JPH0829926A - Silver halide photographic material processing method - Google Patents

Abstract

PURPOSE:To provide a developer liquid composition which does not need a polyhydroxybenzene-type developer main agent component, improve the stability of the composition at the time of storage of the development processing agent, save the space for storage, and lower the transportation cost by processing a black-and-white photographic material by a developer liquid prepared by using one tablet-type alkaline solid processing agent containing an ascorbic acid-type developer main agent. CONSTITUTION:One tablet-type alkaline solid processing agent containing a developer main agent having a formula is used for a developer liquid. In the formula, R1 and R2 stand for hydroxyl group, amino group, acylamino group, respectively; P and Q stand for hydroxyl group, carboxyl group, alkoxyl group, or P and Q form a bond between them and, together with carbon atoms of two vinyl groups substituted with R1 and R2, form 5-8 membered atom group; and Y stands for =O, =N-R3 where in R3 stands for hydroxyl group, alkyl group, hydroxyalkyl group, sulfoalkyl group, and carboxylalkyl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a processing method and a processing agent for a black and white silver halide photographic light-sensitive material, and particularly to a development prepared by using a one-component type alkaline solid processing agent containing an ascorbic acid type developing agent. The present invention relates to a method of processing a black and white silver halide photographic light-sensitive material with a liquid.

[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 by using a developer containing a polyhydroxybenzene type developing agent represented by hydroquinone and / or a known developing agent as an alkaline aqueous developer composition. That is, when the sensitized silver halide emulsion is exposed to light, a latent image is formed in the silver halide grains of the emulsion,
The latent image is developed by immersing the exposed emulsion in an aqueous developing solution containing a reducing agent or a developing agent.
Hydroquinone or other suitable developer provides a developed photographic image by reducing the exposed silver halide grains.

Developer compositions based on hydroquinone are described, for example, in US Pat. Nos. 2,893,865, 3,738,199, 3,865,591 and 4,046. No. 571, No. 4,205,124,
No. 4,756,990 and No. 4,816,3
No. 84, and the like. Usually, these compositions contain relatively high concentrations of sulfite-based components. In order to obtain a satisfactory effect of this type of composition, it is important to maintain the pH of the composition strictly in the alkaline range. For this reason, caustic alkali (caustic soda or caustic potash) is commonly used in developer compositions.

A developer composition containing hydroquinone as a developing agent has been used without problems for many years.
More recently, the use of hydroquinone, sulfites and caustic components has led to problems with toxicity and environmental damage. That is, due to the toxicity and high pH caused by the various components contained in the developer composition, it protects the health of people who handle this type of composition and protects the environment from which the composition is discharged. In order to do so, it is becoming necessary to comply with various legal guidelines and regulations. The most undesirable components incorporated into commonly used developer compositions are hydroquinone and its related substances and potassium hydroxide. Therefore, it is desirable to find a substance that can substitute for these components and that has low toxicity itself.

On the other hand, in an automatic developing machine for automatically developing, fixing, washing with water and drying a light-sensitive material, it is necessary to supply a processing solution, for example, a developing solution or 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. Further, in order to recover so-called deterioration over time due to oxygen oxidation of a developer component such as a developing agent due to oxygen in the air, or so-called processing fatigue due to exhaustion of the developer or fixing solution due to processing of the photosensitive material, a processing solution or replenishment. The liquid is supplied into the processing tank.

For replenishment of the processing solution for recovering the deterioration of the processing solution due to such processing of the light-sensitive material or deterioration with time, plastic is used in the form of one or a plurality of concentrated solution parts for ease of use. It is put in a bottle and supplied to users as a treatment agent kit. The user simply attaches these treating agent kits to the processing machine, and the processing machine is automatically diluted to a predetermined concentration and supplied as a working solution or a replenisher into the processing tank. However, in the case of a liquid agent, although it is simple to use, it has a large volume and weight because it contains a considerable amount of water in advance, which requires transportation and storage costs. There is a problem such as performance change.

For example, US Pat. No. 2,688,549
No. 36-17599, US Pat. No. 3,82
No. 6,654, No. 5,098,819, No. 5,2
No. 36,816, European Patent Nos. 498,968A1, 461,783A1, 531,582A1 and 573,700A1 and the like, each discloses a hydroquinone-free developer composition. ing. However, these developer compositions are usually in liquid form, and transportation, storage costs or risk of liquid leakage,
Problems such as performance changes during storage have not been resolved.

[0008]

SUMMARY OF THE INVENTION One object of the present invention is to provide a developer composition which does not require the addition of a polyhydroxybenzene type developing agent component. Another object of the present invention is to provide a developer composition having improved storage stability of the development processing agent and reduced storage space and transportation cost.

[0009]

The objects of the present invention have been achieved by the following (1) and (2). (1) In a method of processing a black-and-white silver halide photographic light-sensitive material with an automatic processor, a developer was prepared using a one-component type alkaline solid processing agent containing a developing agent represented by the following general formula (I). A processing method and a solid processing agent for a black and white silver halide photographic light-sensitive material, which is a developing solution. General formula (I)

[0010]

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In the formula, R ₁ and R ₂ each represent a hydroxy group, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group. P and Q represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are mutually It represents an atomic group forming a 5- to 8-membered ring together with two vinyl carbon atoms substituted by R ₁ and R ₂ and a carbon atom substituted by Y. Y represents = O or = N-R _3,. R ₃ represents a hydrogen atom, a hydroxyl group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxylalkyl group. (2) The method for processing a black-and-white silver halide photographic light-sensitive material according to the above (1), wherein the replenishment amount of the development processing agent is 60 g or less in terms of solid content of the processing agent per 1 m ^{2 of the} silver halide photographic light-sensitive material.

The present invention will be described in more detail below. In the general formula (I) which is the developing agent of the present invention, R ₁ , R
Each of ₂ is a hydroxy group, an amino group (including a substituent having an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group) as a substituent, and an acylamino. Group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonyl) Amino group), mercapto group, alkylthio group (methylthio group,
Represents an ethylthio group). Preferred examples of R ₁ and R ₂ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group.

P and Q are a hydroxy group and a hydroxy alk
Group, carboxyl group, carboxyalkyl group, sulfo group
Group, sulfoalkyl group, amino group, aminoalkyl group,
Represents an alkyl group, an alkoxy group, a mercapto group, or
Or P and Q are combined to form R ₁, R₂Replaced by two
With two vinyl carbon atoms and carbon atoms substituted by Y
Represents an atomic group necessary for forming a 5- to 8-membered ring. ring
Specific examples of the structure include -O-, -C (R_Four) (R_Five) −, −
C (R₆) =, -C (= O)-, -N (R₇)-, -N =,
It is configured by combining. However, R_Four, R_Five, R₆,
R₇Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted.
Kill group (hydroxyl group, carboxy group, sulfur group as a substituent
Rupho group), hydroxy group, carbo group
Represents a xy group. Furthermore, the 5- or 7-membered ring is saturated or tired
A fused ring of the sum may be formed.

Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexanone ring and a uracil ring. And preferred examples of the 5- to 7-membered ring include
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
The uracil ring can be mentioned.

Y is a group composed of ═O or ═N—R ₃ . Here, R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group (eg methyl, ethyl), an acyl group (eg acetyl), a hydroxyalkyl group (eg hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg sulfomethyl, sulfoethyl), carboxy. Represents an alkyl group (eg carboxymethyl, carboxyethyl). Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0016]

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[0017]

[Chemical 4]

[0018]

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[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

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Of these, ascorbic acid or erythorbic acid (stereooptical isomers) are preferable, and their alkali metal salts (potassium, sodium, etc.) are also preferable.

In the solid processing agent of the present invention, the amount of the compound of the general formula (I) used is generally in the range of 5 × 10 5 per liter of developer when the solid processing agent of the present invention is dissolved in water. ^-3 mol to 1 mol, particularly preferably 10 ^-2 mol to 0.5 mol. The solid processing agent of the present invention may contain an auxiliary developing agent in addition to the compound of formula (I). As auxiliary developing agents for 1-phenyl-3-pyrazolidone or a derivative thereof that can be used in combination with the present invention, 1-phenyl-3-pyrazolidone, 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 There are, among others, but 1
-Phenyl-3-pyrazolidone or 1-phenyl-4-
Methyl-4-hydroxymethyl-3-pyrazolidone is preferred. Examples of the p-aminophenol-based developing agent that can be used in the present invention include N-methyl-p-aminophenol and p-aminophenol.
-Aminophenol, N- (β-hydroxyethyl)-
p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenyl, p-
Benzylaminophenol and the like. When the combination of the compound represented by the general formula (I) of the present invention and 1-phenyl-3-pyrazolidones or p-aminophenols is used, when the solid treating agent of the present invention is dissolved in water. The latter is usually used in an amount of 10 ⁻³ mol / liter to 0.1 mol / liter, more preferably 10 ⁻³ mol / liter to 0.06 mol / liter.

In the present invention, the term "substantially free of dihydroxybenzenes" means that the concentration of dihydroxybenzenes in the developing solution is taken relative to the amount of the compound of the general formula (I) or the auxiliary developing agent. Not enough (eg 5 × 1
^0-4 mol / liter or less). The developer of the present invention preferably contains no dihydroxybenzenes.

Sulfite salts such as sodium sulfite, potassium sulfite, lithium sulfite, sodium bisulfite, potassium metabisulfite and formaldehyde sodium bisulfite may be added to the solid processing agent of the present invention as a preservative. The sulfite is used in an amount of 0.01 mol / liter or more. When used in large amounts, it dissolves silver halide emulsion grains,
It causes silver stains. Moreover, since it also causes an increase in COD (chemical oxygen demand), the amount added should be minimized.

The pH of the developer prepared by dissolving the solid processing agent used in the development processing of the present invention with water is 8.5 to 12.0.
Is preferred. More preferably 9.0-1
The range is up to 0.5. When the pH is 12.0 or higher, the air oxidation stability of the developer becomes low, which is not preferable. Further, if the pH is 8.5 or less, sufficient contrast cannot be obtained. Alkali agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. The developer of the present invention is disclosed in JP-A-60
A sugar described in No. 93433 (for example, sucrose),
PH buffers such as oximes (eg acetoxime), phenols (eg 5-sulfosalicylic acid), silicates, sodium triphosphate, potassium triphosphate can be used. The concentration of the buffer is preferably 0.3 mol / liter or more. Boron compounds such as boric acid and sodium metaborate may react with the compound of the present invention represented by the general formula (I) to be inactivated, which is not preferable.

Development inhibitors such as potassium bromide and potassium iodide, indazole compounds such as 5-nitroindazole, benzimidazole compounds such as sodium 2-mercaptobenzimidazole-5-sulfonate, 5
-Antifoggants such as benztriazole compounds such as methylbenztriazole may be included in ResearchDi
sclosure Volume 176, No. 17643, Item XXI (1
February issue, 1978). Further, the amine compounds described in U.S. Pat. No. 4,269,929, JP-A-61-267759 and Japanese Patent Application No. 1-291818 may be contained. Further, a color toning agent, a surface active agent and the like may be included if necessary.

The solid treating agent of the present invention may contain a chelating agent having a water softening ability, and examples thereof include the following compounds. That is, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid,
Hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic 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-
3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, sodium hexametaphosphate are mentioned, and particularly preferably, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycoletherdiaminetetraacetic acid. Acetic acid, hydroxyethyl ethylenediamine triacetic acid, 2
-Phosphonobutane-1,2,4-tricarboxylic acid, 1,
1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1-aminoethylidene-1,1-diphosphonic acid, 1 -Hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

In the developer of the present invention, for the purpose of silver stain, Japanese Patent Publication Nos. 62-4702, 62-4703, 63-24123, 3-94955 and 3-94595. The compounds described in Japanese Patent Application No. 3-112275 and Japanese Patent Application No. 3-233718 can be used.

The fixing solution used in the present invention is an aqueous solution containing thiosulfate, and has a pH of 3.8 or higher, preferably 4.2 to 4.2.
Has 6.0. Sodium thiosulfate as a fixing agent,
Examples include ammonium thiosulfate. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 3 mol / liter. The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and they include, for example, aluminum chloride, aluminum sulfate and potassium alum.

For the fixing solution, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per 1 liter of the fixing solution, and particularly, it is preferable that the content of the compound is 0.005.
01 mol / liter to 0.03 mol / liter is particularly effective.

Preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having a water softening ability may be included in the fixing solution, if desired. And compounds described in JP-A-62-78551. In the processing method of the present invention,
After the development and fixing steps, the film is treated with washing water or a stabilizing solution and then dried.

In the developing treatment of the present invention, the temperature and time for development and fixing are each about 60 ° C. or less at 25 ° C. to 50 ° C., preferably 6 ° C. to 45 seconds at 30 ° C. to 40 ° C. In the present invention, the light-sensitive material is developed, fixed, and then washed with water or stabilized. Here, the washing step is
A water-saving treatment can be achieved by using a 2-3-step countercurrent washing method. Further, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank. Further, a part or the whole of the overflow solution from the washing bath or the stabilizing bath can be used as the fixing solution as described in JP-A-60-235133. This is more preferable because the amount of waste liquid is reduced. In addition, anti-fungal agents (for example, "Chemistry of antibacterial and antifungal" by Horiguchi,
The compound described in JP-A-62-115154), a water washing accelerator (such as sulfite), and a chelating agent may be contained. The temperature and time of the washing or stabilizing bath according to the above method are 0 to 50 ° C. and 5 to 60 seconds, respectively.
C. to 40.degree. C. and 5 to 45 seconds are preferable. In the present invention, the photosensitive material which has been developed, fixed and washed with water is dried through a squeeze roller. Drying is performed at 40 ° C. to 80 ° C. for 5 seconds to 60 seconds. The total processing time in the present invention means that after inserting the tip of the film into the insertion port of the automatic developing machine, the film passes through the developing tank, the transition portion, the fixing tank, the transition portion, the washing tank, the transition portion and the drying portion. It is the total time for the tip of the to come out of the drying outlet.

The solid photographic processing agent of the present invention comprises tablets, granules,
It can be powdered, lumpy or pasty, but tablets, granules and powders are preferred, with tablets being most preferred. A method for producing a tablet processing agent is described in, for example, JP-A-51-61
No. 887, No. 54-155038, No. 52-8802
No. 5, British Patent No. 1,213,808 and the like, and can be produced by a general method, and granule treating agents are disclosed in, for example, JP-A Nos. 2-109042, 2-109043, and 3-39735. And the general method described in JP-A-3-39739. Further, the powder processing agent is, for example, JP-A-54-133332 or British Patent No. 725.
892, 729,862 and German Patent No. 3,
It can be produced by the general method described in US Pat. No. 733,861.

When the solid treating agent of the present invention is a tablet, the size of the tablet is preferably 1 cm or more and 7 cm or less, more preferably 2 cm or more and 5 cm or less. The bulk density of the solid processing agent of the present invention is preferably 0.5 to ⁶ g / cm ³ , and more preferably 1.0 to 5 g / cm ³ .

In the present invention, it is preferable that a certain amount of the processing agent is replenished per unit area of the photosensitive material when the photosensitive material is processed. As the replenisher to be replenished, a treatment liquid prepared by using the solid treatment agent of the present invention may be used, or the solid treatment agent of the present invention may be directly replenished to the treatment layer separately from water. It is preferable to replenish the solid processing agent of the present invention directly to the processing layer separately from water. The replenishing amount of the solid processing agent of the present invention or the processing liquid prepared using the solid processing agent of the present invention is 60 g or less in terms of solid content per 1 m ² of the light-sensitive material, and preferably in solid content per 1 m ² of the light-sensitive material. 10-5
0 g.

The processing solution prepared by using a solid processing agent to be injected into the processing tank of the developing machine at the beginning of development may be a processing solution prepared from a solid processing agent having the same composition as the above solid processing agent, You may use the processing liquid prepared from the solid processing agent which changed a part of composition.

The photographic light-sensitive material used in the present invention is not particularly limited and is mainly used as a general black-and-white light-sensitive material. Preferably, the X-ray film for direct photography, the X-ray film for indirect photography, the film for CRT and the like is used for the subject such as human body.
It is used in a system that irradiates a line or the like to convert X-rays that have passed through a subject into visible light and expose it. For example, medical or industrial X-ray photographic materials, X-ray dupe photographic materials,
Examples thereof include photographic materials for medical CRT images.

The aspect ratio of tabular silver halide grains used in the present invention is given by the ratio of the diameter of a circle having an area equal to the projected area of each tabular grain and the thickness of each tabular grain. To be

It is preferable that the tabular silver halide grains are present in an amount of 50% by weight or more, further 80% by weight or more, and more preferably 90% by weight or more based on the total silver halide grains. The silver halide that can be used in the silver halide emulsion used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride and the like. Preferred are silver iodobromide (I = 0 to 10 mol%), silver bromide, and silver chlorobromide. The AgI distribution may be high inside or outside.

The tabular silver halide emulsion is a Cugack (Cug
nac) and Chateau “Advancement of Morphology of Physically Aged Silver Bromide Crystals (Evolution of the Morphology of Silver Promise Crystals Dualing Physical Raising)” E-Industrie Photography, 33
Vol. No. 2 (1962), pp. 121-125, Duffin, "Photographic emulsion chemistry," Focal Press, New York, 19
1966, p. 66-p. 72, APH Trivel
li), WF Smith Photographic Journal, 80, 285 (19)
40) and the like, but JP-A-58-127,9
21, JP-A-58-113,927, JP-A-58-
It can be easily prepared by referring to the method described in No. 113,928.

Further, a relatively low pBr of pBr 1.3 or less
It is obtained by forming a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere of a certain value, and simultaneously adding a silver and a halogen solution while keeping the pBr value at the same level and growing the seed crystal. During this grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated.

The size of the tabular silver halide grains can be adjusted by controlling the temperature, selecting the kind and amount of the solvent, the addition rate of the silver salt used during grain growth, and the halide. In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt,
A thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, and the like may coexist. If necessary, chemical sensitization can be performed.

As the chemical sensitization method, a so-called gold sensitization method with a gold compound, a sensitization method with a metal such as iridium, platinum, rhodium, or palladium, a sulfur sensitization method with a sulfur-containing compound, and a Se sensitizer with Se are used. A sensitization method, a Te sensitization method using a Te sensitizer, a reduction sensitization method using a complex salt, polyamine, or the like, or a combination of two or more thereof can be used.

In the present invention, the swelling percentage is set to 250% or less from the viewpoints of rapid processing (for example, reduction of drying load) and simplification of processing (for example, omission of treatment dura, reduction of treatment agent and number of parts). Is desirable. Here, the swelling percentage is (a) the photographic material is subjected to an incubation treatment at 38 ° C. and 50% relative humidity for 3 days, (b) the thickness of the hydrophilic colloid layer is measured, and (c) the photographic material is
It can be determined by soaking in distilled water at 0 ° C. for 3 minutes and measuring the percentage change in layer thickness compared to the hydrophilic colloid layer thickness measured in step (d) step (b).

Such rapid processing and simplification of processing can be better achieved by further reducing the swelling percentage. On the other hand, if the swelling percentage is lowered, the speed of development, fixing, washing with water, etc. is lowered, so it is not preferable to lower it more than necessary. Those skilled in the art can easily control the swelling percentage to 250% or less by, for example, increasing the amount of the hardener used in the light-sensitive material.

Therefore, the swelling percentage of the hydrophilic colloid layer containing at least one silver halide emulsion layer is 250.
% Or less, preferably 100% or more and 230% or less, and more preferably 150% or more and 230% or less.

Examples of hardeners that can be used include aldehyde compounds, compounds having an active halogen described in US Pat. No. 3,288,775, and US Pat.
35,718 and the like, compounds having a reactive ethylenically unsaturated group, U.S. Pat. No. 3,091,537
Organic compounds such as epoxy compounds and halogenocarboxaldehydes such as mucochloric acid are known. Of these, vinyl sulfone type hardeners are preferable. Further, a polymeric hardener can be preferably used in the present invention.

The sensitizing dyes used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes include cyanine dyes, merocyanine dyes, and dyes belonging to complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. 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 nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzthiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzo Imidazole nucleus,
A quinoline nucleus or the like can be applied. These nuclei may be substituted on carbon atoms.

The merocyanine dye or the complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, and a rhodanine as a nucleus having a ketomethylene structure. 5 such as nucleus, thioparbituric acid nucleus
~ 6-membered heterocyclic nuclei can be applied. For example, the compounds described in Research Disclosure 17643, page 23, item IV (December 1978) or the compounds described in the cited documents can be used. More specifically, the following compounds can be used. 5,5'-dichloro-
3,3'-Diethylthiacyanine bromide, 5,5'-dichloro-3,3'-di (4-sulfobutyl) -thiacyanine Na salt, 5-methoxy-4,5-benzo-3,3'-
Di (3-sulfopropyl) thiacyanine Na salt, 5,
5'-dichloro-3,3'-diethylselenacyanine iodide, 5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) thiacarbocyanine pyridinium salt, anhydro-5,5 ′ -Dichloro-9-ethyl-
3- (4-sulfobutyl) -3'-ethyl hydroxide,
1,1-diethyl-2,2'-cyanine bromide, 1,1
-Dipentyl-2,2'-cyanine perchloric acid, 9-methyl-3,3'-di (4-sulfobutyl) -thiacarbocyanine pyridinium salt, 5,5'-diphenyl-9-ethyl-3,3 ' -Di (2-sulfoethyl) -oxacarbocyanine Na salt, 5-chloro-5'-phenyl-9-
Ethyl-3- (3-sulfopropyl) -3 '-(2-sulfoethyl) oxacarbocyanine Na salt, 5,5'-
Dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine Na salt, 5,5'-dichloro-6,6'-dichloro-1,1'-diethyl-3,
3'-di (3-sulfopropyl) imidacarbocyanine Na salt, 5,5'-diphenyl-9-ethyl-3,3 '
-Di (3-sulfopropyl) thiacarbocyanine Na
The salt and the sensitizing dye used in the present invention are usually added to the emulsion before the emulsion is coated on a suitable support, but may be a chemical ripening step or a silver halide grain forming step. .

The emulsion layer of the photographic light-sensitive material used in the present invention may contain a polymer such as an alkyl acrylate latex, an emulsion, or a plasticizer such as a polyol such as trimethylolpropane in order to improve pressure characteristics. For the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material used in the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization. For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride,
Alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and the like; nonionic surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates A carboxy group, such as esters, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as sulfo group, phospho group, sulfuric acid ester group and phosphoric acid ester group; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amines Amphoteric surfactants such as oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. Cationic surfactants such as

As an antistatic agent, especially Japanese Patent Laid-Open No. 62-1
09044, 62-215272, and fluorine-containing surfactants or polymers described in JP-A-60-76742.
No. 60, No. 60-80846, No. 60-80848, No. 60-80839, No. 60-76741, No. 58-
208743, 62-172343, 62-1
No. 73459, No. 62-215272, and other nonionic surfactants, or JP-A-57-57.
The conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in JP-A-204540 and JP-A-62-215272 can be preferably used. Further, as an inorganic antistatic agent, JP-A-57-118242
A conductive oxide such as tin oxide, zinc oxide, or a complex oxide obtained by doping antimony or the like into a metal oxide thereof can be preferably used.

As the antistatic agent, it is particularly preferable to use a fluorosurfactant. In the present invention, it is preferable that the emulsion layer and / or the other hydrophilic colloid layer contain an organic substance which can flow out in the development processing step. When the substance to be washed away is gelatin, gelatin species that are not involved in the crosslinking reaction of gelatin with a hardening agent are preferable, and examples thereof include acetylated gelatin and phthalated gelatin, and those having a small molecular weight are preferable. On the other hand, as polymeric substances other than gelatin, US Pat.
No. 271,158, polyacrylamide, or hydrophilic polymers such as polyvinyl alcohol and polyvinylpyrrolidone can be effectively used, and dextran, sucrose, pullulan, and the like are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. It is effective that the amount of outflow in the processing is 10% or more and 50% or less of the total weight of the applied organic substance other than the silver halide grains.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, azaindenes such as triazaindenes,
Tetraazaindenes (especially 4-hydroxy substitution (1,
3,3a, 7) Tetrazaindenes), pentaazaindenes, etc .; Add many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. be able to.

In the present invention, as a matting agent, polys as described in US Pat. Nos. 2,992,101, 2,701,245, 4,142,894 and 4,396,706. A homopolymer of methyl methacrylate or a copolymer of methyl methacrylate and methacrylic acid, an organic compound such as starch, and fine particles of an inorganic compound such as silica, titanium dioxide, sulfuric acid, and strontium barium can be used. The particle size is 1.0 to 10
It is preferably μm, particularly preferably 2 to 5 μm.

There are no particular restrictions on various other additives used in the light-sensitive material preferably used in 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 emulsions and JP-A-2-68539, page 8, lower right column, line 6 from the bottom, or from its production, page 10 upper right column, line 12 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 and agent, 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. Surfactants / antistatic From page 11, upper left column, line 14 to page 12, upper left column, line 9 Stopper 6. Matting agent, slip agent, page 12, upper left column, line 10 to upper right column, line 10 14th Plasticizer Page 10, lower left column, line 10 to lower right column, line 1 7. Hydrophilic colloid, page 12, right upper column, line 11 to left lower 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

[0057]

【Example】

Example 1 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto. <Preparation of Solid Developer> A one-component alkaline solid developer D-2 containing the compound of the present invention represented by the general formula (I) shown in Table 1 was prepared by the method described below. Compound I of the present invention
-1 49.1 g was ground in an air jet mill to an average particle size of 10μ and this fine powder was sprayed with 10 ml of water at room temperature for about 8 minutes in a commercial fluidized bed spray granulator, After granulating to an average particle size of 150 μ, the granulated product is dried at an air temperature of 65 ° C. for about 7 minutes and then vacuum dried at 40 ° C. for 90 minutes to completely remove the water content, and the granulated product is S- Prepare 1. Sodium bisulfite 23.8 g, sodium sulfite 31.0 g, sodium carbonate 49.5 g, diethylenetriamine pentaacetic acid 4.0 g and potassium bromide 3.5.
g in an air jet fine crusher
Grind until mixed and mix. This fine powder is sprayed with 30 ml of water at room temperature for about 8 minutes in a commercial fluidized bed spray granulator to granulate to an average particle size of 150μ, and then the granulated product is dried at an air temperature of 65 ° C for about 7 minutes. Then, the product is dried in vacuum at 40 ° C. for 90 minutes to completely remove the water content to prepare a granulated product S-2.

4-hydroxymethyl-4-methyl-1-
6.6 g of phenyl-3-pyrazolidone were crushed in an air jet mill to an average particle size of 10μ and this fine powder in a commercial fluid bed spray granulator at room temperature in 10 ml of water for about 8 minutes. After spraying and granulating to an average particle size of 150μ,
The granules are dried at an air temperature of 65 ° C for about 7 minutes, then 40
Vacuum dry at 90 ° C. for 90 minutes to completely remove the water content to prepare a granulated product S-3. 0.2 g of 5-methylbenzotriazole and 0.3 g of 3,3'-diphenyl-3,3'-dithiopropionic acid are pulverized and mixed in an air jet fine pulverizer until the average particle size becomes 10 μm. This fine powder is sprayed with 30 ml of water at room temperature for about 8 minutes in a commercial fluidized bed spray granulator to granulate to an average particle size of 150μ, and then the granulated product is dried at an air temperature of 65 ° C for about 7 minutes. Then, the product is dried in vacuum at 40 ° C. for 90 minutes to completely remove the water content to prepare a granulated product S-4.

The granules of S-1 to S-4 are sieved,
168.0 as granules with particles of 300μ to 1000μ
g was obtained. The granules were molded with a tableting machine at a compression pressure of 800 kg / cm ² to prepare 16 tablets D-2 having a diameter of 4 cm and a weight of 10.5 g. Similarly, one-component type alkaline solid developers D-3 to D-4 shown in Table 1 were also prepared. As a comparative example, a developer D-1 containing hydroquinone as a developing agent was also prepared and is also shown in Table 1.

[0060]

[Table 1]

<Preparation of developing mother liquor> A developing mother liquor was prepared by the following method. 256 solid developing agents D-2 were dissolved in 15 liters of water, and the pH was adjusted to 9.0 with acetic acid.

<Fixing Solution Formulation Example 1> Sodium thiosulfate 290 g Ethylenediaminetetratetraacetic acid dihydrate 0.05 g Sodium bisulfite 25 g Sodium hydroxide 2.35 g Water is added to make 1 liter (pH 5.6).

<Evaluation of Photographic Property> Fuji X-Ray Film Super HR-A30, GREN, Fuji Photo Film Co., Ltd.
The EX orthoscreen HR-4 was brought into close contact with both sides using a cassette, exposed from both sides for 0.05 seconds, and X-ray sensitometry was performed. The exposure amount was adjusted by changing the distance between the X-rays and the cassette. After exposure, Fuji Photo Film Co., Ltd.'s automatic processor CEPRO
Treatment with S-M at the temperature and time shown below,
Sensitometry was obtained. Process Temperature Processing time Image 35 ° C 13 seconds Settling 35 ° C 12 seconds Water wash 25 ° C 6 seconds Dry 55 ° C 14 seconds Total-45 seconds In development process, 3 tablets per 1 m ² of light-sensitive material (solid content 3
1.5 g) and 150 ml of water, photosensitive material 1 in the fixing step
150 ml per m ² (47.5 g solids) were each replenished.

The evaluation of photographic properties was performed as follows. The sensitivity was 1. When the photosensitive material was treated with a new developer D-1 solution, the density was 1.
The reciprocal of the exposure amount required to obtain 0 was set as 100 and shown relatively. The gradation is represented by a value obtained by dividing the difference between the density 2.5 and the density 0.2 by the difference between the logarithm of the exposure amount giving the density 2.5 and the logarithm of the exposure amount giving the density 0.2.

As is clear from Table 2, the one-component type alkaline solid developer containing the compound represented by the general formula (I) of the present invention and containing substantially no hydroquinone is compared with the developer containing hydroquinone. The storage stability is good and the developing solution prepared after storage does not affect the photographic properties. Further, since the developing agent is a tablet, it is obvious that the storage space and transportation cost are reduced.

[0066]

[Table 2]

In this example, Fuji Medical X-Ray film, Super HR-C, Super HR-S3 were used.
0, Super HR-G30, Super HR-HA30,
Even if processing is performed with Super HR-L30, etc.
Note that it showed the same effect as.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 3, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction content]

Developer compositions based on hydroquinone are described, for example, in US Pat. Nos. 2,893,865, 3,733,199, 3,865,591 and 4,046. No. 571, No. 4,205,124,
No. 4,756,990 and No. 4,816,3
No. 84, and the like. Usually, these compositions contain relatively high concentrations of sulfite-based components. In order to obtain a satisfactory effect of this type of composition, it is important to maintain the pH of the composition strictly in the alkaline range. For this reason, caustic alkali (caustic soda or caustic potash) is commonly used in developer compositions.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction content]

P and Q are a hydroxy group and a hydroxy alk
Group, carboxyl group, carboxyalkyl group, sulfo group
Group, sulfoalkyl group, amino group, aminoalkyl group,
Represents an alkyl group, an alkoxy group, a mercapto group, or
Or P and Q are combined to form R ₁, R₂Replaced by two
With two vinyl carbon atoms and carbon atoms substituted by Y
Represents an atomic group necessary for forming a 5- to 8-membered ring. ring
Specific examples of the structure include -O-, -C (R_Four) (R_Five) −, −
C (R₆) =, -C (= O)-, -N (R₇)-, -N =,
It is configured by combining. However, R_Four, R_Five, R₆,
R₇Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted.
Kill group (hydroxyl group, carboxy group, sulfur group as a substituent
Rupho group), hydroxy group, carbo group
Represents a xy group. Furthermore, the 5- or 8-membered ring is saturated or tired
A fused ring of the sum may be formed.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction content]

Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexanone ring and a uracil ring. And examples of preferred 5- to 8-membered rings include
Dihydrofuranone ring, cyclopentenone ring, cyclohexenone ring, pyrazolinone ring, azacyclohexenone ring,
The uracil ring can be mentioned.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction content]

For the fixing solution, tartaric acid, citric acid, gluconic acid or their derivatives can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.0001 mol or more per liter of the fixing solution, and particularly 0.001 mol / liter to 0.03 mol / liter is particularly effective.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

In the present invention, it is preferable that a certain amount of the processing agent is replenished per unit area of the photosensitive material when the photosensitive material is processed. As the replenisher to be replenished, a treatment liquid prepared by using the solid treatment agent of the present invention may be used, or the solid treatment agent of the present invention may be directly replenished to the treatment tank separately from water. It is preferable to replenish the solid processing agent of the present invention directly to the processing tank separately from water. The replenishing amount of the solid processing agent of the present invention or the processing liquid prepared using the solid processing agent of the present invention is 60 g or less in terms of solid content per 1 m ² of the light-sensitive material, and preferably in solid content per 1 m ² of the light-sensitive material. 10-5
0 g.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction content]

The evaluation of photographic properties was performed as follows. The sensitivity was 1. When the photosensitive material was treated with a new developer D-1 solution, the density was 1.
The reciprocal of the exposure amount required to obtain 0 was set as 100 and shown relatively. The gradation is represented by a value obtained by dividing the difference between the density of 2.0 and the density of 0.25 by the difference between the logarithm of the exposure amount giving the density of 2.0 and the logarithm of the exposure amount giving the density of 0.25.

Claims (2)

[Claims] 1. A method of processing a black-and-white silver halide photographic light-sensitive material with an automatic processor, wherein the developer is represented by the following general formula (I).
A method for processing a black-and-white silver halide photographic light-sensitive material, which is a developer prepared by using a one-component type alkaline solid processing agent containing a developing agent represented by General formula (I) In the formula, R ₁ and R ₂ are each a hydroxy group, an amino group,
It represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P, Q
Is a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group,
Represents a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or P and Q are bonded to each other and two vinyl carbon atoms substituted by R ₁ and R ₂ are substituted by Y; Represents a group of atoms forming a 5- to 8-membered ring with existing carbon atoms. Y represents = O or = N-R _3,. R ₃ is a hydrogen atom, a hydroxyl group, an alkyl group,
Acyl group, hydroxyalkyl group, sulfoalkyl group,
Represents a carboxylalkyl group. ^{2. The method} for processing a black-and-white silver halide photographic light-sensitive material according to claim 1, wherein the replenishment amount of the development processing agent is 60 g or less in terms of solid content of the processing agent per 1 m ^{2 of the} silver halide photographic light-sensitive material.