JP2002229162A - Developing solution for silver halide photographic sensitive material and processing method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the preservability and crystal depositing property of a developing solution using dihydroxybenzene as a developing agent and not substantially containing a boron compound, the suitability of a silver halide photosensitive material containing a relatively large amount of silver to long- term running and the roller mark trouble and color leaving property of a silver halide photographic sensitive material containing flat platy silver halide grains having an aspect ratio of >=8. SOLUTION: The developing solution for a silver halide photographic sensitive material contains dihydroxybenzene, 0.23-0.58 mol carbonate based on 1 mol dihydroxybenzene, 0.15-0.30 mol gelatin hardening agent based on 1 mol dihydroxybenzene, a sulfite and a benzenecarboxylic acid of formula (1), saccharides, linear tricarboxylic acids or amino acids and does not substantially contain a boron compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer for a silver halide photographic light-sensitive material and a processing method of the silver halide photographic light-sensitive material using the same. The present invention relates to a developing solution using dihydroxybenzenes having good preservability and the like as a developing agent and a processing method using the same.

[0002]

2. Description of the Related Art In general, a silver halide photographic light-sensitive material is processed in the steps of development, fixing, washing, and drying after exposure.
In recent years, most of them have been processed using automatic developing machines. In the developing step, a dihydroxybenzene compound represented by hydroquinone is mainly used as a developing agent. It has long been known that this dihydroxybenzene compound is an indispensable compound as a developing agent of a developing solution for a black-and-white silver halide photographic light-sensitive material that requires high-contrast images in the medical and printing fields. , Is commonly used.

Further, a developer containing a dihydroxybenzene compound represented by hydroquinone as a developing agent contains a sulfite as a preservative (antioxidant). Such a developer suffers from processing fatigue due to processing of the photosensitive material and temporal fatigue due to oxidation of the developing agent and sulfite by oxygen in the air. Processing fatigue is the consumption of the developing agent due to the reduction of the exposed silver halide by the developing agent to form a silver image, and the stoichiometric reduction of the developing agent concentration due to this development reaction and the decrease in pH Invite. The pH of the developer is set in the alkaline range in order to exhibit its developability. However, the decrease in the pH lowers the activity of the developer, causing a decrease in sensitivity and maximum density (Dmax). In order to reduce such processing fatigue, it is effective to use a photosensitive material which provides a high concentration with a small amount of silver as much as possible. 2.0g / m per side
² or more) In most cases, photosensitive materials are used.

[0004] On the other hand, fatigue with time due to air oxidation is accompanied by an increase in pH as the concentration of the developing agent decreases. The decrease in the solution activity due to the decrease in the concentration of the developing agent is the same as the processing fatigue.
It acts to suppress a decrease in ax. To improve the fatigue with time, there is an increase in the concentration of sulfite. However, when the concentration is increased, the sulfite ion has a dissolving effect on silver halide, and causes silver stain called silver sludge.

Further, since the pH of the developer is set in the alkaline region as described above, the developer contains an alkaline agent, and the alkaline agent is mainly a water-soluble inorganic alkali metal salt (eg, potassium hydroxide, Sodium hydroxide). Further, in order to further cause pH fluctuation due to processing fatigue and aging fatigue, the developer itself must be a pH buffer. Therefore, carbonates and boron compounds represented by borates are used as pH buffering agents (buffering agents). However, it is well known that boron compounds such as borates form 1: 1 and / or 1: 2 complexes with 1,2-diol derivatives. It is known that an ene derivative such as a benzene derivative or ascorbic acid easily forms a complex with a borate, so that the developing power is extremely reduced.

On the other hand, boron compounds such as boric acid and borax, which are used as a buffer of a developing solution containing hydroquinone as a developing agent, not only serve as a buffer but also have a large developing property with hydroquinone, particularly, a liquid storage property in long-term running. It has been found that boron compounds are indispensable chemical species in a developing solution using hydroquinone as a developing agent.

[0007] In addition, since high-temperature rapid development processing has become mainstream with the introduction of recent automatic developing machines, deposits are often generated on the inner wall of the development processing tank, the shaft of the film transport roller, and the gear portion due to long-term running. In many cases, the precipitate is started by the decomposition and polymerization of an oxide of a dihydroxybenzene developing agent such as hydroquinone to form a tar-like substance called humic acid. It has further been found that the boron compound has an effect of suppressing the formation of humic acid by reacting with the oxide of the hydroquinone drug.

[0008] However, boron compounds represented by boric acid include boron as an environmentally unfavorable element.
In February 1999, an environmental standard for boron was enacted. When a boron compound is contained in the photographic processing agent, the boron compound in the processing agent is carried into the washing step by the photosensitive material and is released into the environment together with the washing wastewater. Therefore, there has been a strong demand for removing boron compounds from photographic processing agents.

On the other hand, it is customary to include a gelatin hardening agent in a developing solution in order to impart high-temperature rapid developing property, and to cause a hardening reaction during the developing process. In most cases, glutaraldehyde is used as a hardening agent because of its high reactivity in a developing solution and rapid hardening reaction. However, it has been newly found that glutaraldehyde reacts with gelatin eluted from a photosensitive material into a processing solution during long-term running, and this becomes a nucleus of a crystal to be precipitated, thereby promoting the problem of promoting crystal precipitation.

Also, due to the problems of rapid processing and silver saving, photosensitive materials containing tabular grains having excellent developability and high density with a small amount of silver have been developed and used, and have become mainstream. . In particular, thin tabular silver halide grains having a high aspect ratio (for example, an aspect ratio of 8 or more) have high sensitivity and a high Dmax, and can also adsorb a large amount of a sensitizing dye from their large specific surface area. It is known that it has excellent sensitizing properties. However, tabular grains with a high aspect ratio have poor pressure resistance due to their peculiar shape, and have weak points such as bending blackening, roller mark generation in rapid processing by a roller transport type automatic developing machine, and residual color of sensitizing dyes. Have. It is effective to increase the amount of gelatin hardener represented by glutaraldehyde in the developer as an improvement means.However, if the amount of glutaraldehyde or the like is simply increased, a new problem that fog easily occurs occurs. In addition to the above-mentioned problem of promoting crystallization, improvement is desired.

[0011]

The present invention solves the above-mentioned problems by improving the liquid preservability and crystal precipitation of a developer containing a dihydroxybenzene compound as a developing agent and containing no boron compound. The use of silver halide photographic materials having a relatively large amount of silver improves the long-term running performance of the silver halide photographic materials, and furthermore, the roller mark failure of silver halide photographic materials containing high aspect ratio silver halide grains having an aspect ratio of 8 or more. Another object of the present invention is to provide a processing method with improved residual color.

[0012]

Means for Solving the Problems As a result of earnest study, the present inventor has found that the object of the present invention can be achieved by the following means. Dihydroxybenzene compound, 0.23 to 0.58 mol of carbonate per 1 mol of dihydroxybenzene compound,
It contains a sulfite, 0.15 to 0.30 mol of a gelatin hardener per 1 mol of a dihydroxybenzene compound, and benzenecarboxylic acid represented by the general formula (1), and contains substantially no boron compound. A developing solution for silver halide photographic materials. Dihydroxybenzene compound, 0.23 to 0.58 mol of carbonate per 1 mol of dihydroxybenzene compound,
A developer for a silver halide photographic light-sensitive material, comprising a sulfite, 0.15 to 0.30 mol of a gelatin hardener per 1 mol of a dihydroxybenzene compound, and a saccharide, and substantially free of a boron compound. . Dihydroxybenzene compound, 0.23 to 0.58 mol of carbonate per 1 mol of dihydroxybenzene compound,
A silver halide photographic light-sensitive material containing a sulfite, 0.15 to 0.30 mol of a gelatin hardener per 1 mol of a dihydroxybenzene compound, and a linear tricarboxylic acid, and substantially containing no boron compound. Developer. Dihydroxybenzene compound, 0.23 to 0.58 mol of carbonate per 1 mol of dihydroxybenzene compound,
A silver halide photographic light-sensitive material, comprising a sulfite, 0.15 to 0.30 mol of a gelatin hardener per 1 mol of a dihydroxybenzene compound, and amino acids, and substantially containing no boron compound. liquid. A method for processing a silver halide photographic light-sensitive material comprising at least a developing step and a fixing step, wherein the silver halide photographic light-sensitive material has a photosensitive silver halide emulsion layer on at least one side of a support, and at least one side has a light-sensitive silver halide emulsion layer. A silver halide emulsion layer having a silver content of 2.0 to 5.5 g per m ² , and a developing solution used in the developing step being a developing solution described in any one of the above (1) to (3). Processing method. A silver halide photographic light-sensitive material containing 70 to 100% of the projected area of tabular silver halide grains having an aspect ratio of 8.0 or more is developed with the developer according to any one of the above-mentioned items. A method for processing a silver halide photographic material.

According to the present invention, a dihydroxybenzene developing agent, in particular, a developing solution containing hydroquinone as a developing agent contains a boron compound to improve the liquid preservability during long-term running or the like. Due to environmental conservation problems, the results of intensive studies on a developing solution containing a boron compound and containing no hydroquinone as a developing agent containing a boron compound and having performance equal to or higher than that of a developing solution containing hydroquinone as a developing agent were obtained. It is a thing.

Hereinafter, the present invention will be described in detail. First, the dihydroxybenzenes, carbonates, sulfites, and gelatin hardeners contained in the developer of the present invention will be described.

The dihydroxybenzenes used in the developer of the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, dichlorohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, methoxyhydroquinone and 2,5-dimethylhydroquinone. And dihydroxybenzene compounds known as developing agents for black-and-white silver halide photographic light-sensitive materials, such as potassium hydroquinonesulfonate, sodium hydroquinone monosulfonate, and catechols. Hydroquinone is particularly preferred.

In the developing solution of the present invention, dihydroxybenzenes are preferably used in an amount of 0.18 to 0.50 mol per liter of the developing solution, particularly preferably 0.1 to 0.50 mol.
The amount is preferably from 22 mol to 0.30 mol.

The carbonate used in the developer of the present invention is preferably sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, etc., and particularly preferably potassium carbonate. In the developer of the present invention, the amount of carbonate is 0.23 to 1 per mol of dihydroxybenzene developing agent.
0.58 mol, preferably 0.26 to 0.40
Is a mole. The amount of carbonate per liter of the developer is preferably 0.03 mol or more and 0.13 mol or less,
Furthermore, 0.04 mol or more and 0.10 mol or less, especially 0.0
5 mol or more and 0.07 mol or less are preferable. When the amount of carbonate is less than 0.23 mol per mol of dihydroxybenzene developing agent, the buffer performance is greatly reduced. When entering the fixing solution, fine bubbles are generated on the surface of the photosensitive material, and uneven development is likely to occur.

As the sulfite used in the developing solution of the present invention, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite and the like are preferable, and sodium bisulfite, potassium bisulfite, sodium metabisulfite, Potassium bisulfite, formaldehyde sodium bisulfite and the like are also preferably used. The amount of sulfite is preferably from 0.20 mol to 0.50 mol, more preferably from 0.25 mol to 0.48 mol, particularly preferably from 0.30 mol to 0.45 mol per liter of the developer. . In addition, since sodium metabisulfite and potassium metabisulfite generate 2 mol of sulfite ions from 1 mol of them by reacting with water, when these are used, 1/2 mol of the above preferable amount is appropriate. is there.

As the gelatin hardener (hardener) used in the developer of the present invention, dialdehydes are preferable, and among them, glutaraldehyde is preferable. The amount of the gelatin hardener is 0.15 mol to 0.30 mol per 1 mol of dihydroxybenzenes, and preferably 0.19 mol to 0.39 mol.
0.25 mol. The amount of gelatin hardener per liter of developer is preferably 0.03 mol or more and 0.06 mol or less, more preferably 0.04 mol or more and 0.05 mol or less. When the amount of the gelatin hardener is less than 0.15 mol per mol of dihydroxybenzenes, roller mark failure tends to occur. On the other hand, when the amount exceeds 0.30 mol per mol of dihydroxybenzenes, the residual color deteriorates. .

The developer of the present invention contains substantially no boron compounds such as boric acid, potassium borate and borax. In the present invention, "substantially contains no boron compound" means that the boron compound is 0.04 mol or less per liter of the developer, and preferably 0.1 to 0.1 mol per liter of the developer.
02 mol or less, particularly preferably not containing at all.

The developer of the present invention contains dihydroxybenzenes and 0.23 to 1 mol per mole of dihydroxybenzenes.
It contains 0.15 to 0.30 mol of gelatin hardener per 1 mol of carbonate, sulfite, and dihydroxybenzenes, contains no boron compound, and is represented by the general formula (1). Benzenecarboxylic acids, sugars, linear tricarboxylic acids, or amino acids.

The benzenecarboxylic acids represented by the general formula (1) to be contained in the developer according to claim 1 of the present invention include benzoic acid, toluic acid, o-ethylbenzoic acid, p-
Isopropylbenzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, phthalic acid, isophthalic acid, methylisophthalic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, benzenepentacarboxylic acid, benzenehexacarboxylic acid, sodium benzoate, potassium benzoate, phthalate Potassium hydrogen oxyoxide, potassium phthalate, fluorobenzoic acid, chlorobenzoic acid, dichlorobenzoic acid, trichlorobenzoic acid, bromobenzoic acid, dibromobenzoic acid, iodobenzoic acid, dichlorophthalic acid, tetrachlorophthalic acid, nitrobenzoic acid, nitrophthalic acid Acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, sodium salicylate, dihydroxybenzoic acid, trihydroxysalicylic acid, gallic acid, hydroxytoluic acid, hydroxyphthalic acid, hydrophthalic acid Thiophthalic acid, anisic acid, vanillic acid, isovanillic acid, 2-hydroxy-3-methoxybenzoic acid, veratric acid, piperonyl acid, acetylsalicylic acid, phthalaldehyde acid, sulfobenzoic acid, sulfamoylbenzoic acid, 5-sulfosalicylic acid, anthranilic acid , M-aminobenzoic acid, p-aminobenzoic acid, phthalamic acid, tropic acid and the like. Benzoic acid, salicylic acid, dihydroxybenzoic acid, gallic acid, 5-sulfosalicylic acid, and salts thereof are preferably used in the present invention.

The benzene carboxylic acids represented by the general formula (1) can contain one kind or two or more kinds, and at least one kind selected from saccharides, linear tricarboxylic acids and amino acids is used in combination. can do.

The saccharide to be contained in the developer according to the second aspect of the present invention means a monosaccharide, a polysaccharide in which these are glycooxide-bound, and a decomposition product thereof. Polysaccharides are more preferably used than monosaccharides in the developer of the present invention, and disaccharides are particularly preferably used among polysaccharides.
A disaccharide is a compound having a cyclic structure in which one molecule of water can be removed from two molecules of a monosaccharide, and a compound in which the reducing groups of two molecules of a monosaccharide have a glycooxide bond is a non-reducing disaccharide. One in which the reducing group of one monosaccharide and the hydroxyl group of another monosaccharide are glycoside-linked is called a reducing disaccharide. The former includes sucrose (sucrose-sucrose) and trehalose, and the latter includes maltose (maltose), lactose (lactose), gentiobiose, cellobiose, and melibiose.

Examples of the polysaccharide include stachyose, cellotriose, raffinose, celluloses, dextrins, cyclodextrins and the like. Particularly preferred for use in the present invention are non-reducing disaccharides, especially trehalose.

The developer of the present invention may contain one or more saccharides, and may be selected from benzenecarboxylic acids, linear tricarboxylic acids, and amino acids represented by the general formula (1). At least one of these can be used in combination.

The straight-chain tricarboxylic acids contained in the developer according to claim 3 of the present invention have three carboxyl groups in one molecule, and the carbon atoms to which the carboxyl groups are bonded are linearly connected. And its salts and esters, for example, 1,2,3-propanetricarboxylic acid, aconitic acid, citric acid, ammonium citrate,
Examples thereof include diammonium citrate, sodium citrate, potassium citrate, triethyl citrate, and desoxalic acid. Particularly preferred are citric acid and its salts. One or more linear tricarboxylic acids can be contained, and at least one selected from benzenecarboxylic acids, saccharides and amino acids represented by the general formula (1) can be used in combination. .

The amino acids to be contained in the developer according to claim 4 of the present invention mean a compound having an amino group and a carboxyl group in the same molecule. Generally, the amino group and the carboxyl group are bonded to the same carbon. Are α-amino acids,
Amino acids are referred to as β-, γ-, δ-,... Amino acids as the distance from the carboxyl group increases. Furthermore, amino acids having one amino group and one carboxyl group in the molecule are called neutral amino acids because they show almost neutrality,
An amino acid having one amino group and two carboxyl groups is called an acidic amino acid, an amino acid having two amino groups, or a basic amino acid having one amino group, a basic group and one carboxyl group. Acidic amino acids are preferably used in the present invention, and aspartic acid and salts thereof, and glutamic acid and salts thereof are particularly preferable.

One or more amino acids can be contained, and at least one selected from benzenecarboxylic acids, linear tricarboxylic acids, and saccharides represented by the general formula (1) is used in combination. be able to.

The developing solution of the present invention preferably contains a dihydroxybenzene developing agent and 3-pyrazolidones having superadditivity as auxiliary agents. 3 used in the present invention
-Pyrazolidones include 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3- Pyrazolidone, 1
-Phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-
3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-
3-pyrazolidone, 1- (2-benzothiazolyl) -3
-Pyrazolidone, 3-acetoxy-1-phenyl-3-
Pyrazolidone and the like.

The amount of 3-pyrazolidones in the developer of the present invention is practically preferably from 0.2 to 30 g / l, more preferably from 1.0 to 15 g / l. The above-mentioned 3-pyrazolidones may contain one kind or two or more kinds.

The developer of the present invention may further include an alkali agent (eg, sodium hydroxide, potassium hydroxide, etc.), a solubilizing agent (eg, polyethylene glycols and their esters, etc.), and a pH adjuster (eg, acetic acid). Sensitizers (e.g., quaternary ammonium salts), development accelerators, surfactants, antifoggants, (e.g., azole organic antifoggants (indazole, imidazole, benzimidazole, etc.) , Triazole-based, benztriazole-based, tetrazole-based, thiadiazole-based, etc.), concealing agents (for example, sodium hexametaphosphate, calcium hexametaphosphate, polyphosphoric acid) for concealing calcium ions mixed in tap water used for liquid preparation Salt, ethylenediaminetetraacetic acid, diethylenetriamine5
Acetic acid and the like). Further, JP-A-5-28
The silver stain preventive described in No. 9255 can also be used.

The developing solution of the present invention includes JP-A-56-106.
Amino compounds such as alkanolamines described in JP-A-224 can be used. In addition, L. F. A. Meson, Photographic Processing Chemistry, Focal Press (1966) 22-2
29, U.S. Pat. Nos. 2,193,015 and 2,5
Compounds described in JP-A-92-364 and JP-A-48-64933 may be used.

The pH of the developer of the present invention is preferably 11.0 or lower, more preferably in the range of 9.0 to 10.7, and particularly preferably in the range of 9.5 to 10.5.

The fixing solution used in the processing method using the developing solution of the present invention preferably contains a thiosulfate as a fixing agent. Thiosulfates are specifically lithium,
Although it is used as a potassium, sodium or ammonium salt, it is preferable to use ammonium thiosulfate and / or sodium thiosulfate since a fixing solution having a high fixing speed can be obtained. In addition, an iodide salt or a thiocyanate may be contained as an auxiliary fixing agent.

Further, the fixing solution preferably contains a water-soluble aluminum salt as a hardening agent. Examples of the water-soluble aluminum salt include potassium alum, ammonium alum, calcined alum, calcined ammonium alum, aluminum chloride,
Examples include potassium aluminum chloride and aluminum sulfate.

It is desirable that the fixing solution used in the processing method using the developing solution of the present invention does not contain a boron compound represented by boric acid. On the other hand, it is desirable to contain a carboxylic acid or a derivative thereof or a salt thereof for stabilizing aluminum.

The fixing solution used in the processing method using the developing solution of the present invention may contain a carboxylic acid or a derivative thereof and a salt thereof. As the carboxylic acid or its derivative and its salt, acetic acid, tartaric acid, citric acid, gluconic acid, lactic acid and the like or their derivatives and their salts are preferable. 5 mol or less, preferably 0.01 mol or more and 1.0 mol or less. Further, the fixing solution preferably contains a preservative such as sulfurous acid, metabisulfite and the like, and salts thereof. As the salt, lithium,
Potassium, sodium, ammonium salts and the like. Further, as a pH buffering agent, for example, acetic acid, carbonic acid, phosphoric acid and salts thereof may be contained, and acetic acid and acetate salts are most preferably used. Further, if necessary, sodium hydroxide, sulfuric acid or the like may be contained as a pH adjuster. Surfactants may be further contained, and examples of the surfactant that can be used include, for example, anionic surfactants such as sulfated and sulfonated compounds, polyethylene glycol-based, and ester-based nonionic surfactants, And amphoteric activators. The humectant may contain a humectant. Examples of the humectant that can be used include alkanolamine and alkylene glycol. Further, a fixing accelerator may be contained. Examples of the fixing accelerator that can be used include thiourea derivatives, alcohols having a triple bond in the molecule, thioethers, and the like. The pH of the fixing solution is 4.0 or more and 5.5.
Below, more preferably 4.2 or more and 5.0 or less. The replenishing amount of the fixing solution is preferably from 80 to 300 ml per 1 m ² of the photosensitive material from the viewpoint of reducing the amount of waste liquid, and particularly preferably from 100 to 250 m ^2.
l is preferred.

The developing solution of the present invention and the fixing solution used in the processing method using the developing solution of the present invention may be a developing solution and a fixing solution obtained by diluting and mixing a concentrated solution to a predetermined concentration. The concentrated solution used for preparing the developing solution and the fixing solution is preferably a concentrated solution kit composed of 1 to 3 parts, more preferably 1 to 2 parts, and particularly preferably 1 to 2 parts.
It is preferably a concentrated liquid kit composed of parts.

Further, the developer of the present invention can be supplied as a solid processing agent containing a developer component, and the solid processing agent can be dissolved in water to a predetermined concentration. Examples of the solid processing agent include powders, granules, tablets and the like, and tablets are preferable in handling.

The silver halide photographic light-sensitive material developed with the developing solution of the present invention will be described. Developer of the present invention is a light-sensitive material having at least one light-sensitive silver halide emulsion layer of the support, the silver amount on one side of the emulsion layer is relatively silver amount of 1 m ² per 2.0~5.5g The effect of the present invention is more remarkable when used in the development processing of a large amount of silver halide photosensitive material. In particular, when the light-sensitive material having a silver halide emulsion layer on both sides of the support, the silver amount per 1 m ² of one side 2.
0 to 3.5 g of a light-sensitive material, or in the case of a silver halide photographic light-sensitive material having a silver halide light-sensitive material only on one side of a support, a silver amount per square meter of ^2.5 to 5.5 g. The effect of the present invention is particularly large when developing is carried out in a long-term running.

The silver halide grains of the silver halide emulsion used in the light-sensitive material developed with the developing solution of the present invention are normal crystal grains, that is, all areotropically grown, such as cubic, octahedral and tetrahedral. It may be a so-called regular particle, a polyhedral crystal type such as a sphere, a twin crystal having plane defects, or a mixed or composite type thereof, and particularly a tabular particle. Is preferred.

The silver halide emulsion used in the silver halide photographic material developed with the developer of the present invention can be produced by a known method. For example, Research Disclosure (hereinafter referred to as “RD”) No. 17643 (1978
"Emulsion Pr", p. 22-23.
RD No. 18716 (November 1979),
The method described on page 648; H. James "The The
Theory of the Photograph
ic process, 4th edition, published by Macmillan (1977), pp. 38-104;
F. Duffin, "Photographic Em
ulsion Chemistry ", Focal P
Res., 1966, p. Glafkids
Written by Chimie et Physique Photo
OGriqueque, published by Paul Montel (1967) or VL Zelikman et al., "M
aking And Coating Photogra
phi Emulsion ”Focal Pres
It can be prepared by the method described in s Co., Ltd. (1964). That is, acidic solution, ammonia method, solution conditions such as neutral method, forward mixing method, back mixing method, double jet method, mixing conditions such as control double jet method,
The particles can be produced by using particle preparation conditions such as a conversion method and a core / shell method and a combination thereof.

As a preferred embodiment of the silver halide emulsion used in the silver halide photographic light-sensitive material developed with the developing solution of the present invention, a monodisperse emulsion in which silver iodide is localized inside grains is mentioned.

The crystal structure of silver halide used in the silver halide photographic light-sensitive material developed with the developing solution of the present invention is as follows:
The inside and outside may have different silver halide compositions. That is, the core has a core / shell structure including at least one or more shells having different halogen compositions. The silver iodide content of the high iodine part is 20
-40 mol%, particularly preferably 20-30 mol%.

Preferred silver halide emulsions are described, for example, in JP-A-59-177535 and JP-A-61-132943.
And high internal iodine type monodispersed particles disclosed in JP-A-63-49751 and JP-A-63-49751. The crystal habit is cubic,
Octahedron, tetrahedron and {111} plane and {10} between them
0 ° planes may be arbitrarily mixed. The method of producing the core / shell type emulsion is known, and for example, British Patent 1,027,
146, U.S. Pat. Nos. 3,505,068 and 4,44
4,877 or JP-A-60-143331 can be referred to.

When the silver halide grains contained in the silver halide emulsion are regular grains, the average grain size is 0.1 to 1.
Those having a diameter of 5 μm are preferred, and those having a diameter of 0.3 to 1.0 μm are particularly preferred. Here, the average particle size of the regular particles is defined as the average diameter of a sphere having the same volume, that is, the average diameter of a circle that projects the sphere. Defined similarly.

The particle size distribution of the silver halide grains may be monodispersed. Specifically, the monodispersion referred to here means that the coefficient of variation of the particle size, that is, the value (%) obtained by dividing the standard deviation of the particle size by the average particle size by 100 is 30% or less. Say. A method for producing a monodisperse emulsion is known. Pho
t. Sci, 12.242-251, (1963), JP-A-48-36890, JP-A-52-16364, and JP-A-5-16364.
5-142329, 58-49938, British Patent 1,413,748, U.S. Patent 3,574,628
Nos. 3,655,394 and the like. As a method for obtaining a monodisperse emulsion, for example, an emulsion obtained by using a seed crystal and supplying silver ions and halide ions using the seed crystal as a growth nucleus to grow is particularly preferable.

As the light-sensitive material processed with the developing solution of the present invention, tabular silver halide grains having a projected area of 70 to 100
A light-sensitive material having a silver halide emulsion layer containing 0.1% by weight is particularly preferred. As tabular silver halide grains,
Those having a main plane composed of {100} planes and / or {111} planes are preferred, and the average particle size is 0.3 to 3.0 μm
It is particularly preferable that the thickness be 0.5 to 2.0 μm. Incidentally, the average grain size of the tabular silver halide grains refers to the length of the side of a square having an area equal to the projected area of the main plane of the grain in the case of a tabular grain having a {100} main plane as observed from an electron micrograph. In the case of tabular grains having a {111} major plane, they are defined as the average of the diameters of circles having an area equal to the projected area of the major plane.

The tabular silver halide grains are high aspect ratio grains having an average value of grain size / thickness (referred to as aspect ratio) (referred to as average aspect ratio) of 8.0 or more and an aspect ratio of 8.8. 5 to 20.0, especially 10.0 to 15.0
Is preferred. At least 1 to determine average aspect ratio
A 00 particle sample is measured.

The average thickness of the tabular silver halide grains is 0.5.
5 μm or less is preferable, and particularly preferably 0.02 to 0.2 μm.
3 μm. Here, the thickness of the silver halide grain is
It is defined as the smallest of the distances between the main planes, that is, the distance between the two crystal planes having the largest areas and forming the tabular silver halide grains. The thickness of the tabular silver halide grains is determined from an electron micrograph with shadows of the silver halide grains by a carbon replica method or the like or a tomographic electron micrograph of a sample obtained by coating a silver halide emulsion on a support and drying. be able to.

The tabular silver halide grains may have a crystal plane other than the main plane, such as a {110} plane. As the silver halide emulsion containing tabular silver halide grains, those which are monodisperse are preferably used, and those having a variation coefficient of grain size within a range of 20% or less are particularly preferably used. Different monodisperse tabular silver halide emulsions, or polydisperse tabular emulsions having a wide grain size distribution, normal crystal emulsions such as cubic, octahedral, and tetradecahedral, and multiple twins having many twin planes Crystal emulsions may be mixed.

When the developing solution of the present invention is used for a silver halide photographic light-sensitive material having tabular silver halide grains having a high aspect ratio, it is highly effective in improving roller mark failure and residual colorability. The above effects are remarkable when a silver halide photographic light-sensitive material having 70 to 100% of the projected area of 8.0 or more tabular silver halide grains is developed.

The silver halide composition of the silver halide emulsion of the light-sensitive material developed with the developing solution of the present invention is not limited, and may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and the like. However, silver bromide, silver iodochloride, silver iodobromide or silver iodochlorobromide is preferred, and silver bromide is particularly preferred. When silver iodide is contained, the average silver iodide content is preferably 0.8 mol% or less, particularly preferably 0.5 mol% or less. Further, the tabular silver halide grains may have a uniform halogen composition within the grains, or may be core / shell type grains having a localized portion of silver iodide therein. It may have a portion having a high silver halide content. The average silver iodide content of the tabular silver halide emulsion is
It can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of chloride, bromide and iodide.

A method for producing a tabular silver halide emulsion having {100} principal planes is described in US Pat. 798 can also be referred to. The size and shape of the tabular silver halide grains can be controlled by the temperature during grain formation, pAg (pBr, pCl), pH, the rate of addition of a water-soluble silver salt and an aqueous halide solution, and the like. PAg when forming tabular silver halide grains
Is preferably in the range of 6.0 to 9.9.
g is preferably in the range of 8.0 to 9.9. During the production of the tabular silver halide emulsion, silver halide solvents such as ammonia, thioether, and thiourea may be used, if necessary, and the aspect ratio is changed by adding these solvents during grain formation. You can also.

The silver halide emulsion of the silver halide photographic light-sensitive material developed with the developing solution of the present invention, including the above-described tabular silver halide emulsion, is a surface latent image type which forms a latent image on the grain surface, or Either an internal latent image type in which a latent image is formed inside the grain or a type in which a latent image is formed on the surface and inside may be used. These emulsions are used at the stage of grain formation.
Iron salts, cadmium salts, lead salts, zinc salts, thallium salts, ruthenium salts, osmium salts, iridium salts or complex salts thereof,
Rhodium salts or complex salts thereof may be added to perform metal doping inside the silver halide grains.

The silver halide emulsion of the light-sensitive material developed with the developing solution of the present invention is subjected to a water washing method such as a Nudel washing method or a flocculation sedimentation method to remove soluble salts (desalting step). Good. As a preferred water washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086,
Alternatively, a method using G3, G8, etc., as an example of an aggregating polymer agent described in JP-A-63-158644 is mentioned as a particularly preferred desalting method.

Gelatin is advantageously used as a protective colloid used in the preparation of a silver halide emulsion, for example, in a dispersion medium, and as a binder for a hydrophilic colloid layer of a light-sensitive material. Colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers of polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be.

Examples of gelatin include lime-treated gelatin, alkali-treated gelatin, acid-treated gelatin,
l. Soc. Sci. Photo. Japan, No. 1
6, P30 (1966), an oxygen-treated gelatin may be used, and a hydrolyzate or an oxygen-decomposed product of gelatin may also be used. No. 4,713,323, a low methionine content, i.e. gelatin 1
Gelatin with a methion content of less than 30 micromoles per gram, especially less than 12 micromoles, is preferably used.

The silver halide emulsion of the light-sensitive material developed with the developing solution of the present invention is preferably subjected to chemical ripening, that is, to chemical sensitization. Preferred pH, preferred pH
Ranges from 4.0 to 10.0, more preferably 5.
It is 0 or more and 8.0 or less.

The noble metal sensitization is preferably gold sensitization, and a gold compound, mainly a gold complex such as a gold-thiocyanate complex, is used as a sensitizer. As a noble metal other than gold, complex salts such as platinum, iridium, osmium, palladium, rhodium and ruthenium can be used. For gold sensitization, gold sensitizers such as chloroaurate, gold thiourea complex, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanouric amide, ammonium aurothiocyanate, pyridyl Trichlorogold and the like. The addition amount of these gold sensitizers can be varied widely under various conditions.
5 × 10 ^{−7 to} 5 × 10 ⁻³ mol per mol is preferable, and
X 10 ^-6 to 4 X 10 ^-4 mol is more preferred.

Among the chalcogen sensitizers, examples of the sulfur sensitizer used for sulfur sensitization include thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like. Can be Other U.S. Pat. Nos. 1,574,944 and 3,656,955, German Patent 1,422,869
No., JP-B-56-24937, and JP-A-55-4501.
No. 6 and the like can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount can be varied in various conditions, that is, in a wide range such as the size of silver halide grains, but the standard is 5 × 10 ^{−8 to} 5 × 10 ⁻⁸ per mol of silver halide.
× 10 ^-5 mol is preferred.

Further, selenium sensitization and / or tellurium sensitization are preferably used in combination with sulfur sensitization as chalcogen sensitization. As the selenium sensitizer, a conventionally known compound can be used. That is, the normally unstable selenium compound and / or
Alternatively, the emulsion is sensitized by adding a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time.

As the unstable selenium compound, for example, the compounds described in JP-B-44-15748, JP-B-43-13489, JP-A-2-130976 and the like can be used. Specific examples of unstable selenium sensitizers include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (for example, 2-selenocarboxylic acid). Propionic acid, 2-selenobutyric acid), selenoesters, diacyl selenides (eg, bis-3-chloro-2,6-dimethoxybenzoyl selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like. Can be

While the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. In the art, speaking of an unstable selenium compound as a sensitizer of a photographic emulsion, the structure of the selenium compound is not very important as long as selenium is unstable, and the organic part of the selenium sensitizer molecule is selenium sensitizer. And has no role other than to cause it to be present in the emulsion in an unstable form. Unstable selenium compounds of such a broad concept are advantageously used for selenium sensitization. Non-labile selenium compounds include, for example, JP-B-46-4553 and JP-B-53-4553.
Compounds described in JP-A-34492 and JP-A-52-34491 are used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, ヂ aryl selenides,
{Aryl} selenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinthion and derivatives thereof.

The amount of the selenium sensitizer used depends on the amount of selenium used.
Depends on compound, silver halide grains, chemical ripening conditions, etc.
However, it is generally preferred that 1 × per mole of silver halide be used.
10 ^-8More than mole. More preferably 1 × 10^-7Mole
More than 1 × 10^-3Less than mol is added during chemical sensitization. Attachment
The addition method depends on the nature of the selenium compound to be used.
Is dissolved in an organic solvent such as ethanol alone or in a mixed solvent
Or pre-mix with gelatin solution
May be added as described in JP-A-4-14039.
Disclosed method is to polymer with an organic solvent-soluble polymer
A method of adding in the form of an emulsified dispersion of a mixed solution may be used.

As tellurium sensitizers, US Pat.
No. 2,031, British Patent 235,211, Canadian Patent 800,958, J.P. Chem. Soc. Chem.
Commun. 635 (1980), ibid 11
02 (1979); ibid645 (1979);
Chem. Soc. Perkin Trans. ; 1,
It is preferable to use the compounds described in 2191 (1988) and the like.

The silver halide emulsion of the light-sensitive material developed with the developing solution of the present invention may be spectrally sensitized. As the spectral sensitizing dye, usually a methine dye is preferably used, and examples thereof include cyan dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, hemicyanine dye, styryl dye, and hemioxonol dye. Included. For example, JP-A-7-2
Oxacarbocyanine, benzimidazolocarbocyanine, benzimidazolo-oxacarbocyanine and the like as described in 39536. Further, dyes having a sensitizing effect in the blue light region described in JP-A-6-332102 are also preferably used. These spectral sensitizing dyes can be used alone or in combination. The addition amount of the spectral sensitizing dye is not uniform depending on the kind of the dye and the emulsion conditions, but is preferably from 10 to 900 mg per mol of silver of the silver halide emulsion, and from 60 to 4 mg.
00 mg is particularly preferred. The spectral sensitizing dye is preferably added before the completion of the chemical ripening step, and may be added in several portions before the completion of the chemical ripening step. More preferably, after the growth step of the silver halide grains and before the completion of the chemical ripening step, particularly preferably before the start of the chemical ripening.

The chemical ripening can be stopped by, for example, cooling the emulsion to stop the reaction. However, considering the stability of the emulsion, a method using a chemical ripening stopper is preferable. Examples of the chemical ripening stopper include halides (eg, potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (eg, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene). These may be used alone or in combination of a plurality of compounds.

In the silver halide emulsion, various photographic additives can be used during the physical ripening step during the formation of silver halide grains, before or after chemical ripening, and in the step of preparing an emulsion coating solution. Known additives include, for example, RDNo. 176
No. 43 (December 1978); 18716 (19
No. 1979) and the same No. 308119 (December 1989). The types of compounds and the locations described in these three RDs are described below.

Additives 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 648-649 996-8 IVA desensitizing dye 23 IV 998 VB dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XIII 648 Upper right antifoggant / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surface activity Agents 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 1009 XVII For photosensitive material developed with the developing solution of the present invention Examples of the support that can be used include the aforementioned RD-1764.
3 and page 1009 of RD-308119.

Suitable supports include polyethylene terephthalate film and the like. The surface of these supports may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. to improve the adhesion of the coating layer. Is also good. It is preferable to provide a layer containing a crossover cut dye for further improving sharpness.

[0073]

EXAMPLES Example 1 [Preparation of Developing Solution and Fixing Solution] Developing solutions 1 to 49 and a fixing solution having the following formulations were prepared. Developer 1: Hydroquinone developing agent (boric acid formulation) Potassium sulfite 66.4 g (0.42 mol) Ethylenediaminetetraacetic acid / 3 sodium (35% aqueous solution) 8.0 g 5-methylbenzotriazole 0.02 g Boric acid 10.0 g (0.16 mol) Hydroquinone 26.4 g (0.24 mol) 1-phenyl-3-pyrazolidone 1.2 g 1-phenyl-5-mercapto-1,2,3,4-tetrazole 0.015 g 5-nitrobenzo Imidazole 11.8 g Glutaraldehyde (50% aqueous solution) 8.6 g (0.043 mol) Sodium hydroxide (48% aqueous solution) 49.3 g Acetic acid (90% aqueous solution) pH adjustment amount (90% aqueous solution) to adjust the pH to 10.25. Developing solution 2: Hydroquinone developing agent-potassium carbonate formulation (developing solution using potassium carbonate after removing boric acid of developing solution 1) Potassium sulfite 66.4 g (0.42 mol) Ethylenediaminetetraacetic acid / 3 sodium (35 % Aqueous solution) 8.0 g 5-methylbenzotriazole 0.02 g potassium carbonate 9.0 g (0.065 mol) hydroquinone 26.4 g (0.24 mol) 1-phenyl-3-pyrazolidone 1.2 g 1-phenyl-5 -Mercapto-1,2,3,4-tetrazole 0.015 g 5-nitrobenzimidazole 0.03 g triethylene glycol 11.8 g glutaraldehyde (50% aqueous solution) 8.6 g (0.043 mol) sodium hydroxide (48 % Aqueous solution) 34.9 g Acetic acid (90% aqueous solution) pH adjustment amount Add 1 liter of water Torr and adjusted to pH 10.25 by adding acetic acid (90% aqueous solution). Developing solution 3 To the formula of developing solution 2, 2.73 g of potassium benzoate was added.
(0.017 mol), pH adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 4 To the formulation of Developer 2, 5.46 g of potassium benzoate
(0.034 mol), and the pH was adjusted to 10.25 with acetic acid (90% aqueous solution). Developing solution 5 To the formula of developing solution 2, 8.19 g of potassium benzoate was added.
(0.051 mol), and the pH was adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 6 In the formulation of Developer 2, 2.90 g (0.02 g) of salicylic acid was added.
1 mol) and adjust the pH with acetic acid (90% aqueous solution).
Developer adjusted to 25. Developer 7 To the formulation of Developer 2, add 8.70 g (0.06 g) of salicylic acid.
3 mol) and adjust the pH to 10 with acetic acid (90% aqueous solution).
Developer adjusted to 25. Developing solution 8 In the formula of developing solution 4, 6.9 g of potassium carbonate was added.
(0.050 mol), and the pH was adjusted to 10.25 with potassium hydroxide (48% aqueous solution). Developing solution 9 In the formula of developing solution 4, 7.9 g of potassium carbonate was added.
(0.057 mol), and the pH was adjusted to 10.25 with potassium hydroxide (48% aqueous solution). Developing solution 10 In the formula of developing solution 4, 13.0 g of potassium carbonate was added.
(0.094 mol), and the pH was adjusted to 10.25 with acetic acid (90% aqueous solution). Developing solution 11 In the formula of developing solution 4, 20.0 g of potassium carbonate was added.
(0.145 mol), and the pH was adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 12 To the formulation of Developer 2 was added 5.0 g of trehalose,
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developing solution 13 A developing solution in which 10.0 g of trehalose was added to the formulation of developing solution 2 and the pH was adjusted to 10.25 with acetic acid (90% aqueous solution). Developing solution 14 To the formula of developing solution 2, 5.0 sodium citrate dihydrate was added.
g (0.016 mol), and the pH was adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 15 In the formulation of Developer 2, sodium citrate dihydrate was added.
0 g (0.032 mol) of a developing solution whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 16 To the formulation of Developer 2, 10.0 g (0.057 mol) of 1,2,3-propanetricarboxylic acid was added, and the pH was adjusted to KO.
A developer adjusted to 10.25 with H (48% aqueous solution). Developing solution 17 To the formula of developing solution 2, 2.9 g of L-aspartic acid was added.
(0.022 mol), and the pH was adjusted to 10.25 with KOH (48% aqueous solution). Developer 18 To the formulation of Developer 2, 5.8 g of L-aspartic acid was added.
(0.044 mol), and the pH was adjusted to 10.25 with KOH (48% aqueous solution). Developing solution 19 10.0 g of L-aspartic acid was added to the formula of developing solution 2.
(0.075 mol), and the pH was adjusted to 10.25 with KOH (48% aqueous solution). Developer 20 To the formulation of Developer 2, 5.0 g (0.027 mol) of sodium hydrogen glutamate monohydrate was added, and the pH was adjusted to acetic acid (9
(0% aqueous solution) adjusted to 10.25. Developer 21 A developer prepared by adding 10.1 g (0.054 mol) of sodium hydrogen glutamate monohydrate to the formulation of Developer 2 and adjusting the pH to 10.25 with acetic acid (90% aqueous solution). Developer 22 In the formulation of Developer 1, glutaraldehyde (50%
Aqueous solution) and the pH was adjusted to 1 with acetic acid (90% aqueous solution).
Developer adjusted to 0.25. Developer 23 In the formulation of Developer 2, glutaraldehyde (50%
Aqueous solution) and the pH was adjusted to 1 with acetic acid (90% aqueous solution).
Developer adjusted to 0.25. Developer 24 In the formulation of Developer 4, glutaraldehyde (50%
Aqueous solution) and the pH was adjusted to 1 with acetic acid (90% aqueous solution).
Developer adjusted to 0.25. Developer 25 In the formulation of Developer 10, glutaraldehyde (50
% Aqueous solution) and a pH adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 26 In the formulation of developer 13, glutaraldehyde (50
% Aqueous solution) and a pH adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 27 In the formulation of developer 16, glutaraldehyde (50
% Aqueous solution) and a pH adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 28 In the formulation of developer 18, glutaraldehyde (50
% Aqueous solution) and a pH adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 29 In the formulation of Developer 1, glutaraldehyde (50%
Aqueous solution) to 7.4 g (0.037 mol) and pH
Developer adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 30 In the formulation of Developer 2, glutaraldehyde (50%
Aqueous solution) to 7.4 g (0.037 mol) and pH
Developer adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 31 In the formulation of Developer 4, glutaraldehyde (50%
Aqueous solution) to 7.4 g (0.037 mol) and pH
Developer adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 32 In the formulation of Developer 10, glutaraldehyde (50
% Aqueous solution) to 7.4 g (0.037 mol),
A developer in which H is adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 33 In the formulation of developer 13, glutaraldehyde (50
% Aqueous solution) to 7.4 g (0.037 mol),
A developer in which H is adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 34 In the formulation of developer 16, glutaraldehyde (50
% Aqueous solution) to 7.4 g (0.037 mol),
A developer in which H is adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 35 In the formulation of developer 18, glutaraldehyde (50
% Aqueous solution) to 7.4 g (0.037 mol),
A developer in which H is adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 36 In the formulation of Developer 1, glutaraldehyde (50%
Aqueous solution) to 13.6 g (0.068 mol)
A developer in which H is adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 37 In the formulation of Developer 2, glutaraldehyde (50%
Aqueous solution) to 13.6 g (0.068 mol)
A developer in which H is adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 38 In the formulation of Developer 4, glutaraldehyde (50%
Aqueous solution) to 13.6 g (0.068 mol)
A developer in which H is adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 39 In the formulation of Developer 10, glutaraldehyde (50
% Aqueous solution) to 13.6 g (0.068 mol),
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 40 In the formulation of developer 13, glutaraldehyde (50
% Aqueous solution) to 13.6 g (0.068 mol),
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 41 In the formulation of developer 16, glutaraldehyde (50
% Aqueous solution) to 13.6 g (0.068 mol),
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 42 In the formulation of Developer 18, glutaraldehyde (50
% Aqueous solution) to 13.6 g (0.068 mol),
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 43 In the formulation of Developer 1, glutaraldehyde (50%
Aqueous solution) to 15.5 g (0.075 mol)
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 44 In the formulation of Developer 2, glutaraldehyde (50%
Aqueous solution) to 15.5 g (0.075 mol)
A developer in which H is adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 45 In the formulation of Developer 4, glutaraldehyde (50%
Aqueous solution) to 15.5 g (0.075 mol)
A developer in which H is adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 46 In the formulation of Developer 10, glutaraldehyde (50
% Aqueous solution) to 15.5 g (0.075 mol),
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 47 In the formulation of developer 13, glutaraldehyde (50
% Aqueous solution) to 15.5 g (0.075 mol),
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 48 In the formulation of developer 16, glutaraldehyde (50
% Aqueous solution) to 15.5 g (0.075 mol),
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Developer 49 In the formulation of Developer 18, glutaraldehyde (50
% Aqueous solution) to 15.5 g (0.075 mol),
A developer whose pH has been adjusted to 10.25 with acetic acid (90% aqueous solution). Fixing solution Ammonium thiosulfate (75% aqueous solution) 245.5 g Sodium sulfite 12.0 g Sodium gluconate 2.0 g Citric acid / monohydrate 2.4 g Acetic acid (80% aqueous solution) 22.5 g Aluminum sulfate solution (8% in terms of aluminum oxide) Aqueous solution) 36.8 g sodium hydroxide (49% aqueous solution) 13.4 g 75% sulfuric acid pH adjustment amount Water was added to make up to 1 liter, and the pH was adjusted to 5.35 with 75% sulfuric acid.

[Preparation of Photosensitive Material 1] Preparation of Monodisperse Core / Shell Emulsion << Preparation of Seed Emulsion >> The following solutions were prepared.

[0075] <A ₁ Eki_> water 11.5l potassium bromide 2.05g ossein gelatin 100g <B ₁ liquid> water 2.6l potassium bromide and potassium iodide 65g 1.8g ossein gelatin 55g 0.2M sulfuric acid 38 .5ml a ₁ to <C ₁ solution> aqueous 3.0l potassium bromide 950g potassium iodide 27g ossein gelatin 75 g <D ₁ solution> aqueous 2.7l silver nitrate 95 g <E ₁ solution> aqueous 3.2l nitrate 1410g reactor Add the solution and keep it at 60 ° C.
The solution was kept warm at ℃ and added. At this time, solution B _{1 and} solution D ₁ were added over 30 minutes by the control double jet method, and then solution C _{1 and} solution E ₁ were added over 105 minutes by the control double jet method. The stirring speed is 5
The test was performed at 00 rpm. The flow rate is increased in proportion to the total surface area of the silver halide grains as the grains grow, and no new growth nuclei are generated when the additive liquid flows in, and so-called Ostwald ripening is caused to increase the grain size distribution. The addition was at a non-spreading flow rate. During the addition of silver ionic liquid and halide ionic liquid,
The pAg was adjusted to 8.3 ± 0.05 using an aqueous potassium bromide solution.
And the pH was adjusted to 2.0 ± 0.1 using sulfuric acid. The resulting emulsion had an average grain size of 0.30 μm, 5% of {111} planes, and {100} in the others, as determined by electron micrograph.
Cubic tetradecahedral monodispersed grains having a silver iodide content of 2 mol% with slightly lacking face corners were obtained.

Next, in order to remove excess salts, precipitation was carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate, and the supernatant was discarded. did.

<< Growth Step of Seed Emulsion >> First, the following solution was prepared. All amounts are given per mole of silver halide.

[0078] <J ₁ solution> Gelatin 10g of ammonia (28% aqueous solution) 28 ml glacial acetic acid 3ml water in 600 ml <K ₁ solution> 110 ml potassium bromide 5g potassium iodide 3g gelatin 0.8g Water <L ₁ solution> bromide Potassium 90 g Gelatin 2.0 g 240 ml with water <M ₁ solution> Silver nitrate 9.9 g ammonia (28% aqueous solution) 7.0 ml 110 ml with water <N ₁ solution> Silver nitrate 130 g ammonia (28% aqueous solution) 100 ml 240 ml with water <O ₁ Solution> 94 g of potassium bromide 165 ml with water <P ₁ solution> 9.9 g of silver nitrate 7.0 ml of ammonia (28% aqueous solution) 7.0 ml with water 110 ml The J ₁ solution was placed in a reaction vessel, kept warm at 40 ° C., and 800 stirred with a stirrer.
Stirring was performed at rpm. The pH of the J1 solution was adjusted to 9.90 using acetic acid, and the seed emulsion was added to the silver halide ₁ solution.
0.119 mol per mole was collected and dispersed and suspended. Then, pAg was added at a constant rate over a P ₁ solution for 7 minutes
Was set to 7.3. Further, the K ₁ solution and the M ₁ solution were simultaneously added over 20 minutes by the controlled double jet method. The pAg at this time was constant at 7.30. Further, the pH was adjusted to 8.8 using an aqueous solution of potassium bromide and acetic acid over 10 minutes.
3, was adjusted to pAg = 9.0, L ₁ solution were added simultaneously over 30 minutes by the controlled double jet method N ₁ solution. At this time, the ratio of the inflow rate at the start of addition and the end of addition was 1:10, and the flow rate was increased with time.
Also, the pH was reduced from 8.83 to 8.00 with acetic acid in proportion to the inflow. When the L ₁ solution and the N ₁ solution were added in only ２ of the total amount, the O ₁ solution was additionally injected and added at a constant speed over 8 minutes. At this time, the pAg increased from 9.0 to 11.0. After the addition was completed, the pH was adjusted to 6.0 by adding acetic acid, and the excess salt was removed by the same desalting method as in the seed emulsion to obtain emulsion EM-1. When the obtained emulsion was observed with an electron microscope, it was found that the obtained emulsion was monodisperse particles having a spherical average particle size of {100} and {111} surfaces of 0.61 μm and a variation coefficient of the particle size distribution of 12%. This was a core / shell emulsion having a silver content of 30 mol% and a total silver iodide content of 2 mol%.

<< Chemical Sensitization >> Next, the obtained emulsion EM-1 was prepared.
Was optimally chemically sensitized at 50 ° C. by adding ammonium thiocyanate, chloroauric acid and sodium thiosulfate. To terminate the chemical sensitization, 4-hydroxy-6-methyl- was added as a stabilizer while cooling the temperature of the emulsion.
An appropriate amount of 1,3,3a, 7-tetrazaindene was added.

<< Preparation of Photosensitive Material 1 >> Additives described below were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a coating solution for a protective layer described later was prepared. The amount of silver applied per side was 3.0 g / m ² , and the amount of gelatin applied was 3.0 g / m ² .
Two-sided simultaneously coated on the support at a speed per minute 80m using each two slide hopper type coater so that 7 g / m ^2, dried for 2 minutes 20 seconds to obtain a photosensitive material 1. As a support, a copolymer obtained by diluting a copolymer composed of three monomers of glycidyl methacrylate 50% by mass, methyl acrylate 10% by mass, and butyl methacrylate 40% by mass so as to have a concentration of 10% by mass. A polyethylene terephthalate film base which was colored blue to a concentration of 0.186 for an X-ray film having a thickness of 175 μm and obtained by subtracting the aqueous dispersion was used.

The additives used in the emulsion layer are as follows.
The amount of addition is shown per mole of silver halide. In addition,
The amount of gelatin added was 2.4 g / m ² .

1,1-Dimethylol-1-bromo-1-nitromethane 3.3 mg tert-butyl-catechol 40 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 1.7 g nitrophenyl- Triphenylphosphonium chloride 12.9 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 3.4 g 2-Sodium 2-mercaptobenzimidazole-5-sulfonate 5.2 mg pentaerythritol 6.7 g Sodium-isoamyl-n-decylsulfosuccinate Nate 13.7mg

[0083]

Embedded image

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 430 mg 1-phenyl-5-mercaptotetrazole 5.1 mg Dextran (average molecular weight 60,000) 600 mg Sodium polyacrylate (average molecular weight 3 Next, each additive was prepared as a coating liquid for a protective layer so that the following coating was performed.

Gelatin 1.3 g / m ² sodium-isoamyl-n-decylsulfosuccinate 10 mg / m ² polymethyl methacrylate (matting agent having an area average particle size of 5.5 μm) 23 mg / m ² Ludox AM (manufactured by DuPont) (Colloidal silica) 1.2 g / m ² formalin 4.5 mg / m ² glyoxal 19.4 mg / m ²

[0086]

Embedded image

The photosensitive material 1 thus obtained was run for a long period of time with the above-mentioned developer, and was evaluated by sensitometry.

Sensitometry (Evaluation of photographic performance) Sensitometry is performed by using two sheets of calcium tungstate phosphor intensifying screen (NR160, Konica Corporation)
Tube voltage of 60kV via aluminum wedge
X-ray irradiation was performed at a current of 200 mA for 0.064 seconds. Then, using a small automatic developing machine (SRX-101, manufactured by Konica Corporation), the above-mentioned necessary amounts of the developing solution and the fixing solution were prepared, and the replenishing amounts were 40 ml / quadruple development and 70 ml / quadrant fixing. And a development temperature of 35 ° C.

The processing time is 120 from dry to dry.
After a second treatment, the concentration of the obtained sample was measured to obtain a characteristic curve. Fog (Fog), sensitivity (S), average gradient (G), and maximum density (Dmax) were determined from the characteristic curves. The sensitivity is represented by the reciprocal of the exposure amount giving a density of fog + 0.5, and is represented by a relative sensitivity with the sensitivity in the developing solution 1 being 100. The average gradient was determined as the average slope between the fog + 0.25 and fog + 2.0 densities.

Incidentally, the entire surface of the sample after the development processing has a density of 0.3.
The coated sample uniformly exposed to 95 to 1.10.
Performs long-term running for 10 months per sheet for 3 months in terms of cutting size. Evaluates sensitometry and uneven development at the start of running. Was evaluated for the generation level of crystal precipitates generated in the rotating gear portion. The evaluation rank is shown below. << Evaluation rank of development unevenness >> 5: Almost no development unevenness is observed 4: Slight streak-like unevenness is observed, but there is no problem. 3: Streak-like unevenness is observed in several places, but is an allowable level 2: Many irregularities are observed, which is a problem level. 1: Irregularities are observed on the entire surface of the sample, which is a serious problem. << Generation level of crystal precipitates >> ：: Wall surface of developing tank, developing rack and transport roller回 転: Crystal precipitates are hardly observed on the rotating gear portion of Δ: Crystal precipitates are observed on the wall surface of the developing tank but at an acceptable level. X: Crystal precipitates are generated and are not easily peeled off. A large amount of crystal precipitates are generated on the wall surface, the developing rack, and the rotating gear portion of the transport roller, which hinders the transport of the film, and is at a problem level. ² /
The developer was left in a constant-temperature air-conditioning room set at 30 ° C. and 65% RH, and the number of days until the developer was blackened by air oxidation was compared and evaluated.

The type of buffer, the content of carbonate (mol / l), the molar ratio of carbonate to hydroquinone, and the content of glutaraldehyde (mol /
l), the molar ratio of glutaraldehyde to hydroquinone,
And additive compounds (benzene carboxylic acids, saccharides, linear tricarboxylic acids, and amino acids represented by the general formula (1))
Are shown in Tables 1 and 2, and the evaluation results of Developers 1 to 49 are shown in Tables 3 and 4 below.

[0092]

[Table 1]

[0093]

[Table 2]

In the table, GA represents glutaraldehyde, and HQ represents hydroquinone.

[0095]

[Table 3]

[0096]

[Table 4]

Example 2 [Preparation of photosensitive material 2] Preparation of high aspect ratio tabular emulsion << Grain formation >> The following solution was prepared.

[0098] <A ₂ Eki_> alkali-treated gelatin 0.71 g 4 mol / l nitric acid 3.57ml of sodium bromide 0.95g Water 850ml Compound A 56 mg <B ₂ solution> 4.536Ml silver nitrate 613mg Water <C ₂ solution> Sodium bromide 392 mg 4.536 ml with water <D ₂ solution> 1.24 g sodium bromide 12.09 ml with water <E ₂ solution> Ammonium sulfate 2.86 g 2.5M sodium hydroxide 25.0 ml 39.15 ml with water <F Solution ₂ > Alkaline-treated gelatin 14.2 g 4 mol / L nitric acid 11.15 ml Compound A 93.6 mg With water 153.2 ml <G ₂ solution> Silver nitrate 868.1 mg With water 6.383 ml <H ₂ solution> Sodium bromide 561 0.753 mg / water 6.553 ml <I ₂ solution> Silver nitrate 109.8 g 40.40 ml / water <J ₂ solution> 69.8 g of sodium bromide 403.5 ml of water <K ₂ solution> 58.6 g of silver nitrate 215.6 ml of water <L ₂ solution> 36.94 g of sodium bromide 213.7 ml of water Put the A ₂ solution in a reaction vessel, Keep at 45 ° C and 950rpm
With stirring. PAg value of the A ₂ solution was 9.39. Solution B _{2 and} solution C ₂ were simultaneously added to solution A ₂ under stirring at a constant speed for 1 minute, and 1 minute after the addition, solution D ₂ was added. Next, the liquid temperature in the reactor was raised to 60 ° C. over 10 minutes. 60 after heating
℃ to was added to leave E ₂ solution was kept stirred for 10 minutes, F ₂
The solution was added over 2 minutes. Next, the solution G _{2 and the} solution H ₂ were simultaneously added at a constant rate over 5 minutes, and the solution I _{2 and the} solution J ₂ were further linearly changed from a flow rate of 1.5 ml / min to a flow rate of 1.62 ml / min. The mixture was added simultaneously for 3 hours and 58 minutes while gradually increasing, and then added simultaneously for 64 minutes at a flow rate of 1.62 ml / min. Further, the K ₂ solution and the L ₂ solution were simultaneously added at a constant speed over 20 minutes. When the obtained emulsion was observed with an electron microscope, the projected area of tabular grains having an aspect ratio of 8.0 or more was 100%, and the average equivalent circle diameter of the main plane was 1.28.
It was a monodisperse, high aspect ratio tabular emulsion having an average grain thickness of 0.11 μm, an average aspect ratio of 11.6, and a coefficient of variation of equivalent circle diameter of 7.4%. The calculated equivalent spherical equivalent diameter of the tabular grains is 0.645 μm.

Next, a tabular emulsion redispersed by removing excess salts by the same desalting method as in the emulsion EM-1 of Example 1 and adding additional gelatin was designated as EM-2.

[0100]

Embedded image

<< Chemical Sensitization >> Subsequently, the obtained emulsion EM
-2 was redissolved and kept at 50 ° C. with stirring. Thereafter, the following sensitizing dye (A) was used in an amount of 400 m per mol of silver.
g, sensitizing dye (B) was added as a dispersion in the form of solid fine particles so as to be 50 mg. After 30 minutes, a dispersion of a selenium sensitizer (equivalent to 5 × 10 ⁻⁶ mol of triphenylphosphine selenide) and 65 m of ammonium thiocyanate
g, 4.6 mg of chloroauric acid and 5 × sodium thiosulfate
A mixed aqueous solution equivalent to 10 ^-6 mol was added, and after 40 minutes, a silver iodide fine grain emulsion was added. Thereafter, to terminate the chemical sensitization, 4-hydroxy-6-methyl-1,
200 mg of 3,3a, 7-tetrazaindene was added,
Upon cooling, each emulsion was subjected to optimal chemical sensitization.

Solid fine particle dispersions of the following spectral sensitizing dyes (A) and (B) were prepared according to the method described in JP-A-5-297496. That is, a predetermined amount of the following spectral sensitizing dye was added to water previously adjusted to 27 ° C., and the mixture was stirred with a high-speed stirrer (dissolver) at 500 rpm for 30 to 120 minutes.

The spectral sensitizing dyes (A) and (B) are shown below. -Spectral sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,3'-di- (sulfopropyl) oxacarbocyanine-sodium salt anhydride-Spectral sensitizing dye (B) 5,5 ' -Di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride Triphenylphosphine selenide dispersion is triphenylphosphine selenide. 120 g of phosphine selenide was added to 30 kg of ethyl acetate at 50 ° C. and stirred, completely dissolved,
3.8 kg of gelatin for photography is dissolved in 38 kg of pure water, mixed with a solution to which 93 g of a 25 mass% aqueous solution of sodium dodecylbenzenesulfonate is added, and dispersed at 50 ° C. by a high-speed stirring type disperser having a 10 cm diameter dissolver. Dispersion was performed at a peripheral speed of 40 m / sec for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3% by mass or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg.

<< Preparation of Photosensitive Material 2 >> (Preparation of Filter Layer) Glycidyl methacrylate 50
Mass%, methyl acrylate 10 mass%, butyl methacrylate
Copolymerization of three types of monomers of 40% by mass of acrylate
Copolymer obtained by diluting so that the body concentration becomes 10% by mass
175μm thick blue coated body dispersion as subbing liquid
On both sides of the colored polyethylene terephthalate support,
1m on one side ^TwoSo that the coating amount per
A support coated with a luster layer was prepared.

[0105] Solid fine particle dispersion dye (AH) 12.8 mg / m ² Gelatin 0.2 g / m ² Latex (L) 312 mg / m ² Sodium polystyrenesulfonate 4.4 mg / m ² topside 300 (Pakemuajia Co. 0.4 mg / m ^{2 The} following coating solution was further applied onto the support coated with the above-described filter layer in the order of an emulsion layer and a protective layer using a slide hopper type coater.

(Preparation of Emulsion Layer Coating Solution) Emulsion E obtained above
The following various additives were added to M-2.

1,1-Dimethylol-1-bromo-1-nitromethane 0.1 mg / m ² tert-butyl-catechol 1.75 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 13.5 mg / m ² polystyrene sulfonic acid Sodium 40 mg / m ² Trimethylolpropane 110 mg / m ² Ammonium 1,3-dihydroxybenzene-4-sulfonate 28 mg / m ² Latex (L) 1.27 mg / m ² n-C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 260 mg / m ² Thallium nitrate 0.5 mg / m ² Compound (M) 5 mg / m ² Compound (N) 1.5 mg / m ² Colloidal silica (Ludox AM: particle size manufactured by DuPont) 0.013μm) 2.55g / m ² dextran (average molecular weight 40,000) 320 mg / m ² of gelatin .2g / m ² (Preparation of protective layer coating solution) Gelatin 0.8 g / m ² Polymethyl methacrylate consisting matting agent (area average particle diameter 6.0 .mu.m) 27 mg / m ² Compound (P) 50 mg / m ² Compound ( S-1) 4.4 mg / m ² compound (S-2) 185 mg / m ² compound (S-3) 48 mg / m ² Topside 300 (manufactured by Perchem Asia Co., Ltd.) 0.6 mg / m ² the amount of force of the material is a single-sided 1m ² per,
The amount of silver applied was adjusted to be 1.6 g / m ² on one side.

[0108]

Embedded image

(Coating) Using these coating solutions, the above filter was used at a speed of 120 m / min using two slide hopper type coaters so that the coating amount was 1.6 g / m ² per one side. Photosensitive material 2 was prepared by simultaneous coating on both sides of the support sample coated with the layer and drying for 2 minutes and 20 seconds.

For the obtained photosensitive material 2, developing solutions 1 to 49 used in Example 1 were prepared in the same manner, and sensitometry and development unevenness were evaluated at the start of running. The crystal deposition property was evaluated.

Sensitometry (Evaluation of photographic performance) Sensitometry is such that a photosensitive material 2 is sandwiched between two rare earth intensifying screens (SRO-250: manufactured by Konica Corporation), and a tube voltage of 80 kVp is applied through an aluminum wedge. Tube current 100 mA,
X-rays were irradiated for 0.05 seconds. Next, a small automatic processor (S
RX-101: manufactured by Konica Corporation), the necessary amounts of the above-described developer and the fixing solution of Example 1 were prepared and processed at a development temperature of 35 ° C. Processing time is dry to d
ry for 90 seconds, the sample obtained was subjected to concentration measurement to obtain a characteristic curve. From the characteristic curve, fog (Fog), sensitivity (S), average gradient (G), maximum density (Dma)
x) was determined for each. The sensitivity is represented by the reciprocal of the exposure amount giving a density of fog + 0.5.
The relative sensitivity was shown.

The long-term running was performed in the same manner as in Example 1. At the start of the running and after the long-term running (3 months), the sensitometry, roller mark and residual color were evaluated. Further, the crystalline precipitate was evaluated.

<< Evaluation of Remaining Color >> The coated sample was subjected to a developing treatment without being exposed, and the developed sample thus obtained was evaluated according to the following evaluation rank.

A: Almost no residual color B: Slightly residual color but not bothersome C: Remaining color is anxious but practically acceptable level D: Remaining color, problematic level E: Many residual colors Unsuitable for practical use << Evaluation of roller mark >> Samples developed to a density of 1.0 by uniform exposure were observed and evaluated according to the following evaluation rank.

5: No roller mark occurred 4: Very slight occurrence but no problem 3: Occurred but practically acceptable level 2: Occurred and problematic level 1: Extremely large occurrence and practical Not possible Note that development unevenness and crystal precipitation were evaluated in the same rank as the evaluation shown in Example 1. The evaluation results are shown in Tables 5 and 6 below.
Shown in

[0116]

[Table 5]

[0117]

[Table 6]

[0118]

According to the present invention, there is provided a developer having excellent preservability and crystal precipitation when subjected to a long-term running treatment with a developer containing dihydroxybenzene as a developing agent and containing substantially no boron compound, Further, the long-term running property of the silver halide photographic light-sensitive material having a relatively large amount of silver is improved. The present invention provides a processing method having excellent roller mark failure and residual color.

Claims (6)

[Claims] 1. A dihydroxybenzene compound, 0.23 to 0.58 mol of carbonate, sulfite and dihydroxybenzene compound per 1 mol of dihydroxybenzene compound.
0.15 to 0.30 mol of gelatin hardener per mol,
And a benzenecarboxylic acid represented by the following general formula (1), and substantially free of a boron compound. Embedded image In the formula, R _{1 to} R ₅ each represent a hydrogen atom, a hydroxyl group,
Alkyl group, halogen group, ether group, carboxylic acid group,
Represents an ester group, an acyl group, an acetonitrile group, a sulfino group, a sulfo group, an amino group, a nitriso group, or a nitro group, and M represents a hydrogen atom, an alkali metal atom, or an ammonium group. 2. A dihydroxybenzene compound, 0.23 to 0.58 mol of carbonate, sulfite and dihydroxybenzene compound per 1 mol of dihydroxybenzene compound.
0.15 to 0.30 mol of gelatin hardener per mol,
And a saccharide and substantially no boron compound. 3. A dihydroxybenzene compound, 0.23 to 0.58 mol of carbonate, sulfite and dihydroxybenzene compound per 1 mol of dihydroxybenzene compound.
0.15 to 0.30 mol of gelatin hardener per mol,
And a straight-chain tricarboxylic acid, and substantially no boron compound. 4. A dihydroxybenzene compound, 0.23 to 0.58 mol of carbonate, sulfite, 1 mol of dihydroxybenzene compound per 1 mol of dihydroxybenzene compound.
0.15 to 0.30 mol of gelatin hardener per mol,
A developer for a silver halide photographic light-sensitive material, characterized by containing, and an amino acid, and substantially not containing a boron compound. 5. A method for processing a silver halide photographic light-sensitive material comprising at least a developing step and a fixing step, wherein the silver halide photographic light-sensitive material has a light-sensitive silver halide emulsion layer on at least one side of a support, and The silver content of at least one photosensitive silver halide emulsion layer is from 2.0 to 2.0 per m ² .
5.5 g, wherein the developing solution used in the developing step is
5. A method for processing a silver halide photographic light-sensitive material, which is a developer according to any one of claims 1 to 4. 6. The developer according to claim 1, wherein the silver halide photographic material contains 70 to 100% of the projected area of tabular silver halide grains having an aspect ratio of 8.0 or more. A method for processing a silver halide photographic light-sensitive material, characterized by performing development processing with