JPH08286332A - Processing method for silver halide photosensitive material - Google Patents

Abstract

PURPOSE: To make processing with a developing solution composition which does not need a hydroquinone developing agent possible by containing hydroquinone monosulfonate or its derivative and an auxiliary developing agent indicating superadditivity in a developing solution. CONSTITUTION: In a processing method for a silver halide photosensitive material, hydroquinone monosulfonate or its derivative and an auxiliary developing agent indicating superadditivity are included in a developing solution. As the auxiliary developing agent indicating superadditivity, 1-phenyl-3-pyrazolidone family auxiliary developing agent and p-aminophenol family auxiliary developing agent are listed. As the 1-phenyl-3-pyrazolidone family auxiliary developing agent, 1-phenyl-3-pyrazolidone or 1-phenyl-4-methyl-4-hydroxymethyl-3- pyrazolidone is preferable. As the p-aminophenol family auxiliary developing agent, N-methyl-p-aminophenol is preferable.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method of developing and processing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art Generally, a silver halide photographic light-sensitive material is processed in the steps of developing, fixing, washing with water and drying after exposure. Recently, most of them are processed by using an automatic processor (hereinafter, abbreviated as an automatic processor). The developing step is usually carried out using an alkaline aqueous developer composition containing a polyhydroxybenzene type developing agent typified by hydroquinone. That is, when a sensitized silver halide emulsion is exposed to light, a latent image is formed in the silver halide grains of the emulsion, and the latent image is formed by immersing the exposed emulsion in a developing solution containing the developing agent. By doing so, development processing is performed.
Developers such as hydroquinone provide developed photographic images by reducing the exposed silver halide grains.

A developer composition containing hydroquinone as a developing agent has been used without problems for many years.
Relatively recently, the use of hydroquinone has raised concerns about toxicity and environmental damage. In other words, due to the toxicity brought about by hydroquinone, it is necessary to comply with various legal guidelines and regulations to protect the health of the people who handle this kind of composition and to protect the discharged environment. ing.
Therefore, a component that can substitute for hydroquinone,
It is desirable to find substances that are themselves less toxic.

On the other hand, in an automatic developing machine for automatically developing, fixing, washing with water and drying a photosensitive material, it is necessary to supply a processing solution such as a developing solution and a fixing solution. For example, there is a case where the processing solution is first supplied to an empty processing tank before the start of processing, or a case where the processing solution in the processing tank is reduced by taking out the processing solution by the photosensitive material to be processed. In addition, the automatic developing machine is provided with a passage for the photosensitive material to automatically and sequentially transfer the photosensitive material to each tank for development, fixing, and washing, so that the contact area between each processing solution and air is large. Especially, the roller type automatic developing machine tends to have a large aperture ratio. Here, the opening ratio is a value obtained by dividing the contact area cm ² between the processing liquid and the air in the processing liquid tank portion by the processing liquid amount cm ³ in the processing liquid tank. The aperture ratio of currently used automatic developing machines is generally 0.05 to 0.15.
As described above, so-called deterioration over time due to oxygen oxidation of the developer component such as the developing agent due to oxygen in the air due to the large aperture ratio, and so-called process fatigue due to consumption of the developer or fixer due to the processing of the photosensitive material are caused. A processing solution or a replenishing solution is supplied into the processing tank for recovery.

Conventionally, the replenishment amount required per unit area of the light-sensitive material is generally 300 ml or more per 1 m ² of a so-called sheet-shaped light-sensitive material such as a light-sensitive material for X-ray photography and graphic arts. there were. However, photographic developer wastes, especially photographic developer wastes containing hydroquinone as a developing agent, have high chemical oxygen demands (so-called COD) or biological oxygen demands (so-called BO).
Due to the fact that it has D), it is carried out that the developing waste liquid is chemically or biologically treated to render it harmless before being made into a waste liquid. A great economic burden is imposed on the treatment of these waste liquids.

However, the reduction of the replenishment amount required per unit area of the light-sensitive material reduces the economical burden on the waste liquid treatment, but the treatment liquid stays in the treatment tank for a long period of time, especially in the developing tank. There is a concern that silver eluted from the material may be deposited, stain the processing tank and the roller, and contaminate the image when the photosensitive material is processed.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a development processing method with a developer composition which does not require the incorporation of a hydroquinone developing agent. It is a second object of the present invention to provide a method of developing with a small replenishing amount per unit area of a light-sensitive material. A third object of the present invention is to provide a development processing method which prevents silver stains on the processing tank and rollers of the developing machine.

[0008]

The above objects of the present invention have been achieved by the following items (1) to (3). (1) A method for developing a silver halide photographic light-sensitive material, characterized in that the developing solution contains an auxiliary developing agent which exhibits superadditivity with hydroquinone monosulfonate or its derivative. Processing method of photographic light-sensitive material.

(2) The method for processing a silver halide photographic light-sensitive material described in (1), wherein the developer contains a compound represented by the following general formula (I) and / or (II). . General formula (I)

[0010]

Embedded image

General formula (II)

[0012]

[Chemical 4]

In the formula, R ₄ and R ₅ are each a hydrogen atom,
Represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, R ₆
And R ₇ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. m and n are 0, 1 or 2.
R ₈ represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms. R ₉ represents a group represented by R ₈ or a hydrogen atom. M represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a sulfonyl group, an amino group, an acyl group or an alkoxycarbonyl group.

(3) The silver halide photographic light-sensitive material as described in (1) or (2) above, wherein the replenishing amount of the developing solution is 25 ml or more and 200 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material. Processing method.

The present invention will be described in more detail below. First, the hydroquinone monosulfonate or its derivative contained as a developing agent in the developer of the present invention will be described. The hydroquinone monosulfonate or its derivative contained as a developing agent in the developer of the present invention is preferably a compound represented by the following general formula (III). General formula (III)

[0016]

Embedded image

In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom, an alkyl group, an aryl group, an alkylthio group, a heterocyclic group, an arylthio group, an alkoxy group, an aryloxy group, an amino group, a carbonamido group and a sulfone. It represents an amide group, an alkoxycarbonylamino group, a ureido group, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group, a sulfonyl group, a cyano group, a halogen atom, an acyl group, a carboxy group, a sulfo group or a nitro group. still,
R ₁ and R ₂ may combine to form a ring. M ⁺ is a hydrogen ion or a monovalent or polyvalent counterion. R ₁ and R ₂ are preferably a hydrogen atom, an alkylthio group, an alkoxy group, an aryloxy group, an amide group, a sulfonamide group, an alkoxycarbonylamino group or a ureido group, more preferably a hydrogen atom, an alkylthio group,
Alkoxy group, carbonamide group, sulfonamide group,
It is an alkoxycarbonylamino group or an ureido group.
R ₁ and R ₂ may combine to form a ring.

R ₃ is preferably a hydrogen atom, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group,
It is a sulfonyl group, a cyano group, an acyl group or a heterocyclic group, more preferably a hydrogen atom, a carbamoyl group, an alkoxycarbonyl group, a sulfamoyl group or a cyano group. Specific examples of the hydroquinone monosulfonate or its derivative of the present invention are shown below, but the present invention is not limited thereto.

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

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[0022]

[Chemical 9]

Next, the auxiliary developing agent exhibiting superadditivity of the present invention will be described. Examples of the auxiliary developing agent exhibiting superadditivity include 1-phenyl-3-pyrazolidones auxiliary developing agents and p-aminophenols auxiliary developing agents.
As 1-phenyl-3-pyrazolidones auxiliary developing agents, 1-phenyl-3-pyrazolidone and 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-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 and the like. Of these, 1-phenyl-3-pyrazolidone or 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone is preferable.

P-aminophenols auxiliary developing agents include N-methyl-p-aminophenol and N- (β-
Hydroxyethyl) -p-aminophenol, N- (4
-Hydroxyphenyl) -glycine, 2-methyl-p-
There are aminophenol, p-benzylaminophenol and the like, and among them, N-methyl-p-aminophenol is preferable.

The amount of the auxiliary developing agent exhibiting superadditivity together with the developing agent of hydroquinone monosulfonate or its derivative of the present invention is 0.01 mol / liter to 0.6 mol / liter for the former and 0. It is preferably used in an amount of 001 mol / l to 0.1 mol / l, especially the latter of 0.005 mol / l to 0.06.
It is preferably used in an amount of mol / liter.

The development processing solution of the present invention contains substantially no hydroquinone. Here, the term "substantially free from" means preferably 0.0001 mol / liter or less, and most preferably free.

Next, the compound represented by the general formula (I) or the general formula (II) contained in the developing solution of the present invention will be described. General formula (I)

[0028]

[Chemical 10]

General formula (II)

[0030]

[Chemical 11]

In the formula, R ₄ and R ₅ are each a hydrogen atom,
An alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl,
i-propyl) or a phenyl group, and R ₆ and R ₇ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (eg, methyl, ethyl, i-propyl). m and n
Are 0, 1 or 2, respectively. R ₈ is a hydroxyl group, an amino group [eg, unsubstituted amino, acylamino group (eg, acetylamino), alkylamino group (eg, dimethylamino), alkylsulfonylamino group (eg, methanesulfonylamino), arylsulfonylamino group (eg, Phenylsulfonylamino)] or an alkyl group having 1 to 3 carbon atoms (for example, methyl, ethyl, i
-Propyl). R ₉ represents a group represented by R ₈ or a hydrogen atom. M represents a hydrogen atom, an alkali metal atom or an ammonium group. X is a hydrogen atom and has 1 to 3 carbon atoms
Alkyl group (for example, methyl, ethyl, i-propyl), sulfonyl group (for example, methanesulfonyl), amino group [for example, unsubstituted amino, acylamino group (for example, acetylamino), alkylamino group (for example, dimethylamino), An alkylsulfonylamino group (for example,
Methanesulfonylamino), an arylsulfonylamino group (eg phenylsulfonylamino)], an acyl group (eg acetyl, propionyl) or an alkoxycarbonyl group (eg acetoxy, methoxycarbonyl, ethoxycarbonyl).

The concentration of the compound of the general formula (I) or (II) of the present invention in the developing solution is preferably 0.01 mmol / liter to 50 mmol / liter, more preferably 0.05 mmol / liter to It is 10 mmol / liter, particularly preferably 0.1 mmol / liter to 5 mmol / liter.

The processing method of the present invention is effective for the processing using an automatic processor, and the presence of the compound of the general formula (I) or (II) of the present invention in the developing solution at the above concentration It is possible to prevent silver stains on the development processing tank and rollers of the automatic processor.

Specific examples of the compound represented by formula (I) or formula (II) that can be used in the present invention are shown below, but the present invention is not limited thereto.

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

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The developer used in the present invention may contain an amino compound for promoting development. In particular, JP-A-56-1
06244, JP-A-61-267759, JP-A-2
The amino compound described in -208652 may be used.
The pH of the developer used in the present invention is 8.0 to 13.0, preferably 9.0 to 12.5, and more preferably 10.0 to 12.0.

The alkaline agent used for setting the pH of the developing solution used in the present invention is a usual water-soluble inorganic alkali metal salt (eg sodium hydroxide, sodium carbonate).
Can be used. The developer of the present invention may further contain a pH buffering agent such as dibasic sodium phosphate, dibasic potassium phosphate, monobasic sodium phosphate and monobasic potassium phosphate, and a pH buffering agent described in JP-A-60-93433. Agents can be used. The addition amount of the alkaline agent or the pH buffering agent used for setting the pH value of the developing solution of the present invention is 0.01
Mol / l or more and preferably 1.8 mol / l,
Particularly, it is preferably 0.1 mol / liter or more and 1 mol / liter or less.

Examples of sulfite-based preservatives that can be used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite. Sulfite is 0.01 mol / liter or more, especially 0.02 mol / liter
It is preferably used in an amount of liter or more and 2.5 mol / liter or less. The developer of the present invention may contain ascorbic acid or / and a derivative thereof in addition to the sulfite preservative. Preferred is ascorbic acid or erythorbic acid (a diastereomer of ascorbic acid). The amount of ascorbic acid or / and its derivative used is generally in the range of 5 × 10 ⁻³ mol / liter to 1 mol / liter, particularly preferably 5 × 10 ⁻² mol / liter to 0.5.
Mol / liter. In addition, L. F. A. Mason's "Photographic Processing Chemistry" published by Focal Press (1966) 226-2
29, US Pat. No. 2,193,015, US Pat. No. 2,592,364, and JP-A-48-64933 may be used.

In the developer used in the present invention, in addition to the above amino compounds and alkali agents, development inhibitors such as potassium bromide and potassium iodide, organic compounds such as dimethylformamide, methyscellosolve, ethylene glycol, ethanol and methanol. An antifoggant such as a solvent, 5-methylbenztriazole, 5-chlorobenztriazole, 5-bromobenztriazole, 5-butylbenztriazole or benztriazole may be added.

If necessary, a toning agent, a surfactant, a water softener, a hardener, etc. may be added. As the chelating agent in the developing solution, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid. Acetic acid, hydroxyethyliminodiacetic acid,
1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1- Hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,
2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,3,3-tricarboxylic acid, catechol-3,4-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be mentioned. However, particularly preferably diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid,
2-phosphonobutane-1,2,4-tricarboxylic acid,
1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonone Acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

The developing solution of the present invention can be used as a concentrated solution in order to reduce transportation costs and storage space. In the case of using a concentrated solution, it is preferably 3 times or less, more preferably 2 times or less, for the purpose of preventing precipitation of the developer component at a low temperature. Further, components having different solubilities may be divided into some parts and stored, and may be mixed and diluted before use.

The replenishing amount of the developer of the present invention is 200 ml or less and 25 ml or more, preferably 180 ml or less and 30 ml or more per 1 m ² of the light-sensitive material as a diluted developer.
More preferably, it is 150 ml or less and 60 ml or more.

In the processing of the present invention, the photosensitive material which has undergone the development processing is subjected to the fixing processing. Next, the fixing solution in the processing of the present invention will be described. The fixing solution in the processing of the present invention contains a thiosulfate such as sodium thiosulfate and ammonium thiosulfate as a commonly used fixing agent, but sodium thiosulfate is preferably used in view of environmental problems. The content of the thiosulfate contained in the fixing solution in the processing of the present invention is 0.1 mol / liter or more and 3 mol / liter or less, preferably 0.3 mol / liter or more and 1.5 mol / liter or less. Is.

If desired, the fixing solution may include a hardening agent (eg, aluminum chloride, aluminum sulfate, water-soluble aluminum such as potassium alum), a preservative (eg, sulfite, bisulfite, etc.), and a pH buffer (eg, Acetic acid, boric acid, etc., pH adjusters (eg, ammonia, sulfuric acid, etc.), chelating agents, surfactants (eg, anionic surfactants such as sulfonates, polyethylene type surfactants, JP-A-57-6804).
Amphoteric surfactants, etc.), wetting agents (eg alkanolamines, alkylene glycols, etc.), fixing accelerators (eg JP-B-45-35754, JP-B-58-12).
No. 2535, Japanese Patent Publication No. 58-122536, thiourea derivatives, alcohols having a triple bond in the molecule, thioether compounds described in US Pat. No. 4,126,459, JP-A-4-143755, JP-A-4-143756, JP-A-4-143756. 4-143757, mesoionic compounds described in JP-A-4-170539 and the like) can be included.

In the fixing solution in the processing of the present invention, tartaric acid, citric acid, gluconic acid or their derivatives may be used alone or in combination of two or more in addition to the above compounds. The fixer used in the process of the present invention has a pH of 3 or higher,
It is preferably 4.2 to 6.3. The fixing processing temperature and the fixing processing time in the fixing processing in the processing of the present invention are preferably about 20 ° C. to 50 ° C. and 5 seconds to 1 minute.

The fixing solution used in the process of the present invention can be a concentrated solution in order to reduce transportation costs and storage space. In the case of using a concentrated solution, it is preferably 3 times or less for the purpose of preventing precipitation of the fixer component at low temperature, and further 2
It is more preferably equal to or less than twice. Further, components having different solubilities may be divided into some parts and stored, and may be mixed and diluted before use.

In the processing of the present invention, the replenishing amount of the fixing solution is 200 ml or less per 1 m ² of the light-sensitive material as a diluted fixing solution.
5 ml or more, preferably 180 ml or less 30 ml
It is above, and more preferably 150 ml or less and 60 ml or more.

In the present invention, when the supply of the developing solution and the fixing solution is the concentrated developing solution and the concentrated fixing solution, they are diluted with the used solution and used as a replenishing solution or a mother solution. As a method of diluting, a prediluted diluted developing solution and diluted fixing solution may be added to the developing tank and the fixing tank, respectively.
It is preferable that each of the concentrated developing solution and the concentrated fixing solution and water are diluted into a working solution in each tank and supplied as a replenishing solution (direct mixing dilution system). When the chemical mixer is incorporated in the automatic developing machine, it is preferable that the automatic developing machine has a mechanism in which the cartridges of the developing solution and the fixing solution are used up at the same time.

In the processing method of the present invention, after the development and fixing steps, the solution is treated with washing water or a stabilizing solution and then dried. The washing water used in the present invention may be preferably pretreated by removing dust and organic substances existing in water through a filter member or a filter of activated carbon as a pretreatment.

Japanese Unexamined Patent Publication No. Sho 60, which is known as an anti-fungal means.
UV irradiation method described in US Pat.
No. 0-263940, the method using a magnetic field, the method described in JP-A No. 61-131632 to make pure water using an ion exchange resin, and the ozone described in JP-A No. 4-151143 while blowing ozone. A method of circulating a filter and an adsorbent column, a method of microbial decomposition described in JP-A-4-240636, and JP-A-62-115.
154, JP-A-62-153952, JP-A-62-1952
220951 and the method using a bacteriostatic agent described in JP-A No. 62-209532 can be used in combination.

Furthermore, M. W. Each, "Mic
robotic Groths in Mo
"tion-picture Processing"
SMPTE Journal Vol. 85 (197
6), R. O. Deegan, “Photo Proc
essing Wash Water Biocade
s "J. Imaging Tech. Vol. 10,
No. 6 (1984) and JP-A-57-8542, JP-A-57-58143, and JP-A-58-105145.
JP-A-57-132146, JP-A-58-186
31, JP-A-57-97530, JP-A-57-25
Antibacterial agents, antifungal agents, surfactants and the like described in 7244 can be used in combination as necessary.

If necessary, the washing bath (or stabilizing bath) may be R. T. Kreiman, J. Image
e. Tech. Vol. 10, No. The isothiazoline compounds described in 6,242 (1984),
Bromochlorodimethylhydantoin, Research
Disclosure Volume 205, No. 20526
(May 1981, May issue), Research Disc
Loss Volume 228, No. 22845 (1983
The isothiazoline-based compounds described in JP-A-62-209532 and the like can be used in combination as a bacteriostatic agent.

In addition, Hiroshi Horiguchi, "Science and Antibacterial Science",
Compounds such as those described in Mitsui Shuppan (1982), "Handbook of Antibacterial and Antibacterial Technology", Japan Society for Antibacterial and Antibacterial Agent, Hakuhodo (1986) may be included. As the automatic developing machine that can be used in the present invention, it is preferable to use an automatic developing machine in which a solenoid valve is installed at the drain port of the washing tank as a measure for preventing water stains on the washing tank.

The photosensitive material which has been developed, fixed and washed (or stabilized) is squeezed out of the washing water, that is, dried through a squeeze roller. The drying is carried out at about 40 ° C. to about 100 ° C., and the drying time is appropriately changed depending on the ambient conditions, but it is usually about 5 seconds to 3 minutes, particularly preferably 40 to
It is about 5 seconds to 2 minutes at 80 degreeC.

As the automatic developing machine used in the present invention, various types of automatic developing machines such as a roller carrying type and a belt carrying type can be used, but a roller carrying type developing machine is preferable.
Further, a developing machine of a developing tank having a small opening ratio as described in JP-A No. 1-193853 is preferable, and the opening ratio is 0.1.
04 or less and 0.01 or more are preferable, and the aperture ratio is 0.0
3 or less and 0.01 or more are preferable, and especially the aperture ratio is 0.025.
The most preferable is an automatic developing machine having a developing tank of 0.01 or more. As a result, air oxidation of the developing agent and the like and evaporation of water are small, and the replenishment amount can be reduced. Under the processing environment, the washing water is squeezed out, that is, dried through a squeeze roller. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time may be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 3 minutes, particularly preferably about 40 ° C. to 80 ° C.
Seconds to 2 minutes.

Next, a silver halide photograph used in the present invention
The photosensitive material will be described. Halogen used in the present invention
The amount of silver contained in the silver halide photographic light-sensitive material depends on both sides of the support.
Of 4.0g / m²The following is good. In the photosensitive material
Silver amount is 4.0g / m ²More is one of the purposes of the present invention
Reduction to a certain environmental load will not be achieved. Both sides of the support
The total amount of silver contained on the side is preferably 3.6 g / m
²1.5g / m or less²Above, especially 3.2 g / m²
2 g / m or less²The above is more preferable.

The photographic light-sensitive material used in the present invention may optionally contain a hydrophilic colloid layer in addition to the silver halide photographic light-sensitive layer, and it is preferable to provide a surface protective layer according to a known method. . ^{2. The} amount of gelatin on the side having the hydrophilic colloid layer including the emulsion layer is 2.0 g / m ² or more.
It is preferably in the range of less than 2 g / m ² , particularly 2.
It is desirable to be in the range of ² g / m ² or more and less than 3.0 g / m ² . The melting time of the photographic light-sensitive material used in the present invention is preferably set to 20 minutes or more and 100 minutes or less. Here, the measuring method of the melting time is according to the method described in JP-A-62-221341.

The hydrophilic colloid layer of the photographic light-sensitive material used in the present invention has a swelling ratio in water of 100% or more and less than 300%, particularly 150% or more and 25% by a known hardening agent.
It is preferably set to 0% or less. Here, the swelling rate has the same definition as described in JP-A-58-111933.

Next, the emulsion grains of the silver halide photographic light-sensitive material used in the present invention will be described. The silver halide emulsion containing at least the dispersion medium and the silver halide grains of the silver halide photographic light-sensitive material used in the present invention preferably has a Cl ^- content of 20 to 100 mol%, preferably 30 to 100 mol%.
100 mol%, more preferably 40 to 100 mol%, further preferably 50 to 100 mol% of a silver halide emulsion, and 50% or more of the total projected area of the silver halide grains,
Preferably 60% to 100%, more preferably 70 to 1
Tabular grains having a major plane of (100) or (111) planes of 00%. Here, the tabular grains are grains having an aspect ratio (diameter / thickness) larger than 1. The principal plane refers to the maximum outer surface of tabular grains. The thickness of the tabular grains is 0.35 μm or less, more preferably 0.05 to 0.3 μm, still more preferably 0.05 to 0.25 μm. The average aspect ratio is 2 or more, preferably 2 to 25, more preferably 5 to 20. Here, the diameter means the diameter of a circle having an area equal to the projected area of the tabular grains, and the thickness means the distance between two principal planes. The average aspect ratio is the average aspect ratio of all tabular grains.

Among the emulsions of the present invention, the nucleation of the emulsion having the (111) plane as the principal plane is described in JP-B-64-8326.
No. 64-8325, No. 64-8324, JP-A No. 1-250943, Japanese Patent Publication No. 3-14328, Japanese Patent Publication No. 4-81782, Japanese Patent Publication No. 5-40298, 5-3.
No. 9459, No. 5-12696 and JP-A-63-213.
No. 836, No. 63-218938, No. 63-2811
49, JP-A-62-218959 and the like, and as the prior art of tabular grains having a (100) plane as the main plane, JP-A-5-204073 and 51- 88017, JP-A-63-24238,
It is described in Japanese Patent Application No. 5-264059.

In the present invention, any of the nucleation methods described in these prior arts can be used.
The method of crystal growth of the present invention by physical ripening in the presence of fine silver halide grains (fine grains are dissolved and substrate grains grow) is described below. In the fine grain emulsion addition method, it is 0.
An AgX fine grain emulsion having a diameter of 15 μm or less, preferably 0.1 μm or less, more preferably 0.06 to 0.006 μm is added, and the tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or continuously. Fine grain emulsion is AgNO in mixer provided in the vicinity of the reaction vessel ₃ solution and X ^-
The salt solution may be supplied and continuously prepared, and then immediately added continuously to the reaction vessel, or may be previously prepared in a batch manner in another vessel and then continuously or continuously added. The fine grain emulsion can be added in a liquid form or as a dry powder. It is also possible to mix the dry powder with water immediately before addition to liquefy it and add it. The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes. If the disappearance time becomes long, ripening occurs between the fine particles and the particle size becomes large, which is not preferable. Therefore, it is preferable not to add the entire amount at once. It is preferable that the fine particles are substantially free of twinned grains. Here, the multi-twin grain means a grain having two or more twin planes per grain. The term "substantially free" means that the number ratio of multiple twinned grains is 5% or less, preferably 1% or less, more preferably 0.1% or less. Further, it is preferable that substantially no single twin crystal grains are contained. Furthermore, it is preferable that the screw dislocation is not substantially contained. Here, the term "substantially free" is in accordance with the above-mentioned rules.

The halogen composition of the fine particles is AgCl, Ag
Br, AgBrl (I ^- content is preferably 10 mol% or less, more preferably 5 mol% or less) and a mixed crystal of two or more thereof. For other details, see Japanese Patent Application No. 4-2141.
The description of No. 09 can be referred to. The total amount of fine grains added should be 20% or more of the total amount of silver halide.
It is preferably 40% or more, and more preferably 50% or more and 98% or less. The Cl content of the fine particles is preferably 10% or more, more preferably 50% or more and 100% or less.

As a dispersion medium for nucleation, ripening and growth, a conventionally known dispersion medium for an AgX emulsion can be used, but the methionine content is preferably 0 to 50 μmol / g, more preferably 0. -30 μmol / g gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. In addition, Japanese Patent Publication Sho 52
-16365, Journal of the Photographic Society of Japan, Volume 29 (1), 1
7, 22 (1966), Volume 30 (1), 10, 19
(1967), Volume 30 (2), 17 (1967)
1), 33 (3), 24 (1967). The pH during growth due to addition of fine particles needs to be 2.0 or higher, but is preferably 6 or higher and 10 or lower. More preferably p
It is H6 or more and 9 or less. Further, pCl needs to be 1.0 or more, but 1.6 or more is preferable. It is more preferably 2.0 or more and 3.0 or less. These growth conditions are particularly preferable for tabular grains having the (100) plane as the main plane. Here pCl and the activity of Cl ions in the solution ^- to pCl = -log [Cl] ^- defined by [Cl]. THJames THE THEORY OF THE RHOTO
It is described in detail in Chapter 1 of the GRAPHIC PROCESS, 4th Edition.

When the pH is 2.0 or less, for example, in the case of tabular grains having the (100) plane as the principal plane, lateral growth is suppressed and the aspect ratio is lowered, so that the emulsion covering power is reduced. Tends to be low, and the sensitivity becomes low. When the pH is 2.0 or more, the growth rate in the lateral direction becomes high, an emulsion having a high aspect ratio and a high covering power can be obtained, but fog is high and desensitization is likely to occur. p
When Cl is 1.0 or less, growth in the vertical direction is promoted, the aspect ratio is lowered, the covering power of the emulsion is low, and the sensitivity is lowered. When pCl is 1.6 or more, the aspect ratio is increased and the covering power is increased, but fog is high and the sensitivity is easily lowered. At this time, when the substrate particles are grown with silver halide fine particles, the fog is low even if the pH is 6 or more and / or the pCl is 1.6 or more, and the feeling is high and the aspect ratio is high and the covering power is high.

Regarding the monodispersity of the emulsion of the present invention, when considering the monodispersity based on the coefficient of variation defined by the method described in JP-A-59-745481, it is preferably 30% or less and 5% or more and 25% or more. % Or less is preferable. Particularly when used for a sensitive material having a high contrast, it is preferably 5% or more and 15% or less.

Selenium, which is the preferred sensitization method in the present invention,
Tellurium sensitization is described. These may be used alone or in combination. Particularly preferred examples of use and compounds of these are described in, for example, JP-A-3-116132,
No. 5-113635, No. 5-165136, No. 5-
165137, 5-134345 and the like. As particularly preferred selenium sensitizers, for example, compounds represented by the general formula (I) or (II) of JP-A-5-165137 and compound examples I-1 to I-20, II- described therein 1-II-19
Can be mentioned. Regarding the tellurium sensitizer, it is disclosed in Japanese Patent Laid-Open No. H5-
-134345 Compounds represented by general formulas (IV) and (V) and compound examples IV-1 to IV-2 described therein
2 and V-1 to V-16 can be mentioned.

For forming the tabular grains containing silver chloride of the present invention, JP-A-4-139439 and JP-A-4-139 are used.
440, Japanese Patent Laid-Open No. 4-139441 and US Pat.
Nucleation and growth can be preferably carried out by adding a halogen aqueous solution and a silver nitrate aqueous solution to the reaction vessel immediately before mixing using an apparatus such as a multiple coaxial nozzle described in No. 04,786. There are no particular restrictions on various additives used in the light-sensitive material of the present invention, and for example, those described in the following relevant parts of JP-A-2-68539 can be used. Item This section 1. Silver halide emulsion and JP-A-2-68539, page 8, lower right column, lower column, 6 from its manufacturing line, to page 10, upper right column, 12th column. 2. Chemical sensitization method, page 10, upper right column, line 13 to lower left column, line 16 3. Antifoggant / stabilization, page 10, lower left column, line 17 to page 11, upper left column, line 7 agent, and page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. 5. Surfactant / antistatic, page 11, upper left column, line 14 to page 12, upper left column, line 9 antistatic agent. 6. Matting agent / slip agent ・ From page 12, upper left column, line 10 to upper right column, line 10 Plasticizer, page 14, lower left column, line 10 to lower right column, line 1 7. Hydrophilic colloid, page 12, upper right column, line 11 to lower left column, line 16 8. Hardener, page 12, lower left column, line 17 to page 13, upper right column, line 6 9. Support, page 13, upper right column, lines 7 to 20. 10. Dyes / mordanting agents, page 13, lower left column, line 1 to page 14, lower left column, line 9

As a method of forming an image using the light-sensitive material of the present invention, a method of forming an image in combination with a phosphor having a main peak at 400 nm or less is preferable.
More preferably, a method of forming an image by combining with a phosphor having a main peak at 380 nm or less is preferable. 400 nm
Below, the screen having the main emission peak is described in JP-A-6-11.
The screens described in No. 804 and WO93 / 01521 are used, but not limited to them.

There are no particular restrictions on the photographic light-sensitive material used in the development processing method of the light-sensitive material of the present invention, and general black-and-white light-sensitive materials are mainly used. In particular, it is used for photographic materials for laser light sources, printing sensitive materials, medical direct photographing X-ray sensitive materials, medical indirect photographing X-ray sensitive materials, CRT image recording sensitive materials, microfilm, general photographing sensitive materials and the like. You can also The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

[0072]

【Example】

Example 1 Preparation of (100) tabular emulsion A 1582 ml of gelatin aqueous solution (gelatin-1) was placed in a reaction vessel.
(Deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 19.5 g, HNO ₃ 1N liquid 7.
Containing 8 ml, pH 4.3, NaCl-1 solution (100 ml)
13 ml of NaCl (containing 10 g) was added and the temperature was adjusted to 4
While keeping the temperature at 0 ° C, Ag-1 solution (100 mL of AgNO
₃ including 20 g) and X-1 solution (NaCl in 100ml
(Including 7.05 g) was simultaneously mixed and added at 62.4 ml / min in 15.6 ml portions. After stirring for 3 minutes, Ag-2 solution (1
AgNO ₃ containing 2g) and X-2 solution in 100 ml (100
1.4g of KBr in ml) 80.6ml / min 2
Simultaneous mixing of 8.2 ml each. After stirring for 3 minutes, Ag-
Solution 1 and solution X-1 were simultaneously mixed and added at a rate of 62.4 ml / minute and 46.8 ml each. After stirring for 2 minutes, gelatin aqueous solution 20
3 ml (gelatin-113 g, NaCl 1.3 g, pH
(Including NaOH 1N solution to obtain 6), pCl
Was set to 1.8, the temperature was raised to 75 ° C., pCl was set to 1.8, and the mixture was aged for 42 minutes. AgCl fine grain emulsion (average grain diameter 0.1 μm) was 2.68 × 10 ⁻² mol /
The addition rate was 1 minute AgCl for 20 minutes. 10 after addition
After aging for a minute, a precipitating agent was added and the temperature was lowered to 35 ° C.
The precipitate was washed with water. Add gelatin aqueous solution, pH at 60 ℃
Adjusted to 6.0. A transmission electron micrograph image (hereinafter referred to as TEM) of the particle replica was observed. The obtained grains were high silver chloride (100) tabular grains containing 0.44 mol% of AgBr based on silver. The shape characteristic values of the particles were as follows. (Total projected area of tabular grains having an aspect ratio larger than 1 / sum of projected areas of all AgX grains) × 100 = a ₁ = 90% (average aspect ratio (average diameter / average thickness) of tabular grains) = a ₂ = 9.3 (average diameter of the tabular grains) = a ₃ = 1.67 .mu.m (average thickness) = a ₄ = 0.18 .mu.m

(111) Preparation of Tabular Emulsion B Silver chloride tabular grains were prepared as follows.

[0074]

[Chemical 15]

[0075]

Solution (2) and solution (3) were simultaneously added to solution (1) kept at 35 ° C. with stirring over 1 minute,
The temperature of the solution was raised to 50 ° C over 15 minutes. At this point, grains corresponding to about 5.7% of total silver were formed. Next, the solution (4) and the solution (5) were simultaneously added over 24 minutes, and the solution (6) and the solution (7) were simultaneously added over 40 minutes to obtain a silver chloride tabular emulsion. The emulsion was washed with water and desalted by the precipitation method, and then 30 g of gelatin and H ₂
O was added, and further 2.0 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener.
Was added and redispersed with caustic soda to pH 6.0. The emulsion thus obtained had a ₁ = 90% and a ₃ =
It is a silver chloride tabular emulsion having a (111) plane as the main plane with 1.55 μm, a ₄ = 0.18 μm, a ₂ = 8.6, and a coefficient of variation of projected area diameter corresponding to circle of 19%.

Preparation of Tabular Emulsion C 4.5 g of potassium bromide, 1.5 g of potassium chloride, and low molecular weight gelatin having an average molecular weight of 15,000 in 1 liter of water 7.
0 g of the solution was added to a container kept at 55 ° C. while stirring, and 37 cc of an aqueous solution of silver nitrate (4.00 g of silver nitrate) and 38 cc of an aqueous solution containing 5.9 g of potassium bromide were added in 37 seconds by the double jet method. Next, after adding 18.6 g of gelatin, the temperature was raised to 70 ° C. and 89 cc of silver nitrate aqueous solution (9.80 g of silver nitrate) was added over 22 minutes. 25% here
Add 7 cc of ammonia aqueous solution at 10 at the same temperature
After physically ripening for minutes, 6.5 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 153 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the pAg at 8.5. Next, 15 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C.
a ₁ = 95%, average projected area diameter a ₃ = 1.50 μm,
Thickness a ₄ = 0.185 μm, average aspect ratio a ₂ =
8.1, variation coefficient of diameter 18.5%, silver chloride content 24%
To obtain monodispersed silver chlorobromide tabular grains. After this, the soluble salts were removed by the sedimentation method. The temperature was raised to 40 ° C. again, and 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener.
Was added, and the pH was adjusted to 5.90 with a caustic soda solution and a silver nitrate solution.
It was adjusted to Ag 8.00.

Chemical Sensitization The particles A to C prepared as described above were heated to 60 ° C. with stirring.
Chemical sensitization was carried out while maintaining. First, thiosulfonic acid
Compound-I was added in an amount of 10 per mol of silver halide.^-FourMolar addition
Then, add AgBr fine particles with a diameter of 0.10 μm to the total silver amount.
1.0 mol% with respect to
1 × 10^-6Add mol / mol Ag and hold for 22 minutes
I had it and gave reduction sensitization. Next, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetraazaindene 3 ×
10^-FourMol / mol Ag and sensitizing dyes-1, 2 respectively
Added Further calcium chloride was added. Continue to
Sodium sulphate (6 x 10^-6Mol / mol Ag) and
Ren compound-I (4 x 10 ^-6Mol / mol Ag)
Was. Chloroauric acid 1 × 10^-FiveMol / mol Ag and chi
Potassium cyanate 3.0 x 10^-3Mol / mol Ag
After 40 minutes, the mixture was cooled to 35 ° C. Thus the emulsion tone
The production (chemical aging) was completed.

[0079]

Embedded image

(Preparation of emulsion coating layer) An emulsion coating solution was prepared by adding the following chemicals to 1 mole of silver halide to the chemically sensitized emulsion.・ Gelatin (including gelatin in emulsion) 111 g ・ Dextran (average molecular weight 39,000) 21.5 g ・ Sodium polyacrylate (average molecular weight 400,000) 5.1 g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.2 g-Hardener 1,2-bis (vinylsulfonylacetamide) ethane Addition amount is adjusted so that the swelling rate is 230% -Compound-I 42.1 mg-Compound-II 10.3 g-Compound-III 0.11 g- Compound-IV 8.5 mg-Compound-V 0.43 g-Compound-VI 0.004 g-Compound-VII 0.1 g-Compound-VIII 0.1 g pH adjusted to 6.1 with NaOH

[0081]

[Chemical 17]

[0082]

Embedded image

With respect to the above coating solution, ultraviolet absorbing dye-I-
Dye emulsion A was added so that III was 10 mg / m ^{2 on} each side.

[0084]

[Chemical 19]

(Preparation of Dye Emulsion A) The above Dyes-I to II
20 g of each I and 62.
8 g, 62.8 g of -II and 60 g of 333 g of ethyl acetate.
Melted at ° C. Next, 65 cc of a 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 cc of water were added, and the mixture was emulsified and dispersed by a dissolver at 60 ° C. for 30 minutes.
Next, 2 g of the following compound-IX and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, using Asahi Kasei's ultrafiltration laboratory module ACP1050, the total amount was concentrated to 2 kg, and 1 g of the compound-IX was added to obtain a dye emulsion A.

[0086]

Embedded image

(Preparation of Coating Solution for Surface Protective Layer) A coating solution for surface protective layer was prepared so that each component had the following coating amount.・ Gelatin 0.780 g / m ²・ Sodium polyacrylate (average molecular weight 400,000) 0.035 ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 0.0012 ・ Polymethyl methacrylate (average particle size 3.7 μm) 0.036 ・ Polymethyl methacrylate / styrene / Methacrylic acid copolymer (copolymerization ratio 70/20/10 mol%) (average particle size 3.7 μm) 0.036 ・ Coating aid-I 0.020 ・ Coating aid-II 0.037 ・ Coating aid-III 0.0080 ・ Coating aid Agent-IV 0.0032 ・ Coating aid-V 0.0025 ・ Coating aid-VII 0.0022 ・ Proxel 0.0010 (pH adjusted to 6.8 with NaOH)

[0088]

[Chemical 21]

(Preparation of Support) Biaxially Stretched Thickness 17
Corona discharge was performed on a polyethylene terephthalate film having a thickness of 5 μm, and a first undercoating liquid having the following composition was applied by a wire converter so that the applied amount was 4.9 cc / m ^2, and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.06 wt% of dye-IV and 0.06 wt% of dye-V.

[0090]

[Chemical formula 22]

-Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 cc-2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 cc・ Distilled water 801 cc * The latex solution contains the following compounds as an emulsifying dispersant in an amount of 0.4 wt% of the latex solids.

[0092]

[Chemical formula 23]

(Preparation of Photographic Material) The above-prepared support was combined with the above emulsion layer and surface protective layer and coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . In this way, the samples shown in Table 1 were prepared.

[0094]

[Table 1]

Fuji Photo Film Co., Ltd. was used as the photographic material of Table 1.
The orthoscreen HR-4 manufactured by Kabushiki Kaisha was adhered to both sides using a cassette, and exposed for 0.05 seconds from both sides, and X-ray sensitometry was performed. The exposure amount was adjusted by changing the distance between the X-ray tube and the cassette. After exposure, Fuji Photo Film Co., Ltd. automatic processor CEPR
Using OS-30, the replenishing amount was modified to replenish the developing replenisher and the fixing replenisher with 103 ml per 1 m ² of the light-sensitive material, and 30 sheets were processed every day at the temperature and time shown below to run for about one month. Then, sensitometry before and after running was obtained. Process Temperature Treatment time Current image 35 ° C 8.8 seconds Settling 32 ° C 7.7 seconds Water washing 17 ° C 3.8 seconds Squeeze 4.4 seconds Dry 58 ° C 5.3 seconds Total -30 seconds (concentration Preparation of developer) <Developer> Part agent A potassium hydroxide 330 g potassium sulfite 630 g sodium sulfite 255 g potassium carbonate 90 g boric acid 45 g diethylene glycol 180 g diethylenetriaminepentaacetic acid 30 g 1- (N, N-diethylamine) Ethyl-5-mercaptotetrazole 0.75 g Developing agent listed in Table 2 Amount listed in Table 2 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone Amount listed in Table 2 Water added 4125 ml

Parts agent B Diethylene glycol 525 g Compound shown in Table 2 Amount shown in Table 2 Glacial acetic acid 102.6 g 2-Nitroindazole 3.75 g 1-Phenyl-3-pyrazolidone 34.5 g Water 750 ml

Parts agent C Glutaraldehyde (50 wt / wt%) 150 g Potassium bromide 15 g Potassium metabisulfite 105 g Water 750 ml

[0098]

[Table 2]

<Fixer> Ammonium thiosulfate (70 wt / vol%) 3000 ml Ethylenediaminetetraacetic acid / disodium dihydrate 0.45 g Sodium sulfite 225 g Sodium gluconate 15 g 1- (N, N-diethylamine) -ethyl- 5-mercaptotetrazole 15 g Tartaric acid 48 g Glacial acetic acid 675 g Sodium hydroxide 225 g Sulfuric acid (36N) 58.5 g Aluminum sulfate 150 g Water 6000 ml pH 4.68

(Preparation of Processing Solution) The above concentrated developer was filled in the following containers for each parts agent. In this container, the partial containers of the parts agents A, B and C are connected together by the container itself. The concentrated fixing solution was also filled in the same kind of container. First, as a starter in the developing tank,
Aqueous solution 30 containing 54 g of acetic acid and 55.5 g of potassium bromide
0 ml was added. Insert the above treatment agent container upside down and insert it into the perforation blade of the treatment solution stock tank mounted on the side of the automatic processing machine to break the sealing film of the cap and transfer each treatment agent in the container to the stock tank. Filled. These processing agents were filled in the developing tank and fixing tank of the developing machine at the following ratios by operating the pumps installed in the developing machine. Also,
Every time 8 sheets of photosensitive material were processed in terms of 4-cut size, the processing agent stock solution and water were mixed at this ratio and replenished in the processing tank of the developing machine.

Developer solution Part solution A 25 ml Part solution B 5 ml Part solution C 5 ml Water 65 ml pH 10.50 Fixer concentrate 40 ml Water 60 ml pH 4.62 The wash tank was filled with tap water.

As a water stain inhibitor, 0.4 g of actinomycetes supported on perlite having an average particle size of 100 μm and an average pore size of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. Prepare three pieces filled with water and fungi from the cloth), two of them at the bottom of the washing tank, and one at the bottom of the stock tank for washing water (liquid volume 0.2 liters). I sunk each.

(Evaluation of Photographic Property) Photographic property was evaluated as follows. The sensitivity is 100, which is the reciprocal of the exposure amount required to obtain a density of 1.0 when a photosensitive material is treated with a new solution of developer 7.
As relative. Gradation is density 2.0 and density 0.2
The difference of 5 gives a density of 2.0 and the logarithm of the exposure dose and a density of 0.2
It is shown as a value divided by the difference from the logarithm of the exposure amount giving 5.

[0104]

[Table 3]

As shown in Table 3, hydroquinone monosulfonate or a derivative thereof as a developing agent and an auxiliary developing agent exhibiting superadditivity are contained, and further, the compound represented by the general formula (I) is used.
And / or (II) by treatment with a developer of the present invention containing a compound, stable photographic properties are obtained before and after running as in the case of a developer containing hydroquinone as a developing agent, A processing method was obtained in which silver stains did not adhere to the processing tank and rollers of the automatic processing machine.

Example 2 (Preparation of silver halide photosensitive material) The same silver halide photosensitive material as that used in Example 1 was used.

(Preparation of Concentrated Developer) The hydroquinone monosulfonate or its derivative of the present invention having the following formulation is used as a developing agent, an auxiliary developing agent exhibiting superadditivity, and general formulas (I) and / or (II). A concentrated developer containing a compound represented by

Diethylenetriamine pentaacetic acid 8.0 g Sodium sulfite 50.0 g Sodium carbonate monohydrate 52.0 g Potassium carbonate 55.0 g Developer III-1 120.0 g 4-hydroxymethyl-4 of the present invention -Methyl-1-phenyl-3-pyrazolidone 13.2 g Compound II-14 1.44 g Diethylene glycol 50.0 g Adjust to pH 12.0 with sodium hydroxide. Add water to make 1 liter.

(Preparation of development replenisher)
It was diluted twice and used as a development replenisher.

(Preparation of developing mother liquor) 2 liters of the above concentrated developer was diluted to 4 liters with water, and 20 ml was added to 1 liter of the diluted starter solution having the following composition, p
The developing solution of H11.8 was used as the developing mother solution. Starter solution Potassium bromide 3.7 g Acetic acid 3.6 g Water is added to make 20 ml.

(Preparation of Concentrated Fixing Solution) A fixing solution having the following composition was prepared. Water 5 l Ethylenediaminetetraacetic acid dihydrate 0.5 g Sodium thiosulfate pentahydrate 2900 g Sodium bisulfite 491 g Sodium hydroxide 47.3 g Water is added to make 10 liters (concentrated liquid) (pH = 5. 42)

(Preparation of Fixing Replenisher)
It was diluted twice and used as a fixing replenisher.

(Preparation of fixing mother liquor) 2 liters of the concentrated fixing solution was diluted with water to 4 liters. The pH was 5.6.

(Exposure and Processing of Photographic Material) The photographic light-sensitive material prepared in Example 1 was adhered to both sides of an orthoscreen HG-M manufactured by Fuji Photo Film Co., Ltd. using a cassette, and 0.05 seconds from both sides. Exposure was performed and X-ray sensitometry was performed. The exposure amount was adjusted by changing the distance between the X-ray tube and the cassette. After the exposure, an automatic developing machine FPM-800 manufactured by Fuji Photo Film Co., Ltd. in which the driving system and the aperture ratio were improved to 0.02 was used to develop a developing replenisher and a fixing replenisher by using the developing mother liquor and the fixing mother liquor. 600 ml while replenishing 130 ml per 1 m ^{2 of} light-sensitive material
One sheet was processed. Process Temperature Processing time Development 35 ° C 25 seconds Fixing 35 ° C 25 seconds Water washing 18 ° C 22 seconds Drying 55 ° C 40 seconds Total (dry to dry) 120 seconds

(Evaluation of Photographic Property) Photographic property was evaluated in Example 1.
Evaluation was made in exactly the same manner as.

Also in Example 2, as in Example 1, hydroquinone monosulfonate or its derivative as a developing agent and an auxiliary developing agent exhibiting superadditivity are contained, and further the general formula (I) and / or (II) is used. By processing with the developing solution of the present invention containing a compound represented by the following, stable photographic properties can be obtained before and after running as in the case of a developing solution containing hydroquinone as a developing agent, and a processing tank of a developing machine is obtained. And a processing method was obtained in which silver stains did not adhere to the rollers.

Example 3 The photographic light-sensitive material prepared in Example 1 was processed with the following developer. [Automatic processor processing] The automatic processor is "Fuji X Ray Processor CEPROS-M" manufactured by Fuji Photo Film Co., Ltd.
Was used so that the total processing time was 90 seconds. The dry blowing temperature was set to 55 ° C. Developer formulation PartA Potassium hydroxide 18.0 g Potassium sulfite 30.0 g Sodium carbonate 30.0 g Diethylene glycol 10.0 g Diethylenetriamine pentaacetic acid 2.0 g 1- (N, N-diethylamino) ethyl-5-mercaptotetrazole 0.1 g Developer III-1 of the present invention 45.0 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 3.0 g Water added 300 ml

Part B Triethylene glycol 45.0 g Compound II-14 of the present invention 0.2 g Glacial acetic acid 5.0 g 5-nitroindazole 0.3 g 1-Phenyl-3-pyrazolidone 5.5 g Water 60 ml

PartC Glutaraldehyde (50%) 10.0 g Potassium bromide 4.0 g Potassium metabisulfite 10.0 g Water was added to 50 ml PartA 300 ml, PartB 60 ml and PartC 50m.
Add water to 1 to make 1 liter and adjust to pH 10.90. Part A 4.50 liters, Part B 0.90 liters, and Part C 0.75 liters were used by filling a CE-DF1 bottle manufactured by FUJIFILM Corporation for 15 liters of the working solution. Development Starter Solution Acetic acid was added to the development replenisher solution to adjust the pH to 10.20, which was used as a development starter solution.

As the fixing solution, CE-F1 manufactured by Fuji Photo Film Co., Ltd. was used. Development temperature: 35 ° C Fixing temperature: 35 ° C Drying temperature: 55 ° C Replenishment amount (both developer and fixer) 12.5ml / 10 × 2
When the 1-inch (161 ml / m ² ) sample 10 × 12-inch size film was subjected to running processing on 600 sheets, the developer of the present invention showed good performance.

Example 4 The light-sensitive material used in Example 1 was subjected to image formation by X-ray exposure using the phosphor screen described in JP-A-6-11804, and the developer 3 of the invention of Example 1 was used. Upon processing, it was confirmed that a good X-ray image was formed. In addition, in Examples 1, 2, 3 and 4, the Fuji medical X-ray film, Super HRA-30, and Super HR-S3 were used.
0, Super HR-G30, Super HR-HA30,
It should be noted that the same effects as those of Examples 1, 2, 3 and 4 were exhibited even when the treatment was carried out with Super HR-L30, UR-1, UR-2 and the like.

Preferred Embodiment 1 The silver halide grains contain 10 to 100 mol% of silver chloride,
3. The processing method according to claim 1 or 2, wherein a silver halide photographic light-sensitive material containing 10 to 100 mol% of silver bromide and 0 to 5 mol% of silver iodide is used. 2 The total processing time (Dry to Dr.
y) is 20 seconds to 100 seconds. 3. A processing method using the developing solution according to claim 1, wherein the heating means for the roller portion in contact with the photosensitive material before the drying portion of the automatic development processing device is at 70 ° C. or higher. (4) A processing method characterized by an automatic development processing apparatus having a mechanism in which a developer and a fixing solution cartridge are used up at the same time when a chemical mixer is built into the automatic development processing apparatus.

5. A processing method characterized in that the opening ratio of the developing tank of the automatic development processing apparatus using the developing solution according to claim 1 is 0.04 cm ^-1 or less. 6 Development Concentration Solution and Fixing Concentration Solution consist of 1 part, and each Concentration Solution and Water are diluted to a working solution in each tank and supplied as a replenishing solution (immediately before mixing dilution method) . 7. A processing method, wherein the containers of the developing concentrate and the fixing concentrate according to claim 1 are integrated packaging materials. 8. A processing method comprising using an automatic developing machine having a rinse tank and a rinse roller (crossover roller) provided between the developing tank and the fixing tank using the developer of claim 1 and between the fixing tank and the washing tank. 9. A processing method characterized by using an automatic processor equipped with a stock tank of water in which various water redness preventive agents (antibacterial agents) are supplied to a washing tank and a rinse tank. 10 A processing method characterized by using an automatic processor having a solenoid valve installed at the drain of the washing tank. 11. The developer according to claim 1, wherein 70 mol% or more of all cations in the developer are potassium ions. 12. The developer according to claim 1, wherein the developer is powder. 13 A processing method characterized in that the developing solution and the fixing solution are used liquid types. 14 A processing method characterized in that the water washing tank of the automatic development processor has a multi-chamber tank and a multi-stage countercurrent water washing method.

[0124]

The silver halide photographic light-sensitive material is treated with a developing solution containing a hydroquinone monosulfonate or its derivative developing agent and a super-additive auxiliary developing agent in an automatic developing machine to reduce the replenishment amount. Stable photographic properties were obtained even when the above was done.

Claims (3)

[Claims] 1. A method for developing an imagewise exposed silver halide photographic light-sensitive material, wherein the developing solution contains an auxiliary developing agent exhibiting superadditivity with hydroquinone monosulfonate or its derivative. A method for processing a silver halide photographic light-sensitive material, comprising: 2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the developer contains a compound represented by the following general formula (I) and / or (II). General formula (I) General formula (II) In the formula, R ₄ and R ₅ are each a hydrogen atom and have 1 to 3 carbon atoms.
Represents an alkyl group or phenyl group, and R ₆ and R ₇ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
m and n are 0, 1 or 2. R ₈ represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms. R ₉ represents a group represented by R ₈ or a hydrogen atom. M
Represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a sulfonyl group, an amino group, an acyl group or an alkoxycarbonyl group. 3. The method of processing a silver halide photographic light-sensitive material according to claim 1, wherein the replenishing amount of the developing solution is 25 ml or more and 200 ml or less per 1 m ^{2 of the} silver halide photographic light-sensitive material.