JP2000075451A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for processing a silver halide photographic sensitive material containing a hydrazine compound capable of giving good photographic performance, especially even in the case of reducing developing and fixing replenishing solutions per unit area of the photosensitive material and also capable of giving stable photographic performance for a long period without affecting the fixability of the photosensitive material. SOLUTION: The silver halide photographic sensitive material containing a hydrazine compound in a photosensitive silver halide emulsion layer and/or another hydrophilic colloidal layer is processed with a developing solution characterized by containing inorganic salts in an amount of >=1.0 mol/l and a Na to K molar ratio of 20-80 to 60-40 and a development replenishing amount of <=200 ml/m2 and a fixing replenishing amount of <=280 ml/m2, and the fixing solution being an acidic film-hardening solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more particularly to a method for processing a silver halide light-sensitive material containing a hydrazine compound without causing a decrease in sensitivity, generation of black spots, and inhibition of fixing. In addition, the present invention relates to a processing method for reducing the replenishment amounts of a developing solution and a fixing solution.

[0002]

2. Description of the Related Art Ultra-high contrast photographic characteristics having a gamma value of more than 10 include photographic reproduction of a continuous tone image using a dot image useful for printing plate making, whether a negative image or a positive image. Very useful for line drawing reproduction. Therefore, there is a strong demand for obtaining ultra-high contrast photographic characteristics useful for the reproduction of halftone images and line drawings using a high-sensitivity emulsion and a stable developer.

As a means for obtaining ultra-high contrast photographic characteristics having a gamma value of more than 10, a hydrazine compound is added to a silver halide photographic material or a developing solution to obtain ultra-high contrast photographic characteristics having a gamma value of 10 or more. See, for example, U.S. Pat.
8,977, 4,224,401, 4,24
No. 3,739, No. 4,269,929, No. 4,27
Nos. 2,614 and 4,323,643, JP-A-62-178246, and JP-A-62-180361.

A black-and-white developer used for developing a silver halide light-sensitive material containing a hydrazine compound includes:
As the developing agent, dihydroxybenzene-based ones such as hydroquinone, ascorbic acid and derivatives thereof are generally known. Among them, it is known that the pH of a hydroquinone-based developer in particular increases due to air oxidation, and the pH decreases due to processing of a photosensitive material. Hydroquinone reacts with quinone generated by air oxidation and sulfite ion to form hydroquinone monosulfonate. Hydroxide ions are generated at the same time as this reaction, which causes an increase in pH due to air oxidation of the developer. This increase in pH significantly changes the photographic characteristics of the silver halide light-sensitive material to be processed, which has been a problem. In particular, hydrazine-containing photographic materials having ultra-high contrast properties, which are used as photographic materials for plate making in recent years, are remarkably susceptible to the influence of the pH of the developing solution (particularly, an increase in pH).

[0005] For this reason, a developing solution for processing a silver halide light-sensitive material containing hydrazine uses a large amount of a sulfite preservative such as sodium sulfite, potassium sulfite, or sodium pyrosulfite, thereby preserving it against air oxidation. Maintains stability. At this time, a relatively large amount of buffer is added so that the change in pH of the developing solution is reduced with respect to the release of hydroxide ions. Particularly, in recent years, the pH of the developer has been lowered in order to improve the temporal stability of the developer against air oxidation, and carbonate is preferably used as a buffer.

In recent years, photographic processing waste liquids have been required to be reduced due to environmental problems, and a development processing method with a reduced replenishment amount has been demanded. When a silver halide light-sensitive material containing a hydrazine compound is subjected to long-term running processing in an automatic processor, the concentration of the developing agent, sulfite and carbonate must be increased in order to reduce the amount of the developing replenisher to 200 ml / m ² or less. There is a need to. However, when a developer having a high inorganic salt concentration is used, there are problems in stability of sensitivity and generation of black spots in running processing. Although the mechanism of the occurrence of black spots is not clear, it is the formation of a developed silver image that looks like sand in a non-image area, that is, looks like waving pepper, which is a trouble in making a plate making film.

Further, when a developer having a high inorganic salt concentration is used, the photosensitive material to be processed brings the developer into the fixing solution, and if the developer brought into the fixing solution is liable to hinder the fixing. There is a problem to say. In particular, this problem tends to occur in a running process in an automatic developing machine. This has been a major obstacle to reducing the fixing replenishment amount. Therefore, the replenishment rate of the fixing solution was generally 380 ml / m ² or more.

[0008] Similarly to the developing solution, the fixing solution is required to reduce the replenishing amount. The acidic hardening fixer not only dissolves and removes unexposed silver halide, but also stops the development reaction and hardens the gelatin layer swollen in the developing tank to improve the drying property after washing with water. There is. Generally, an aluminum compound is used as a hardener. A borate is generally used to prevent the precipitation of the aluminum compound. However, the discharge of borate into rivers and the like is regulated, and a fixing solution not using borate is desired.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the sensitivity of a silver halide photosensitive material when a silver halide photosensitive material containing a hydrazine compound is subjected to a long-term running process using an automatic processor. Another object of the present invention is to reduce the replenishment amounts of the developing solution and the fixing solution at the same time without causing black spots and fixing hindrance. It is a further object of the present invention to provide an acid hardening fixer that is substantially free of borate and reduces the amount of replenishing fixation.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material containing a hydrazine compound in a silver halide emulsion layer and / or another hydrophilic colloid layer. Are inorganic salts.
0 mol / L or more, and the content molar ratio (Na / K) of sodium ion to potassium ion is 20/80 to 6
0/40, the development replenishment amount is 200 ml / m ² or less, and the fixer is an acidic hardening fixer, and the replenishment amount is 280 ml / m ² or less. Achieved by the processing method of the photosensitive material.

That is, the inventor has set the replenishment amount of the developer to 2
Be reduced to 100 ml / m ² or less sensitive, stable, and exploring capable of reducing processing method replenishment amount of the fixer fluid without causing further fixing interference less occurrence of black peppers in 280 ml / m ² or less, The above conclusion was reached.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The pH of the developer of the present invention is preferably 9.5 to 11.2,
In particular, 9.5 to 10.7 is preferable. Accordingly, carbonate is most preferred as the buffer used. The developer of the present invention contains a carbonate in an amount of 0.20 to 0.75 mol / L, preferably 0.25 to 0.55 mol / L. If the carbonate is less than this, the replenishment rate of the developer replenisher is reduced to 200 ml / m ^2.
When the content is reduced below, the fluctuation of the pH of the developer becomes large when the silver halide light-sensitive material is processed, which affects the photographic properties. If the amount of the carbonate is larger than the above range, the pH of the fixing solution is increased, so that an aluminum compound in the fixing solution is precipitated, and the hardening effect of aluminum is weakened, and the drying property is reduced.

The inorganic salts contained in the developing solution of the present invention include carbonates as buffering agents, sulfites as preservatives for developing agents, and sodium bromide, potassium bromide and iodine as development inhibitors. And alkali metal halides such as potassium halide. When the replenishment amount of the developer replenisher is 200
When the amount is reduced to not more than ml / m ^{2, the} amount of the inorganic salt added is 1.
It is necessary to be 0 mol / L or more. Preferably, the total content of carbonate and sulfite is 1.0 mol / L or more, and more preferably, 1.0 to 1.4 mol.
/ L, more preferably 1.1 to 1.3 mol / L.

The molar ratio of sodium ions to potassium ions (Na / K) in the developer of the present invention is from 20/80 to 60.
/ 40, preferably 30/70 to 50/50. When the ratio of sodium ions is more than 60/40, the effect on fixation inhibition caused by the introduction of the developing solution into the fixing solution is reduced, but practical concentration becomes difficult, and Black spots are likely to occur. Conversely, if the ratio of potassium ions is larger than Na / K = 20/80, practical concentration becomes easy, but the fixing property (fixing speed) is affected by the potassium ions in the developer brought into the fixer. ). Furthermore, potassium sulfate crystals generated by air oxidation of the developing solution may be precipitated in the developing tank of the automatic developing machine and on the surface of the transport rack by a long-term running process.

The fixing solution of the present invention is an acidic hardening solution containing an aluminum compound such as aluminum sulfate, aluminum chloride, potassium alum, etc. in order to improve the hardening property of the light-sensitive material. The aluminum compound contained in the fixing solution is 0.01 to 0.15 mol, preferably 0.03 to 0.15 mol per liter of the working solution in terms of aluminum in terms of aluminum.
10 mol.

The fixing solution of the present invention preferably contains a polycarboxylic acid such as tartaric acid, citric acid, malic acid, and phthalic acid, or a salt thereof in order to prevent precipitation of aluminum. Conventionally, boric acid or borate has been generally used to prevent aluminum precipitation.
With the regulation of discharge of borate compounds into rivers, borates are being reduced. Although the reduction of borate promoted the precipitation of aluminum in the fixer and hindered the replenishment of the fixer, the use of the above polycarboxylic acid enabled the use of the above-mentioned polycarboxylic acid to eliminate aluminum even without borate. Precipitation can be prevented,
Low replenishment in the absence of borate is possible. The amount of the polyvalent carboxylic acid or salt thereof added to the fixing solution is 0.
005 to 0.1 mol / L, preferably 0.01 to 0.1 mol / L.
06 mol / L.

The developing agents used in the developer of the present invention include dihydroxybenzene-based developing agents such as hydroquinone, chlorohydroquinone, bromohydroquinone, and the like.
Isopropyl hydroquinone, methyl hydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
There are 5-dimethylhydroquinone and hydroquinone monosulfonate, but hydroquinone is particularly preferred.

In the present invention, a 3-pyrazolidone-based and / or P-aminophenol-based developing agent can be used in combination with or alone with a dihydroxybenzene-based developing agent.
1-phenyl-3 as a 3-pyrazolidone developing agent
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3
-Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-5-
Methyl-3-pyrazolidone, 1-p-aminophenyl-
Examples include 4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone. The p-aminophenol-based developing agents used in the present invention include N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, and 2-methyl- There are p-aminophenol, p-benzylaminophenol and the like,
Among them, N-methyl-p-aminophenol is preferred.

Further, ascorbic acid and its derivatives can be used as a developing agent. Ascorbic acid and its derivatives can be used alone or in combination with a dihydroxybenzene-based developing agent and / or a 3-pyrazolidone-based or P-aminophenol-based developing agent.

The developing agent is usually 0.03 mol / L to 1.0.
It is used in an amount of mol / L. In the present invention, it is preferable to use a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols. In this case, the former is preferably used in an amount of 0.25 mol / L to 1.0 mol / L, and the latter is preferably used in an amount of 0.001 to 0.1 mol / L.

The preservatives of the developing agent used in the present invention include sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The amount used is 0.3 mol / L or more, preferably from 0.5 mol / L to
The range is 1.0 mol / L.

In the developing solution, an alkali agent (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.) and a dissolution aid (polyethylene glycol,
These esters), a pH adjuster (for example, an organic acid such as acetic acid), a development accelerator, a surfactant, a hardener and the like can be contained. Further, a so-called pH increase inhibitor of a developing solution disclosed in JP-A-8-64383, JP-A-8-89131, JP-A-8-127324 and the like can be contained.

The developer may further contain an antifoggant (for example, 5
Benzotriazoles such as -nitroindazole, 5-nitro-benzimidazole, 5-methyl-benzotriazole, 5-nitrobenzotriazole, benzothiazole, tetrazole such as 1-phenyl-5-mercapto-tetrazole, thiazole or British Patent 1,2
No. 69,268), chelating agents (eg, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, alkali metal salts thereof, polyphosphates,
Nitrilo acetate). In addition, black spots (a developed silver that looks like sand in a non-image area, that is, a so-called pepper shake) of a photosensitive material containing a hydrazine derivative disclosed in JP-A-9-180947 and JP-A-9-62835. That an image is formed,
Trouble in making film for plate making. ) Inhibitors can be included.

Other additives used in addition to the above-mentioned components include development inhibitors such as sodium bromide and potassium iodide, ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol. And an organic solvent such as a color tone agent, an antifoaming agent, a water softener, and
No. 44 may be included.

The pH value of the developer adjusted in this way is selected to a degree sufficient to give a desired density and contrast, but is preferably in the range of about 9.5 to 11.2.

In recent years, photographic processing waste liquids have been required to be reduced due to environmental problems. Generally, a developer replenishment amount of 300 ml / m ² or more was necessary, but by using the processing method of the present invention, the developer replenishment amount was 200 ml / m ² or less, and more preferably 15 ml / m ² or less.
It can be used stably with a developer replenishment amount of 0 ml / m ² or less. The replenishing amount of the fixing solution is 380 ml / m ² or more were common, the processing method of the present invention is 280 ml / m ² or less, particularly 260 ml / m ² or less, more fixer replenishment rate of 230 ml / m ² Can be used stably.

The replenisher of the present invention is supplied from a reservoir for the concentrated replenisher and a reservoir for the dilution water provided in the replenisher by a bellows pump or the like so that the concentrated replenisher and the dilution water are mixed at a predetermined mixing ratio. It is supplied to the developing tank of the automatic developing machine. Bellows pumps for replenisher and dilution water are prepared. The predetermined dilution rate, replenishment amount, etc. are measured by measuring a discharge amount when a pump installed in the replenishment device is operated for a predetermined time, and a discharge amount per unit time from the measured discharge amount and the predetermined time. Is determined, and the operation time of the pump is determined from the required replenishment amount and the discharge amount per unit time, and is determined and implemented.

The concentrated replenisher and the diluting water sent from the pump may be directly replenished to the developing tank of the automatic developing machine, or may be replenished with the concentrated replenishing liquid before being replenished to the developing tank of the automatic developing machine. Although the water may be mixed and replenished, the former method is generally used in many cases.

Examples of the automatic developing machine that can be used in the processing of the present invention include LN manufactured by Dainippon Screen Mfg. Co., Ltd.
D281Q, LD360, LD381, LDT106
0, LDT1100, FG6 manufactured by Fuji Photo Film Co., Ltd.
80A, FG950A, FG710A, etc., but are not limited to the type of automatic developing machine. When processing is performed using these automatic developing machines, processing can be performed for a long time by replenishing the developing solution. In general, replenishment can be divided into replenishment accompanying processing of the photosensitive material (processing replenishment) and replenishment due to air oxidation (oxidation replenishment). You can do both.

A replenishing device for supplying the developing solution of the present invention to an automatic developing machine is, for example, AR21 manufactured by Dainippon Screen Mfg. Co., Ltd.
0Q, AR211Q, B-300 manufactured by Mitsubishi Paper Mills, and the like, but are not particularly limited to these models. At least the replenishment method of the replenishing device is that the automatic developing machine body inserts the photosensitive material and the film sensor detects the width, and at the same time calculates the length from the transport speed and calculates the entire area of the photosensitive material, a certain area Is reached, a pulse signal is sent from the automatic developing machine to the replenishing device, and a replenishing device having a function of performing replenishment according to this signal is preferable.

The development processing temperature and time of the light-sensitive material are interrelated and are determined in relation to the total processing time, and are generally from about 20 to 50 ° C. for 10 seconds to 3 minutes. Is from 10 to 40 seconds at about 30-50 ° C.

The silver halide photographic material used in the present invention may be a black-and-white photographic material (for example, a photographic material such as a medical or industrial X-ray photographic material, a lithographic photographic material, a micro photographic material, an X-ray photographic material). Micro reversal photographic material, computer typesetting paper, negative photographic material for general photography, photographic paper, etc.)
There is.

As the fixing agent used in the fixing solution of the present invention, thiosulfates such as sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate and lithium thiosulfate can be used. From the viewpoint of fixing speed, sodium thiosulfate and ammonium thiosulfate are preferably used. The concentration of thiosulfate added to the fixing solution is 0.8 to 1.3 mol / L.

The fixing solution of the present invention contains sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite for the purpose of preventing decomposition of the fixing agent.
It may contain a sulfite such as potassium metabisulfite.
The concentration of the sulfite added to the fixing solution is 0.05 to 0.4 mol, preferably 0.07 to 1 mol per liter of the working solution.
0.1 mol.

The fixing solution of the present invention contains an acetate such as acetic acid, sodium acetate, potassium acetate or the like as a buffer in order to prevent the pH of the fixing solution from rising due to carry-in of the developing solution. Acetate ion concentration is 0.2 ~ per 1 liter of working solution.
0.8 mol, preferably 0.4 to 0.6 mol.

In the fixing solution of the present invention, alkanolamine, alkylene glycol or the like is used as a lubricant, and nitrilotriacetic acid, ETDA, PTPA, TT is used as a chelating agent.
HA and the like can be contained.

The hydrazine derivative used in the present invention includes a compound represented by the following general formula 1.

[0038]

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In the general formula 1, A ¹ and A ^{2 each} represent a hydrogen atom or one of them represents a hydrogen atom and the other represents a sulfonyl group or an acyl group, and R ⁷ represents an aliphatic group, an aromatic group or a heterocyclic group. G ¹ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group; R ⁸ represents a hydrogen atom, an aliphatic group, an aromatic group, an alkoxy group, an aryloxy group, an amino group or , And represents general formula 2.

[0040]

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In the general formula 2, Q ⁺ represents a group containing a cationic group, and A ⁻ represents an anion. However, it is unnecessary when Q ⁺ contains a sulfo group.

Next, the general formulas 1 and 2 will be described in detail. In formula 1 Te at, A ^1, A ² is a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms and an arylsulfonyl group (preferably a phenylsulfonyl group or a sum of Hammett's sigma _p becomes -0.5 or more Phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or the sum of Hammett's σ _p is-
A benzoyl group substituted so as to be 0.5 or more, or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, an amide Group, a hydroxy group, a carboxy group, and a sulfo group.), A ¹ ,
A ² is most preferably a hydrogen atom. The aliphatic group represented by R ⁷ is a linear, branched or cyclic alkyl group,
An alkenyl group and an alkynyl group. The aromatic group represented by R ⁷ is a monocyclic or bicyclic aryl group, and examples include a phenyl group and a naphthyl group. The heterocyclic group represented by R ⁷ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms;
These may be a single ring or may form a condensed ring with another aromatic or heterocyclic ring. The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic group, and includes, for example, a pyridyl group, an imidazolyl group, a quinolyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolyl group, a thiazolyl group, and a benzothiazolyl group. Are preferred. R ⁷ may be substituted with a substituent.
Examples of the substituent include the following. These groups may be further substituted. For example, alkyl group, aralkyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, A sulfinyl group, a hydroxy group, a halogen atom, a cyano group, a sulfo group, a carboxy group, an ammonium group, a pyridinium group, a thiuronium group, an isothioureido group, and the like. When possible, these groups may be linked to each other to form a ring. Preferred as R ⁷ is an aromatic group, more preferably an aryl group. or,
R ⁷ may have incorporated therein a ballast group commonly used in immobile photographic additives such as couplers. A ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties, such as an alkyl group,
It can be selected from an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group and the like. Q ⁺ in the general formula 2 is a group containing a cationic group having at least one quaternary nitrogen atom,
Bonded to G ¹ through a linear or branched hydrocarbon chain having 1 to 4 carbon atoms, and a part or all of this chain may constitute a part of a heterocyclic ring having a quaternary nitrogen atom. Good.
Preferred examples of Q ⁺ include a trialkylammonioalkyl group, a pyridinium-1-ylalkyl group, a 1-alkylpyridinium-2-yl group, a 1-alkylpyridinium-3-yl group, and a 1-alkylpyridinium-4-yl group.
Examples thereof include an yl group, a thiazolinium-3-ylalkyl group, an oxazolinium-3-ylalkyl group, and a 1-alkylimidazolium-3-ylalkyl group. These groups may be substituted, and the substituents are preferably those exemplified as the substituent of R ⁷ . Further, when these groups form a ring structure, they may be condensed with another ring. A ^- is a counter anion of Q ^+, Cl preferred examples ^-, Br -, ^{p-toluenesulfonate,} but like methyl sulfonate, having a sulfo group as a Q ⁺ substituents, inner salt Is not present when forming

G ¹ represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group, an oxalyl group or an iminomethylene group, and G ¹ is preferably a carbonyl group or an oxalyl group. The aliphatic group represented by R ⁸ is preferably an alkyl group having 1 to 5 carbon atoms, and the aromatic group is preferably a monocyclic or bicyclic aryl group (for example, those containing a benzene ring). When G ¹ is a carbonyl group, R ⁸
Preferred among the groups represented by are a hydrogen atom, an alkyl group (for example, a methyl group, a trifluoromethyl group,
Hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (eg, 2-hydroxybenzyl group, etc.), aryl group (eg, phenyl group, 3,5-dichlorophenyl group, 2-methane) A sulfonamidophenyl group, a 4-methanesulfonamidophenyl group, a 2-hydroxymethylphenyl group, etc.), a general formula 2 and the like, and a hydrogen atom and a general formula 4 are particularly preferable. R ⁸ may be substituted, and as the substituent, the substituents listed for R ⁷ can be applied.
When G ¹ is an oxalyl group, preferred as R ⁸ are:
Alkoxy group (for example, methoxy group, ethoxy group, isopropoxy group, methoxyethoxy group, etc.), aryloxy group (for example, phenoxy group, 2-hydroxymethylphenoxy group, 4-chlorophenoxy group, etc.), amino group (for example, 3-hydroxypropylamino group, 2,3-
Dihydroxypropylamino group, 2-dimethylaminoethylamino group, 3-diethylaminopropylamino group, etc.), general formula 2 and the like, and an amino group is particularly preferable. R
⁷ and R ⁸ may have incorporated therein a group which enhances the adsorption to the surface of the silver halide grains. Examples of the adsorptive groups include thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups, and triazole groups.
The groups described in US Pat. No. 5,105 are exemplified. R ⁸ may also be such as to cause a cyclization reaction that cleaves the G ¹ -R ⁸ moiety from the residual molecule to form a cyclic structure containing atoms of the -G ¹ -R ⁸ moiety. , For example,
JP-A-63-29751 and the like can be mentioned. Specific examples of the compound represented by Formula 1 are shown below, but the present invention is not limited to the following compounds.

[0044]

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[0045]

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[0046]

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[0047]

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The hydrazine compounds of the present invention are described, for example, in JP-A-61-213847, JP-A-62-178246, JP-A-62-180361, JP-A-62-260153 and JP-A-6-260153.
No. 3-253357, JP-A-1-269936, U.S. Pat. Nos. 4,684,604, and 3,379,529.
No. 4,377,634, No. 4,332,87
No. 8, No. 4,937,160 and the like.

The hydrazine compound of the present invention can be used in a suitable water-miscible organic solvent, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethylacetamide, dimethylsulfoxide,
It can be used by dissolving it in methylcellosolve or the like.
Also, by an already well-known emulsification dispersion method, dimethyl phthalate, tricresyl phosphate, glyceryl triacetate or an oil such as diethyl phthalate is dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. Things can be created and used. Alternatively, a hydrazine compound powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

Further, the photographic emulsion used in the present invention can contain amines, alcohols, pyridines, onium salts and other high contrast accelerators. Among them, preferred tertiary amine compounds (for example, US Pat. No. 4,975,354, JP-B-6-124)
06, Tokiko 7-36076, KD2354, KD
2462) and phosphonium salt compounds (for example, compounds described in JP-A-61-167939). The high contrast accelerator is preferably contained in the surface latent image type silver halide emulsion layer, but may be contained in the hydrophilic colloid layer adjacent to the surface latent image type silver halide emulsion layer. Since the content of the high-contrast accelerator in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound and the development conditions, the appropriate content may vary over a wide range. It is preferably from 1 × 10 ^-5 to 1 × 10 ^-2 mol per mol of silver in the silver halide emulsion. Further, a high contrast accelerator may be added to the developer, and in that case, the amount is preferably 1 × 10 ⁻³ to 1 mol per liter of the developer.

The silver halide used in the photosensitive silver halide emulsion of the light-sensitive material of the present invention is not particularly limited, but a surface latent image type silver halide emulsion is preferred. Silver bromide, silver chloroiodobromide, silver iodobromide, silver bromide and the like can be used. When silver chloroiodobromide or silver iodobromide is used, the content of silver iodide is 5%. It is preferably in the range of mol% or less. The form, crystal habit, size distribution and the like of the silver halide grains are not particularly limited, but the grain size is 0.7
Those having a size of μm or less are preferred. Silver halide emulsions include gold compounds such as chloroaurate and gold trichloride, sulfur compounds which form silver sulfide by reacting with salts of noble metals such as rhodium and iridium and silver salts, stannous salts, Sensitivity can be increased without reducing particles with a reducing substance such as an amine. Also, salts of precious metals such as rhodium and iridium,
An iron compound such as a red blood salt may be present during physical ripening or nucleation of silver halide grains. In particular, the addition of a rhodium salt or a complex salt thereof is preferable because the effect of the present invention of achieving ultra-high contrast photographic properties in a short development time is further promoted.

In the present invention, the surface latent image type silver halide emulsion is an emulsion comprising silver halide grains having a surface sensitivity higher than the internal sensitivity. This emulsion is preferably a US Pat. No. 4,224,224. It has a difference between the surface sensitivity and the internal sensitivity specified in No. 401. The silver halide emulsion is desirably monodispersed, and in particular in the above-mentioned U.S. Pat.
Emulsions having the monodispersity specified in JP-A-4,401 are preferred. The silver halide emulsion used in the present invention includes a water-soluble rhodium salt (for example, rhodium dichloride, rhodium trichloride, potassium hexachloride (III), rhodium hexachloride).
(III) ammonium salt) is preferable,
It is preferable to add these rhodium salts before the completion of the first ripening at the time of emulsion production. The addition amount of the rhodium salt is from 1 × 10 ⁻⁷ mol to 1 mol per mol of silver halide.
× 10 ^-4 mol is preferred. The average grain size of the silver halide used in the present invention is preferably 0.7 μm or less, particularly preferably 0.1 to 0.4 μm. The shape of the silver halide grains may be a regular one such as cubic or octahedral, or a mixed crystal, but it is preferably a so-called monodisperse emulsion having a relatively narrow grain size distribution. The monodisperse emulsion as used herein means an average grain size of ±
It refers to an emulsion in which 90%, more preferably 95%, of the total number of grains falls in the 40% grain size range. The method of reacting the soluble silver salt with the soluble halide salt for preparing the silver halide emulsion in the present invention may be any method such as a single jet method, a double jet method, or a reverse mixing method in which the silver halide emulsion is formed in excess of silver ions. For the purpose of the present invention, a double jet method in which a soluble silver salt and a soluble halogen salt are simultaneously added in an acidic solution to form grains is particularly preferable. The silver halide emulsion thus prepared may or may not be chemically sensitized. In the case of chemical sensitization, usual sulfur sensitization, selenium sensitization, reduction sensitization and the like are used.

The photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are
It is a dye belonging to a cyanine dye, a merocyanine dye, and a complex merocyanine dye. These sensitizing dyes may be used alone or in combination.
Combinations of sensitizing dyes are often used, especially 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.

As a binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol Polyacetal partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and various kinds of synthetic hydrophilic polymer materials such as copolymers such as polyvinylimidazole can be used. . As gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Phot.Japan, No.
16, P30 (1966) may be used, and hydrolyzate or enzymatically decomposed gelatin may be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, azoles,
For example, benzothiazolium salts, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazole; mercaptopyrimidines, mercaptotriazines, thioketo compounds, azaindenes, etc. Many compounds, better known as antifoggants or stabilizers, can be added. Of these, particularly preferred are
Benzotriazoles (eg, 5-methylbenzotriazoles) and nitroindazoles (eg, 5-nitroindazole). These compounds may be contained in the processing solution.

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 (such as chrome alum), aldehydes (such as formaldehyde and glyoxal), N-methylol compounds, dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds, and active halogen compounds (such as 2,4-dichloro-6) −
Hydroxy-S-triazine, etc.) alone or in combination. The photosensitive silver halide emulsion layer or an adjacent layer may be provided with a research disclosure (R) for the purpose of increasing sensitivity, increasing contrast, or accelerating development.
(Esearch Disclosure) No. 17465, XXI, Sections B to D, and it is particularly preferable to add polyethylene glycol or a derivative thereof.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may contain a coating aid, an antistatic agent, an improvement in slipperiness, an emulsification / dispersion, an adhesion prevention and an improvement in photographic properties (for example, development Surfactants may be included for various purposes such as acceleration, contrast enhancement, and sensitization. For example, nonionics such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants, alkyl carboxylates, alkyl sulfates,
Carboxy groups, such as alkyl phosphates,
Anionic surfactants containing acidic groups such as sulfo groups, phospho groups, sulfate groups, and phosphate groups, amino acids,
Amphoteric surfactants such as aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphoric acid esters, cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium Can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or hardly soluble synthetic polymer decomposition product in a photographic emulsion layer or other hydrophilic colloid layers for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl acetate, acrylonitrile, olefins, styrene and the like alone or in combination, or acrylic acid,
A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like can be used.

[0059]

The present invention will be described in more detail with reference to the following examples, which do not limit the embodiments of the present invention.

Example 1 Preparation of silver halide light-sensitive material (preparation of emulsion); mixed aqueous solution of sodium chloride and potassium bromide containing 2.0 × 10 ^-7 mol of water-soluble rhodium salt per mol of silver and aqueous solution of silver nitrate Was mixed by a pAg control double jet method to prepare a silver chloroiodobromide emulsion (silver chloride content: 70 mol%) consisting of cubic monodisperse particles (coefficient of variation: 13%) having an average particle size of 0.20 μm. A 10% potassium iodide solution was added to this emulsion so that the silver iodide content was 0.2 mol%, and conversion was performed. This emulsion was washed with precipitate and washed and dissolved again by flocculation. This emulsion contains 6 m of sodium thiosulfate per mole of silver.
g and 8 mg of chloroauric acid, heated at 60 ° C. for 50 minutes and subjected to a chemical sensitization treatment, and then 2-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer to silver 1 50 mg was added per mole.

The emulsion obtained above was used as a sensitizing dye in anhydrous-5,5'-dichloro-9-ethyl-3,
After adding 300 mg per mol of silver of sodium 3'-di- (3-sulfopropyl) -oxacarbocyanine hydroxide, the emulsion was allowed to stand at about 40 ° C. for 45 minutes to stabilize the spectral sensitizing effect, and then divided. Then, sodium dodecylbenzenesulfonate was used as a surfactant for 20 m each.
g / m ² , 100 mg / m ^{2 of} hydroquinone, and 10 mg / m ^{2 of} a nucleation accelerator represented by the following structural formula (7). Then, the hydrazine derivative represented by D-4 was added.
Further, as a hardening agent, 1,3-divinylsulfonyl-2
- adding propanol 100 mg / m ^2. The emulsion thus obtained was coated on a polyethylene terephthalate film with silver nitrate at 5 g / m ² and gelatin at 2 g / m ² .

[0062]

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As a protective layer on the emulsion layer, gelatin 1 g / m ² and sodium dodecylbenzenesulfonate were added in an amount of 3 g / m ² .
0 mg / m ² and a fluorine-based surfactant 5 mg / m ² was added, the average particle size of about 3.5μm of an amorphous SiO ₂ matting agent after adding 20 mg / m ^2, as a hardening agent 1,3-divinyl 50 mg / m ^{2 of} sulfonyl-2-propanol was added, and the mixture was coated and dried to prepare a light-sensitive material. This light-sensitive material was processed using the following developing solution and fixing solution.

<Preparation of Developer> Water 400 ml Sulfite (potassium or sodium sulfite) Amount shown in Table 1 Carbonate (potassium or sodium carbonate) Amount shown in Table 1 Hydroquinone 35 g Sarcosine soda 5 g 1-Phenyl-4-human peroxymethyl-4 -Methyl-3-hydroxyperitoneone 0.6 g Potassium bromide 5 g Diethylene glycol 30 g Diethylenetriaminepentaacetic acid 2 g Benzotriazole 0.25 g Compound 8 0.15 g Trans-cinnamic acid 3 g Add water to make up to 1 liter. Adjusted to pH 10.55

[0065]

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[0066]

[Table 1]

As the fixing solution, the following fixing solutions were prepared. <Fixing concentrated solution> Ammonium thiosulfate (58.2% solution) 220 g Sodium sulfite 23 g Acetic acid 11 g Tartaric acid 5.6 g Aluminum sulfate 11 g Water was added to adjust 1 liter to pH 4.7 ± 0.1.

A developing solution was prepared in a developing tank of an automatic developing machine LD221 manufactured by Dainippon Screen Mfg. Co., Ltd. (12 L starting with sample Nos. 1 to 15 as a starting liquid, and further 12 L of the fixing liquid in a fixing tank as a starting liquid. A running process was performed.

In the running processing, the automatic developing machine was operated for 10 hours a day at a developing temperature of 35 ° C. Each time one sheet of the photosensitive material (50.8 cm × 61 cm) was processed, the developing solution and the fixing solution described in Table 1 were used in the following Table 2
And the replenishment amount in Table 3. Approximately 50 photosensitive materials were processed a day, and this was continued for 4 weeks. The blackening ratio of the photosensitive material to be passed was set to 50%. On Saturdays and Sundays, the day was a stoppage, and on Monday morning, replenishment (approximately 1.6 L) was performed to compensate for the lowering of the developer level in the developing tank of the automatic developing machine.

The sensitivity, black spots, defective fixing, and aluminum deposition after the running treatment were evaluated by the following methods. The results are shown in Tables 2 and 3.

<Sensitivity> Sensitometry exposure was performed using a light source having a color temperature of 5400 ° K. through a red filter (Ratten No. 29) and a wedge. The sensitivity was calculated as the reciprocal of the exposure amount required to obtain a transmission density of 3.0, and the sensitivity after development processing with the starting solution before the running processing was defined as 100, and the sensitivity after the running processing for 4 weeks was relative ( %).

<Black spots> Black spots were processed by developing an unexposed sample, and the sample was magnified 100 times with a microscope, and the number of black spots per square centimeter was counted. Evaluation is 5
It was evaluated on a scale. 5 is the best number of occurrences, 0, 4 is the number of occurrences 1 to 5, 3 is the number of occurrences 6 to 10, 2 is the number of occurrences 11 to 1
5, 1 and 16 or more.

<Poor Fixing> Poor fixing was evaluated on the following three levels. ○: no problem at all, Δ: partial discoloration observed, ×: apparently poor fixing observed
It was expressed by.

<Precipitation of Aluminum> For the deposition of aluminum, the first roller of the fixing rack was observed three weeks after the start of the running process and before passing the photosensitive material. When white precipitation of aluminum was observed, it was represented by x, and when no aluminum was precipitated, it was represented by ○.

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

As can be seen from the above examples, the present invention is capable of significantly reducing the replenishment of the developing solution and the fixing solution without deteriorating photographic characteristics due to running processing, generating black spots, and preventing fixing. Can be achieved. Further, it was possible to provide a processing method that does not cause precipitation of aluminum even when the boric acid compound is removed from the fixing solution.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 5/395 G03C 5/395

Claims (2)

[Claims] 1. A method for processing a silver halide photographic material containing a hydrazine compound in a silver halide emulsion layer and / or another hydrophilic colloid layer, wherein the developer contains at least 1.0 mol / L of an inorganic salt. And the molar ratio of sodium ions to potassium ions (Na / K) is 2
0 / 80-60 / 40, and the development replenishment amount is 200 ml
/ M ² or less, and the fixer is an acidic hardening fixer, and the replenishment amount is 280 ml / m ² or less. 2. The processing method according to claim 1, wherein the fixing solution is a fixing solution containing no boric acid or a salt thereof.