JPH08272053A - Development processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a development processing method for the silver halide photographic sensitive material good in developability and superior in stability against time lapse. CONSTITUTION: The silver halide photographic sensitive material is imagewise exposed and processed with a pretreatment solution having a pH of <7 and processed with an aqueous alkaline solution, and this photosensitive material contains a compound represented by the formula in which each of R1 and R2 is an hydroxyl, amino, acylamino, alkylsulfonylamido, arylsulfonylamido, alkoxycarbonylamido, mercapto, or alkylthio group; and X is an atomic group necessary to form a 5- or 6-membered heterocyclic or hydrocarbon ring.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method of developing and processing a silver halide photographic light-sensitive material excellent in developability and stability over time.

[0002]

2. Description of the Related Art Conventionally, many developing processes are carried out with a developing solution consisting of one solution. However, with this method, the developing agent in the developing solution is air-oxidized with the lapse of time to deteriorate the developing activity, and it is difficult to maintain a stable developing level. When the development level changes, stable image density cannot be obtained,
Good images cannot be obtained. Further, increasing the developing activity of the developing solution and increasing the processing amount of the silver halide photographic light-sensitive material per unit processing solution can reduce the amount of waste liquid and is preferable from the environmental aspect. However, raising the pH of the developer as a means of increasing the development activity of the developer accelerates air oxidation and further deteriorates the stability over time. Therefore, both the developability and the stability over time are superior to the conventional technology. It was not possible to obtain a treatment method.

Further, in the processing method for a reversal light-sensitive material, it is preferred that the developing solution has a two-component constitution.
No. 28 and JP-A-63-103237, and in tanning development, the developer is composed of two liquids, JP-A-63-318556 and JP-A-63-3185.
No. 57. However, there is no description of a pretreatment liquid containing the compound represented by the general formula [1], and no description is given of the constitution of the present invention exhibiting excellent effects in both developability and stability over time.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which has good developability and excellent stability over time.

[0005]

The object of the present invention is achieved by the following constitutions.

1. A silver halide photographic light-sensitive material containing a compound represented by the following general formula [1] and exposed imagewise with a pretreatment liquid having a pH of less than 7 and then treated with an alkaline aqueous solution. Development processing method of silver halide photographic light-sensitive material.

[0007]

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(In the general formula [1], R ₁ and R ₂ each represent a hydroxyl group, an amino group, an acylamino group, an alkylsulfonylamide group, an arylsulfonylamide group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group, X represents an atomic group necessary for forming a 5- or 6-membered heterocycle or carbocycle.

2. Item 2. The method for developing a silver halide photographic light-sensitive material as described in Item 1, wherein the pH of the pretreatment liquid is 3 or more.

3. 2. The development processing method for a silver halide photographic light-sensitive material according to item 1, wherein the alkaline aqueous solution contains a buffering agent and has a pH of 9 or more.

4. 2. The development processing method for a silver halide photographic light-sensitive material according to item 1, wherein the alkaline aqueous solution contains a buffering agent and has a pH of 10.5 or higher.

5. 2. The development processing of the silver halide photographic light-sensitive material according to item 1, wherein the silver halide photographic light-sensitive material contains a silver halide emulsion layer containing silver halide grains having an average aspect ratio of 2 or more. Method.

6. Item 2. The silver halide photograph according to Item 1, wherein the silver halide photographic light-sensitive material contains a silver halide emulsion layer containing silver halide grains having an average aspect ratio in the range of 3 to 8. Development processing method of photosensitive material.

The present invention will be described in detail below.

First, the compound represented by the general formula [1] will be described. In the general formula [1], R ₁ and R ₂ are each a hydroxyl group, an amino group, an acylamino group, an alkylsulfonylamide group, an arylsulfonylamide group,
It represents an alkoxycarbonylamino group, a mercapto group or an alkylthio group, and X represents an atomic group necessary for forming a 5- or 6-membered heterocycle or carbocycle.

The non-metal atom constituting the heterocycle of X is preferably a carbon atom, as well as an oxygen atom and / or a nitrogen atom, and particularly the non-metal atom group is --O-- or --C (R ₃ ).
_{(R 4) -, - C} (R 5) =, - CO -, - N (R 6)
It is preferable to be configured by combining − and −N =. However, R ₃ , R ₄ , R ₅ , and R ₆ represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a hydroxyl group, or a carboxyl group. The 5- or 6-membered heterocycle or carbocycle composed of two vinyl carbons and carbonyl carbons substituted by X, R ₁ and R ₂ in the general formula [1] is a saturated or unsaturated condensed ring. May be formed. Further, the 5-membered or 6-membered heterocyclic ring or carbocyclic ring composed of two vinyl carbons and carbonyl carbons substituted by X, R ₁ and R ₂ in the general formula [1] has a substituent. May be. Examples of the 5- or 6-membered heterocyclic ring and carbocyclic ring include a dihydrofuran ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring. Further, each of the above groups and each ring also include those having a substituent. Any of these substituents may be adopted,
It is necessary that the compound represented by the general formula [1] is dissolved in the pretreatment liquid of the present invention, and a hydroxyl group, a carboxyl group, a sulfo group, a lower alkyl group such as a methyl group and an ethyl group, and a phenyl group are preferable. . Specific examples of the compound represented by the general formula [1] are shown below, but the invention is not limited thereto.

[0017]

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[0018]

[Chemical 4]

Further, the pretreatment liquid of the present invention is an aqueous solution containing the compound represented by the general formula [1] (hereinafter, the compound of the present invention), and the content of the compound is generally the above compound. Since it is water-soluble, it is optional, but is preferably 0.057 to 0.57 mol per liter of the pretreatment liquid, and particularly preferably 0.11 to 0.2 per liter of the pretreatment liquid.
3 mol.

The compounds of the present invention generally have poor storability under neutral and alkaline conditions. From that point as well, the pretreatment liquid of the present invention is preferably placed under acidic conditions, and in the processing method of the present invention, development is carried out from the pretreatment liquid of the present invention to an alkaline aqueous solution by means of a silver halide photographic light-sensitive material. Made by the compound of the present invention. Therefore, various additives that are added to conventional developers can be used in the alkaline aqueous solution. The present invention was able to achieve the above-mentioned object by utilizing the characteristics of the compound of the present invention, which was completely unpredictable from the conventional two-liquid treatment.

PH of pretreatment liquid containing the compound of the present invention
Is less than 7, and more preferably the p of the pretreatment liquid used
H is 3 or more and less than 7. The pretreatment liquid and the alkaline aqueous solution containing the compound of the present invention are used as development accelerators in Japanese Patent Publication Nos. 37-16088, 37-5987, 38-7826,
44-12380, 45-9019 and U.S. Pat.Nos. 3,813,247, thioether compounds, p-phenylenediamine compounds represented by JP-A-52-49829 and 51-15554, 50-137726, JP-B-44-30074, JP-A-56-
Quaternary ammonium salts represented by 156826 and 52-43429, etc., described in US Pat. Nos. 2,610,122 and 4,119,462
p-Aminophenols, U.S. Patents 2,494,903 and 3,12
No.8,182, No.4,230,796, No.32-53919, Japanese Patent Publication No.41-114
31, U.S. Patents 2,482,546, 2,596,926 and 3,58.
Amine compounds described in 2,346, etc., Japanese Examined Patent Publication No. 37-16088
No. 42-25201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11
431, 42-23883 and U.S. Pat. No. 3,532,501 and other polyalkylene oxides and other 1-phenyl-3-
Pyrazolidones, hydrazines, mesoionic compounds,
Ionic compounds, imidazoles and the like can be added as necessary.

In the pretreatment liquid and the alkaline aqueous solution containing the compound of the present invention, an alkali metal halide such as potassium iodide and an organic antifoggant can be used as an antifoggant. As the organic antifoggant, for example,
Benzotriazole, 6-nitrobenzimidazole, 5-
Nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole,
A typical example of the nitrogen-containing heterocyclic compound such as hydroxyazaindolizine and adenine is 1-phenyl-5-mercaptotetrazole.

The pH of the alkaline aqueous solution of the present invention may be 7 or more, but 9 or more is preferably used, and more preferably 10.5 or more. The upper limit of the pH of the alkaline aqueous solution of the present invention is not particularly limited, but in practice p
It is H14 or less.

The alkaline aqueous solution of the present invention preferably contains a buffer. As a preferable buffering agent,
Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate , Sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2
-Sodium hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The pretreatment solution and the alkaline aqueous solution containing the compound of the present invention are methyl cellosolve, methanol,
Acetone, dimethylformamide, a cyclodextrin compound, and other compounds described in JP-B Nos. 47-33378 and 44-9509 can be added and used. further,
Various additives such as an anti-stain agent, an anti-sludge agent and a multi-layer effect accelerator can be added and used.

In addition to the dihydroxybenzenes, aminophenols and pyrazolidones described in Japanese Patent Application No. 4-286232 (pages 19 to 20), reductones described in JP-A-5-165161 are preferably added and used. You can

The treatment temperature of the pretreatment liquid and the alkaline aqueous solution containing the compound of the present invention is preferably 10 to 45 ° C, more preferably 25 to 38 ° C. In the processing method according to the present invention, the image silver is formed imagewise by processing with the alkaline aqueous solution as described above. The silver halide that has not been imaged is optionally subjected to ordinary fixing treatment, desilvering, washing with water and drying treatment to obtain a photographic material. On the other hand, before the treatment with the pretreatment liquid according to the present invention, a pretreatment such as a predural treatment may be performed. Known arbitrary processing is applied to the processing such as fixing which is arbitrarily performed.

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No.176
43 (December 1978) ・ Pages 22-23 1. Emulsion manufacturing method (Emulsion
Preparation and types) and the same (RD) No. 18716 (1979 1
January) -Can be prepared by the method described on page 648. For example, see “The theory of the photogr” by TH James.
aphic process ”4th edition, published by Macmillan (1977) 38-10
Method described on page 4, GF Daufin "Photoemulsion Chemistry""Ph
otographic emulsion Chemistry ”, published by Focal press (1
966), P. Glafkides, "The Physics and Chemistry of Photography," Chimie et
physique photographique ”published by Paul Montel (1967
), VL Zelikman et al., "Manufacturing and Coating of Photographic Emulsions""Ma
king and Coating Photographic Emulsion ”Focal pres
It is prepared by the method described in, for example, s company publication (1964).

The silver halide emulsions preferably used in the present invention are, for example, JP-A-59-177535 and 61-802237.
No. 61-132943, No. 63-49751 and JP-A No. 63-238225.
No. 6,096,849, and the like. Examples thereof include silver halide emulsions containing internal high iodine type monodisperse silver halide grains. The crystal habits of the crystals of these silver halide grains are cubic, tetradecahedral, and 8
The (111) face and the (100) face in the face and the intermediate face may be arbitrarily mixed. The crystal structure of silver halide may be composed of different silver halide compositions inside and outside. A preferred embodiment of the emulsion is a core / shell type monodisperse emulsion having a multi-layered silver halide grain comprising a low iodine shell layer in a high iodine core portion. The silver iodide content of the high iodine portion is 20 to 40 mol%, preferably 20 to 30 mol%. Examples of these include, for example, J.Phot.Sic.12.242 ~ 2
51 pages (1963), JP-A-48-36890, 52-16364, 55-1
42329, 58-49938, British Patent 1,413,748, U.S. Patent 3,574,628, 3,655,394, British Patent 1,027,146
U.S. Pat.Nos. 3,505,068 and 4,444,877, JP-A-60-1
It is described in publications such as 4331.

The silver halide emulsion used in the processing method of the present invention is preferably a silver halide emulsion containing tabular grains having an average aspect ratio of 2 or more.
Furthermore, tabular grains having an average aspect ratio in the range of 3 to 8 are preferably used. The average aspect ratio is obtained by dividing the average grain size of silver halide grains by the average grain thickness.
The aspect ratio referred to here is, in a twin grain having two or more parallel twin planes, when a grain is projected from a direction perpendicular to the twin plane, the projected image of the grain becomes a circular image of the same area. It is the ratio (ratio of particle diameter / particle thickness) of the converted diameter and the distance (particle thickness) between the surfaces of two particles parallel to the twin plane. The particle size is, for example, 10,000 times to 5 times with an electron microscope.
It is obtained by enlarging the image by a factor of 10,000 and measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is indiscriminately 1000 or more).
Similarly, the particle thickness can be obtained by actually measuring an electron micrograph. Silver halide emulsions containing these tabular grains are described in British Patent 2,112,157 and U.S. Patent 4,439,520.
Issue 4,433,048, Issue 4,414,310, Issue 4,434,226,
JP-A-58-113927, 58-127921, 63-138342,
63-284272, 63-305343, etc.
It can be easily prepared by the methods described in these publications. In particular, Japanese Patent Application No. 4-289002 (pages 1 to 3), JP-A-59-17753
5 (pages 2-5), Japanese Patent Application No. 4-277369 (pages 5-6), JP-A-62-42
146 (14 to 15) is preferably used, and it was found that the treatment liquid of the present invention has a good effect on the stability over time. Particularly preferably used in the present invention is a silver halide photographic light-sensitive material containing a silver halide emulsion which is entirely composed of tabular grain emulsions.

As the silver halide emulsion, a silver halide emulsion having a silver chloride content of 50 mol% or more can be used.

The above-described silver halide emulsions are classified into a surface latent image type which forms a latent image on the surface of a grain, an internal latent image type which forms a latent image inside the grain, and a type which forms a latent image on the surface and inside. It may be an emulsion. In these emulsions, a cadmium salt, a lead salt, a zinc acid, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof, or the like may be used in the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts.
As a preferred washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or G3, G8 as an aggregation polymer agent described in JP-A-63-158644, etc. The method used is mentioned as a preferable desalting method. The chemical ripening method of the emulsion used in the light-sensitive material of the present invention is preferably gold sensitization, sulfur sensitization, reduction sensitization, sensitization with a chalcogen compound, or a combination thereof.

The emulsion of the light-sensitive material used in the present invention can use various photographic additives in the steps of physical ripening or chemical ripening. It is also possible to add a hydrazine compound, preferably the compound of Japanese Patent Application No. 5-134743,
In particular, the general formula [5] and the general formula [7] as a nucleation accelerator are
The compound of [8] is preferable. A tetrazolium salt may be added, and those described in JP-A-2-250050 are particularly preferable. Other known additives include, for example, Research Disclosure No. 17643 (December 1978), No. 1
8716 (November 1979) and 308119 (December 1989). The following table lists the types of compounds and the locations where they are described in these three Research Disclosures.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648 to 649 966 to 8 IV Desensitizing dye 23 IV 998 B Dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII Supports usable in the light-sensitive material of the present invention include, for example, RD17643, page 28 and RD-308119, 1009.
The thing described in the page is mentioned.

A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided.

Emulsion layers may be present on both sides of the support,
It may be on only one side. In the case of both sides, both sides may have the same performance or different performances. The silver halide photographic light-sensitive material according to the present invention comprises a silver halide emulsion layer on the above-mentioned support, a non-light-sensitive hydrophilic colloid layer such as a protective layer, an intermediate layer and an undercoat layer, and simultaneous multi-layer coating. Is applied and manufactured.

[0037]

【Example】

Example 1 (1) Preparation of silver halide photographic light-sensitive material A <Preparation of silver halide grain emulsion> 1.3 mol% of silver iodide,
A tabular silver iodobromide emulsion containing the remaining 98.7 mol% of silver bromide was prepared. This emulsion had an average grain size of 1.22 μm, an average grain thickness of 0.41 μm (average aspect ratio: 2.98) and a grain size dispersibility of 0.23. The obtained emulsion was designated as emulsion (A).

Similarly, 1.3 mol% of silver iodide and the remaining 98.7
Prepare a silver iodobromide emulsion in which mol% is tabular silver bromide,
An emulsion having an average grain size of 0.69 μm, an average grain size thickness of 0.24 μm (average aspect ratio: 2.88) and a grain size dispersibility with a variation coefficient of 0.26 was obtained and designated as emulsion (B).

Further, a silver iodobromide emulsion containing 1.4 mol% of silver iodide and 98.6 mol% of the remaining silver bromide was prepared. This emulsion was an octahedron having an average grain size of 0.58 μm, and the dispersibility of grain size was 0.17 in terms of variation coefficient. The obtained emulsion was designated as emulsion (C).

<Preparation of Sample> The obtained emulsion (A),
The following sensitizing dyes (X) and (Y) were added to (B) and (C) at 55 ° C. in a weight ratio of 20: 1 to 400 mg per (A) per mol of total silver halide, (B). 900mg, (C)
1100 mg was added.

Sensitizing dye (X); 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl), oxacarbocyanine-sodium salt anhydride Sensitizing dye (Y ); 5,5'-di- (butoxycarbonyl), 1,
1'-diethyl-3,3'-di- (4-sulfobutyl), benzimidazolocarbocyanine-sodium salt anhydride 10 minutes after addition, a suitable amount of chloroauric acid, sodium thiosulfate,
Chemical aging was carried out by adding ammonium thiocyanate and triphenylphosphine selenalate. 40 minutes before ripening, 0.06 μm silver iodide fine grain emulsion was added at 6 × 10 ⁻⁴ mol / Ag.
Then, 4-hydroxy-6-methyl 1,3,3a, 7-tetrazaindene was added in an amount of 3 × 10 ^-2 mol per mol of silver halide to prepare each emulsion, and then each emulsion was added. It was dispersed in an aqueous solution containing 70 g of gelatin.

After that, the emulsions (A), (B) and (C) were mixed at a molar ratio of silver halide of 10:65:25.

[0043]

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Further, 1.0 g of the following dye emulsion dispersion was added to prepare a silver halide emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresylphosphite and 85 liters of ethyl acetate.
This is called an oil-based solvent. On the other hand, a 9.3% gelatin aqueous solution containing 1.35 kg of anionic surfactant (AS) was prepared. This is called an aqueous solvent.

Next, an oil-based solvent and an aqueous solvent were placed in a dispersion pot and dispersed while maintaining the liquid temperature at 40 ° C. to prepare a dye emulsion dispersion.

[0047]

[Chemical 6]

The coating liquid for protective layer was prepared as follows. The added amount is shown as an amount per 1 liter of the coating liquid.

Coating liquid for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Polymethylmethacrylate (matting agent having an area average particle size of 6.0 μm) 1.1 g Silicon dioxide particles (matting agent having an area average particle size of 3.0 μm) 0.5 g Glyoxal 40% aqueous solution (hardener) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 500 mg C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0050]

[Chemical 7]

Support Substrate: A 175 μm thick polyethylene terephthalate support colored in blue at a concentration of 0.15 was coated on both sides with an undercoat coating solution prepared so that the coating amount per one side would be the following composition to form an undercoat layer. did.

Dye (exemplified compound below) 30 mg / m ² gelatin 0.7 g / m ² nonylphenoxy polyethylene oxide (polymerization degree = 10) 6 mg / m ² 1-morpholinocarbonyl-3- (pyridinio) methanesulfonate 80 mg / m ² poly Methyl methacrylate (matting agent with an average particle size of 2.5 μm) 2 mg / m ²

[0053]

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On the above-mentioned undercoated support, the emulsion coating solution was 1.9 g / m ^{2 in} terms of silver per side, the amount with gelatin was 2.0 g / m ² , and the amount with gelatin in the protective layer was 0.9 g / m ² . The emulsion layer and the surface protective layer were simultaneously extruded so as to be m ² and coated at a speed of 90 m / min by a coating method, and dried for 2 minutes and 30 seconds to produce a silver halide photographic light-sensitive material A.

(2) Preparation of silver halide photographic light-sensitive material B <Preparation of silver halide grain emulsion> 1.3 mol% of silver iodide,
A tabular silver iodobromide emulsion containing the remaining 98.7 mol% of silver bromide was prepared. This emulsion had an average grain size of 1.62 μm and an average grain thickness of 0.23 μm (average aspect ratio: 7.04). The resulting emulsion was designated as (A) '.

Similarly, 1.3 mol% of silver iodide and the remaining 98.7
A tabular silver iodobromide emulsion having a mol% of silver bromide was prepared,
An emulsion having an average grain size of 0.76 μm, an average grain size thickness of 0.22 μm (average aspect ratio: 3.45) and a grain size dispersibility of 0.26 was obtained as Emulsion (B) ′.

Further, a tabular silver iodobromide emulsion having 1.4 mol% of silver iodide and the remaining 98.6 mol% of silver bromide was prepared.
This emulsion has an average grain size of 1.04 μm, an average grain size of 0.21 μm (average aspect ratio: 4.95) and a grain size dispersibility of 0.27. The emulsion was designated as (C) '. A silver halide photographic light-sensitive material B is manufactured in the same manner as the silver halide photographic light-sensitive material A, such as sample preparation, dye dispersion preparation, protective layer coating liquid, support formation and emulsion coating liquid. did. Regarding the mixing ratio of the emulsions, the emulsions (A) ', (B)' and (C) 'were mixed at a molar ratio of silver halide of 10:65:25.

(3) Preparation of silver halide photographic light-sensitive material C <Preparation of silver halide grain emulsion> 1.3 mol% of silver iodide,
An octahedral silver iodobromide emulsion in which the remaining 98.7 mol% was silver bromide was prepared. This emulsion had an average grain size of 0.97 μm and an average grain thickness of 0.23 μm. The obtained emulsion was designated as (A) ″.

Similarly, 1.3 mol% of silver iodide and the remaining 98.7%
Prepare an octahedral silver iodobromide emulsion with a mol% of silver bromide, and obtain an emulsion with an average grain size of 0.56 μm, an average grain size thickness of 0.22 μm and a grain size dispersibility with a coefficient of variation of 0.26. (B) ".

Further, an octahedral silver iodobromide emulsion having 1.4 mol% of silver iodide and the remaining 98.6 mol% of silver bromide was prepared. This emulsion had an average particle size of 1.04 μm, an average particle size thickness of 0.21 μm and a particle size dispersibility of 0.27, and was designated as (C) ″. A silver halide photographic light-sensitive material B was produced in the same manner as in the preparation of the silver halide photographic light-sensitive material A, including the method for preparing the solution, the coating solution for the protective layer, the method for forming the support and the method for the emulsion coating solution. Emulsions (A) ″, (B) ″, and (C) ″ were mixed at a molar ratio of silver halide of 10:65:25.

(4) Preparation of pretreatment liquid Preparation of pretreatment liquid A Potassium sulfite 25 g Diethylenetriamine pentaacetic acid sodium salt 10 g 5-Methylbenzotriazole 0.2 g Glacial acetic acid 10 g Triethylene glycol 10 g 5-Nitroindazole 0.5 g Compound A- 2 30g Sodium phosphate 10g Make up to 1 liter with water.

The pH is 6.0 with potassium hydroxide and acetic acid.
Adjusted to.

Preparation of Pretreatment Liquid B Pretreatment liquid B was prepared in the same manner as in the preparation of pretreatment liquid A, except that compound A-2 was replaced with A-1.

Preparation of Comparative Pretreatment Liquid C Pretreatment liquid C was prepared in the same manner as in the preparation of pretreatment liquid A, except that the pH was adjusted to 8.0.

Preparation of Comparative Pretreatment Liquid D A comparative pretreatment liquid D was prepared in the same manner as in the preparation of the pretreatment liquid A, except that the compound A-2 was replaced with hydroquinone.

(5) Preparation of Alkaline Aqueous Solution and Comparative Solution Preparation of Treatment Liquid X Potassium hydroxide 25 g Sodium hydrogencarbonate 10 g Boric acid 1 g Water to 1 liter.

The pH was adjusted to 10 with potassium hydroxide and acetic acid.
Adjusted to 5.

Preparation of Treatment Liquid Z Potassium hydroxide 25 g Sodium hydrogencarbonate 10 g Boric acid 1 g Water to make up to 1 liter.

The pH is 8.5 with potassium hydroxide and acetic acid.
Adjusted to.

Preparation of Treatment Liquid W Potassium hydroxide 25 g Sodium hydrogencarbonate 10 g Boric acid 1 g Water to make 1 liter.

The pH is 9.0 with potassium hydroxide and acetic acid.
Adjusted to.

Preparation of Treatment Liquid V Potassium hydroxide 25 g Sodium hydrogencarbonate 10 g Boric acid 1 g Hydroquinone 25 g 50% Potassium sulfite 80 g Water is made up to 1 liter.

The pH was adjusted to 10 with potassium hydroxide and acetic acid.
Adjusted to 5.

Preparation of Comparative Treatment Liquid Y Sodium phosphate 25 g Phosphoric acid 5 g Boric acid 1 g Water to 1 liter.

The pH is 6.5 with potassium hydroxide and acetic acid.
Adjusted to.

(6) Preparation of Fixing Solution Ammonium thiosulfate 160 g Ethylenediaminetetraacetic acid disodium dihydrate 0.02 g Sodium sulfite 12 g Boric acid 10 g Sodium hydroxide 5 g Glacial acetic acid 10 g Aluminum sulfate 18-hydrate 35 g Sulfuric acid (50 wt%) 5 g Water To 1 liter.

The pH is 4.3 with potassium hydroxide and acetic acid.
Adjusted to.

The above silver halide photographic light-sensitive material A was pretreated with pretreatment liquids A, B, C and D and alkaline aqueous solutions X, Y,
Development processing was performed in combination with V, W and Z to prepare sample numbers 1 to 8 and 10. A sample 9 was prepared by developing the silver halide photographic light-sensitive material B with the pretreatment liquid B and the alkaline aqueous solution X. Further, the silver halide photographic light-sensitive material C was developed with the pretreatment liquid B and then the alkaline aqueous solution X to prepare Sample No. 11. The evaluation results of the developability and the stability with time are shown in Table 1 as the development activity.

Development Processing In the development processing, the sample film was processed with an intensifying screen XG-S.
Exposing by X-ray exposure, sandwiched between {manufactured by Konica Corp.},
At the temperature of each treatment liquid of 30 ° C., pretreatment 1 was for 15 seconds, then alkaline aqueous treatment 2 was for 15 seconds, fixing was for 20 seconds, and water washing was for 15 seconds.

The pretreatment liquid and the alkaline aqueous solution were subjected to development treatment immediately after preparation of each treatment liquid, 10 days after natural standing and 30 days after natural standing.

Evaluation of Development Activity Value The development activity value was determined as the reciprocal of the X-ray dose required to obtain the density of fog +1.0 for sample numbers 1 to 11. The results are shown as relative sensitivity values when the value immediately after preparation of sample number 1 is 100, and the results are shown in Table 1.

[0082]

[Table 1]

As is clear from Table 1, Samples 1, 2, 7, 8, 10 and 11 of the present invention have a high development activity immediately after preparation and have no deterioration in development activity over time. Recognize. It can be seen that Sample 3, which is treated with the comparative treatment liquid having a pH of 6.5 after the pretreatment liquid, has a very low development activity immediately after preparation, and also has a poor development activity after being naturally left. Sample 4 uses a pretreatment liquid other than the present invention, but since it is treated with the alkaline aqueous solution of the present invention, the development activity immediately after preparation is good, but the development activity deteriorates significantly with time. To do. Sample 5 has a pH of 8.0 and uses a pretreatment liquid other than the present invention, and is treated with the pretreatment liquid of the present invention, so the development activity immediately after preparation is good, but the development activity It can be seen that the deterioration with time is extremely large.

Further, it can be seen that Sample 9 of the present invention, which is composed of all tabular grain emulsions, has a good development activity among the samples of the present invention not only immediately after preparation but also after natural standing.

[0085]

According to the present invention, it is possible to provide a development processing method for a silver halide photographic light-sensitive material having good developability and excellent stability over time.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material containing a compound represented by the following general formula [1] and exposed imagewise with a pretreatment liquid having a pH of less than 7 is treated with an alkaline aqueous solution. A method for developing a silver halide photographic light-sensitive material, which is characterized by the above. Embedded image (In the general formula [1], R ₁ and R ₂ each represent a hydroxyl group, an amino group, an acylamino group, an alkylsulfonylamide group, an arylsulfonylamide group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group, and X represents 5 Represents a group of atoms necessary for forming a 6-membered or 6-membered heterocycle or carbocycle.) 2. The method of developing a silver halide photographic light-sensitive material according to claim 1, wherein the pH of the pretreatment liquid is 3 or more. 3. The method of developing a silver halide photographic light-sensitive material according to claim 1, wherein the alkaline aqueous solution contains a buffering agent and has a pH of 9 or more. 4. The alkaline aqueous solution contains a buffering agent and has a pH of 10.5 or higher.
A method for developing and processing a silver halide photographic light-sensitive material as described above. 5. The silver halide photographic material according to claim 1, wherein the silver halide photographic light-sensitive material contains a silver halide emulsion layer containing silver halide grains having an average aspect ratio of 2 or more. Development processing method of photographic light-sensitive material. 6. The silver halide photographic light-sensitive material contains a silver halide emulsion layer containing silver halide grains having an average aspect ratio in the range of 3 to 8. A method for developing and processing a silver halide photographic light-sensitive material as described above.