JP2000105444A - Developing solution for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the developing solution capable of relieving silver stains occurring in a developing tank and/or on developing racks or rollers at the time of processing the rapidly processable silver halide photosensitive material. SOLUTION: The developing solution contains at least 2 compounds selected from dimercaptopyrimidine, dimercapto-1,3,5-triazine, and dimercapto-1,2,4-triazine, or in addition to them at least one kind of compound represented by the formula in which Z is a nonmetallic atomic group for forming a 5-membered N-containing hetero rings together with N and C and M is a hydrogen or cation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing method used for processing a silver halide photographic material (hereinafter, also referred to as a "photosensitive material") and a developing solution used therefor. More specifically, in the rapid development of black-and-white photographic light-sensitive materials for general use, black-and-white photographic light-sensitive materials for printing, medical and industrial X-ray photographic light-sensitive materials, developing tanks, developing racks and rollers for photosensitive materials and automatic developing machines The present invention relates to a method for reducing silver stains (silver sludge) adhering to or settling on the surface and facilitating daily maintenance of equipment and machinery.

[0002]

2. Description of the Related Art Generally, in the development processing of a silver halide photosensitive material, an automatic developing machine (hereinafter referred to as an automatic developing machine) is often used from the viewpoints of speed, simplicity and handling. . When an automatic developing machine is used, a process of developing-fixing-washing-drying is usually performed. In recent years, there has been an increasing demand for faster development processing.
One of the means for rapid processing is to increase the activity of the developer. For rapid processing of black-and-white photosensitive materials, increasing the concentration of the developing agent or increasing the pH of the developer can increase the activity, but the deterioration of the developer by air oxidation is remarkable and it is difficult to maintain the activity. . In addition, approaches from photosensitive materials have been actively studied for rapid processing. Reducing the film thickness (for example, protective layer) of the photosensitive material is effective for rapid processing.

The use of sulfite to prevent the deterioration of the developer has been known for a long time, but since it has a dissolving effect on silver halide, silver is eluted from the photosensitive material as a silver sulfite complex into the developer. Would. As the silver complex is reduced in the developing solution, silver gradually adheres to and accumulates on the developing tank and the developing roller. This is called silver dirt or silver sludge, which adheres to the photosensitive material to be processed and stains the image, so that it is necessary to periodically clean and maintain the equipment.

On the other hand, as a method of reducing this silver stain,
As described in JP-A-56-24347, JP-A-8-6215, JP-A-9-212810, JP-A-9-274289, etc., silver ions eluted in a developer are reduced and / or silver ions are eluted. A method of adding a compound that suppresses reduction to silver is known. However, in order to obtain a sufficient silver stain preventing effect with the materials described in JP-A-56-24347, it is necessary to increase the amount of the compound to be added, and this has an effect on photographic properties such as low sensitivity and increased fog. Is big. These adverse effects are particularly remarkable in a super-high contrast material containing a hydrazine compound.

On the other hand, Japanese Patent Application Laid-Open Nos.
In the case of the dimercaptotriazine compound described in JP-A-2111810 and the dimercaptopyrimidine compound described in JP-A-9-274289, the so-called silver stain preventing ability is high and silver sludge can be prevented from adhering and depositing on rollers and a developing tank. It was found that the addition of a large amount has an effect of inhibiting fixing.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing silver halide light-sensitive materials which can be rapidly processed, firstly, to remove silver stains generated in a developing tank and / or a developing rack and rollers. The second is to reduce silver stain without affecting photographic characteristics at all, and the third is to reduce silver stain without impairing fixability.

[0007]

As a result of repeated studies, the present inventors have surprisingly found that two kinds of compounds selected from dimercaptotriazine compounds or dimercaptopyrimidine compounds are contained in a developer. It has been found that the coexistence thereof makes it possible to improve the fixing property, and that a sufficient effect of preventing silver stains can be obtained. Therefore, the above object is characterized by containing at least two compounds selected from dimercaptopyrimidine compounds, dimercapto-1,3,5-triazine compounds or dimercapto-1,2,4-triazine compounds. Achieved by a developer for a silver halide photosensitive material. Further, at least two compounds selected from a dimercaptopyrimidine compound, a dimercapto-1,3,5-triazine compound or a dimercapto-1,2,4-triazine compound, and a compound represented by the following general formula (I) This has been achieved even more highly by a developer for a silver halide photosensitive material, characterized by containing at least one compound selected from compounds. General formula (I)

[0008]

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In the formula, Z represents a non-metallic atomic group which forms a 5-membered nitrogen-containing aromatic heterocycle together with N and C, and M represents a hydrogen atom or a cation.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the dimercaptopyrimidine compound, dimercapto-1,3,5-triazine compound and dimercapto-1,2,4-triazine compound used in the present invention will be described in detail. The mercapto group of these dimercapto heterocyclic compounds also includes those in which a hydrogen atom is substituted with a Na atom, a K atom and an ammonium cation. Further, these dimercaptoheterocyclic compounds may have various substituents, and the substituents include the following. Halogen atom (eg, fluorine atom, chlorine atom, bromine atom), alkyl group (eg, methyl group, ethyl group, i-propyl group, t-butyl group, n-octyl group, cyclopropyl group, cyclohexyl group), alkenyl Groups (eg, allyl, 2-butenyl, 3-pentenyl), alkynyl (eg, propargyl, 3-
Pentynyl group), aralkyl group (for example, benzyl group,
Phenethyl group), aryl group (eg, phenyl group, naphthyl group, 4-methylphenyl group), heterocyclic group (eg, pyridyl group, furyl group, imidazolyl group, piperidyl group, morpholino group), alkoxy group (eg, methoxy group) Group, ethoxy group, butoxy group), aryloxy group (eg, phenoxy group, 2-naphthyloxy group), amino group (eg, unsubstituted amino group, dimethylamino group, ethylamino group, anilino group), ureido group ( For example, unsubstituted ureido group, N-methylureido group, N-phenylureido group), urethane group (eg, methoxycarbonylamino group, phenoxycarbonylamino group), sulfonyl group (eg, mesyl group, tosyl group), sulfinyl group (Eg, methylsulfinyl group, phenylsulfinyl group), sulfonamide group For example, methanesulfonamide group), sulfamoyl group (eg, N-methylsulfamoyl group), alkyloxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group), aryloxycarbonyl group (eg, phenoxycarbonyl group), acyl Groups (eg, acetyl, benzoyl,
Formyl group, pivaloyl group), acyloxy group (eg, acetoxy group, benzoyloxy group), alkylthio group (eg, methylthio group, ethylthio group), arylthio group (eg, phenylthio group), cyano group, hydroxy group, mercapto group, Carboxy group, phosphono group,
Nitro group, sulfo group, sulfino group, ammonium group (for example, trimethylammonio group), silyl group (for example,
Trimethylsilyl group) and the like. Preferred substituents are water-soluble groups or substituents substituted with water-soluble groups. These groups may be further substituted. When there are two or more substituents, they may be the same or different.

The dimercaptopyrimidine compound is preferably a 2,4-dimercaptopyrimidine compound or a 2,4-dimercaptopyrimidine compound.
A 6-dimercaptopyrimidine compound is used, and the hydrogen atom of the mercapto group may be replaced with a Na atom, a K atom, a Li atom, or an ammonium cation as described above. More preferably, the above 2,4-dimercaptopyrimidine compound having a water-soluble group, or the above 2,6-dimer having a water-soluble group
Dimercaptopyrimidine compounds are used. Here, the water-soluble group is a sulfonic acid or a carboxylic acid or a salt thereof, a salt such as an ammonium group, or a group containing a dissociable group that can be partially or completely dissociated by an alkaline developer. Specifically, a sulfo group (or a salt thereof), a carboxy group (or a salt thereof), a hydroxy group, a mercapto group, an amino group, an ammonium group, a sulfonamide group, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group, It represents an active methine group, a phosphono group or a substituent containing these groups. In the present invention, the active methine group refers to a methyl group substituted with two electron-withdrawing groups, specifically, dicyanomethyl, α-cyano-
groups such as α-ethoxycarbonylmethyl and α-acetyl-α-ethoxycarbonylmethyl.

The dimercapto-1,3,5-triazine compound is preferably a dimercapto having a water-soluble group.
A -1,3,5-triazine compound is used. Here, the water-soluble group has the same meaning as that described for the dimercaptopyrimidine compound. The dimercapto-1,2,4-triazine compound is preferably a dimercapto having a water-soluble group.
A -1,2,4-triazine compound is used. Here, the water-soluble group has the same meaning as that described for the dimercaptopyrimidine compound. Next, the compound represented by formula (I) will be described in detail. In the general formula (I), M is a hydrogen atom or a cation. Examples of the cation include sodium, potassium, lithium, calcium, ammonium, and triethylammonium. Z represents a nonmetallic atomic group which forms a 5-membered nitrogen-containing aromatic heterocycle together with N and C. The 5-membered nitrogen-containing aromatic heterocyclic ring formed by Z, N and C includes, in addition to nitrogen, carbon, oxygen,
It is formed by a combination of elements selected from sulfur and may be further condensed with a hydrocarbon ring or a heterocyclic ring, for example, pyrazole, imidazole, oxazole, thiazole, triazole, thiadiazole, oxadiazole, indazole, benzimidazole ,
Examples include benzoxazole and benzothiazole.

The 5-membered nitrogen-containing aromatic heterocyclic ring formed by Z, N and C is preferably imidazole, triazole, thiadiazole, oxadiazole, benzimidazole, benzoxazole, benzothiazole, and further has a water-soluble substituent. It has a functional group. Here, the water-soluble group has the same meaning as the water-soluble group described above in the dimercaptopyrimidine compound, the dimercapto-1,3,5-triazine compound and the dimercapto-1,2,4-triazine compound. More preferably, the 5-membered nitrogen-containing aromatic heterocycle formed by Z, N and C is benzimidazole, and further has a water-soluble group as a substituent. Specific examples of the compound used in the present invention are shown below, but the compound of the present invention is not limited thereto. (Dimercaptopyrimidine compounds in group A, dimercapto-1,3,5-
(The triazine compound is group B, the dimercapto-1,2,4-triazine compound is group C, and the compound of formula (I) is group I.)

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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The dimercaptopyrimidine compound used in the present invention can be synthesized based on the method and literature described in JP-A-9-274289. Further, dimercaptotriazine compounds are described in JP-A-9-21806, JP-A-8-6215, JP-A-3-282457 and JP-A-9-21181.
Compounds can be synthesized based on the method described in No. 0 and literatures. Next, the methods for producing the Na salt, K salt or Li salt of the dimercaptopyrimidine compound and the Na salt, K salt or Li salt of the dimercaptotriazine compound used in the present invention will be described in detail. The compound used in the developer of the present invention is a dichloropyrimidine compound or a dichlorotriazine compound represented by X ¹ X ² S (where X ¹ and X ² represent a hydrogen atom and an alkali metal ion (Na, K, Li, etc.)). ), Followed by crystallization by adding a water-soluble organic solvent as a poor solvent, wherein a dimercaptopyrimidine compound or a sodium salt, a K salt or a dimercaptopyrimidine compound of
The production method of Li salt has made it possible to provide it at low cost. That is, a 2,4- or 2,6-dichloropyrimidine compound or a 4,6-dichloropyrimidine compound or a 2,4-dichloro-S-triazine compound or a dichloro-1,2,4-triazine compound is represented by X ^After reacting with ¹ X ² S to make a dimercaptopyrimidine compound or a dimercaptotriazine compound or a salt thereof, the pH of the reaction solution is adjusted to 5 or more, and a water-soluble organic solvent is added as a poor solvent for crystallization. . More specifically, X ¹ X ² S is, for example, Na ₂ S, NaHS, K ₂ S, KHS, H ₂ S
Etc., and NaHS and KHS are more preferably used.

The 2,4- and 2,6-dichloropyrimidine compounds and 4,6-dichloropyrimidine compounds used in the production method are described by DJ Brown, The Pyrimidines (The Chemistry of Heterocyclic Compounds Series, Inter Can be synthesized according to the method described in Scientific Publishers). The dichlorotriazine compound used in the production method is EM Smolin, R. Rapoport, s-Triazines and Derivatives, and JG Ericsson, PF Wiley, The
1,2,3-and 1,2,4-triazines tetrazines
The compound can be synthesized according to the method described in AND PENTAZINS (The Chemistry of Heterocyclic Compounds Series, published by Interscience Publishers) and the like.

In the production method, a 2,4- or 2,6-dichloropyrimidine compound, a 4,6-dichloropyrimidine compound or a dichlorotriazine compound is reacted with X ¹ X ² S to obtain a dimercaptopyrimidine compound or In order to obtain a salt thereof, X ¹ X ² S is added at 2 to 5 times mol of the dichloropyrimidine compound or the dichlorotriazine compound, and the mixture is reacted at a reaction temperature of 50 ° C. or more for 1 hour to 10 hours. As the solvent in this case, various solvents are used, but a solvent having a high dielectric constant is preferable, for example, water, acetonitrile, methanol, ethanol, isopropyl alcohol, 1-propanol, 1-butanol, t-butanol, dimethylformamide, Dimethylacetamide, N-
It is selected from methylpyrrolidone, N, N-dimethylimidazolidinone, tetramethylurea, sulfolane, dimethylsulfoxide, acetone, methylethylketone, methylbutylketone, dioxane, tetrahydrofuran and the like, and a mixed solvent thereof. Preferably, X ¹ X ² S is added at 2 to 4 times the molar amount of the dichloropyrimidine compound, and the reaction temperature is 65 ° C.
1 to 5 hours at ℃ to 140 ℃, solvent selected from water, methanol, ethanol, isopropyl alcohol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N, N-dimethylimidazolidinone or a mixture thereof The reaction is performed using a solvent. At this time, a carbonate such as Na ₂ CO ₃ , NaHCO ₃ , K ₂ CO ₃ , KHCO ₃ or a base such as triethylamine, sodium acetate, potassium acetate or the like may be used. In addition, 2,4-dichloropyrimidine compound used in this case, 2,6-dichloropyrimidine compound, 4,
The 6-dichloropyrimidine compound or the dichlorotriazine compound may be used alone or as a mixture of two or more.

Next, an acid is added to the reaction mixture to adjust the pH to 6.5 or lower, preferably 6 or lower, and the remaining or excess X ¹ X ² S is converted into H _2.
Removed from the reaction mixture as S gas. As the acid used at this time, various acids such as an inorganic acid such as hydrochloric acid, sulfuric acid, and phosphoric acid, and an organic acid such as toluenesulfonic acid are used. Preferably, hydrochloric acid and sulfuric acid are used. The concentration of the acid is arbitrary, but is preferably at least 0.1 mol / l, more preferably at least 1 mol / l. At this time, a slight amount of sulfur may precipitate, but can be easily removed by filtration. An alkali is added to the reaction mixture thus obtained to adjust the pH to 7 to 13, preferably 7.5 to 11, to form a solution of a salt of the dimercaptopyrimidine compound. Allow to crystallize. Finally, this is filtered to obtain the salt of the dimercaptopyrimidine compound used in the present invention. Here, the water-soluble organic solvent used as the poor solvent is preferably one which is uniformly mixed with water at an arbitrary ratio, and for example, acetonitrile, acetone, isopropyl alcohol, ethanol, methanol, dioxane, tetrahydrofuran and the like are used. Preferably,
Acetonitrile, acetone and isopropyl alcohol are used.

According to the synthesis method of the present invention, an alkali metal salt of a dimercaptopyrimidine compound and an alkali metal salt of a dimercaptotriazine compound can be obtained with a yield of almost 100%. This is because an alkali metal salt of a dimercaptopyrimidine compound and an alkali metal salt of a dimercaptotriazine compound are extremely poorly soluble in a water-soluble organic solvent used as a poor solvent. On the other hand, when a dimercaptopyrimidine compound and a dimercaptotriazine compound are obtained as a mercapto form (-SH),
The yield does not reach 100%. This is because the dimercaptopyrimidine compound and the mercapto compound of the dimercaptotriazine compound have a certain degree of solubility in a solvent. The synthesis yield of the dimercapto form is described in the following literature, by DJ Brown, The Pyrimidines, EM Smolin, R. Rapoport, s-Triazines and Derivatives and JG Ericson, PF Wiley, The
1,2,3-and 1,2,4-triazines tetrazines
And Pentazines (The Chemistry of Heterocyclic Compounds Series, published by Interscience Publishers) and others.
Further, for example, Japanese Patent Application Laid-Open No. 8-6215 discloses a method for synthesizing Exemplified Compound B-7, and the yield is 79%. On the other hand, by using the method described later in the embodiment,
The Na salt of B-7 was synthesized with a yield of 99%.

Next, embodiments of the compound according to the present invention will be described. The amounts of the dimercaptopyrimidine compound, the dimercaptotriazine compound and the compound of the formula (I) used in the present invention are preferably in the range of 0.001 to 10 mmol per liter of the developer, and preferably 0.01 to 3 per 1 liter of the developer. A millimolar range is particularly preferred. The developer for a silver halide light-sensitive material of the present invention includes at least two compounds selected from dimercaptopyrimidine compounds, dimercapto-1,3,5-triazine compounds, and dimercapto-1,2,4-triazine compounds. Preferably, a dimercaptopyrimidine compound, dimercapto-1,
At least two selected from 3,5-triazine compounds
It is preferred to use species compounds. In particular, it is preferable to use at least two kinds of compounds selected from dimercaptopyrimidine compounds. A preferred combination in this case is a combination in which the substituent positions on the pyrimidine ring are different from each other, specifically, 2,4-dimercaptopyrimidine having a substituent at the 5- or 6-position, Alternatively, a combination with 4,6-dimercaptopyrimidine having a substituent at the 5-position may be mentioned. In this case, the substituent is preferably a water-soluble group or a substituent substituted with a water-soluble group.

Hereinafter, processing agents such as a developing solution and a fixing solution, a processing method, and the like in the present invention will be described. However, needless to say, the present invention is not limited to the following description and specific examples.

In the development processing of the present invention, any of the known methods can be used, and a known processing solution can be used. There are no particular restrictions on the developing agents used in the developing solution (hereinafter, both the developing solution and the replenishing solution are collectively referred to as a developing solution) used in the present invention. It preferably contains a monosulfonate, and may be used alone or in combination. In addition, in terms of developing ability, dihydroxybenzenes and ascorbic acid derivatives
A combination of -phenyl-3-pyrazolidones, or a dihydroxybenzene or an ascorbic acid derivative and p-
Combinations of aminophenols are preferred. Examples of the dihydroxybenzene developing agent used in the present invention include hydroquinone, chlorohydroquinone, isopropylhydroquinone, and methylhydroquinone, with hydroquinone being particularly preferred. Ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred from the viewpoint of material cost.

In the present invention, it is preferable to use an auxiliary developing agent. The auxiliary developing agents for 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl −
4-hydroxymethyl-3-pyrazolidone and the like.
N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine as the p-aminophenol-based auxiliary developing agent used in the present invention. Among them, N-methyl-p-aminophenol is preferable.

The dihydroxybenzene-based developing agent is preferably used usually in an amount of 0.05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / l to 0.6 mol / l, preferably 0.23 mol / l. It is preferably used in an amount of from 0.5 mol / l to less than 0.06 mol / l, preferably from 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is preferably used in an amount of usually 0.01 mol / l to 0.5 mol / l, preferably 0.05 mol / l to 0.5 mol / l.
0.3 mol / l is more preferred. When a combination of an ascorbic acid derivative and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the ascorbic acid derivative is used in an amount of 0.01 mol / liter or less.
It is preferable to use 0.5 mol / l, 1-phenyl-3-pyrazolidone or p-aminophenol in an amount of 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention can contain commonly used additives (for example, a developing agent, an alkali agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited to these. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonates, boric acid described in JP-A-62-186259, sugars described in JP-A-60-93433 (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), tertiary phosphorus Acid salts (eg, sodium salt, potassium salt) and the like are used, and preferably, carbonate and boric acid are used. The amount of buffer, especially carbonate, used is preferably at least 0.5 mol / l, especially 0.5 to 1.5 mol / l.

The preservative used in the present invention includes sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. Sulfite is more than 0.2 mol / l, especially 0.3
It is used in an amount of at least mol / l, but if it is added in too large an amount, it causes silver contamination in the developing solution.
Desirably, it is mol / liter. Particularly preferably,
It is 0.35 to 0.7 mol / liter. As the preservative of the dihydroxybenzene developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite.
Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably 0.05 to 0.10. In molar ratio to the dihydroxybenzene-based developing agent. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Other additives to be used include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (for example, 3-
Sodium (5-mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole, etc.) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness preventing agents. Further, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, and a benzimidazole-based compound may be contained as an antifoggant or a black pepper (black pepper) inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole,
5-nitrobenzimidazole, 2-isopropyl-5
-Nitrobenzimidazole, 5-nitrobenzotriazole, sodium 4-((2-mercapto-1,3,4-thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4-thiadiazole- Examples thereof include 2-thiol, methylbenzotriazole, 5-methylbenzotriazole, and 2-mercaptobenzotriazole. The amounts of these additives are usually from 0.01 to 10 mmol per liter of developer,
More preferably, it is 0.1 to 2 mmol.

Further, various kinds of organic,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As aminopolycarboxylic acids, for example,
Aspartic acid acetic acid, iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid, 1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetramine Hexacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and others, JP-A-52-25632, JP-A-55-67747, and JP-A-57-10
2624, and the compounds described in JP-B-53-40900.

Examples of the organic phosphonic acid include hydroxyalkylidene compounds described in, for example, US Pat.
Diphosphonic acid or Research Disclosure No. 181
Vol., Item 18170 (May 1979) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, aminotrimethylenephosphonic acid, and the like.
4, 54-61125, 55-29883, 56
-97347 and the like.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A-52-102726, JP-A-53-42730, JP-A-54-112127, JP-A-55-4024, and JP-A-55-40.
25, 55-126241, 55-65555, 55-65556, and the compounds described in Research Disclosure 18170 described above.

These organic and / or inorganic chelating agents are not limited to those described above. Also,
It may be used in the form of an alkali metal salt or ammonium salt. The addition amount of these chelating agents is preferably 1 × 10 ^-4 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 1 × 10 ^-2 mol per liter of the developer.

The compound of the present invention may be used alone as an antifouling agent, for example, as described in JP-A-56-2434.
7, JP-B-56-46585, JP-B-62-2849,
In addition to the compounds described in JP-A-4-362942, a polyoxyalkylphosphonic acid ester described in U.S. Pat. The addition amount of the silver stain inhibitor is preferably 0.05 to 10 mmol, more preferably 0.1 to 5 mmol, per liter of the developer.

As a dissolution aid, JP-A-61-267 is used.
759 can be used. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hardening agent and the like may be contained.

The preferred pH of the developer is 9.0 to 12.0
And particularly preferably in the range of 9.5 to 11.0. As the alkali agent used for pH adjustment, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

The replenishment amount of the developing solution is 3 per m ² of the photosensitive material.
90 ml or less, preferably 325 to 30 ml, and most preferably 180 to 120 ml. The development replenisher has the same composition and / or
Alternatively, it may have a concentration, or may have a composition and / or concentration different from that of the starting solution.

As the fixing agent of the fixing agent in the present invention, ammonium thiosulfate, sodium thiosulfate, and sodium ammonium thiosulfate can be used. The amount of the fixing agent used can be changed as appropriate, but is generally about 0.7 to 0.7.
It is about 3.0 mol / liter.

The fixing solution in the present invention may contain a water-soluble aluminum salt and a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferred. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are 0.01 to 0.1 as an aluminum ion concentration in the working solution.
It is preferably contained at 5 mol / l. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts having a hardening agent and the like as separate parts, or may be a one-part composition containing all components.

If desired, a preservative (for example, sulfite, bisulfite, metabisulfite, etc.)
15 mol / l or more, preferably 0.02 mol / l to 0.3 mol / l), pH buffer (for example, acetic acid, sodium acetate, sodium carbonate, sodium hydrogencarbonate, phosphoric acid, succinic acid, adipic acid, etc.) 0.1
Mol / l to 1 mol / l, preferably 0.2
Mol / l to 0.7 mol / l), a compound having an aluminum stabilizing ability or a water softening ability (for example, gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid) , Maleic acid, glycolic acid, benzoic acid, salicylic acid, tiron, ascorbic acid, glutaric acid, aspartic acid,
Glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and their derivatives and their salts, saccharides,
0.001 mol / L to 0.5 mol /
Liter, preferably 0.005 mol / l to 0.1 mol / l.
3 mol / l).

In addition, compounds described in JP-A-62-78551, pH adjusters (for example, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators, etc. can also be included. Examples of the surfactant include anionic surfactants such as sulfated sulfone oxides, polyethylene surfactants, and JP-A-57-6840.
The amphoteric surfactants described above may be used, and a known antifoaming agent may be used. Examples of the wetting agent include alkanolamine and alkylene glycol. Examples of the fixing accelerator include alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in JP-A-6-308681, JP-B-45-35754, JP-B-58-122535, and JP-B-58-1.
Thiourea derivatives described in 22536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat. No. 4,126,459, JP-A-64-4739, JP-A-Hei 1-4
739, 1-159645 and 3-101728
And the mesoionic compound and thiocyanate described in 4-1-170539.

The fixing solution of the present invention has a pH of 4.0 or more, preferably 4.5 to 6.0.

The replenishment rate of the fixing solution is 5 per m ² of the photosensitive material.
00 ml or less, preferably 390 ml or less, more preferably 320 to 80 ml. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As a reproducing apparatus, for example, there is Reclaim R-60 manufactured by Fuji Hunt.

When the developing and fixing processing agents used in the present invention are stored in a liquid form, for example, JP-A-61-731
47, it is preferable to store in a packaging material having low oxygen permeability. Further, when these liquids are supplied as a concentrated liquid, they are diluted with water to a predetermined concentration at the time of use, and are diluted at a ratio of 0.2 to 3 parts of water to 1 part of the concentrated liquid.

Even if the developing agent and the fixing agent in the present invention are solidified, the same result as that of the liquid agent can be obtained, but the solid processing agent will be described below.

The solid processing agent in the present invention may be in a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, crushed product, rod, paste, etc.). These solid agents may be coated with a water-soluble coating agent or a coating film to separate components that react with each other upon contact,
Components that react with each other may be separated into a plurality of layers, or they may be used in combination.

Known coatings can be used, but polyvinylpyrrolidone, polyethylene glycol,
Polystyrene sulfonic acid and vinyl compounds are preferred. In addition, gelatin, pectin, polyacrylic acid,
Polyvinyl alcohol, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, alginic acid, chitanic acid gum, gum arabic, tragacanth gum, karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, poly Polyoxyethylene alkyl ethers such as oxyethylene stearyl ether and polyoxyethylene ethyl ether; polyoxyethylene alkyl phenol ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; and water-soluble binders described in Japanese Patent Application No. 2-203165. One or a combination of two or more selected from That. These can also be used as granulation aids.

In the case of forming a plurality of layers, components which do not react even if they come into contact with each other may be sandwiched between components which react with each other, and processed into tablets, briquettes, or the like. It may be packaged in a similar layer configuration. These methods are described, for example, in JP-A-61-25992.
1, JP-A-4-15641, 4-16841, 4-
32837, 4-78848 and 5-93991.

The bulk density of the solid processing agent is 0.5 to 6.0 g.
/ Cm ³ is preferable, and particularly, the tablet is 1.0 to 5.0 g / cm ^3.
The granules are preferably 0.5 to 1.5 g / cm ³ .

As the method for producing the solid processing agent in the present invention, any known method can be used. For example, as a packaging method, Japanese Patent Application Laid-Open Nos. 61-259921 and 4-1
6841 and 4-78848 can be used. As a method of solidification, Japanese Patent Application Laid-Open No.
5533, 4-85534, 4-85535, 5
-134362, 5-197070, 5-2040
98, 5-224361, 6-138604, 6
138605, Japanese Patent Application No. 7-89123, and the like.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt-solidification, briquetting, roller compaction Ing method or the like can be used.

The particle size and shape of the granulated material suitable for the present invention vary depending on the desired characteristics. Considering the durability against destruction of the granulated material due to vibration at the time, in the case of granular, the spherical equivalent particle size is 0.5 to 5
The shape is about 0 mm, preferably about 1 to 15 mm, and the shape is cylindrical, spherical, cubic, rectangular, or the like, and more preferably spherical or cylindrical. The roller compacted product may be crushed or sieved to a diameter of about 2 mm to 1 cm. In the case of briquettes and tablets, the particle size and shape also differ depending on the desired properties, but a diameter of about 2 mm to 5 cm is preferable, and the shape is cylindrical, spherical, cubic, rectangular, etc., more preferably spherical or cylindrical. It is. When the solubility is desired to be improved, a plate having a reduced thickness, a plate having a further reduced center portion, a hollow donut, and the like are also useful. Conversely, the diameter and thickness may be further increased for the purpose of slowly dissolving, and can be arbitrarily adjusted. Further, the surface state (smooth, porous, etc.) may be changed to control the solubility. Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Also, multilayer granulated materials having different compositions on the surface and inside may be used.

The packaging material for the solid processing agent is preferably a material having low oxygen and moisture permeability, and the packaging material may be in a known shape such as a bag, a tube, or a box. Also,
JP-A-6-242555-JP-A 6-242588, JP-A-6-242588
247432, 6-247448, Japanese Patent Application No. 5-306
64, JP-A-7-5664, 7-5666 to 7-5
It is also preferable to use a foldable shape as disclosed in US Pat. No. 669 to reduce the storage space for waste packaging materials. For these packaging materials, a screw cap, a pull-top, an aluminum seal may be attached to the outlet of the treatment agent, or the packaging material may be heat-sealed, but other known materials may be used, and these materials are limited to these. Do not. In addition, recycling or reusing the waste packaging material is preferable in terms of environmental conservation.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. These methods include, for example, a method of dissolving and replenishing a fixed amount with a dissolving device having a stirring function, and a dissolving device having a dissolving portion and a portion for stocking a completed solution as described in Japanese Patent Application No. 7-235499. Dissolve in
Replenishment method from stock section,
4, a method for introducing and dissolving and replenishing a processing agent into a circulating system of an automatic developing machine as described in 6-19102 and 7-261357, and processing a photosensitive material with an automatic developing machine having a dissolving tank built therein. There is a method of adding and dissolving the treating agent according to the method, and any other known method can be used. In addition, the processing agent may be charged by opening it manually, or may be automatically opened and automatically loaded by a dissolution apparatus or an automatic developing machine having an opening mechanism as described in Japanese Patent Application No. 7-235498. The latter is preferable from the viewpoint of the working environment. More specifically, a method of piercing through the outlet, a method of peeling, a method of cutting, a method of pushing out, and a method disclosed in
102, 6-95331.

The photosensitive material which has been developed and fixed is then washed or stabilized (hereinafter, unless otherwise specified, washing including the stabilization treatment is performed. The liquid used for these is water or washing water. .). The water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing liquid. The replenishment amount is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishment amount can be smaller. In particular, when the replenishment amount is 3 liters or less (including 0; that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. If washing with a low replenishment volume,
It is more preferable to provide a washing tank for squeeze rollers and crossover rollers described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

[0063] As a method of reducing the replenishing amount of the washing, a multi-stage countercurrent system (for example, two stages, three stages, etc.) than the old are the known water washing replenishment rate photosensitive material 1 m ² per 200 to 50
Milliliters are preferred. This effect can be similarly obtained by an independent multi-stage system (a method in which a new liquid is individually replenished in a multi-stage washing tank without using countercurrent).

In the method of the present invention, a rinsing step may be provided in the washing step. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. It may be applied to washing water in advance and replenished. Further, it is also preferable to perform different scale prevention means at regular intervals in order to suppress the generation of resistant bacteria. The protective agent is not particularly limited, and known agents can be used. In addition to the oxidizing agents described above, chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxide (for example,
-Mercaptopyridine-N-oxide, etc.) and may be used alone or in combination of two or more. As a method for energizing, Japanese Patent Application Laid-Open Nos.
7, 4-16280, 4-18980 and the like.

In addition, a known water-soluble surfactant or defoamer may be added to prevent unevenness of water bubbles and transfer of dirt. Further, a dye adsorbent described in JP-A-63-163456 may be provided in the washing system to prevent contamination by the dye eluted from the photosensitive material.

A part or all of the overflow solution from the washing step can be mixed with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (for example, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramic), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain a biochemical oxygen demand. Amount (BO
D) Compounds that reduce the chemical oxygen demand (COD), iodine consumption, etc. before draining, or filters that use a polymer having affinity for silver, or compounds that form poorly soluble silver complexes such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by, for example, adding silver to precipitate silver and filtering the mixture with a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment.
JP-A-132435, JP-A-1 102553, JP-A-46-4
A bath containing the compound described in 4446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath may also contain a metal compound such as an ammonium compound, Bi, or Al, a fluorescent brightener, various chelating agents, a film pH regulator, a hardening agent, a bactericide, a deterrent, an alkanolamine or a surfactant. Agents can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths and the stabilizing agents can be solid agents like the above-mentioned developing and fixing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water, and stabilizing solution used in the present invention is incinerated. Further, these waste liquids can be concentrated and liquefied or solidified by a concentrating device described in, for example, Japanese Patent Publication No. 7-83867, US Pat.

In order to reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent evaporation of the liquid and oxidation of the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and are simply referred to as roller transport type automatic developing machines in this specification. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. further,
A rinsing bath may be provided between development and fixing and / or between fixing and washing with water.

In the development processing of the present invention, the time from the start of processing to the end of the drying step is preferably 25 to 160 seconds, the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds, and the temperature of each liquid is 25 to 50 ° C. Is preferable, and 30 to 40 ° C is preferable. The washing temperature and time are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material which has been developed, fixed and washed with water may be squeezed with washing water, that is, dried through a squeeze roller. Drying is about 40 to about 1
The drying is performed at 00 ° C., and the drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation.
534, 5-2256, and 5-289294, heat roller drying, drying by far infrared rays, and the like, and a plurality of methods may be used in combination.

In the silver halide emulsion used in the light-sensitive material of the present invention, there can be used conventional silver halides such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide and silver chloroiodobromide. Any of those used for silver emulsions can be used. Preferably, as a negative silver halide emulsion, silver chlorobromide containing 60 mol% or more of silver chloride or as a positive silver halide is used.
Silver bromochloride, silver bromide, and silver iodobromide containing 0 mol% or more of silver bromide. The silver halide grains may be obtained by any of an acidic method, a neutral method and an ammonia method. The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. Even if the particles are formed as
Further, the particles may be mainly formed inside the particles. Further, the particles may be particles whose surface is previously covered. The silver halide grains according to the present invention may have any shape. One preferred example is $ 10
It is a cube having a 0 ° plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, etc., and the Journal of Photographic Science
(J. Photogr. Sci.) Particles having an octahedral, tetrahedral, dodecahedral, etc. shape can be prepared and used by methods described in documents such as 21-39 (1973). Further, particles having a twin plane may be used. As the silver halide grains according to the present invention, grains having a single shape may be used, or grains having various shapes may be mixed. In the present invention, a monodisperse emulsion is preferred. The monodispersed silver halide grains in the monodispersed emulsion are those in which the weight of silver halide contained within a grain size range of ± 10% around the average grain size γ is 60% or more of the weight of all silver halide grains. Some are preferred. The halogen composition of the silver halide emulsion used in the present invention is not particularly limited. In order to more effectively achieve the object of the present invention, silver chloride, silver chlorobromide and silver chloroiodobromide having a silver chloride content of 50 mol% or more are preferred.
The content of silver iodide should be less than 5 mol%, especially 2 mol%.
Less is preferred.

In the present invention, a photosensitive material suitable for high-illuminance exposure such as scanner exposure and a photosensitive material for line drawing are:
Rhodium compounds are included to achieve high contrast and low fog. As the rhodium compound used in the present invention, a water-soluble rhodium compound can be used. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaaminerhodium ( III) Complex salt, trizalatrodium (II
I) Complex salts and the like. These rhodium compounds are
It is used by dissolving it in water or a suitable solvent, but it is a commonly used method for stabilizing a solution of a rhodium compound, that is, an aqueous solution of hydrogen halide (eg, hydrochloric acid, bromic acid, hydrofluoric acid, etc.), or a halogenated solution. A method of adding an alkali (for example, KCl, NaCl, KBr, NaBr, or the like) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide. The amount of addition is 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ mol, preferably 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per mol of silver of the silver halide emulsion. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. . The photographic emulsion used in the present invention is Chimie et Physique Photograph by P. Glafkides.
ique (Paul Montel, 1967), by GFDufin
Photographic Emulsion Chemistry (The Focal Press
Publishing, 1966), Making and by VLZelikman et al
Coating Photographic Emulsion (The Focal Press,
1964) and the like.

The method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-side mixing method, a simultaneous mixing method, and a combination thereof. Method of forming grains in excess of silver ions (so-called reverse mixing method)
Can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains by using a so-called silver halide solvent such as ammonia, thioether and tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
08, 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. According to the controlled double jet method and the grain forming method using a silver halide solvent, it is easy to produce a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and the silver halide used in the present invention is easy to produce. It is a useful tool for making emulsions.

The grain shape of the silver halide used in the present invention is not particularly limited, and may be cubic, octahedral, spherical,
Research Disclosure 22534 (January 1983)
Any of the tabular silver halide grains having a high aspect ratio described in (1) can be used.

In order to make the particle size uniform,
UK Patent No. 1,535,016, JP-B-48-3689
No. 5,162,364, a method in which the addition rate of silver nitrate or alkali halide is changed in accordance with the grain growth rate, or a method disclosed in British Patent No. 4,242,44.
5. It is preferable to use a method of changing the concentration of the aqueous solution as described in JP-A-55-158124 to grow the solution quickly within a range not exceeding the critical saturation.
The emulsion of the present invention is preferably a monodisperse emulsion, and the coefficient of variation is 20%.
Or less, particularly preferably 15% or less. The average grain size of the grains in the monodispersed silver halide emulsion is 0.5 μm or less, particularly preferably 0.1 μm to 0.4 μm.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. When used in combination,
For example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, and sulfur sensitization, tellurium sensitization and gold sensitization are preferable.

The sulfur sensitization used in the present invention is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer. For example, in addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like are used. be able to. Preferred sulfur compounds are
Thiosulfate and thiourea compounds. The addition amount of the sulfur sensitizer, pH during the chemical ripening, the temperature, but varies depending on various conditions such as the size of the silver halide grains, 10 ^-7 to 10 ^-2 mol per mol of silver halide And more preferably 10 ^-5 to 10 ^-3 mol.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. A specific example is U.S. Pat. No. 1,574,94.
4, 2,278,947, 2,410,689, 2,728,668, 3,501,313, 3,6
56, 955. Preferred sulfur compounds are thiosulfates and thiourea compounds, and the pAg at the time of chemical sensitization is preferably 8.3 or less, more preferably 7.3 to 8.0. Moisar, K
lein Gelationc. Proc. Symp. 2nd.
(1970) using polyvinyl pyrrolidone and thiosulfate in combination also gives good results.

As the selenium sensitizer used in the present invention, known selenium compounds can be used. That is, it is usually carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature of 40 ° C. or higher for a certain time. As the unstable selenium compound, compounds described in JP-B-44-15748 and JP-B-43-13489, JP-A-4-109240, JP-A-4-324855 and the like can be used. In particular, JP-A-4-32485
It is preferable to use the compounds represented by formulas (VIII) and (IX) in (5).

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
313284. Specifically, U.S. Patent Nos. 1,623,499 and 3,3
20,069, 3,772,031, UK Patent No. 2
35, 211; 1,121,496; 1,29
5,462, 1,396,696, Canadian Patent No.8
00,958, JP-A-4-204640, JP-A-4-271
341, 4-330430, 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.)
635 (1980), ibid 1102 (1979), ib
id 645 (1979), Journal of Chemical Society Parkin Transaction (J.Ch
em.Soc.Perkin.Trans.) 1, 2191 (1980);
The Chemistry of Organic Serenium and Telluniu, edited by S. Patai
m Compounds), Vol 1 (1986), Vol 2 (19
87) can be used. Particularly, compounds represented by formulas (II), (III) and (IV) in JP-A-5-313284 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but generally ranges from 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. Specific examples of the gold sensitizer used in the present invention include chloroauric acid, potassium chlorate, potassium aurithiocyanate, and gold sulfide.
About 10 ^-7 to 10 ^-2 mol per mol can be used. In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. A thiosulfonic acid compound may be added to the silver halide emulsion of the present invention by the method described in European Patent Application (EP) -293,917. The silver halide emulsion in the light-sensitive material used in the present invention may be only one kind or two or more kinds (for example, those having different average grain sizes,
Those having different halogen compositions, those having different crystal habits, and those having different conditions of chemical sensitization) may be used in combination.

In the present invention, a silver halide emulsion particularly suitable as a return photographic material is silver halide comprising 90 mol% or more, more preferably 95 mol% or more, of silver chloride. Silver chlorobromide or silver chloroiodobromide containing 1 mol%. When the ratio of silver bromide or silver iodide is increased, the safety of safelight under bright room is deteriorated, or γ
Is undesirably reduced.

The silver halide emulsion used for the return photographic material of the present invention preferably contains a transition metal complex. As transition metals, Rh, Ru, Re, Os, I
r, Cr, and the like. Examples of ligands include nitrosyl and thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenoate ligand Cyanate, tellurocyanate, acid and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands.

Specifically, in order to contain a rhodium atom, a metal salt of an arbitrary form such as a single salt or a complex salt can be added at the time of preparing particles. Examples of the rhodium salt include rhodium monochloride, rhodium dichloride, rhodium trichloride, ammonium hexachlororhodate, and the like. A water-soluble trivalent rhodium halide complex compound such as hexachlororhodium (III) acid or a salt thereof ( Ammonium salt, sodium salt, potassium salt, etc.). The addition amount of these water-soluble rhodium salts is in the range of 1.0 × 10 ^-6 mol to 1.0 × 10 ^-3 mol per mol of silver halide. Preferably, 1.0 × 10 ⁻⁵ mol to 1.0
× 10 ⁻³ mol, particularly preferably 5.0 × 10 ⁻⁵ mol
5.0 × 10 ^-4 mol.

Further, the following transition metal complexes are also preferable. 1 [Ru (NO) Cl ₅ ] ^-22 [Ru (NO) ₂ Cl ₄ ] ^-13 [Ru (NO) (H ₂ O) Cl ₄ ] ^-14 [Ru (NO) Cl ₅ ] ^-2 5 [Rh (NO) Cl _5] ^-2 6 [Re (NO) CN _5] ^-2 7 [Re (NO) ClCN _4] ^-2 8 [Rh (NO) ₂ Cl _4] ^-1 9 [Rh (NO ) (H ₂ O) Cl _4] ^-1 10 [Ru (NO) CN _5] ^-2 11 [Ru (NO) Br _5] ^-2 12 [Rh (NS) Cl _5] ^-2 13 [Os (NO) Cl _5] ^-2 14 [Cr (NO) Cl _5] ^-3 15 [Re (NO) Cl _5] ^-1 16 _{[Os (NS) Cl 4 (TeCN} ) ] ^-2 17 [Ru (NS) I _5] ^-2 18 [Re (NS) Cl ₄ (SeCN)] ^-2 19 [Os (NS) Cl (SCN) ₄ ] ^-2 20 [Ir (NO) Cl ₄ ] ^-2

The spectral sensitizing dye used in the present invention is not particularly limited. The addition amount of the sensitizing dye used in the present invention varies depending on the shape and size of the silver halide grains, but is used in the range of 4 × 10 ^-6 to 8 × 10 ^-3 mol per mol of silver halide. For example, when the silver halide grain size is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. , Especially 6.5 × 10 ^{-7 to} 2.0 ×
An addition amount range of 10 ^-6 mol is preferred.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE ITEM 17643 IV-
Item A (p.23, December 1978), Item 183
Section 1X (August 1978, p. 437), U.S. Pat.
No. 25425 and No. 4425426, which are described in the documents described or cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) For an argon laser light source,
62247, JP-A-2-48653, U.S. Pat.
1,331, West German Patent 936,071, JP-A-5-11
389. Simple merocyanines, B) Helium-
Japanese Patent Application Laid-Open No. 50-6242 discloses a neon laser light source.
5, pp. 54-18726, and 59-102229; C) LED light sources and red semiconductor lasers;
-9609, 55-39818, JP-A-62-284
343, JP-A-2-105135, and D) Tricarbocyanines described in JP-A-59-191332 and JP-A-60-80841 for infrared semiconductor laser light sources. 59-192
242, dicarbocyanines containing a 4-quinoline nucleus and represented by formula (IIIa) and formula (IIIb) of JP-A-3-67242 are advantageously selected. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure, Vol. 176, Volume 17643, issued December 1978, page 23, IV-J.

For an argon light source, refer to Japanese Patent Application No.
S1-1 to S1-13 described in 811 can be preferably used.

For a helium-neon light source, a sensitizing dye represented by the general formula (I) described at the end of page 8, line 42 to column 7, page 11 of Japanese Patent Application No. 6-75322 is particularly preferred. . Specifically, the compounds I-1 to I-35 in the same specification are preferred. In addition to these, those described in the general formula (I) of JP-A-6-75322 and I-1 to I-34 of the general formula (I) of Japanese Patent Application No. 6-103272 are preferably used.

For LED light sources and infrared semiconductor lasers, S3-1 to S3 described in Japanese Patent Application No. 7-37811.
The dye of -8 is particularly preferably used.

In addition to the infrared semiconductor laser light source, S4-1 to S4-9 described in Japanese Patent Application No. 7-37811.
Are preferably used.

For a white light source such as a camera image, a sensitizing dye represented by the general formula (IV) described in JP-A-6-313937 is preferred. It is preferably used. In addition, general formulas (III) and (IV) described in JP-A-4-19647 are preferred, and specifically, III-1 to III-20 and IV-1 to IV-1 in the same specification.
1 is preferably used.

In the case of an X-ray sensitive material, it is preferable to use a tabular silver halide emulsion. In this case, silver bromide or silver iodobromide is preferred.
-5 mol% is preferable, and a high sensitivity is obtained, and it is suitable for rapid processing.

The preferred grain form of the tabular silver halide emulsion has an aspect ratio of 4 to less than 20, more preferably 5 to less than 10. Furthermore, the thickness of the particles is 0.3μ
Or less, particularly preferably 0.2 μm or less. Here, the aspect ratio of the tabular silver halide emulsion is given by the ratio of the average value of the diameter of a circle having an area equal to the projected area of each tabular grain to the average value of the thickness of each tabular grain. . Tabular grains are preferably 80% by weight, more preferably 90% by weight of all grains in the tabular silver halide emulsion.
Preferably, it is present in an amount of at least% by weight. By using a tabular silver halide emulsion, the photographic stability during running processing according to the present invention can be further enhanced. In addition, since the amount of coated silver can be reduced,
In particular, the load on the fixing step and the drying step is reduced, and from this point also, rapid processing becomes possible.

A tabular silver halide emulsion was prepared by using Cug (Cug).
nac) and Chateau "Evolution of Morphology of Silver Bromide Crystals during Physical Ripening (Evolution of the Morphology of Silver Promide Crystals Dualing Physical Ripping)" Science・ E-Industrie Photography, 33
Vol. 2, No. 2 (1962), pp. 121-125, Duffin, "Photographic emulsion chemistry", Focal Press, New York, 196.
6 years, p. 66 to p. 72, APH Tribelli (Tribvll
i), WF Smith Photographic Journal, 80, 285 (194
0), and Japanese Patent Application Laid-Open No. 58-127,92.
1, JP-A-58-113,927, JP-A-58-11
It can be easily prepared by referring to the method described in US Pat. Further, in an atmosphere having a relatively pBr value of pBr 1.3 or less, a seed crystal in which tabular grains are present in an amount of 40% or more by weight is formed. Obtained by growing crystals. It is desirable to add a silver and halogen solution so that no new crystal nuclei are generated during the grain growth process. The size of the tabular silver halide grains can be adjusted by controlling the temperature,
It can be adjusted by selecting the type and amount of the solvent and controlling the addition rate of the silver salt and halide used during grain growth. In the present invention, a tetrazolium compound, a hydrazine compound, and a nucleation accelerator may be added.

The hydrazine derivative used in the present invention is disclosed in JP-A-7-287335 (corresponding EP670516).
It is preferred to use the compounds of the general formula (I) described in A). Specifically, I-1 to I-53 described in the same specification
The compound represented by is used.

The following hydrazine derivatives are also preferably used. Compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the same publication. Compounds represented by formulas (4), (5) and (6) described in JP-A-6-230497, specifically, compound 4-1 described on pages 25 and 26 of the same publication -Compound 4-10, compounds 5-1 to 5-42 described on pages 28 to 36, and compounds 6-1 to 6-7 described on pages 39 and 40. JP-A-6-28
Compounds represented by formulas (1) and (2) described in No. 9520, specifically, compounds 1-1) to 1-17) and 2-1 described in pages 5 to 7 of the same publication ). JP 6
Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-313936, specifically, compounds described on pages 6 to 19 of the same publication. Compounds represented by (Chemical Formula 1) described in JP-A-6-313951, specifically, compounds described on pages 3 to 5 of the same. Compounds represented by formula (I) described in JP-A-7-5610, specifically, compounds I-1 to I-38 described on pages 5 to 10 of the same. Compounds represented by formula (II) described in JP-A-7-77783, specifically, compounds II-1 to II-102 described on pages 10 to 27 of the same publication. Compounds represented by formulas (H) and (Ha) described in JP-A-7-104426, specifically, compounds H-1 to H-44 described on pages 8 to 15 of the same publication. Japanese Patent Application No. 7-
General formulas (1), (A), (B) described in 191007
Compounds represented by (C), specifically, compounds N-1 to N-30 and D-1 to D-55 described in the publication. Regarding the method of adding the hydrazine derivative, the added layer, and the added amount, the above-mentioned JP-A-7-287335 (corresponding EP670516)
What is necessary is just to refer to the description of A).

Various compounds can be added to the photographic emulsion of the present invention in order to prevent a reduction in sensitivity and generation of fog during the production process, storage or processing of the silver halide photographic material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptotetrazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, Nitrobenzotriazoles, etc .; mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetraazaindenes), pentaazaindenes and the like; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonamide, etc. can be added. Among these, benzotriazole (for example, 5-methyl-benzotriazole) and nitroindazoles (for example, 5-nitroindazole) are preferred. Further, these compounds may be contained in the treatment liquid. Further, a compound capable of releasing an inhibitor during development described in JP-A-62-30243 can be contained for the purpose of stabilizing or preventing black spots.

Further, a technique in which a polymer latex is contained in a silver halide emulsion layer and a backing layer to improve dimensional stability can also be used. These techniques are described in, for example, JP-B-39-4272, JP-B-39-17702, and JP-B-43.
-13482, and the like. In addition, for the purpose of dimensional stability, a dispersion of a water-insoluble or poorly-soluble synthetic polymer can be included. For example, using a polymer having a monomer component of alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, or the like alone or in combination, or a combination thereof with acrylic acid, methacrylic acid, or the like. Can be.

The emulsion layer of the photographic light-sensitive material of the present invention may contain a plasticizer such as a polymer such as an alkyl acrylate latex or a polyol such as trimethylolpropane in order to improve pressure characteristics.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic properties, improved slipperiness, emulsification / dispersion, prevention of adhesion and improved photographic properties (for example, development acceleration). For various purposes such as high contrast, high contrast and sensitization), various surfactants may be contained. For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives ( For example, nonionic surfactants such as alkenyl succinic acid polyglyceride and alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and alkyl esters of sugars; alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl Naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl Such as taurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, carboxy group, sulfo group, phospho group, sulfate group, phosphate group, etc. Anionic surfactants containing acidic groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amino oxides; alkylamine salts, aliphatic or aromatic carboxylic acids; Quaternary ammonium salts, pyridinium,
Heterocyclic quaternary ammonium salts such as imidazolium,
And cationic surfactants such as aliphatic or heterocyclic containing phosphonium or sulfonium salts.

The silver halide photographic light-sensitive material used in the invention has at least one silver halide emulsion layer on a support. 127921, 59-90841, 58-
As described in Examples 111934 and 61-201235, those having at least one silver halide emulsion layer on both sides of the support are preferred. The photographic material of the present invention may further have, if necessary, an intermediate layer, a filter layer, an antihalation layer and the like.

The silver content of the light-sensitive material used in the present invention is preferably 0.5 g / m ^{2 to} 5 g / m ² (on one side), more preferably 1 g / m ^{2 to} 4 g / m ² (on one side). It is. Preferably, the suitability for rapid processing does not exceed 5 g / m ² . Further, in order to obtain a constant image density and a constant contrast, 0.5 g / m ² or more is preferable.

Gelatin is used as a binder for the light-sensitive material used in the present invention. Gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single or copolyesters are used. A hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a coalescence can also be used in combination.

As the binder or protective colloid of the photographic emulsion, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, protein hydroxyethylcellulose such as casein, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, Polyvinyl alcohol partial acetal, poly-N
-Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used. As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin enzyme hydrolyzate can also be used.

It is particularly preferable for the X-ray sensitive material to contain an organic substance which flows out in the developing step in the emulsion layer or the hydrophilic colloid layer. When the substance to be washed away is gelatin, a gelatin species which is not involved in the crosslinking reaction of gelatin by the hardener is preferable, such as acetylated gelatin or phthalated gelatin, and a material having a small molecular weight is preferable. On the other hand, as a polymer substance other than gelatin, US Pat. No. 3,271,1
Polyacrylamide as described in No. 58, or a hydrophilic polymer such as polyvinyl alcohol and polyvinylpyrrolidone can be used effectively, and saccharides such as dextran, saccharose and pullulan are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less,
It is more preferably 10,000 or less. The effluent in the processing is 1% of the total weight of the coated organic material other than the silver halide grains.
0% or more and 50% or less are effective, and preferably 15% or more and 30% or less disappear. The layer containing the organic substance flowing out in the treatment of the present invention may be either an emulsion layer or a surface protective layer. It is preferable that the compound is contained in the emulsion layer, and it is more preferable that the compound is contained only in the surface protective layer. In the case of a light-sensitive material having a multi-layered emulsion layer, when the total amount of the organic substance applied is the same, it is preferable to include a large amount in the emulsion layer closer to the surface protective layer.

In the present invention, as a matting agent, US Pat.
4, organic compounds such as polymethyl methacrylate homopolymers or methyl methacrylate and methacrylic acid copolymers and starches as described in 4,396,706;
Fine particles of an inorganic compound such as silica, titanium dioxide, and strontium barium sulfate can be used. The particle size is preferably from 1.0 to 10 μm, particularly preferably from 2 to 5 μm.

The silver halide photographic light-sensitive material of the present invention has a purpose of absorbing light in a specific wavelength range, that is, performing halation or irradiation, or providing a filter layer to adjust the spectral composition of light to be incident on the photographic emulsion layer. The photographic emulsion layer or other layers may be colored with a dye for control or the like. In a double-sided film such as a direct medical X-ray film, a layer for crossover cut may be provided below the emulsion layer. Such dyes include oxonol dyes having pyrazolone nuclei and barbituric acid nuclei, hemioxonol dyes, azo dyes, azomethine dyes, anthraquinone dyes, arylidene dyes, styryl dyes, triarylmethane dyes, merocyanine dyes, cyanine dyes, and the like. Is mentioned. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used are described in German Patent 616,00.
7, British Patents 584,609 and 1,117,429,
JP-B-26-7777, JP-B-39-22069, JP-B-54-
38129, JP-A-48-85130 and JP-A-49-996.
20, 49-144420, 49-129537,
PB Report 74175, Photographic Abstract (Photo. Abstr.) 128 ('21) and the like. In particular, these dyes are preferably used in a light-sensitive room light-sensitive material. In addition, Japanese Patent Application No. 5-2
You may use the solid fine particle dispersion of the dye of 44717 on page 23-30. In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

When these dyes are used, it is an effective technique to mordant an anionic dye into a specific layer in a light-sensitive material using a polymer having a cation site. In this case, it is preferable to use a dye that irreversibly decolorizes in the developing-fixing-washing step. The layer in which the dye is mordanted using a polymer having a cation site may be the emulsion layer, the surface protective layer may be the surface on the side opposite to the emulsion layer and the support, but preferably between the emulsion layer and the support. For the purpose of crossover cutting of medical X-ray double-sided films, it is ideal to mordant into the undercoat layer.

As a coating aid for the undercoat layer, a polyethylene oxide-based nonionic surfactant can be preferably used in combination with a polymer having a cation site. As the polymer providing the cation site, an anion conversion polymer is preferable. Various known quaternary ammonium salt (or phosphonium salt) polymers can be used as the anion conversion polymer. Quaternary ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers and antistatic polymers in the publications listed below. JP-A-59-166940, U.S. Pat. No. 3,958,99
5, JP-A-55-142339, JP-A-54-126,
027, JP-A-54-155835, JP-A-53-3
0328, a water-dispersed latex described in JP-A-54-92274; a polyvinylpyridinium salt described in U.S. Pat. Nos. 2,548,564, 3,148,061 and 3,756,814; U.S. Pat. , 709, 69
0; a water-insoluble quaternary ammonium salt polymer described in U.S. Pat. No. 3,898,088; Further, a monomer having at least 2 or more (preferably 2 to 4) ethylenically unsaturated groups is copolymerized in order to move from a desired layer to another layer or into the processing solution and to have no undesired effect on photography. It is particularly preferable to use a crosslinked aqueous polymer latex.

A method for immobilizing a dye is described in JP-A-55-1.
The solid dispersion method described in 55350 and WO88 / 04794 is also effective.

The photographic light-sensitive material of the present invention may contain a developing agent such as a hydroquinone derivative or a phenidone derivative for various purposes such as a stabilizer and an accelerator.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chrome alum, chromium acetate, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, etc.), dioxane derivatives, active vinyl compounds (1,3,5-triacryloyl- Hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mucochloric acid, etc.), etc. They can be used alone or in combination.

The photographic light-sensitive material of the present invention contains a hydroquinone derivative (so-called DIR-hydroquinone) which releases a development inhibitor in a photographic emulsion layer or another hydrophilic colloid layer in accordance with the density of an image during development. You may. Examples thereof are U.S. Pat. No. 3,379,529, U.S. Pat. No. 3,620,746, and U.S. Pat. No. 4,377,63.
4, U.S. Pat. No. 4,332,878, JP-A-49-12
9,536, JP-A-54-67,419, JP-A-56-
153,336; JP-A-56-153,342; JP-A-59-278,853; 59-90435;
90436 and 59-138808.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include salicylic acid, acetic acid, organic acids such as ascorbic acid and acrylic acid,
A polymer or copolymer having an acid monomer such as maleic acid or phthalic acid as a repeating unit can be given. These compounds are described in JP-A-61-2238.
34, 61-228437, 62-25745, and 62-55642. Among these compounds, particularly preferred are ascorbic acid as a low molecular weight compound, and a high molecular weight compound comprising an acid monomer such as acrylic acid and a crosslinkable monomer having two or more unsaturated groups such as divinylbenzene. It is a water-dispersible latex of a copolymer.

The thus-produced silver halide emulsion is coated and dried on a support such as a cellulose acetate film or a polyethylene terephthalate film by a dipping method, an air knife method, a bead method, an extrusion doctor method, a double-side coating method or the like. You.

The present invention can also be used for color light-sensitive materials. In this case, various color couplers can be used. Here, the color coupler refers to a compound capable of forming a dye by a coupling reaction with an oxidized form of an aromatic primary amine developing agent. Typical examples of useful color couplers include naphthol or phenolic compounds, pyrazolone or pyrazoloazole compounds, and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta, and yellow couplers that can be used in the present invention are Research Disclosure (RD) 17
643 (December 1978), Sections VII-D and 187
17 (November 1979).

In addition, there are no particular restrictions on the various additives used in the light-sensitive material of the present invention, and for example, those described in the following places can be preferably used. Item The present section 1) Nucleation accelerator A compound of the general formula (I), (II), (III), (IV), (V) or (VI) described in JP-A-6-82943. JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10, general formulas (II-m) to (II-p) and compound examples II-1 to II-22; Compounds described in JP-A-1-179939. 2) Spectral sensitizing dyes JP-A-2-12236, page 8, lower left column, line 13 to lower right column, line 4, JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left column 20th line, and spectral sensitizing dyes described in JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, JP-A-5-11389, and Japanese Patent Application No. 3-41164. 3) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to lower right column, line 7, and JP-A-2-18542, page 2, lower left column, line 13 to page 4, lower right column 18th line. 4) Antifoggants JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further disclosed in JP-A-1-237538. The thiosulfinic acid compound according to the above. 5) Polymer latex: JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group: JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1. 7) Matting agent, slip agent, JP-A-2-103536, page 19, upper left column, line 15, plasticizer to page 19, upper right column, line 15; 8) Hardener JP-A-2-103536, page 18, upper right column, line 5 to line 17. 9) Dyes Dyes described in JP-A-2-103536, page 17, lower right column, lines 1 to 18 and solid dyes described in JP-A-2-294638 and JP-A-5-11382. 10) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 11) Black spot inhibitors Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832. 12) Redox compounds The compounds represented by the general formula (I) of JP-A-2-301743 (especially compound examples 1 to 50), and the general formulas (R) described in pages 3 to 20 of JP-A-3-174143. -1), (R-2), (R-3), Compounds The compounds described in Examples 1 to 75, and further described in 5-257239 and 4-278939. 13) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (especially compound examples II-1 to II-26). 14) Dihydroxybenze A compound described in the upper left column of page 11 of JP-A-3-39948 to the lower left column of page 1 of page 2 and EP 452772A.

[0120]

EXAMPLES The present invention will be described below with reference to examples, but embodiments of the present invention are not limited thereto. Example 1 Preparation of Emulsion A 1 liquid 1 liter water 20 g gelatin 20 g sodium chloride 3.0 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 8 mg 2 liquid water 400 ml silver nitrate 100 g 3 liquid water 400 ml sodium chloride 27 0.1 g Potassium bromide 21.0 g Ammonium hexachloroiridium (III) (0.001% aqueous solution) 20 ml 1 Potassium hexachloroiridate (III) (0.001% aqueous solution) 6 ml

Solution 2 and solution 3 were added simultaneously to solution 1 kept at 42 ° C. and pH 4.5 over 15 minutes while stirring.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4 liquid water 400ml 1 silver nitrate 100g 5 liquid water 400ml sodium chloride 27.1g potassium bromide 21.0g potassium hexacyanoferrate (II) (0.1% aqueous solution) 10ml

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method, and 40 g of gelatin was added. pH
5.7, pAg was adjusted to 7.5, and 1.0 mg of sodium thiosulfate, 4.0 mg of chloroauric acid, 1.5 mg of triphenylphosphine selenide, 8 mg of sodium benzenethiosulfonate, and 2 mg of sodium benzenethiosulfinate were added. In addition, chemical sensitization was performed at 55 ° C. so as to obtain an optimum sensitivity. Further, as a stabilizer, 4-hydroxy-6-methyl-1,
100 mg of 3,3a, 7-tetrazaindene and phenoxyethanol as a preservative were added, and finally a silver chloroiodobromide cubic emulsion A containing 70 mol% of silver chloride and having an average particle diameter of 0.25 μm was obtained.

Preparation of coated sample Emulsion A was added with sensitizing dye (1) 3.8 × 10 ^-4 mol / mol Ag
Was added for spectral sensitization. Furthermore, KBr 3.4 × 10
^-4 mol / mol Ag, compound (1) 3.2 × 10 ^-4 mol /
Mol Ag, compound (2) 8.0 × 10 ⁻⁴ mol / mol A
g, hydroquinone 1.2 × 10 ⁻² mol / mol Ag, citric acid 3.0 × 10 ⁻³ mol / mol Ag, compound (3) in l. 0 × 10 ⁻⁴ mol / mol Ag, compound (4) was 6.0.
× 10 ^-4 mol / mol Ag, and 15 to gelatin
wt% of compound A and 25 wt% of compound B, colloidal silica having a particle size of 10 μm at 20 wt% with respect to gelatin,
4% by weight of compound (5) based on gelatin was added,
Ag3.7g / m ² on a polyester support was coated to a gelatin 1.6 g / m ^2. An upper layer of a protective layer and a lower layer of a protective layer having the following composition, and an UL layer having the following composition, were applied thereon. Upper layer of protective layer Gelatin 0.3 g / m ² Silica matting agent having an average of 3.5 μm 25 mg / m ² Compound (6) (gelatin dispersion) 20 mg / m ² Colloidal silica having a particle size of 10 to 20 μm 30 mg / m ² Compound (7 ) 5 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² compound (8) 20mg / m ² protective layer underlying gelatin 0.5 g / m ² compound (9) 15mg / m ² 1,5- dihydroxy-2-Benzuarudo Kissim 10 mg / m ² Polyethyl acrylate latex 150 mg / m ² UL layer Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (5) 40 mg / m ² Compound (10) 10 mg / m ²

The support of the sample used in the present invention has a back layer and a conductive layer having the following compositions. Back layer Gelatin 3.3 g / m ² Sodium dodecylbenzenesulfonate 80 mg / m ² Compound (11) 40 mg / m ² Compound (12) 20 mg / m ² Compound (13) 90 mg / m ² 1,3-divinylsulfonyl-2 -Propanol 60 mg / m ² Polymethyl methacrylate fine particles (average particle size 6.5 μm) 30 mg / m ² Compound (5) 120 mg / m ² Conductive layer Gelatin 0. lg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 200 mg / m ²

[0125]

Embedded image

[0126]

Embedded image

The composition of the concentrated developer solution per liter is shown below. Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75.0 g 5-Methylbenzotriazole 0.24 g 4-Hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 1.35 g Sodium erythorbrate 9.0 g Diethylene glycol 60.0 g pH 10.7 Before use, dilute 2 parts of water with respect to 1 part of the above concentrated liquid. The pH of the working solution is 10.5. Based on this developer solution, a test developer solution as shown in Table 1 was prepared.

[0128]

[Table 1]

The prescription per liter of the concentrated fixing solution is shown below. Ammonium thiosulfate 360.0 g Ethylenediamine tetraacetic acid 2Na dihydrate 0.09 g Sodium thiosulfate pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90.0 g Tartaric acid 8 0.7 g sodium gluconate 5.1 g aluminum sulfate 25.2 g pH 4.85 In use, 1 part of the above concentrated solution is diluted with 2 parts of water. The pH of the working solution is 4.8.

The sample thus prepared was exposed to xenon flash light having a light emission time of 10 ⁻⁶ sec through a step wedge through an interference filter having a peak at 633 nm, and treated with a developer having the above composition at 35 ° C. for 30 seconds. Fixing, washing, drying and processing were performed. For the development, a running test was performed using FG-680A manufactured by Fuji Photo Film Co., Ltd.

The running conditions were as follows: 50% blackening per day (1
Large paper size (5 out of 0 sheets exposed)
0.8 × 61.0cm)
The running, six days off and one day off, was performed three times to evaluate photographic properties and silver stain. The amount of replenishment was 100 ml per development and fixing.

Here, the sensitivity of this sample was determined using developer No. The relative value of the reciprocal of the exposure amount that gives a density of 1.5 was shown as the type when the treatment was performed with the new liquid of No. 1. Sensitivity is 93 ~
107. Fr is a new liquid, and Last is after running.

The silver stain was visually evaluated on a five-point scale. The state where no silver stain was generated on the film, the developing tank, and the roller was designated as 5, and the case where a large amount of silver stain was generated on the developing tank and the roller due to the entire surface of the film was designated as 1. 4 is a level which is not practically generated in the film but is slightly generated in the developing tank and the roller, but is practically acceptable. Below 3 is a practically problematic or impossible level.

The evaluation of the dropping of the fixing was carried out in five steps visually by passing the photosensitive material of the example at the beginning and at the end of running.
The state where no defective defect occurred on the film was designated as 5, and the case where the defective film was entirely formed on the film was designated as 1. No. 4 is a level which is slightly practically acceptable in the film. Below 3 is a practically problematic or impossible level. Table 2 shows the results of photographic properties, silver stains, and fixation loss by running experiments.

[0135]

[Table 2]

As can be seen from Table 2, according to the development processing method of the present invention, good results were obtained with no problems in photographic properties, silver stains and fixing loss.

Example 2 (Preparation of Exemplified Compound A-26) 0.04 mol of 2,6-dichloro-4- (N-carboxymethyl-N-methylamino) pyrimidine and 0.02 mol of sodium carbonate were added to 3 ml of isopropyl alcohol and 20 ml of water. Dissolve in the mixed solvent, add 0.16 mol of NaSH, 70
The mixture was heated and stirred at 1 ° C. for 1 hour and at 90 ° C. for 3 hours. After cooling to 50 ° C. or lower, 5.5 ml of hydrochloric acid and 12 ml of water were added to adjust the pH of the reaction mixture to about 5, and excess NaSH was removed as hydrogen sulfide gas. The sulfur generated at this time was removed by filtration through Celite, and 5N-NaO
H1.5 ml was added to adjust the pH of the reaction solution to about 8, 800 ml of acetone was added dropwise, and the resulting crystals were filtered and dried, and NaCl was added.
23.7 g (yield 100%) of a white powder containing was obtained. This was identified as Exemplified Compound A-26 by its nuclear magnetic resonance spectrum, mass spectrum and infrared spectrum. The content of NaCl in the present white powder was 43% by ion chromatography.

(Production of Exemplified Compound A-27) 4,6-Dichloro-2
Dissolve 0.04 mol of-(N-carboxymethyl-N-methylamino) pyrimidine and 0.02 mol of sodium carbonate in a mixed solvent of 3 ml of isopropyl alcohol and 20 ml of water.
16 mol was added, and the mixture was heated and stirred at 70 ° C. for 1 hour and at 90 ° C. for 3 hours. After cooling to 50 ° C or less, 5.5 ml of hydrochloric acid and 12 ml of water
Was added to adjust the pH of the reaction mixture to about 5, and excess NaSH was removed as hydrogen sulfide gas. The sulfur generated at this time was removed by filtration through celite, and 1.5 ml of 5N-NaOH was added to adjust the pH of the reaction solution to about 8. Then, 800 ml of acetone was added dropwise, and the resulting crystals were filtered and dried to obtain white containing NaCl. 23 g of powder (99% yield) was obtained. This was identified as Exemplified Compound A-27 by its nuclear magnetic resonance spectrum, mass spectrum and infrared spectrum. The content of NaCl in this white powder was 44% by ion chromatography.

(Preparation of a mixture of exemplified compounds A-26 and A-27)
3: 1 mixture of 2,6-dichloro-4- (N-carboxymethyl-N-methylamino) pyrimidine and 4,6-dichloro-2- (N-carboxymethyl-N-methylamino) pyrimidine
(0.04 mol) and 0.02 mol of sodium carbonate in a mixed solvent of 3 ml of isopropyl alcohol and 20 ml of water.
0.16 mol was added, and the mixture was heated and stirred at 70 ° C for 1 hour and at 90 ° C for 3 hours. After cooling to 50 ° C or less, 5.5 ml of hydrochloric acid and 12 m of water
1 was added to adjust the pH of the reaction mixture to about 5, and excess NaSH was removed as hydrogen sulfide gas. The sulfur generated at this time was removed by filtration through celite, and 1.5 ml of 5N-NaOH was added to adjust the pH of the reaction solution to about 8. Then, 800 ml of acetone was added dropwise, and the resulting crystals were filtered and dried to obtain white containing NaCl. 23.6 g of powder (100 yield)
%). These compounds are exemplified by nuclear magnetic resonance spectrum, mass spectrum, and infrared spectrum, and are exemplified compounds A-26 and A-27.
Was identified as a mixture. In addition, A-26 and A-
The molar ratio of 27 was 3: 1. In addition, NaCl in this white powder
Was 43% by ion chromatography.
Met.

[0140]

The developer for a silver halide light-sensitive material of the present invention reduces silver stains generated in a developing tank and / or a developing rack or a roller when processing a silver halide light-sensitive material which can be rapidly processed. can do. In addition, the use of this developer has no effect on photographic characteristics, and
Silver stain can be reduced without impairing fixability.

[Table 1]

Continuation of the front page (72) Inventor Mitsunori Hirano 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H016 AE00 AE02 AE04

Claims (5)

[Claims] 1. A dimercaptopyrimidine compound, a dimercapto-1,3,5-triazine compound or a dimercapto-1,
At least two selected from 2,4-triazine compounds
A developer for a silver halide light-sensitive material, characterized by containing a kind of compound. 2. A dimercaptopyrimidine compound, a dimercapto-1,3,5-triazine compound or a dimercapto-1,
At least two selected from 2,4-triazine compounds
A developer for a silver halide light-sensitive material, comprising: a compound of the formula (I) and at least one compound represented by the following formula (I): General formula (I) In the formula, Z represents a non-metallic atomic group which forms a 5-membered nitrogen-containing aromatic heterocycle together with N and C, and M represents a hydrogen atom or a cation. 3. A method for developing a black-and-white silver halide photographic material, comprising subjecting the black-and-white silver halide photographic material to image processing and then processing with the developer according to claim 1. 4. A black-and-white silver halide photographic light-sensitive material characterized in that after a black-and-white silver halide photographic light-sensitive material is image-exposed, it is processed with a developer according to claim 1, which contains 0.3 mol / l or more of sulfite. Development method. 5. After reacting a dichloropyrimidine compound or a dichlorotriazine compound with X ¹ X ² S (where X ¹ and X ² represent a hydrogen atom and an alkali metal ion), a water-soluble organic solvent is used as a poor solvent. A method for producing a dimercaptopyrimidine compound or a sodium salt, a K salt or a Li salt of a dimercaptotriazine compound, comprising crystallization by adding a solvent.