethylolpropane 9 g ・ Dextran (average molecular weight 39,000) 18.5 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g ・ Hardener 1,2-bis (Vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 230%

[0037]

[Chemical 7]

Preparation of Coating Solution for Surface Protective Layer The surface protective layer was prepared and prepared so that each component had the following coating amount. Contents of surface protective layer Coating amount-Gelatin 1.15 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.023

[0039]

[Chemical 8]

Preparation of Support (1) Preparation of Dye D-1 for Undercoat Layer The following dyes were ball milled by the method described in JP-A-63-197943.

[0041]

[Chemical 9]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 4
The contents added with 00 ml (2 mm diameter) were ground for 4 days.
After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observing the obtained dye dispersion, the particle size of the crushed dye has a wide range of diameters from 0.05 to 1.15 μm, and the average particle size was 0.37 μm. further,
Dye particles having a size of 0.9 μm or more were removed by performing a centrifugation operation. Thus, Dye Dispersion D-1 was obtained. (2) Preparation of support Corona discharge treatment was performed on a polyethylene terephthalate film having a thickness of 183 μm that was biaxially stretched, and the coating amount of the first undercoat liquid having the following composition was 5.1 cc / m ^2. Apply by wire bar coater, 175 ℃
And dried for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0043]

[Chemical 10]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc Distillation Water 900.5 cc * The latex solution contains 0.4 wt% of the following compounds as an emulsion dispersant, based on the latex solid content.

[0045]

[Chemical 11]

A second undercoat layer having the following composition was applied on each of the above-mentioned first undercoat layers one by one so that the coating amount would be the amount described below, and 150 on each side by a wire bar coater system. Coated and dried at ℃.・ Gelatin 160 mg / m ²・ Dye Dispersion D-1 (26 mg / m ² as a solid dye component)

[0047]

[Chemical 12]

Matting agent Polymethylmethacrylate having an average particle size of 2.5 μm 2.5 mg / m ²

Preparation of photographic material On the prepared support, the above emulsion layer and surface protective layer were coated on both sides by the simultaneous extrusion method. The amount of coated silver per one side was 1.35 g / m ² . The amount of coated gelatin and the swelling ratio obtained by the freeze-drying method using liquid nitrogen were adjusted to 230% by adjusting the amount of gelatin added to the emulsion layer and the amount of hardener. The swelling ratio here is measured by the method described in US Pat. No. 4,414,304. The photographic material produced in this way was modified by modifying the drive motor and gear of the automatic developing machine CEPROS-M manufactured by Fuji Photo Film Co., Ltd. without exposing it to D
Processing was performed by setting the processing time of ry to Dry to 30 seconds.

Development Replenisher Part A Potassium hydroxide 13.0 g Potassium sulfite 30.0 g Potassium carbonate 80.0 g Diethylene glycol 10.0 g 1- (N, N diethylamino) ethyl-5-mercapto tetrazole 0.05 g L-ascorbic acid 43. 0 g 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.0 g Diethylenetriaminepentaacetic acid 2.0 g Water was added 400 ml PartB Triethylene glycol 50.0 g 3,3'-Dithiobishydrocinnamic acid 0. 4 g Glacial acetic acid 5.0 g 5-Nitroindazole 0.3 g 1-Phenyl-3-pyrazolidone 3.5 g Water was added to 60 ml Part C Glutaraldehyde 5.0 g Potassium bromide 1.0 g Potassium metabisulfite 10.0 g Water In addition, 60 ml Part A 400 ml, P 60 ml of artB and 60 ml of Part C are added to make 1 liter of working solution, and the pH is adjusted to 11.0. Part
A 4.8 liters of Part A, 720 ml of Part B, and 720 ml of Part C were filled in a CE-D1 bottle manufactured by Fuji Photo Film Co., Ltd. for use in 12 liters of the working solution.

Fixing solution Sodium thiosulfate pentahydrate Addition amount shown in Table 2 Compound of the present invention (compound of Chemical formula 4 and 1) Addition amount shown in Table 2 Boric acid 4.0 g Sodium bisulfite 15.0 g Acetic acid 30.0 g Aluminum sulphate 8.0g Ethylenediamine / tetraacetic acid / disodium 0.025g Add water to adjust the pH to 4.90 with sodium hydroxide 500 ml Add 500 ml of this fixer to make 1 liter and use this fixer 6 liters of C from Fuji Photo Film Co., Ltd.
The E-F1 bottle was filled and used for 12 liters of the working solution.

Development temperature: 35 ° C. Fixing temperature: 35 ° C. Drying temperature: 55 ° C. Replenishment amount (both developing solution and fixing solution) 320 ml / m ² Fixing C. O. D. Table 2 shows the results obtained by evaluating the measurement conditions and running conditions in the same manner as in Example 1. Here, the new solution is a solution adjusted to pH = 10.20 by adding 3.0 g of potassium bromide and acetic acid per 1 liter of the developing replenisher. The results obtained are shown in Table 2.

[0053]

[Table 2]

As shown in the results of Table 2, in the case of the experiment numbers 38, 39, 40, 49, 50 and 51 of the present invention, the C.I. O. D. Despite the low value, good fixing loss can be obtained. In this example, Fuji medical X-ray film, Super HR-S-, Super HR-A,
Super HR-C, Super HR-L, Super HR-
H, MI-NP, MI-NC Fuji image recording film L
It should be noted that development processing with I-FM and LI-HM gave a tendency similar to that of this example.

(Preferred Embodiment of the Present Invention) The processing method according to claim 1, wherein the developing solution is a one-component concentrated developing solution. 2. When the dialdehyde hardener nitroindazoles are contained, it is a concentrated developer containing two or more liquids contained in another part. 3. 2. The processing method according to claim 1, wherein the silver halide grains are tabular grains and a silver halide light-sensitive material having an average aspect ratio of 4 or more is used. 4. The processing method according to claim 2, wherein a silver halide photographic light-sensitive material having a swelling ratio of 150% or more is used. 5. ^2. The processing method according to 1 above, wherein the amount of silver applied to both sides of the photographic light-sensitive material is 3.5 g or less per 1 m ² . 6. 2. The processing method according to claim 1, wherein a cubic silver monodisperse silver halide photographic material having silver halide grains of 0.4 [mu] or less is used. 7. The processing method according to claim 1, wherein a total processing time (Dry to Dry) is 20 seconds to 100 seconds. 8. 2. The processing method according to claim 1, wherein the heating means of the roller portion in contact with the photosensitive material before the drying section of the automatic development processing apparatus is at 70.degree. 9. 3. The processing method according to claim 2, wherein when the chemical mixer is built into the automatic development processing apparatus, the automatic development processing apparatus has a mechanism of simultaneously using up the developing solution and fixing solution cartridges. Ten. The opening ratio of the developing tank of the automatic development processor is 0.04
The method according to claim 2, wherein the treatment method is cm ^-1 or less. 11. A photographic light-sensitive material comprising an emulsion layer spectrally sensitized to 600 nm or more and a colored back layer, which comprises a silver halide grain having a 100/111 face ratio of 5 or more, on a transparent support. Item 1 processing method. 12. A light-sensitive material comprising an emulsion layer spectrally sensitized to 600 nm or more and a colored back layer, which comprises silver halide grains having a 111/100 face ratio of 5 or more, on a transparent support. Item 1 processing method. 13. The developing concentrate and the fixing concentrate consist of one part, and each concentrate and water are diluted to a working solution in each tank and supplied as a replenisher (direct mixing dilution method). The processing method according to claim 1. 14. The processing method according to claim 1, wherein the container of the developing concentrate and the container of the fixing concentrate are integral type packaging materials. 15. An automatic processor equipped with a rinse tank and a rinse roller (crossover roller) between the developing tank and the fixing tank and between the fixing tank and the water washing tank is used.
Processing method. 16. The processing method according to claim 1, wherein various water redness preventive agents (antibacterial agents) are used in an automatic processor installed in a stock tank of water supplied to a washing tank and a rinse tank. 17. The processing method according to claim 1, wherein an automatic processor having a solenoid valve installed at the drain of the washing tank is used. 18. The processing method according to claim 1, wherein the water washing tank of the automatic development processing apparatus has a multi-chamber tank and a multi-stage countercurrent water system.

Claims (2)

[Claims] 1. A treatment using a fixing solution containing a thiosulfate of 0.3 mol / liter or more and less than 0.5 mol / liter and a mesoionic compound represented by the following general formula (I). A method for processing a black and white silver halide photographic light-sensitive material. General formula (I) In the formula, Z represents an atomic group necessary for forming a 5- or 6-membered ring, and is selected from carbon atom, nitrogen atom, oxygen atom, sulfur atom or selenium atom. X ^- is ^-O -, -S ^-, or -N-R
Represents R represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group. 2. The processing method according to claim 1, wherein the processing is carried out using a fixing replenishing solution of 350 ml or less per 1 m ^{2 of the} black and white silver halide photographic light-sensitive material.