JPH11212202A - Silver halide photographic sensitive material and processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material and its processing method superior in pressure resisting performance such as the restraint of roller marks in the rapid processing of low replenishment and without the occurrence of uneven processing. SOLUTION: This silver halide photographic sensitive material is provided on a support with at least one silver halide emulsion layer containing reduction- sensitized silver halide grains and the layer is processed with a developing solution containing reductones. As the processing method, the layer is processed in the replenishing amt. of the developing solution <=200 ml per 1 m<2> of this photographic sensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material (hereinafter also simply referred to as a "photosensitive material") and a processing method thereof. However, the present invention relates to a photosensitive material and a processing method which do not cause processing unevenness.

[0002]

2. Description of the Related Art Since 1995, marine disposal of photographic processing wastewater has been prohibited and incineration has been carried out. However, land-based disposal of wastewater causes an increase in energy costs. Reduction was desired. However, the reduction of the replenisher solution increases the stagnation time of the solution in the processing tank, causes oxidative fatigue of the processing solution, lowers the density or gamma of the photosensitive material to be processed, or causes uneven density, resulting in deterioration of processing stability. Having.

In addition, from the viewpoint of emergency medical care, it is necessary to promptly grasp the condition of a patient and to provide medical image information promptly because of the need for prompt treatment, and there is a strong demand for rapid processing of photosensitive materials. .

In order to meet these demands, the covering power of developed silver is increased by a method such as reducing the average grain size of silver halide grains or using tabular grains having a high aspect ratio and a small thickness.
It is known to reduce the amount of silver applied. However, when the particle size is reduced, the sensitivity is reduced, so sensitization is required to maintain the conventional sensitivity, and the amount of silver in the photosensitive material has been reduced by various sensitization techniques. Is required. Although reduction sensitization is known as one of the sensitizing means, it has a drawback that the pressure resistance performance is deteriorated such as abrasion resistance and roller mark resistance.

[0005]

The inventor of the present invention has developed that a light-sensitive material having reduction-sensitized silver halide grains can be developed with a developer containing reductones to provide low replenishment, rapid processing and good running performance. And led to the present invention.

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material excellent in pressure resistance such as a roller mark by low replenishment rapid processing and free from processing unevenness, and a processing method therefor.

[0007]

The above object of the present invention has been attained by the following constitutions. 1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains reduction-sensitized silver halide grains and contains a developer containing reductones. A silver halide photographic material characterized by being processed by

[0008] 2. 2. The silver halide photographic material according to 1, wherein the reduction-sensitized silver halide grains are tabular silver halide grains having an average aspect ratio of 2 or more.

3. The silver halide photographic light-sensitive material according to item 1 or 2, wherein the replenishment amount of the developing solution is 1
A processing method for a silver halide photographic light-sensitive material, wherein the processing is carried out at 50 to 200 or less per m < ² >.

[0010] 4. 4. The method for processing a silver halide photographic material according to 3, wherein the developer contains a compound represented by the following general formula (1) and / or general formula (2).

[0011]

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In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² , R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxyl group. Where R
^{When 2} , R ³ and R ⁴ are alkyl groups, the alkyl groups may be substituted with a hydroxyl group, a carboxyl group or a sulfo group.

[0013]

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In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group, M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n is an integer selected from 0, 1, and 2. . However, when either or both of R ⁵ and R ⁶ are a methyl group, the alkyl group may be substituted with a carboxyl group or a hydroxyl group.

Hereinafter, the present invention will be described in detail.

The halogen composition of the silver halide emulsion used in the present invention may be arbitrarily selected, for example, any of silver chloride, silver iodochloride, silver chlorobromide, silver bromide, silver iodobromide, silver chloroiodobromide and the like. May be used.

When silver iodide is contained, the silver iodide content is from 0 to 1.0 as an average silver iodide content of the whole silver halide grains.
5 mol% is preferable, and 0 to 1.0 mol% is more preferable.

The average grain size of the silver halide grains is 0.15 to 0.15.
5.0 μm, preferably 0.2 to 4.0 μm
Is more preferable, and most preferably 0.3 to 3.0 μm.

The crystal habit of the silver halide grains may be of any crystal habit such as cubic, octahedral, and twin plane, but is preferably tabular silver halide grains (hereinafter simply tabular grains). ).

A tabular silver halide grain is a grain having two opposing parallel main planes, and the one used in the present invention has a (10) plane having a main plane of (10).
0) The plane may be either a main plane or a plane.

The tabular silver halide grains preferably used in the present invention have an average value of the ratio of the grain size to the grain thickness (hereinafter referred to as aspect ratio) of 2 or more, preferably 3 to 70. Particularly preferably, it is 3 to 40, most preferably 4 to 15.

Here, the grain size is an average projected area diameter, and is represented by a circle equivalent diameter of a projected area of a tabular silver halide grain (diameter of a circle having the same projected area as the silver halide grain). And thickness indicate the distance between two parallel main planes forming tabular silver halide grains.

When tabular grains are used in the present invention, the average thickness of the grains is preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.60 μm, and even more preferably 0.05 to 1.0 μm. 0.50 μm.

The average particle size is preferably from 0.15 to 5.0 μm, more preferably from 0.4 to 3.0 μm, and most preferably from 0.4 to 2.0 μm. The tabular silver halide grains are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grains / average grain size) × 100 = width (%) of grain size distribution When it is defined, it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

Tabular silver halide grains can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to form nuclei with low pCl in the presence of iodide ions under conditions that facilitate formation of the (100) plane. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution.

The tabular silver halide grains are formed from a cadmium salt or a zinc salt during the grain forming step and / or the growing step. Metal ions are added using at least one selected from a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt (including a complex salt), and an iron salt (including a complex salt), and the inside of the particle and / or the surface of the particle are added. It is preferable to include these metal elements in the metal.

Hereinafter, the reduction sensitization of the present invention will be described.

The process for producing a silver halide emulsion used in the light-sensitive material of the present invention is roughly classified into a grain forming process, a desalting process, a chemical sensitizing process and the like. Particle formation is divided into nucleation, ripening, and growth. These steps are not performed uniformly, but the order of the steps is reversed or the steps are repeatedly performed.

Applying reduction sensitization during the production process of a silver halide emulsion basically means that any of the above-mentioned processes may be used.

The reduction sensitization may be performed at the early stage of grain formation, such as nucleation, physical ripening, or growth, or may be performed prior to chemical sensitization other than reduction sensitization. When performing chemical sensitization in combination with gold sensitization, reduction sensitization is preferably performed prior to chemical sensitization so as not to cause undesirable fog. Most preferred is a method of reducing sensitization after desalting.

Here, "growing" means that reduction sensitization is performed while silver halide grains are growing by physical ripening or addition of a water-soluble silver salt and a water-soluble alkali halide. This means that a method of performing growth further after performing reduction sensitization in a stopped state is also included.

The reduction sensitization of the present invention refers to a method in which a reducing agent is added to a silver halide emulsion, or pAg1 to silver ripening.
A method of growing or ripening in a low pAg atmosphere of 7, a high pH of 8 to 11 called high pH ripening
Or an aging method can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

Examples of the reducing agent include stannous salts, amine and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds.

In the present invention, these compounds can be selected and used, and two or more of these compounds can be used in combination.

As the reduction sensitizer, stannous chloride, thiourea dioxide and dimethylamine borane are preferred compounds.

Since the addition amount of the reduction sensitizer depends on the production conditions of the emulsion, it is necessary to select the addition amount.
A range of 10 ^-7 to 10 ^-3 mole per mole is suitable.

In the light-sensitive material of the present invention, an ascorbic acid derivative can be used as a reduction sensitizer.

Specific examples of preferably used ascorbic acid and its derivatives (hereinafter, ascorbic acid compounds) include the following.

(A-1) L = ascorbic acid (A-2) L = sodium ascorbate (A-3) L = potassium ascorbate (A-4) DL = ascorbic acid (A-5) D = ascorbic acid Sodium (A-6) L = ascorbic acid-6-acetate (A-7) L = ascorbic acid-6-palmitate (A-8) L = ascorbic acid-6-benzoate (A-9) L = ascorbic acid- 5,6-diacetate
G (A-10) L = ascorbic acid-5,6-O-iso
Propylidene These ascorbic acid compounds are conventionally favored by reduction sensitizers.
Use a large amount compared to the amount used well
Is desirable. For example, in Japanese Patent Publication No. 57-33572,
The amount of the base agent is usually 0.75 × 10^-2Millimeter
Equivalent (8 × 10 ^-FourMol / AgX mol). nitric acid
0.1 to 10 mg per kg of silver (with ascorbic acid
Then 10^-7-10^-FiveMol / AgX mol) is effective in many cases.
It is effective. "

The ascorbic acid compound can be prepared by the following methods: emulsion grain size, silver halide composition, emulsion preparation temperature, pH, pAg
Although the preferred addition amount is determined by factors such as the above, it is preferable to select a range of 5 × 10 ^-5 to 1 × 10 ^-1 mol, and more preferably 5 × 10 ^-4 to 1 mol per mol of silver halide.
It is preferable to select a range of × 10 ^-2 mol. It is particularly preferable to select from the range of 1 × 10 ⁻³ to 1 × 10 ⁻² mol.

The ascorbic acid compound can be dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during grain formation, before or after chemical sensitization. Particularly preferred is a method of adding during grain growth. It may be added to the reaction vessel in advance, but a method of adding at an appropriate time during the particle formation is preferable. Alternatively, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and particles may be formed using these aqueous solutions. Also, even if the solution of the reduction sensitizer is added in several portions with the formation of grains,
It is also a preferable method to add continuously for a long time.

In the method for chemically sensitizing silver halide grains of the present invention, gold sensitization, sulfur sensitization, sensitization with a chalcogen compound, and a combination thereof are preferably used.

The chemical sensitization method includes so-called sulfur sensitization,
Gold sensitization, noble metals of group VIII of the peri-disciplinary table (for example, Pd, Pt
And the like and combinations of these methods. Among them, a combination of gold sensitization and sulfur sensitization, or a combination of gold sensitization and sensitization with a selenium compound is preferable. The addition amount of the selenium compound can be arbitrarily set, but it is preferable to use it together with sodium thiosulfate during chemical sensitization. More preferably, the molar ratio of the selenium compound to sodium thiosulfate is 2: 1 or less.
More preferably, it is used in a molar ratio of 1: 1 or less. It is also preferable to carry out the reaction in combination with the reduction sensitization.

As the selenium sensitizer to be used in the case of selenium sensitization, a conventionally known selenium sensitizer can be used.

Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and selenoureas (eg, N,
N-dimethylselenourea, N, N, N'-triethylselenourea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-
Heptafluoropropylcarbonylselenourea, N,
N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.) , Selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.),
Selenides (diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenium ketones.

The amount of the selenium sensitizer used varies depending 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.
Use about moles. Depending on the properties of the selenium compound to be used, the addition method may be a method in which water or an organic solvent such as methanol or ethanol is dissolved alone or in a mixed solvent, or a method in which the solvent is premixed with a gelatin solution and added. A method disclosed in JP-A-4-140739, that is, a method of adding a mixed solution with a polymer soluble in an organic solvent in the form of an emulsified dispersion.

The temperature of chemical ripening using a selenium sensitizer is
A range from 40 to 90C is preferred. More preferably, 45
８０80 ° C. Further, the pH is 4 to 9, and the pAg is 6 to
A range of 9.5 is preferred.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of the chemical sensitization in terms of sensitivity and adsorption of a photosensitive dye. In particular, a method of adding silver iodide in the form of fine grains is preferable.

The chemical sensitization is preferably carried out in the presence of a compound having adsorptivity to silver halide.
Among azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, and azaindenes, particularly preferred are compounds having a mercapto group and compounds having a benzene ring.

Also, US Pat. No. 3,615,613,
The combinations described in JP-A Nos. 3,615,641, 3,617,295, and 3,635,721 are particularly useful.

The silver halide grains of the present invention are spectrally sensitized using a spectral sensitizing dye (hereinafter, also simply referred to as a sensitizing dye). 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 those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

The sensitizing dye is used in the same concentration as that used for a normal negative-working silver halide emulsion. In particular, it is advantageous to use the silver halide emulsion at a dye concentration that does not substantially lower the intrinsic sensitivity of the silver halide emulsion. The sensitizing dye is preferably used in an amount of from 1.0 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol per mol of silver halide, and more preferably from 4 × 10 ⁻⁵ mol to 2 × 10 mol per mol of silver halide. It is preferred to use ^-4 molar concentration. These dyes can be applied to any of the nuclei usually used. 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, a pyridine nucleus, and the like. A renin nucleus, a benzindolenine nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In a merocyanine dye or a complex merocyanine dye, pyrazoline-
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thioparbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. Further, together with the sensitizing dye, the dye itself does not have spectral sensitization or a substance that does not substantially absorb visible light, and has a supersensitizing effect, such as a nitrogen-containing heterocyclic nucleus group. It may contain a substituted aminostilbene compound, an aromatic organic formaldehyde condensate, a cadmium salt, an azaindene compound and the like.

The sensitizing dye is preferably added as a solid fine particle dispersion, rather than dissolved in an organic solvent. Particularly, the sensitizing dye is dispersed in an aqueous system free of an organic solvent and / or a surfactant. It is preferably added in the form of a solid fine particle dispersion which is hardly soluble in water. Particle size after dispersion is 1 μm
The following is preferred.

As the hydrophilic colloid and the binder used in the light-sensitive material of the present invention, gelatin is preferably used, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, albumin, protein such as casein hydroxyethylcellulose, carboxymethylcellulose, cellulose derivatives such as cellulose sulfates, sodium alginate, dextran, starch derivatives, polyvinyl alcohol, polyvinyl alcohol Various kinds of synthetic hydrophilic high molecular substances such as homo- or copolymers of partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole and the like can be used.

In particular, the average molecular weight is 5,0 together with gelatin.
It is preferable to use from 100 to 100,000 dextrin or polyacrylamide in combination.

Examples of the gelatin include lime-treated gelatin, acid-treated gelatin, and Bull. Soc. Photo. , Japan,
No. 16, 30 (1966), gelatin derivatives (e.g., acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane saltones, vinylsulfonamides, etc.) Those obtained by reacting various compounds such as maleamide compounds, polyalkylene oxides, epoxy compounds, etc.) are included.

The preferred amount of gelatin is 4.0 g / m ² or less per one surface of the light-sensitive material, preferably 3.0 g / m ^2.
It is more preferred to use g / m ² or less, most preferably 2.5 g / m ² .

When any one of the silver halide emulsion layers or the constituent layers other than the emulsion layers of the light-sensitive material of the present invention contains a dye capable of decoloring or flowing out during development, high sensitivity,
A photosensitive material having high sharpness and suitability for rapid processing can be obtained. The dye used in the photosensitive material can be appropriately selected from dyes capable of improving sharpness by absorbing a desired wavelength and removing the influence of the wavelength according to the photosensitive material. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the color is not visible when the image is completed.

The dye is preferably added as a solid fine particle dispersion. The method for producing the solid fine particle dispersion of the dye is, specifically, using a surfactant, for example, a ball mill, a vibration mill, a planetary mill, It can be prepared using a fine dispersing machine such as a sand mill, a roller mill, a jet mill, and a disk impeller.

A method of dissolving the dye in a weakly alkaline aqueous solution and lowering the pH to make it weakly acidic to precipitate fine solid particles, or simultaneously adjusting the pH of the weakly alkaline solution of the dye and the acidic aqueous solution while adjusting the pH. A dye dispersion can be obtained by a method of preparing a particulate solid by mixing.

The dyes may be used alone, or two or more dyes may be used in combination. When two or more dyes are used in combination, they may be dispersed individually and then mixed.
Also, they can be dispersed at the same time.

The constituent layer of the light-sensitive material to which the dye is added and contained is preferably a silver halide emulsion and / or a layer closer to the support, more preferably a coating layer adjacent to the transparent support. It is effective to add.
It is desirable that the concentration of the dye is higher on the side closer to the support.

The amount of the dye to be added can be changed according to the target of sharpness. Preferably 0.2 to 20 mg /
m ² , more preferably 0.8 to 15 mg / m ² .

In the light-sensitive material of the present invention, the silver halide emulsion layer is preferably colored. In this case, a dye is added to the silver halide emulsion before coating or to an aqueous solution of a hydrophilic colloid to support these liquids. It may be applied to the body by various methods directly or via another hydrophilic colloid layer.

As described above, it is preferable that the concentration of the dye is higher on the side closer to the support, but in order to fix such dye on the side closer to the support, it is necessary to use a mordanting agent. it can. For example, a non-diffusible mordant can be used to bind to at least one of the aforementioned dyes.

The method of combining the dye with the non-diffusible mordant is carried out by various methods known in the art.
In particular, a method of binding in a gelatin binder is preferably applied. In addition, a method for binding in an appropriate binder and dispersing in an aqueous gelatin solution by ultrasonic waves or the like can be applied.

The binding ratio is not uniform depending on the compound, but usually, 0.1 part to 10 parts of the non-diffusible mordant is bound to 1 part of the water-soluble dye. Since the amount added as the water-soluble dye is linked to the non-diffusible mordant, it is preferable to use the dye alone.

When incorporated in the light-sensitive material, a constituent layer having a combination of a dye and a non-diffusible mordant may be newly provided as a constituent layer, and its position can be arbitrarily selected.
Preferably, it is effective to use as a coating layer adjacent to the transparent support.

As the surfactant for preparing the solid particulate dispersion, any of anionic surfactant, nonionic surfactant, cationic surfactant and amphoteric surfactant can be used, but it is preferable. For example, alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, N-acyl-N-alkyl taurines and the like Preferred are anionic surfactants and nonionic surfactants such as saponins, alkylene oxide derivatives, alkyl esters of sugars and the like.

The amount of the anionic surfactant and / or the nonionic surfactant is not uniform depending on the kind of the surfactant or the dispersing condition of the dye, but is usually 0.1 to 2000 mg / g of the dye. And preferably 0.5 to 1000 mg, more preferably 1 to 500 mg.

The concentration of the dispersion of the dye is from 0.01 to
10% by weight is preferable, and 0.1 to 5% by weight is more preferably used. It is preferable to add the surfactant before the start of the dispersion of the dye, and it is preferable to further add the dye dispersion after the completion of the dispersion, if necessary. Each of these anionic surfactants and nonionic surfactants may be used alone, and it is also preferable to use both surfactants in combination.

The emulsion may be subjected to a Nudel washing method, a flocculation sedimentation method, or the like to remove soluble salts. A preferred washing method is, for example, Japanese Patent Publication No. 35-160.
No. 86, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group, or a desalination method using a polymer flocculant, eg, G-3, G-8, etc. described in JP-B-63-158644. Can be.

Various photographic additives can be used in the light-sensitive material of the present invention. Examples of known additives include the aforementioned (RD) 17643 (December, 1978) and No. 18716 (1979). And 308119 (19
(December 1989). The types and locations of the compounds shown in these three (RD) are described below.

[0077]

[Table 1]

When the emulsion used in the light-sensitive material of the present invention is coated on only one side of the support, the layer containing the antihalation dye is usually placed between the emulsion and the support, Although it may be on the opposite side of the layer, it is preferable to provide it as the back layer on the opposite side of the emulsion layer because the range of choice of dyes is widened. The transmission density of the dye content at the wavelength of the exposure light source is preferably 0.4 to 1.5, more preferably 0.45 to 1.5.
-1.2 is more preferable.

The method of adding the dye includes, for example, addition of an aqueous solution, addition of a micelle, and addition of a solid, depending on the nature of the dye.

The support preferably used in the light-sensitive material of the present invention includes those described in the above RD. Suitable supports include polyethylene terephthalate film and polyethylene naphthalate (PEN). An undercoat layer may be provided on the surface to improve the adhesiveness of the coating layer, and may be subjected to corona discharge, ultraviolet irradiation, or the like.

In the method for processing a light-sensitive material of the present invention, continuous processing is performed by using a replenisher for both the developing solution and the fixing solution.

The replenishment amount of the developing solution is 5 per m ² of the photosensitive material.
It is characterized by processing with 0 to 200 ml.

In the processing method of the present invention, processing is performed with an alkaline developer containing reductones.

As the reductone preferably used in the present invention, an ascorbic acid derivative represented by the following general formula [D] is preferable.

[0085]

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In the formula, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkylthio group; R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k is 1, X represents -CO- or -CS-.

In the compound represented by the general formula [D],
R ₁ and R ₂ are bonded to each other to form a ring;
-A] is preferred.

[0088]

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In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, It represents an amide group or a sulfonamide group, Y ₁ represents an oxygen atom or a sulfur atom, and Y ₂ represents an oxygen atom, a sulfur atom or an NR ₄ group.
R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.

The alkyl group in the formula [D] or the formula [Da] is preferably a lower alkyl group, for example, an alkyl group having 1 to 5 carbon atoms, and the amino group is an unsubstituted amino group. Alternatively, an amino group substituted with a lower alkyl group is preferable, an alkoxy group is preferably a lower alkoxy group, and an aryl group is preferably a phenyl group or a naphthyl group. Each of these groups may have a substituent, and as a group that can be substituted, a hydroxyl group,
Preferred are a halogen atom, an alkoxy group, a sulfo group, a carboxyl group, an amide group, a sulfonamide group and the like.

Specific examples of the compound represented by the formula [D] or [Da] are shown below, but it should not be construed that the invention is limited thereto.

[0092]

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[0093]

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The above compounds are typically ascorbic acid, erythorbic acid or derivatives derived therefrom, and are commercially available or can be easily synthesized by known synthesis methods.

Examples of the auxiliary developer having super additivity with the developer represented by the formula [D] include a 3-pyrazolone derivative and a p-aminophenol derivative. Less than,
Specific examples of the auxiliary developer will be given, but the present invention is not limited to these.

1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4'-hydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4, 4'-dimethyl-
3-pyrazolidone, 1-p-tolyl-4, 4'-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-
4'-hydroxymethyl-3-pyrazolidone, N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-amino Phenol, p-benzylaminophenol and the like.

In the method for processing a silver halide photographic light-sensitive material of the present invention, a dihydroxybenzene-based developer may be used in combination. Specific examples include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dibromohydroquinone. The most commonly used is hydroquinone.

The developer of the present invention preferably contains a compound represented by the following general formula (1) and / or general formula (2).

In the general formula (1), R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (eg, methyl, ethyl,
R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (such as a methyl, ethyl, or propyl group), or a carboxyl group.
However, when R ² , R ³ and R ⁴ are alkyl groups, they may be substituted with a hydroxyl group, a carboxyl group or a sulfo group.

In the general formula (2), R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (eg, methyl, ethyl, propyl group, etc.), and M represents a hydrogen atom, an alkali metal Atoms (eg potassium, sodium,
A lithium atom) or an ammonium group, n is 0,
It is an integer selected from 1 and 2. However, when either or both of R ⁵ and R ⁶ are an alkyl group, the alkyl group may be substituted with a carboxyl group or a hydroxyl group.

Preferred specific examples of these compounds are shown below, but the present invention is not limited thereto.

[0102]

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[0103]

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These compounds can be easily synthesized and are easily available as commercial products.

The addition amount of these compounds is preferably 0.001 to 0.5 mol or less per liter of developer.
0.01 to 0.2 mol is more preferred.

In the developer, an organic reducing agent can be used as a preservative in addition to a sulfite as a preservative.
In addition, a bisulfite adduct of a chelating agent or a hardening agent can be used. It is also preferable to add a silver sludge inhibitor. Addition of a cyclodextrin compound is also preferable, and compounds described in JP-A-1-124852 are particularly preferable.

An amine compound other than the general formulas (1) and (2) can be added to the developer.
Compounds described in 69,929 are particularly preferred.

It is necessary to use a buffer in the developing solution. Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate,
Examples include sodium tetraborate, potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium salicylate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfosalicylate, and the like. it can.

Examples of the development accelerator include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, and hydrazine. , Mesoionic compounds, imidazoles and the like can be added as necessary.

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,
Nitrogen-containing heterocyclic compounds such as 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine (typically 1- Phenyl-5-mercaptotetrazole) and the like.

In the developer composition, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, cyclodextrin compound and the like can be used as a solvent for improving the solubility of the developing agent. Furthermore, various additives such as other stain inhibitors, sludge inhibitors, and layering effect promoters can be used.

The fixing solution used in the present invention may contain a compound known as a fixing agent. Further, a fixing agent, a chelating agent, a pH buffer, a hardener, a preservative, and the like can be added. Examples thereof include JP-A-4-242246 (page 4) and JP-A-5-113632 (pages 2 to 4). Those described can be used. In addition, as the hardening agent, a chelating agent described in JP-A-5-289255 (page 20), a bisulfite adduct of the hardening agent described in JP-A-5-289 (page 21), and a known fixing accelerator can be used.

It is preferable to add a starter prior to the treatment. Examples of the starter include an organic acid such as a polycarboxylic acid compound, an alkali earth metal halide such as potassium bromide, an organic inhibitor, a development accelerator and the like. Is used.

In the processing method of the present invention for processing a photographic material, it is preferable that the processing is performed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank.

As a means for supplying the treating agent, when the solid treating agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783 and 63
-97522 and JP-A-1-85732. In the case of granules or powder, the actual opening time is 62-8
1964, 63-84151, JP-A-1-292
375 etc. and the gravity drop method described in
Nos. 59 and 63-195345, etc. can be referred to.

The place where the solid processing agent is charged is in the processing tank, but is preferably interlocked with the processing section for processing the photosensitive material.
Where the processing liquid is flowing between the processing unit,
Further, a structure is preferable in which there is a constant processing liquid circulation amount between the processing section and the dissolved components moving to the processing section. Further, it is preferable that the solid processing agent is introduced into a processing liquid whose temperature is controlled.

In the processing method of the present invention, the total processing time (Dry to Dry) is not particularly limited using an automatic developing machine, but processing is preferably performed for 10 to 90 seconds, preferably 1 to 90 seconds.
5-45 seconds is more preferred. Here, the total development time (Dry
The term "to dry" refers to the period from when the leading edge of the photosensitive material to be processed enters the first transport roller of the film insertion port of the automatic developing machine to when the photosensitive material is discharged from the film discharge port through development, fixing, washing, and drying processes. It's time.

[0118]

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

Example 1 (Preparation of emulsions Em-1 to 3) <Preparation of seed emulsion 1> 60 ° C., pAg = 8, pH = 2.0
Cubic grains of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm were prepared by a double jet method.

The obtained reaction solution was desalted at 40 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and an aqueous solution of magnesium sulfate, and the mixture was reduced and sensitized by adding a reduction sensitizer shown in Table 2 to obtain an aqueous gelatin solution. In addition, it was redispersed to obtain a seed emulsion.

<Preparation of Em-1 type> Using the above seed emulsion, grains were grown as follows. First, the seed emulsion was dispersed in an aqueous gelatin solution kept at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid.

An aqueous solution of ammonium silver nitrate and an aqueous solution of potassium bromide and potassium iodide were added to this solution by a double jet method. During the addition, pAg was controlled to 7.3 and the pH to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, an aqueous ammonium nitrate solution and an aqueous potassium bromide solution were added by a double jet method. PA up to 95% of target particle size
g was maintained at 9.0 and the pH was continuously varied from 9.0 to 8.0. Thereafter, the pAg was adjusted to 11.0 and the pH was adjusted.
It was grown to the target particle size while keeping it at 8.0. Subsequently, the pH was lowered to 6.0 with acetic acid, and the spectral sensitizing dye B described later was added to 4
After adding 00 mg / mol AgX and desalting using an aqueous solution of Demol N manufactured by Kao Atlas Co. and an aqueous solution of magnesium sulfate, a gelatin solution was added and redispersed.

According to this method, a tetrahedral tetrahedron having a vertex having an average silver iodide content of 2.0 mol and an average grain size of 0.65 μm was used.
m, and a monodisperse silver iodobromide emulsion having a coefficient of variation (δ / r) of 0.16 each. This is the Em-1 type.

<Preparation of Seed Emulsion 2> An aqueous solution of silver nitrate and an equimolar aqueous solution of potassium bromide containing gelatin treated with hydrogen peroxide were added to a 0.05 N aqueous solution of potassium bromide containing gelatin treated with hydrogen peroxide which was vigorously stirred at 40 ° C. The mixture was added by a double jet method, and after 1.5 minutes, the liquid temperature was lowered to 25 ° C. over 30 minutes, and then 80 ml of aqueous ammonia (28%) per mol of silver nitrate was added, followed by stirring for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid,
After desalting using an aqueous solution of Demol N manufactured by Kao Atlas Co. and an aqueous solution of magnesium sulfate, reduction sensitization was carried out by adding a reduction sensitizer shown in Table 2, and the resulting mixture was redispersed by adding an aqueous gelatin solution. The resulting seed emulsion had an average particle size of 0.23 μm and a coefficient of variation of 0.
28 spherical particles.

<Preparation of Em-2 type> Using the above seed emulsion, grains were grown as follows. An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by a double jet method to an aqueous solution containing ossein gelatin and propyloxy-polyethyleneoxydisuccinate disodium salt vigorously stirred at 75 ° C. During this time, pH = 5.
8, pAg was kept at 8.5. After the addition is completed, the pH is adjusted to 6.0.
400 mg / mol A of spectral sensitizing dye A described later
gX was added.

After desalting at 40 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd., an aqueous solution of gelatin was added and redispersed. By changing pAg and potassium iodide by this method, the projected area diameter is 1.22 μm, the variation coefficient is 0.25, and the aspect ratio is 3.5 at an average silver iodide content of 0.5 mol%.
To obtain a tabular silver iodobromide emulsion. This was designated as Em-2 type.

<Preparation of Em-3 type> The pAg was changed similarly to the Em-2 type, and the projected area diameter was 1.84 μm.
A tabular silver iodobromide emulsion Em-3 type having a coefficient of variation of 0.29 and an aspect ratio of 7.5 was obtained.

(Chemical sensitization of Em-1 type)
The volume per mole of m-1 type silver halide is 30.
After adding pure water so as to have a volume of 0 ml, the temperature was raised to 50 ° C., 20 g of benzyladenine was added, and 10 minutes later, 0.6 mol of each of the following spectral sensitizing dyes A and B was obtained as a solid fine particle dispersion,
0.006 mol was added, and 10 minutes later, 3 × 10 ⁻³ mol of ammonium thiocyanate was added, followed by addition of appropriate amounts of chloroauric acid and sodium thiosulfate. End of chemical sensitization 60
Minutes before, 4 g of silver iodide fine particles and 2 g of triphenylphosphine selenide dispersion are added, and then an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) is added. , Chemical sensitization was completed.

[0130]

Embedded image

The triphenylphosphine selenide dispersion was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to ethyl acetate 30 at 50 ° C.
It was added to the resulting mixture, stirred and completely dissolved. On the other hand, 3.8 g of photographic gelatin was dissolved in 38 kg of pure water, and a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate 9 was added thereto.
3 g were added. Then, these two liquids are mixed and the diameter 1
Using a high-speed stirring type disperser having a 0 cm dissolver, dispersion was performed at 50 ° C. for 30 minutes at a peripheral speed of the dispersion blade of 40 m / sec. Thereafter, the ethyl acetate was immediately removed under reduced pressure while stirring until the residual concentration of ethyl acetate became 0.3 wt% or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg, and a part of the dispersion thus obtained was fractionated and used.

(Chemical sensitization of Em-2 type and Em-3 type) Chemical sensitization was performed in the same manner as in the Em-1 type.

Emulsion Em- sensitized as described above
Additives described below were added to types 1 to 3 to prepare emulsion layer coating solutions. At the same time, a coating solution for the protective layer was prepared. The coating amount is 2.0 g / g when the silver amount per side is Em-1 type.
m ² , 1.6 g / m ^{2 for} Em-2 type, Em-3
The type is 1.4 g / m ² and the amount with gelatin is 1.
Samples 1 to 23 were obtained by simultaneously coating both surfaces on a support using two slide hopper coaters so that the amount of gelatin applied to the protective layer was 9 g / m ² and the amount of gelatin added to the protective layer was 0.6 g / m ² . . The support was 175 μm thick and had a glycidyl methacrylate of 50 wt.
%, Methyl acrylate 10 wt%, and butyl methacrylate 40 wt%, and the following filter dye and gelatin are dispersed in an aqueous copolymer dispersion obtained by diluting the copolymer to a concentration of 10 wt%. What was applied as an undercoat liquid was used.

Filter dye (solid dispersion)

[0135]

Embedded image

The additives added to the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.0 g 1-phenyl-5-mercaptotetrazole 15 mg

[0138]

Embedded image

Protective Layer Coating Solution The following was prepared as a protective layer coating solution. Additives are shown in amounts per liter of coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2.0 g Sodium-i-amyl-n-decylsulfosuccinate 0.1 g Polymethyl methacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (Mat agent having an area average particle size of 1.2 μm) 0.5 g (CH ₂ ＣＨCHSO ₂ CH ₂ ) ₂ (hardening agent) 500 mg C ₄ F ₉ SO ₃ K 2.0 mg C ₁₂ H ₂₅ CONH (CH ₂ CH) ₂ O) ₅ H 2.0 g

[0141]

Embedded image

A developer and a solid processing agent were prepared as follows.

<Preparation of solid developer α using comparative hydroquinone as a developing agent> Granulated product (A) 3000 g of hydroquinone as a developing agent, 2,000 boric acid
g and 5000 g of sodium sulfite are each ground in a commercially available bantam mill to an average of 10 μm. This fine powder is mixed with pentasodium diethylenetriaminepentaacetate
DTPA-5Na) 300 g, phenidone 500
g, 500 g of sodium erythorbate, 10 g of N-acetyl-D, L-penicillamine, 10 g of 5-nitrobenztriazole, 1.5 g of 1-phenyl-5-mercaptotetrazole, and 100 g of binder mannitol, and mixed in a mill for 30 minutes. After granulating by adding 30 ml of water for about 10 minutes at room temperature in a commercially available stirring granulator, the granulated product is dried at 40 ° C. for 2 hours in a fluidized bed drier to obtain a granulated product. Water is almost completely removed.

Granulated product (B) 11000 g of potassium carbonate, 2000 of sodium bicarbonate
g, glutaraldehyde sodium bisulfite 1000 g
Is ground in a commercially available bantam mill to an average of 10 μm. 100 g of binder mannitol was added to each fine powder, mixed for 30 minutes in a mill, and granulated by adding 30 ml of water at room temperature for about 15 minutes in a commercially available stirring granulator. It is dried at 40 ° C. for 2 hours in a fluidized drier to almost completely remove the water content of the granulated product.

<Preparation of solid developer> The granules (A) and (B) thus obtained were mixed with sodium lauryl sulfate 1
After mixing uniformly for 10 minutes using a mixer in a room conditioned with 00g and 25 ° C., 40% RH or less, the obtained mixture was tough pre-collect 1527 manufactured by Kikusui Seisakusho Co., Ltd.
Filling amount per tablet is 10g using a tableting machine with modified HU
To obtain 18000 hydroquinone-based developed tablets.

<Preparation of solid developer β using reductones of the present invention as a developing agent> Granules (A ₁ ) 500 g of 1-phenyl-3-pyrazolidone, 10 g of N-acetyl-D, L-penicillamine, glutar 1000 g of sodium aldehyde sodium bisulfite are each ground in a commercially available bantam mill to an average of 10 μm. To this fine powder, 300 g of DTPA · 5Na, 300 g of dimezone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone), and 4000 sodium erythorbate
g, sodium sulfite 2000 g, 1-phenyl-5-
After adding 7.0 g of mercaptotetrazole and 400 g of binder mannitol, mixing in a mill for 30 minutes, and granulating by adding 30 ml of water at room temperature for about 10 minutes in a commercial stirring granulator, and then granulating. The material is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated material.

Granules (B ₁ ) 10,000 g of potassium carbonate, 1000 g of sodium bicarbonate
g in a commercially available bantam mill to an average of 10 μm. 800g binder mannitol for each fine powder
After mixing for 30 minutes in a mill and granulating in a commercially available stirred granulator at room temperature for about 15 minutes by adding 30 ml of water, the granulated product is dried in a fluidized drier at 40 ° C. for 2 minutes. After drying for a time, the water content of the granules is almost completely removed.

<Preparation of Solid Developer> The granules (A ₁ ) and (B ₁ ) thus obtained were mixed with 100 g of sodium lauryl sulfate in a room conditioned at 25 ° C. and 40% RH or less. After uniformly mixing for 10 minutes using a machine, the obtained mixture is tough pre-sect collect 152 manufactured by Kikusui Seisakusho Co., Ltd.
7HU modified tableting machine to reduce filling amount per tablet to 10
g, and compression tableting was performed to prepare a developed tablet containing reductone as a main agent.

Both a solid developer β using a reducton machine as a developing agent and a solid developer α using hydroquinone as a developing agent are contained in a pillow bag containing aluminum for moisture proofing.
Enclosed and packaged in liter quantities.

A solid fixing agent was prepared in the following manner.

Granulated product (A ₂ ) Ammonium thiosulfate / sodium thiosulfate (90/1
15000 g, 0,500 g of β-alanine and 4000 g of sodium acetate are each ground in a commercially available bantam mill to an average of 10μ.

The fine powder was mixed with 500 g of sodium sulfite and N
750 g of a ₂ S ₂ O _{5 and} 1300 g of a binder mannitol were added, and the mixture was stirred and granulated with a water addition amount of 50 ml. The granulated product was dried at 40 ° C. with a fluidized bed drier to remove water almost completely.

Granulated product (B ₂ ) 700 g of boric acid, 1500 g of aluminum sulfate / 18-hydrate, and 1200 g of succinic acid are ground in the same manner as in (A2). 200 g of sodium hydrogen sulfate was added to this fine powder, and the amount of water added was 30 ml.
Then, the granulated material is dried at 40 ° C. with a fluidized bed drier to completely remove water.

<Preparation of Solid Fixing Agent> The granules (A ₂ ) and (B ₂ ) thus obtained were mixed with 150 g of sodium lauryl sulfate in a room conditioned at 25 ° C. and 40% RH or less. After the mixture was uniformly mixed for 10 minutes using a mixer, the resulting mixture was tough press collect 1527 manufactured by Kikusui Seisakusho Co., Ltd.
Filling amount per tablet is 10g using a tableting machine with modified HU
And compression tableting was performed to prepare a fixing tablet. this,
The pillow bag containing aluminum for moisture proofing was sealed and packaged in an amount of 3.0 liters.

The developer in the developing tank at the start is 18 for the solid developing tablet α, and 1 for the solid developing tablet β.
Five were diluted with dilution water to make 1 liter. 7.8 liters of the developing solution adjusted in this ratio is supplied to the automatic developing machine SRX.
-201 (manufactured by Konica Corporation), the following starter was added thereto, and the processing was started by filling the developing tank as a starting solution. The starter addition amount was 40 cc / liter.
Twenty-one solid fixing agents were diluted to 1 liter with dilution water. 5.6 liters of the fixing solution adjusted in this ratio was put into a fixing processing tank of the same SRX-201 to be used as a starting solution.

Starter formulation KBr 3.5 g CH ₃ N (C ₂ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 0.05 g Methyl-β-cyclodextrin 5.0 g Sodium metabisulfite Water finish 40cc For both development and fixing, set each packaging bag opened by hand at the inlet of each solid agent, drop the tablets into the built-in chemical mixer, and simultaneously pour warm water (25-30 ° C) and dissolve with stirring. The solution is adjusted to 3.0 liters with a dissolution time of 25 minutes. This was used as a developing and fixing replenisher.

Further, the compounds represented by the general formula (1) or (2) were added to the developing solution in the amounts shown in Tables 2 and 3.

The pH when the developer was dissolved was 10.55 for the hydroquinone-based developer and 10.0 for the reductone-based developer. The dissolution pH of the fixing solution was 4.80.

<Evaluation of Running Stability> Each of the samples prepared above was cut into large-sized pieces, and the entire surface was uniformly exposed so that the optical density after development was 1.0. Processing time 45 seconds, replenishment amount of developer 200m
1000 sheets were run at 1 / m ² . The samples before and after the running process were evaluated for density unevenness by the following method.

Evaluation Criteria 5: Density unevenness is not recognized 4: Density unevenness is slightly observed at the periphery of the film when gazing, but there is no problem in practical use 3: Level is slightly uneven throughout the film when gazing However, there is no problem in practical use 2: Density unevenness clearly occurs at the periphery of the film, and there is a problem in practical use 1: Density unevenness occurs strongly on the entire surface of the film, making it impractical.

<Evaluation of Roller Mark> The optical density was 1.
The film which was uniformly exposed so as to be 0 and which was developed with the processing solution after the running process was visually observed, and evaluated on a 5-point scale based on the following criteria.

Evaluation criteria 5: No pressure spots were observed. 4: When observed, light spots were scattered at the periphery of the film, but at a level where there was no problem in practical use. 3: Light spots were scattered at the center of the film. No problem in practical use 2: Dark spots are scattered around the edge of the film and there is a problem in practical use 1: Dark spots are scattered in the center and the edge of the film, making it impractical.

Tables 2 and 3 show the obtained results.

[0164]

[Table 2]

[0165]

[Table 3]

Tables 2 and 3 show that the light-sensitive material having reduction-sensitized silver halide grains of the present invention has a low replenishment with a developing solution containing reductones as a developing agent, and unevenness in processing occurs before and after running processing in rapid processing. It can be seen that there is no occurrence of roller marks.

[0167]

According to the present invention, a light-sensitive material which is excellent in pressure resistance such as a roller mark by low replenishment rapid processing and free from processing unevenness, and a processing method thereof can be obtained.

Claims (4)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic material, wherein the silver halide emulsion layer contains reduction-sensitized silver halide grains and is processed with a developer containing reductones. 2. The silver halide photographic light-sensitive material according to claim 1, wherein said reduction-sensitized silver halide grains are tabular silver halide grains having an average aspect ratio of 2 or more. 3. A silver halide photographic material characterized in that the silver halide photographic light-sensitive material according to claim 1 or 2 is processed at a replenishment amount of a developing solution of 50 to 200 ml per 1 m ^{2 of the} silver halide photographic light-sensitive material. Processing method of photosensitive material. 4. The method for processing a silver halide photographic material according to claim 3, wherein the developer contains a compound represented by the following general formula (1) and / or general formula (2). Embedded image In the formula, R ¹ represents a hydrogen atom or an alkyl group, and R ² , R ³ ,
R ⁴ independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a carboxyl group. However, when R ² , R ³ and R ⁴ are an alkyl group, the alkyl group is a hydroxyl group,
It may be substituted with a carboxyl group or a sulfo group. Embedded image In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group, M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n is an integer selected from 0, 1, and 2. However, when either or both of R ⁵ and R ⁶ are an alkyl group, the alkyl group may be substituted with a carboxyl group or a hydroxyl group.