JP2001249424A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method for a silver halide photographic sensitive material using a developing solution for a silver halide photographic sensitive material less liable to affect the human body, ensuring an improved silver tone and less liable to cause the rise of fog even after long-term use. SOLUTION: In the processing method, a silver halide photographic sensitive material having a hydrophilic colloidal layer on at least one side of the support and also having a layer containing compounds of formulae 1-4 (where W is an electron withdrawing group; D is an electron donative group; and H is a hydrogen atom) is processed with a developing solution containing reductones.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for processing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials have not only been internationally banned from dumping wastewater from the viewpoint of safety and environmental considerations, but also have the potential to remove hydroquinone, boric acid, and aldehydes that are harmful to the human body. There is a strong demand for the development of a treatment method using a treatment agent that is not used.

A technique using reductones as a developing agent having little effect on the human body is disclosed in JP-A-7-77781 and JP-A-7-77781.
No. 110554. However, although the effect on the human body is improved, the silver tone of the image after development processing is remarkably deteriorated, and there is a drawback that fog increases when used for a long time in an automatic developing machine. .

Further, when a developer excluding boric acid and aldehydes is used, there is a disadvantage that the silver tone after processing and the fog increase during long-term use are deteriorated.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material developing solution which has little effect on the human body, has an improved silver tone, and has little rise in fog even after long-term use. An object of the present invention is to provide a method for processing a silver photographic light-sensitive material.

[0006]

The above object is achieved by the following means.

[0007] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer on at least one side of a support and having a layer containing a compound of the general formulas (1) to (4) is treated with a developer containing reductones. A method for processing a silver halide photographic light-sensitive material, characterized by processing.

[0008] 2. 0.01-carbonate per liter
2. The method for processing a silver halide photographic material as described in 1 above, wherein the processing is performed with a developer containing 0.15 mol.

3. A silver halide photographic material having a hydrophilic colloid layer on at least one side of the support and having a layer containing the compound of the above formulas (1) to (4) is substantially free of boric acid. A method for processing a silver halide photographic material, characterized by processing with a developer.

[0010] 4. 0.01-carbonate per liter
4. The method for processing a silver halide photographic light-sensitive material according to the above item 3, wherein the processing is carried out with a developer containing 0.15 mol.

5. A silver halide photographic material having a hydrophilic colloid layer on at least one side of the support and having a layer containing the compound of the above general formulas (1) to (4) is substantially prepared from a dialdehyde-based hard photographic material. A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed with a developer containing no film-forming agent.

6. 0.01-carbonate per liter
6. The method for processing a silver halide photographic light-sensitive material according to the above item 5, wherein the processing is performed with a developer containing 0.15 mol.

Hereinafter, the present invention will be described in detail. The silver halide photographic light-sensitive material of the present invention contains compounds represented by formulas (1) to (4). By containing such a substituted alkene derivative, the silver color tone is improved, and a silver halide photographic light-sensitive material having less fog even after long-term use can be obtained.

Next, the substituted alkene derivatives represented by the general formulas (1) to (4) will be described. General formula (1)-
In (4), W represents an electron-withdrawing group, D represents an electron-donating group, and H represents a hydrogen atom. The groups represented by W or D on the same carbon atom may form a cyclic structure with each other, and when W or D can be either a trans structure or a cis structure, either structure can be used. You may take it.

In the present invention, the electron-withdrawing group represented by W in the general formulas (1) to (4) is a substituent having a positive Hammett's substituent constant σp and is a halogen atom, a cyano group or a nitro group. , Alkenyl group, alkynyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, carboxamide group, sulfamoyl group, sulfonamide group, trifluoromethyl group, trichloromethyl group,
A phenyl group substituted by a phosphoryl group, a carboxy group (or a salt thereof), a sulfo group (or a salt thereof), a heterocyclic group, an imino group, or an electron-withdrawing group thereof. These groups may have a substituent, for example, a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom), an alkyl group (an aralkyl group, a cycloalkyl group, an active methine group). Alkenyl group, alkynyl group, aryl group, heterocyclic group, quaternary heterocyclic group containing a nitrogen atom (eg, pyridinio group), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl Group, carboxy group or a salt thereof, sulfonylcarbamoyl group, acylcarbamoyl group, sulfamoylcarbamoyl group, carbazoyl group, oxalyl group, oxamoyl group, cyano group, thiocarbamoyl group, hydroxy group, alkoxy group (ethyleneoxy group or propyleneoxy group) (Including groups containing repeating group units), Aryloxy group, heterocyclic oxy group,
Acyloxy group, (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group, sulfonyloxy group, amino group, (alkyl, aryl or heterocycle) amino group, N-substituted nitrogen-containing heterocyclic group,
Acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonium group, oxamoyl Amino group,
(Alkyl or aryl) sulfonyluureido group,
Acylureido group, acylsulfamoylamino group, nitro group, mercapto group, (alkyl, aryl, or heterocycle) thio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group,
A sulfo group or a salt thereof, a sulfamoyl group, an acylsulfamoyl group, a sulfonylsulfamoyl group or a salt thereof, a group having a phosphoric acid amide or a phosphoric ester structure, and the like. These substituents may further have a substituent.

The electron-withdrawing group is preferably a cyano group, a nitro group, an alkenyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group,
Substituted with a sulfamoyl group, a trifluoromethyl group, a phosphoryl group, a heterocyclic group (a 5- to 6-membered heterocyclic group, which may be condensed with a benzene ring or a naphthalene ring), or any electron-withdrawing group Phenyl group. However, the heterocyclic group in the general formula (2) is a non-aromatic heterocyclic group.

In the present invention, the electron-donating group represented by D in the general formulas (1) to (4) is a substituent having a Hammett's substituent constant σp of a negative value, such as an alkyl group, an aryl group, or a hydroxy group. (Or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group,
A heterocyclic amino group or a phenyl group substituted with these electron donating groups. These groups may have a substituent, and examples of the substituent include those described for W.

The electron donating group is preferably an alkyl group, an aryl group, a hydroxy group (or a salt thereof), a mercapto group (or a salt thereof), an alkoxy group, an alkylthio group, an arylthio group, an amino group, an alkylamino group,
An arylamino group or a phenyl group substituted with an arbitrary electron donating group.

The ring formed by W and D is 4
A saturated or unsaturated carbocyclic or heterocyclic ring which may have a condensed ring of 6 to 6 members is mentioned, and a cyclic ketone may be used. The heterocyclic ring is preferably a heterocyclic ring containing at least one atom of N, O and S, more preferably one or two atoms.

Next, specific examples of the compounds represented by formulas (1) to (4) are shown below. However, the present invention is not limited to these.

[0021]

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[0024]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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The compounds of the present invention can be easily synthesized by known methods, and can also be purchased directly from drug manufacturers.

These compounds are dissolved in water or a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. Can be used.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used for dissolution, and mechanical An emulsified dispersion can be prepared and used. Alternatively, powders of these compounds can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves and used by a method known as a solid dispersion method.

The present invention is represented by the general formulas (1) to (4).
The compounds may be used alone or in combination of two or more. Good
The preferred addition amount is 1 × 10^-6~ 1 mole
More preferably 1 × 10^-Five~ 1 × 10^-1In mole
And most preferably 1 × 10 ^-Five~ 1 × 10^-2In mole
You. The layer to be added may be a layer outside the emulsion layer with respect to the support or
Is preferably an emulsion layer.

The silver halide grains used in the present invention are:
Usually used cubic, octahedral, tabular, etc.
Preferably, it is a tabular crystal. The silver halide grains have two opposing parallel main planes, the main plane being a (111) plane or a (100) plane. The circle equivalent diameter is 0.5-5.0
μm, and preferably 0.5 to 2.0 μm. The thickness is 0.07 to 0.7 μm, preferably 0.1 to
0.7 μm. The method for producing these tabular silver halide grains is a known technique and is disclosed in U.S. Pat.
No. 4,226, No. 4,439,520, No. 4,4
No. 14,310, No. 5,314,793, No. 5,
Nos. 334,495, 5,358,840 and 5,372,927.

The halogen composition of the silver halide grains used in the present invention is preferably any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. When silver iodide is contained, the silver iodide content is preferably from 0.25 to 10 mol%,
0.25 to 6 mol% is more preferable, and 0.4 to 2 mol%.
Is particularly preferred. Tabular silver halide grains can contain a small amount of silver chloride. For example, US Pat. No. 5,372,927 discloses that a silver chloride content of 0.4 to 2 is used.
There is a description about 0 mol% of silver chlorobromide tabular grains.

In the present invention, the circle-equivalent diameter means an average projected area diameter (hereinafter, referred to as a particle diameter), and is a circle-equivalent diameter of the projected area of the tabular silver halide grains (ie, the tabular halide halide). (Diameter of a circle having the same projected area as the silver grain), and the thickness is 2 to form a tabular silver halide grain.
Shows the distance between two parallel principal planes.

The tabular silver halide grains of the present invention are crystallographically classified as twins. Twins are silver halide crystals having one or more twin planes in one grain, and the twins are classified according to a report by Klein and Moiser in Photograph Corspondents (Photograh).
phisher Korespondenz) 99 vol.9
The details are described on page 9, page 100, page 57.

In preparing the silver halide emulsion used in the present invention, there are no particular restrictions on the ultrafiltration module and the circulating pump that can be used when performing ultrafiltration. It is preferable to avoid materials and structures that adversely affect photographic performance. In addition, the molecular weight of the ultrafiltration membrane used in the ultrafiltration module can be arbitrarily selected.

The tabular silver halide grains used in the present invention are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, the width of grain size distribution (%) = (standard deviation of grain size / average grain size) 25% when the width of distribution is defined by (diameter) x 100
The following are preferred, more preferably 20% or less, and particularly preferably 15% or less.

The tabular silver halide grains used in the present invention preferably have a small thickness distribution. Specifically, width of thickness distribution (%) = (standard deviation of thickness / average thickness)
When the width of the distribution is defined by × 100, it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The tabular silver halide grains used in the present invention may be so-called halogen conversion type (conversion type) grains. The halogen conversion amount is preferably from 0.2 to 0.5 mol% based on the silver amount, and the conversion may be performed during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a smaller solubility product with silver than the halogen composition of the grain surface before the halogen conversion is usually added. The particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (E
Electron Probe Micro Analysis
zer method). In this method, a sample in which emulsion grains are well dispersed so as not to contact each other is prepared, an electron beam is irradiated, and X-ray analysis is performed by electron beam excitation. Elemental analysis of an extremely small portion can be performed. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the silver halide composition of each grain can be determined. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content is determined from the average thereof.

In the production of tabular silver halide grains used in the present invention, stirring conditions during production are extremely important. As the stirrer, an apparatus described in JP-A-62-160128, in which an additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer, is particularly preferably used. In this case, the rotation speed of the stirring is preferably set to 100 to 1200 rpm.

The silver halide grains used in the present invention may have dislocations. The dislocation is described, for example, in J. Mol. F. Ham
ilton, Photo. Sci. Eng. , 57 (19
67); Shiozawa, J .; Soc. Pho
t. Sci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method in a state of cooling. At this time, since the electron beam becomes more difficult to penetrate as the thickness of the particles increases, a high-pressure type (200 μm for particles having a thickness of
(kV or more) can be observed more clearly using an electron microscope. The silver halide grains used in the present invention may have silver halide projections epitaxially grown after the growth of the host grains.

The tabular silver halide grains used in the present invention may be formed during the formation and / or growth of the grains by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium. Metal ions can be added using at least one selected from salts (including complex salts) and iron salts (including complex salts), and these metal elements can be contained inside and / or on the surface of the particles.

The tabular silver halide grains used in the present invention are spectrally sensitized by methine dyes and the like. As the sensitizing dye used in the light-sensitive material of the present invention, dyes such as cyanine, merocyanine, composite cyanine, composite merocyanine, holographic polar cyanine, hemicyanine, styryl, and hemioxonol can be used, and the above-mentioned site director may be used. Particularly useful dyes are those belonging to cyanines, merocyanines and complex merocyanines.

As these dyes, any of the nuclei usually used can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and the like, and furthermore, a nucleus in which an aliphatic hydrocarbon ring is fused to these nuclei, Indolenine nucleus, benzindolenin nucleus, indole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye has pyrazoline- as a nucleus having a ketomethine structure.
A 5- to 6-membered heterocyclic nucleus such as a 5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazoline-2,4-dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus is applied. can do.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, it may contain an aminostilbene compound substituted with a nitrogen-containing heterocyclic nucleus group, an aromatic organic acid formaldehyde condensate, a cadmium salt, an azaindene compound, or the like.

It is preferable to add the spectral sensitizing dye as a dispersion of solid fine particles, rather than as a solution of an organic solvent. In particular, it is preferable to disperse in a water system substantially free of an organic solvent and / or a surfactant, and to add in a state of a solid fine particle dispersion substantially insoluble in water. The particle size after dispersion is preferably 1 μm or less.

The timing of the addition is not added as a site director at the time of forming the silver halide projection, but can be added at any time after the formation of the silver halide projection and before the preparation of the emulsion coating solution.

In the present invention, the conditions of the chemical ripening step, for example, pH, pAg, temperature, time and the like are not particularly limited, and can be carried out under conditions generally used in the art.

For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin,
Selenium sensitization method using a selenium compound, tellurium sensitization method using a tellurium compound, reduction sensitization method using a reducing substance, noble metal sensitization method using gold or other noble metal, etc. can be used alone or in combination, among which Sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and the like are preferably used.

In the case of selenium sensitization, the selenium sensitizer used includes a wide variety of selenium compounds, and useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate). ), Selenoureas (N, N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoropropylselenourea, N, N, N'- Trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, selenoketones (selenoacetone, selenoacetophenone, etc.), selenoamides (selenoacetamide) , N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (2-sele Propionate, methyl 3-selenobutylate), selenophosphates (tri -p-
Triselenophosphate, etc.), and selenides (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, selenides.

The amount of the selenium sensitizer used depends on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but is generally 10 ^-8 to 10 ^-4 per mol of silver halide.
Is a mole. Depending on the properties of the selenium compound to be used, the method of addition may be a method of adding it alone or in a mixed solvent of water or an organic solvent such as methanol or ethanol, or a method of adding it by premixing with a gelatin solution. However, a method disclosed in JP-A-4-140739, that is, a method of adding an emulsion of a mixed solution with a polymer soluble in an organic solvent, may also be used.

The temperature of chemical ripening using a selenium sensitizer is as follows:
It is preferably in the range of 40 to 90 ° C, more preferably 45 to 90 ° C.
80 ° C. The pH is 4 to 9, and the pAg is 6 to 9.5.
Is preferable.

With respect to tellurium sensitizers and sensitization methods, a wide range of tellurium sensitizers are used, and examples of useful tellurium sensitizers include telluroureas (N, N-dimethyltellurourea,
Tetramethyltellurourea, N-carboxyethyl-N,
N'-dimethyltellurourea, N, N'-dimethyl-N '
-Phenyltellurourea), phosphine tellurides (tributylphosphine telluride, tricyclohexylphosphine telluride, tri-iso-propylphosphine telluride, butyl-di-iso-propylphosphine telluride, dibutylphenylphosphine telluride, etc.) , Telluroamides (telluroacetamide, N, N-dimethyltellurobenzamide, etc.), telluroketones, telluroesters, isotellurocyanates and the like. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

When the silver halide photographic light-sensitive material of the present invention is subjected to development processing, it is preferably processed by an automatic processor, and the steps from development to drying are preferably completed within 15 to 120 seconds. That is, the time from when the tip of the photosensitive material starts to be immersed in the developing solution to when the tip comes out of the drying zone through the processing step (so-called Dry to Dry time).
Is preferably within 15 to 120 seconds, more preferably within 15 to 90 seconds.

The development time is preferably from 3 to 40 seconds, more preferably from 6 to 20 seconds. The development temperature is preferably 2
The temperature is 5 to 50C, more preferably 30 to 40C. The fixing temperature is preferably about 20-40 ° C, more preferably 29-37 ° C, and the fixing time is preferably 3-30 seconds, more preferably 4-20 seconds.

In the drying step, hot air of usually 35 to 100 ° C., preferably 40 to 80 ° C. may be blown, or a drying zone provided with a heating means by far infrared rays may be provided in the automatic developing machine.

The automatic developing machine is provided with a mechanism for applying water or a rinsing solution of an acidic solution having no fixing ability to the photosensitive material during each of the developing, fixing and washing steps (Japanese Patent Laid-Open No.
-264953) may be used. Further, a device capable of adjusting a developing solution or a fixing solution may be incorporated.

In the processing method of the present invention, the replenishment amounts of the developing solution and the fixing solution are each preferably 180 ml / m ² or less, more preferably 8 to 160 ml / m ² .
It is particularly preferred that the treatment is performed at 10 to 100 ml / m ² .

Reductones are used in the developing solution used in the processing method according to the first and second aspects of the present invention. Examples of the reductone include an enediol type, an enaminol type, an enediamine type, a thiol enol type and an enamine thiol type, and are preferably compounds represented by the general formula (A).

[0075]

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In the general formula (A), R ¹ and R ² are each a hydroxy group, an amino group (which may have an alkyl group such as ethyl, butyl or hydroxyethyl as a substituent), an acylamino group (acetylamino group). , Benzoylamino, etc.), alkylsulfonylamino group (methanesulfonylamino, butanesulfonylamino, etc.), arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino, etc.), alkoxycarbonylamino group (methoxycarbonylamino, etc.), mercapto Represents a group or an alkylthio group (e.g., methylthio, ethylthio), and R ¹ and R ² preferably include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are each a hydroxy group, a carboxyl group, an alkoxy group (methoxy, ethoxy, butoxy, etc.), a hydroxyalkyl group (hydroxymethyl, hydroxyethyl, etc.), a carboxyalkyl group (carboxymethyl, carboxyethyl, etc.), Sulfo group (including salt), sulfoalkyl group (sulfoethyl, sulfopropyl, etc.), amino group (including alkyl substitution), aminoalkyl group (aminoethyl, aminopropyl, etc.), alkyl group (methyl, ethyl, propyl, butyl) , Pentyl, etc.)
Or an aryl group (phenyl, p-tolyl, naphthyl, etc.)
Or a non-metallic atomic group bonded to each other to form a 5- to 8-membered ring together with two vinyl carbon atoms substituted by R ¹ and R ² and a carbon atom substituted by Y. These 5-8
The membered rings may form a saturated or unsaturated fused ring. Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, a uracil ring, a cycloheptenone ring, a cyclohexanone ring, and azepine. And a cyclooctenone ring, with a 5- or 6-membered ring being preferred. Among them, 5 is preferable.
Examples of the 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexanone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

Y represents oxygen or NR ³ , and R ³ represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. The above R ¹ , R ² ,
The same groups as those described for P and Q can be used.

Hereinafter, specific examples of the compound represented by formula (A) are shown, but the present invention is not limited thereto.

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The salts of the reductones include, for example, lithium, sodium, potassium, ammonium and the like.

Among these, preferred are ascorbic acid and erythorbic acid (stereoisomer) (A-1)
It is.

The amount of these reductones to be added to the developing solution is not particularly limited, but is practically 0.1 to 100 g, preferably 0.5 to 80 g, more preferably 1 to 70 g per liter of the processing solution. It is.

The reductones may contain only one kind or two or more kinds. Claims 3 to 6 of the present invention
As the developing agent used in the processing method of the invention described in (1), any of reductones of the general formula (A), phenidone, hydroquinone, and other commonly used photographic processing agents may be used.

Further, in addition to sulfite, an organic reducing agent can be used as a preservative. In addition, bisulfite adducts of chelating agents and hardeners can be used. It is also preferable to add a silver sludge inhibitor.
It is also preferable to add a cyclodextrin compound.
Compounds described in -124853 are particularly preferred. An amine compound can be added to the developer, and for example, compounds described in US Pat. No. 4,269,929 are particularly preferable.

When developing the silver halide photographic light-sensitive material of the present invention, a buffer may be used as a developer, and the buffer may be sodium carbonate, potassium carbonate, or the like.
Sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium o-hydroxybenzoate (sodium salicylate), o
And potassium 5-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like.

Examples of the development accelerator include, for example, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, and other 1-phenyl-
3-Pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles and the like can be added as needed.

As an antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole,
5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2
Examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine, and typical examples include 1-phenyl-5-mercaptotetrazole.

Further, in the developer composition, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound and the like can be used as an organic solvent for increasing the solubility of the developing agent. Further, various additives such as a stain inhibitor, an anti-sludge agent and a layering effect promoter can be used.

The developer used in the processing method according to the fifth and sixth aspects of the present invention contains substantially no dialdehyde hardener or bisulfite adduct thereof. Substantially not containing means that the concentration is 0 to 0.005 mol / L.

The processing according to the third and fourth aspects of the present invention.
In the method, the developing solution and the fixing solution during the processing step are substantially added to
It does not contain boric acid or its salts. Departure
The term “boric acid” or “salt thereof” as referred to in the specification means specifically_ThreeBO_Three,
HBO_Two, NaBO_Two, KBO _Two, Na_TwoB_FourO₇, KB_FiveO₈
And the like. Where boric acid is substantially contained
“No” means that boric acid concentration is 0.04 mol / L or less.
However, it is preferable not to contain at all.

In the processing method according to the second, fourth and sixth aspects of the present invention, the developing solution in the processing step preferably contains 0.01 to 0.15 mol / L carbonate as a buffer. Any known carbonate may be used,
Preferred are sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.

When developing the silver halide photographic light-sensitive material of the present invention, a compound known as a fixing agent can be added as a fixing agent. Fixing agents, chelating agents, pH buffers, hardeners, preservatives, and the like can be added. These are described in, for example, JP-A-4-242246 (page 4) and JP-A-5-136.
No. 32 (pages 2 to 4) can be used. Other known fixing accelerators can also be used.

Prior to the treatment, it is preferable to add a starter, and it is also preferable to add the solidified starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkali metal such as KBr, an organic inhibitor, and a development accelerator are used.

In the emulsion used in the silver halide photographic light-sensitive material of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening.

Compounds used in such a step include, for example, Research Disclosure (hereinafter referred to as RD).
No.). 17643 (December 1978), R
DNo. 18716 (November 1979) and RDN
o. 308119 (December 1989) can be used. Hydrophilic colloids are also described. The types and locations of the compounds described in these three RDs are described below.

[0099]

[Table 1]

The support used in the silver halide photographic light-sensitive material of the present invention includes those described in the above RD. A suitable support is a polyethylene terephthalate film or the like, and the surface of the support is coated. In order to improve the adhesiveness of the layer, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied.

[0101]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 [Preparation of photosensitive material] (Preparation of seed emulsion) A seed emulsion was prepared as follows.

A1 Ossein gelatin 24.2 g Water 9657 ml Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5 mol / L silver nitrate aqueous solution 2,825 ml of C1 potassium bromide 841 g of water 2825 ml of D1 1.75 mol / L aqueous solution of potassium bromide The following silver potential control amount at 42 ° C: JP-B-58-58288, 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. in 60 minutes, the pH was adjusted to 6.0 with 3% KOH, and then the solution was again added. The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mV and +16 mV.

After completion of the addition, the pH was adjusted to 6 with 3% KOH.
It was desalted and washed immediately with 0. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm. It was confirmed with an electron microscope that the diameter (in terms of circular diameter) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Growth Grain Emulsion) A growth grain emulsion was prepared using a seed emulsion and the following four kinds of solutions.

A2 Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous solution of ethanol) 2.25 ml Seed emulsion 1.722 mol equivalent Equivalent to 3150 ml with water B2 1734 g potassium bromide 3644 ml with water C2 Silver nitrate 2478 g Finished to 4165 ml with water D2 Fine grain emulsion composed of 3% by mass of gelatin and silver iodide grains (average grain size 0.05 μm) (*) Equivalent to 0.080 mol * Fine grain emulsion 0.06 mol 4. containing potassium iodide
To 6.64 L of a 0% by mass aqueous gelatin solution, 2 L of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the particles are formed, p is added using an aqueous sodium carbonate solution.
H was adjusted to 6.0.

In the reaction vessel, the solution A2 was vigorously stirred while keeping it at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and a part of the solution B2, a part of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. The total amount of the remaining solutions B2 and C2 was added thereto over 33 minutes. During this time, the pH was 5.8 and the pAg was 8.8.
I kept it at 8. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.984 μm and the average thickness was 0.1 mm.
Tabular silver halide grains having a size of 22 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% were obtained. Also,
The average of the twin plane distance is 0.020 μm, and grains having a twin plane distance to thickness ratio of 5 or more are 97% (number) of all tabular silver halide grains and 10 or more grains are 49 or more. %, 15
These particles accounted for 17%.

After completion of the addition, the emulsion was cooled to 40 ° C. and subjected to an ultrafiltration module (manufactured by Asahi Kasei Kogyo Co., Ltd., molecular weight cut off 1).
Type A using 3000 polyacrylonitrile membrane
After performing ultrafiltration desalting with LP-1010), a 10% gelatin solution was added, and the mixture was stirred at 50 ° C for 30 minutes and redispersed. After redispersion, at 40 ° C., the pH was 5.80 and the pAg was 8.
06.

(Chemical sensitization)
C., the sensitizing dyes (A) and (B) were added as the following solid fine particle dispersion, and then a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and triphenylphosphine were added. A selenide dispersion was added, and after 30 minutes, a silver iodide fine grain emulsion was added, followed by ripening for a total of 2 hours. At the end of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-
An appropriate amount of tetrazaindene (TAI) was added. The above additives and the amounts added per mole of silver are shown below.

Sensitizing dye (A): 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine-sodium salt anhydride 0.6 mmol Sensitizing dye (B ): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride 0.006 mmol adenine 15 mg potassium thiocyanate 95 mg of chloroauric acid 2.5 mg of sodium thiosulfate 2.0 mg of triphenylphosphine selenide 0.2 mg of stabilizer (TAI) 500 mg of solid fine particle dispersion of spectral sensitizing dye is disclosed in JP-A-5-297.
No. 496, prepared by the method according to the method.
That is, it was obtained by adding a predetermined amount of the spectral sensitizing dye to water previously adjusted to 27 ° C. and stirring with a high-speed stirrer (dissolver) at 3.500 rpm for 30 to 120 minutes.

The above-mentioned dispersion of triphenylphosphine selenide was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to ethyl acetate 3 at 50 ° C.
It was added to 0 kg, stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25% by mass aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at 50 ° C. at a peripheral speed of 40 m / sec for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3% by mass or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Preparation and Coating of Coating Solution) Then, the concentration was 0.15.
On both sides of a polyethylene terephthalate film base (thickness: 175 μm) for X-ray colored blue,
Using a support on which a crossover cut layer was previously coated, the following emulsion layer and protective layer were simultaneously coated on both sides of the support from the support side so that the following coating amounts were obtained, dried, and dried. . 1-1 to 1-3 were obtained. The additives used for each coating solution are as follows. The amount of addition is shown per 1 m ^{2 on} one side of the photosensitive material.

First Layer (Crossover Cut Layer) Solid Fine Particle Dispersion Dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium Dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Second layer (silver halide emulsion layer) Emulsion obtained above The following various additives were added.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone ( 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3 ammonium dihydroxybenzene-4-sulfonic acid 500 mg / m ² 2-mercaptobenzimidazole-5-sulfonate sodium 5 mg / m ² compound ^{(H) 0.5mg / m 2 n} -C 4 H 9 OCH ₂ CH (OH) CH ₂ N ( CH ₂ COOH) ₂ 350 mg / m ² Compound (P) 0.2 g / m ² Compound (Q) Compound Table 2, wherein the amount of 0.2 g / m ² Formula (1) to (4) However, as the gelatins 0 It was adjusted to be 0.8 g / m ² .

Third layer (protective layer) Gelatin 0.6 g / m ² Polymethyl methacrylate matting agent (area average particle size 7.0 μm) 50 mg / m ² 2,4-dichloro-6-hydroxy-1,3 2,5-Triazine sodium salt 10 mg / m ² Bis-vinylsulfonyl methyl ether 36 mg / m ² Polyacrylamide (average molecular weight 10,000) 0.1 g / m ² Sodium polyacrylate 30 mg / m ² Polysiloxane (S1) 20 mg / m ² Compound (I) 12 mg / m ² Compound (J) 2 mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² Compound (O) 50 mg / m ² Compound (S-2) 5 mg / m ² C ₉ F ₁₉ O (CH ₂ CH ₂ O) ₁₁ H 3 mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ H 2 mg / m ² C _{8 F 17 SO 2 N- (C} 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 SO 3 Na 1mg / m 2 hardener (A) 120 mg / m ² Formula (1) - ( 4) Compounds listed in Table 2

[0118]

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[0119]

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[0120]

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[0121]

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The amount of the above-mentioned material is equivalent to one side.
The coating amount of the emulsion layer was adjusted so that the amount of silver was 1.3 g / m ² on one side, and the coating was performed to prepare nine types of samples.

[Preparation of Solid Developer] (Preparation of Developing Agent) A developing tablet and a fixing tablet were prepared according to the following operations (A) to (D).

Operation (A) Preparation of Tablet A for Developing Agent 13,000 g of sodium erythorbate as a developing agent
Is ground to a mean particle size of 10 μm in a commercially available bantam mill. 4880 g of sodium sulfite, 1
-Phenyl-3-pyrazolidone (phenidone) to 975
g, pentasodium diethylenetriaminepentaacetic acid (DTP
A.5Na) 1,635 g and boric acid 440 g were added, mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 10 minutes in a commercial stirring granulator. Is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the water content of the granulated product.

The granules thus prepared were uniformly mixed with 2172 g of D-mannitol for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH, and the resulting mixture was mixed with Kikusui Seisakusho. Tough Presto Collect 1
Using a modified tableting machine of 527HU, the filling amount per tablet was set to 10.15 g, and compression tableting was performed to prepare 2500 tablets A for development.

Operation (B) Preparation of tablet B for development 19500 g of potassium carbonate, 8.15 g of 1-phenyl-5-mercaptotetrazole, 32 of sodium hydrogen carbonate
50 g, glutaraldehyde sulfite adduct 650 g, D
Grinding 1354 g of mannitol as in operation (A),
Granulate. The amount of water added was 30.0 ml and after granulation, 50
After drying at 30 ° C. for 30 minutes, the water content of the granules is almost completely removed.

The mixture thus obtained was subjected to compression tableting using a tableting machine similar to the above with a filling amount per tablet of 9.90 g to prepare 2500 tablets B for development.

Operation (C) Preparation of Tablet C for Fixing Example 18560 g of ammonium thiosulfate, 1392 g of sodium sulfite, 580 g of sodium hydroxide, and 2.32 g of disodium ethylenediaminetetraacetate were pulverized and granulated in the same manner as in the operation (A). After adding 500 ml of water and granulating, the granulated material is dried at 60 ° C. for 30 minutes to almost completely remove the water content of the granulated material. The mixture thus obtained was filled with 8.214 g per tablet using the above tableting machine.
To 2500 tablets of fixing tablets C were prepared.

Operation (D) Preparation of tablet D for fixation 186 g of boric acid, 6500 aluminum sulfate / 18 hydrate
g, 1860 g of glacial acetic acid, and 925 g of sulfuric acid (50% by mass) are pulverized and granulated in the same manner as in the operation (A). Water addition amount is 10
After the granulation, the mixture is dried at 50 ° C. for 30 minutes to remove the moisture of the granulated product almost completely.

The mixture thus obtained was compressed and tableted with the above tableting machine at a filling amount of 4.459 g per tablet to prepare 2500 fixing tablets D.

(Preparation of Developing Solution) 16.5 L of a developing solution having the following composition was prepared by using 127 prepared developing tablets A and 254 B tablets. 330 ml of a starter having the following composition with respect to 16.5 L of the obtained developer having a pH of 10.70.
Was added to adjust the pH to 10.45 to obtain a development start solution.

Composition of Development Initiating Solution (Amount per 1 L) Potassium carbonate 120.0 g Sodium erythorbate 40.0 g DTPA / 5Na 5.0 g 1-phenyl-5-mercaptotetrazole 0.05 g Sodium bicarbonate 20.0 g Phenidone 3. 0 g Sodium sulfite 15.0 g D-mannitol 15.0 g Glutaraldehyde sulfite adduct 4.0 g (Preparation of developer starter) Water was added to 210 g of glacial acetic acid and 530 g of KBr to make 1 L.

(Preparation of Fixing Initiating Solution) Using 237 of the above prepared fixing tablets C and 149 of fixing agents, 11 L of a fixing solution having the following composition was prepared and used as a fixing starting solution. The pH of the resulting fixing start solution was 4.80.

Fixing start solution composition (amount per liter) Ammonium thiosulfate 160.0 g Sodium sulfite 12.0 g Boric acid 1.0 g Sodium hydroxide 5.0 g Glacial acetic acid 10.0 g Aluminum sulfate / 18-hydrate 35.0 g Sulfuric acid (50 (Mass%) 5.0 g Disodium ethylenediaminetetraacetate / dihydrate 0.02 g (Preparation of replenisher) The replenisher for both the developer and the fixer is supplied to each of the above-mentioned developer tablet and fixer at the refill tablet inlet. The packaging bag is opened and set. The tablets are put into each of the built-in chemical mixers, and at the same time, a required amount of warm water of 25 to 30 ° C. is injected. , And used as a replenisher for development and fixing.
In the automatic developing machine used, SRX-502 was modified so as to satisfy the following processing conditions, and a processing for sample evaluation was performed using the above processing agent.

[0135] [Evaluation of Samples] (Evaluation of silver tone) For each of the nine types of photosensitive material samples, two intensifying screens (KO-250 manufactured by Konica Corporation) were used.
At a tube voltage of 80 kVp and a density of 1.1 after development processing.
Adjust the tube current and irradiation time to be ± 0.05,
It was exposed to X-rays. After processing by SRX-502,
The silver tone was visually evaluated according to the following evaluation criteria.

Evaluation Criteria A: Cool black tone B: Slightly yellowish felt C: Yellowishness felt and gives discomfort to viewers (Evaluation of fog increase after long-term running use) Evaluation of 9 types of photosensitive materials The sample was treated with the new solution without exposure.
Next, the samples exposed to light in the same manner as in the evaluation of the silver tone were processed for one month at a size of 4 pieces per day for 70 sheets to prepare a running solution, and an unexposed sample of each sample was treated with this running solution. Processed. For each sample, the fog between the new solution and the running solution treated for one month was measured, and the difference was evaluated as an increase in fog.

Table 2 shows the results.

[0138]

[Table 2]

It can be seen that the sample of the present invention has a good silver tone and a small increase in fog after long-term use.

Example 2 [Preparation of photosensitive material] Nine kinds of samples were prepared in the same manner as in Example 1.

[Preparation of Solid Developer] In the preparation of a developing tablet and a fixing tablet, without adding boric acid, the filling amount of the developer A per tablet was 10.15 g, and the fixing agent was A solid processing agent was produced in the same manner as in Example 1 except that the amount of granulation was set to 4.37 g. Therefore, the developing and fixing starting liquid does not contain boric acid.

[Evaluation of Sample] The evaluation of the sample was performed in the same manner as in Example 1. Table 3 shows the results.

[0143]

[Table 3]

It can be seen that the sample of the present invention has a good silver tone and a small rise in fog after long-term running use.

Example 3 [Production of photosensitive material] Nine kinds of samples were produced in the same manner as in Example 1.

[Preparation of Developer] (Preparation of Developer) Part-A (for finishing 12 L) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium hydrogen bicarbonate 132 g Boric acid 40 g 5- Methylbenzotriazole 1.4 g 5-Nitrobenzimidazole 0.4 g 1-phenyl-5-mercaptotetrazole 0.25 g 4-hydroxymethyl-4-methyl-1-phenylpyrazolidone 120 g Hydroquinone 400 g Add water to make 6000 ml. Part-B (for 12L finish) glacial acetic acid 70 g 5-nitroindazole 0.6 g N-acetyl -DL- penicillamine 1.2g starter glacial acetic acid 120g potassium bromide _{225g HO (CH 2) 2 S} (CH 2) 2 S CH ₂₎ finished in _{2 OH 1.0g CH 3 N (C} 3 H 6 NHCONHC 2 HSC 2 H 5) by addition of ₂ 1.0 g 5-methylbenzotriazole 1.5g water 1.0 L (Preparation of fixer) Part-A (for 18.3 L finishing) Ammonium thiosulfate (70% by mass / volume) 4500 g Sodium sulfite 450 g Sodium acetate trihydrate 450 g Boric acid 110 g Tartaric acid 60 g Sodium citrate 10 g Gluconic acid 70 g 1- (N, N-dimethylamino) ) -Ethyl-5-mercaptotetrazole 18 g Glacial acetic acid 330 g Aluminum sulfate 62 g Add water to make up to 7200 ml This developer does not contain a dialdehyde-based hardener.

The developer was prepared by adding Part-A to about 5 L of water,
Part-B was added at the same time, water was added while stirring and dissolving, and the mixture was adjusted to 12 L and the pH was adjusted to 10.53 with glacial acetic acid.
This is used as a development replenisher. The starter was added to 1 L of this replenisher at 20 ml / L to adjust the pH to 10.3.
Adjust to 0 and use as working solution.

For the preparation of the fixing solution, Part-A was simultaneously added to about 5 L of water, and water was added thereto while stirring and dissolving to make 18.3 L, and the pH was adjusted to 4.6 using sulfuric acid and NaOH. This is used as a fixing replenisher.

The automatic developing machine used was SRX-50.
3, the processing temperature was 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing, 50 ° C. for drying, and the processing time was dry to dr.
y is 25 seconds. The replenishment rate was 65 ml for both development and fixing per m ² of film.

[Evaluation of Sample] Evaluation was performed in the same manner as in Example 1 except that the processing agent used in the processing was changed to the above-mentioned processing agent and the automatic developing machine was changed to the above-mentioned SRX-503. Table 4 shows the results.

[0151]

[Table 4]

It can be seen that the sample of the present invention has a good silver tone and a small rise in fog after long-term running use.

[0153]

According to the present invention, there is provided a method for processing a silver halide photographic light-sensitive material using a developer for a silver halide photographic light-sensitive material, which has little effect on the human body, has an improved silver tone, and has little fog even after long-term use. be able to.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer on at least one side of a support and having a layer containing a compound of the general formula (1) to (4), and a reductone. A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed with a developing solution. Embedded image (In the general formulas (1) to (4), W is an electron withdrawing group, D is
Represents an electron donating group, and H represents a hydrogen atom. The groups represented by W or D on the same carbon may form a cyclic structure with each other, and W or D may have either a trans structure or a cis structure when both are possible. ) 2. The method according to claim 1, wherein the carbonate ion is contained in an amount of 0.01 to 0.1 / L.
2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the processing is performed with a developer containing 15 mol. 3. A silver halide photographic light-sensitive material having a hydrophilic colloid layer on at least one side of a support and having a layer containing a compound of the above general formula (1) to (4).
A method for processing a silver halide photographic light-sensitive material, characterized by processing with a developer substantially free of boric acid. 4. The method according to claim 1, wherein the carbonate ion is contained in an amount of 0.01 to 0.1 / L.
4. The method for processing a silver halide photographic light-sensitive material according to claim 3, wherein the processing is performed with a developer containing 15 mol. 5. A silver halide photographic light-sensitive material having a hydrophilic colloid layer on at least one side of a support and having a layer containing a compound of the above formulas (1) to (4).
A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed with a developer that does not substantially contain a dialdehyde-based hardener. 6. A carbonate ion is added in an amount of 0.01 to 0.1 per liter.
6. The method for processing a silver halide photographic light-sensitive material according to claim 5, wherein the processing is performed with a developer containing 15 mol.