JP3320251B2 - Developer for silver halide photographic material and processing method using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer for a silver halide photographic light-sensitive material and a developing method using the same.

[0002]

2. Description of the Related Art Generally used black-and-white silver halide photographic light-sensitive materials (for X-rays, plate making, micro and negatives) use hydroquinone, hydroquinone monosulfonic acid or ascorbic acid and derivatives thereof as developing agents. And an alkaline developing solution containing a 3-pyrazolidone compound or an aminophenol compound as an auxiliary developing agent and a sulfite as a preservative for the developing agent.

[0003] Sulfite in a developer gradually dissolves silver halide in a photographic light-sensitive material to form silver sulfite in the developer. The silver sulfite is reduced by the developing agent in the developing solution to produce metallic silver, which adheres to the bottom and walls of the developing tank, rollers of an automatic developing machine, and the like. This so-called silver stain becomes a serious failure if it adheres to the image of the film to be processed next. A method for preventing such silver contamination is disclosed in Japanese Patent Publication No. 56-46585.
No., JP-B-62-4702, JP-B-62-4703, JP-A-58-1
No. 69147, U.S. Pat.Nos. 4,254,215, 3,318,701,
JP-A-58-203439, JP-A-62-56959, JP-A-62-28459,
62-178247, JP-A-1-200249, 4-362942, 5-
These are described in 303179, 5-53257 and 5-289255, but they are still effective, although they are effective. When the automatic developing machine is used continuously for one to two months, a problem of silver contamination occurs unless the racks and rollers of the automatic developing machine are sometimes washed. Such a problem of silver stain becomes serious when a long-term running of about two months is performed or when an ascorbic acid-based developing agent is used as a developing agent.

On the other hand, since the development waste liquid has a high chemical oxygen demand (so-called COD) and a high biological oxygen demand (so-called BOD), it is economically added to the waste liquid treatment. It has been desired to reduce the replenishment amount per unit area of a silver halide photographic light-sensitive material (especially for black and white) in order to reduce the replenishment. Simply, when the replenishing amount is reduced, the amount of silver eluted from the silver halide light-sensitive material into the developing solution increases, and the problem that silver stain increases increases.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
In addition, the use of a silver halide photographic light-sensitive material developer and a silver halide photographic light-sensitive material, which makes it possible to further improve the occurrence of silver stains when the silver halide photographic light-sensitive material is subjected to long-term running processing by an automatic processor, as compared with the conventional method. Is to provide an appropriate processing method. A second object of the present invention is to provide a silver halide photographic light-sensitive material developer capable of reducing the amount of replenisher and a processing method using the same.

[0006]

This and other objects are achieved by the following constitutions (1) to (3). (1) A silver halide photograph containing an ascorbic acid-based developing agent, a compound represented by the following chemical formula 6, and at least one selected from compounds represented by the following chemical formulas 7, 8, 9, and 10: Developer for photosensitive materials.

[0007]

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[0008]

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[0009]

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[0010]

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[0011]

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Wherein R ₁ is a hydrogen atom and has 1 to 6 carbon atoms.
Or an aminoalkyl group, a dialkylaminoalkyl group or a carboxyalkyl group each having an alkyl moiety having 1 to 6 carbon atoms. In the chemical formula 7, R
₂ and R ₃ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. However, R ₂ and R ₃ are not simultaneously hydrogen atoms. R ₄ and R ₅ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ₆ represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms. R ₇ and R ₈ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 18 or less carbon atoms, or a —COOM ₁₀ group. Here, M ₁₀ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group or having 15 or less of the aralkyl group having a carbon. However, R ₇ and R ₈ are not simultaneously hydrogen atoms. M ₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. k is 0, 1 or 2.
In Chemical formula 8, X represents a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group. M ₂ and M ₃ may be the same or different and each represents a hydrogen atom, an alkali metal atom or an ammonium group. In Chemical formula 9, D ₁ and B ₁ each independently represent an alkylene group. E ₂ and A
₂ independently of one another, respectively, -COOM, -SO ₂ M, -OM, -
_{SZ, -SO 2 N (X 1} ) (Y 1) or -CO (X ₁₎ representing the (Y _1). Here, M represents a monovalent cation. X ₁ and Y ₁ each represent a hydrogen atom, a hydroxy group, an alkyl group or a phenyl group optionally substituted by a sulfonic acid or a carboxylic acid, or a sulfonyl group optionally substituted by an alkyl group or a phenyl group. Z has the same meaning as X ₁ and Y ₁ , but is not a hydrogen atom. p is 1-2, m
And n are each an integer of 1 to 3. Wherein R ₉ and R ₁₀ are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, a mercapto group, a carboxy group, a sulfo group, a phosphono group, an amino group, a nitro group, a cyano group, a halogen atom, Represents an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group or a heterocyclic group. Also R ₉
And R ₁₀ may be linked to each other to form a ring. (2) A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material that has been imagewise exposed using the developer for the silver halide photographic light-sensitive material of the above (1) is developed. (3) method for processing a silver halide photographic light-sensitive material of the replenishment rate of the developing solution is treated as a photosensitive material 1 m ² per 25~250ml / m ² (1) above.

Incidentally, for example, Japanese Patent Publication No. 56-46585 shows Chemical Formula 9,
JP-A-64-2702 proposes a squirrel-type developer using the compound of formula 8 alone, but the effect of preventing silver stain is insufficient. JP-A-58-169141 proposes a squirrel-type developer in which a compound represented by the formula (6) and a benzotriazole compound are used in combination. Can not.

[0014]

[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail. The developer of the present invention and a developer prepared from the developer contain a compound represented by Chemical formula 6 and at least one compound represented by Chemical formulas 7 to 10.

In the following, Chemical Formula 6 is explained.
R ₁ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (for example, methyl or ethyl), an aminoalkyl group having an alkyl moiety having 1 to 6 carbon atoms (for example, aminomethyl or aminoethyl), or a dialkylaminoalkyl group (for example, Dimethylaminomethyl, dimethylaminoethyl), and a carboxyalkyl group which may have a substituent (for example, carboxymethyl, carboxyethyl, 1,2-dicarboxyethyl).

Specific examples of the compound of formula 6 are shown below. Among them, 11-1 is most preferable.

[0017]

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The compound of formula 6 may be used alone or in combination of two or more. The content of this compound in the developer is preferably 0.01 to 10 mmol / l, more preferably 0.1 to 2.0 mmol / l.

The chemical formula 7 is explained.
₂ and R ₃ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (eg, methyl, ethyl, propyl). Where R ₂ and R ₃
Are not simultaneously hydrogen atoms, and both are preferably alkyl groups. R ₄ and R ₅ represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (eg, methyl, ethyl, propyl), and R ₆ represents a hydroxyl group (including a metal salt), an amino group, or an alkyl group having 1 to 3 carbon atoms. Groups (eg methyl,
Ethyl, propyl). R ₇ and R _{8 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, methyl, ethyl, propyl), an acyl group having 18 or less carbon atoms, usually 2 to 18 carbon atoms (eg, acetyl, propionyl) or —COOM ₁₀ groups. Represent. Here _{M 10} represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group, having 15 or less carbon atoms, an aralkyl group usually 7 to 15. Where R ₇ and R
₈ cannot be a hydrogen atom at the same time. M ₁ represents a hydrogen atom, an alkali metal atom, or an ammonium group. k represents 0, 1 or 2.

Specific examples of the compound of formula 7 are shown below.

[0021]

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Describing the chemical formula 8, in formula 8, X
Represents a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group. M ₂ and M ₃ may be the same or different and each represents a hydrogen atom, an alkali metal atom or an ammonium group.

Hereinafter, specific examples of the compound of formula 8 will be shown. Among them, 13-1 is most preferable.

[0024]

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The chemical formula 9 will be described.
D ₁ and B ₁ are each independently an alkylene group which may have a substituent (eg, methylene, ethylene,
Dimethylmethylene, dimethylethylene, phenylethylene, methylphenylmethylene). E ₂ and A ₂
Each independently of one _{another, -COOM, -SO 2 M, -OM} , -SZ,
—SO ₂ N (X ₁ ) (Y ₁ ) and —CO (X ₁ ) (Y ₁ ). Where M is 1
Represents a positive cation (eg, H ⁺ ). X ₁ and Y ₁ each represent a hydrogen atom, a hydroxy group, an alkyl group or a phenyl group optionally substituted with a sulfonic acid or a carboxylic acid, or a sulfonyl group optionally substituted with an alkyl group or a phenyl group. Z has the same meaning as X ₁ and Y ₁ , but is not a hydrogen atom. p is 1 to
2, m and n are integers of 1 to 3.

A specific example of Chemical formula 9 is shown below.

[0027]

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In the chemical formula ₁₀ , R ₉ and R ₁₀ are each a hydrogen atom, an alkyl group (which may have a substituent, for example, methyl, ethyl, propyl, morpholinomethyl, 4-methylpiperazyl) Methyl, diaminomethyl), an aryl group (for example, phenyl), an aralkyl group, a hydroxy group, a mercapto group, a carboxy group, a sulfo group, a phosphono group, an amino group, a nitro group, a cyano group, a halogen atom, an alkoxy group, an alkoxycarbonyl group,
Represents an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, or a heterocyclic group. R ₉ and R ₁₀ may be linked to each other to form a ring (for example, cyclohexene).

The following are specific examples of the compound of formula (10).

[0030]

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The compounds of formulas 7 to 10 may be used alone or in combination of two or more. The content in the developer is preferably 0.01 to 10 mmol / l, more preferably 0.1 to 2.0 mmol / l.

The developing agent used in the developer or developer of the present invention is an ascorbic acid-based developing agent.

As the ascorbic acid-based developing agent, a compound represented by the following formula (16) is preferable.

[0034]

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In the formula, R ¹ and R ² each represent a hydroxy group, an amino group, a mercapto group or an alkylthio group. P and Q each represent a hydroxy group, a carboxy group, an alkoxy group, an alkyl group, a sulfo group, an amino group or an aryl group, or P and Q are bonded to each other to form R ¹ , R ² Represents an atomic group forming a 5- to 8-membered ring together with two substituted vinyl carbon atoms and a carbon atom substituted with Y ¹ . Y ¹ is ＯO or ＮN—R ³ Represents Where R ³
Represents a hydrogen atom, a hydroxy group, an alkyl group, or an acyl group.

The compound of formula (16) will be described in detail.

In Formula 16, R ¹ , R ² Is a hydroxy group, an amino group, a mercapto group or an alkylthio group (for example, methylthio, ethylthio), and the amino group may have a substituent, and the substituted amino group is an alkyl-substituted amino group having 1 to 10 carbon atoms. (E.g., methylamino, ethylamino, n-butylamino, hydroxyethylamino), acylamino groups (e.g., acetylamino,
Benzoylamino), an alkylsulfonylamino group (eg, methanesulfonylamino), an arylsulfonylamino group (eg, benzenesulfonylamino, p-toluenesulfonylamino), and an alkoxycarbonylamino group (eg, methoxycarbonylamino). R
¹ , R ² Preferred examples include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonyl group.

P and Q are a hydroxy group, a carboxy group, an alkoxy group, an alkyl group, a sulfo group, an amino group,
Represents an aryl group, or P and Q are linked together to form R
¹ , R ² Represents an atomic group forming a 5- to 8-membered ring together with two substituted vinyl carbon atoms and a carbon atom substituted with Y ¹ . An alkoxy group, an alkyl group, an amino group, and an aryl group may be substituted. Specific examples of the ring structure ^{-O -, - C (R 9} ) (R 10) -, - C (R 11)
=, - C (= O) -, - N (R 12) -, - formed by combining the N = like. Where R ⁹ , R ¹⁰ , R ¹¹ and R ¹² each represent a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms, which may have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, and a sulfo group. ), A hydroxy group or a carboxy group.
Further, a saturated or unsaturated condensed ring may be formed on the 5- to 8-membered ring.

Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrroline ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring and a uracil ring. Examples of the preferable 5- to 8-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

Y ¹ is ＯO or ＮN—R ³ Represents R
^Three Represents a hydrogen atom, a hydroxy group, an alkyl group (eg, methyl, ethyl) or an acyl group (eg, acetyl). The alkyl group and the acyl group may be substituted. Examples of the substituted alkyl group include a hydroxyalkyl group (eg, hydroxymethyl, hydroxyethyl), a sulfoalkyl group (eg, sulfomethyl, sulfoethyl), and a carboxyalkyl group (eg, carboxymethyl, carboxyethyl).

Specific examples of the ascorbic acid-based developing agent of the present invention are shown below, but the present invention is not limited to these.

[0042]

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[0043]

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[0044]

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[0045]

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Of these, preferred are ascorbic acid or erythorbic acid (diastereomer of ascorbic acid) represented by I-1 and alkali metal salts thereof such as lithium salt, sodium salt and potassium salt.

Since an ascorbic acid-based developing agent is used, the developer or developer of the present invention preferably does not substantially contain a polyhydroxybenzene compound represented by dihydroxybenzene such as hydroquinone. . That is, the content of the polyhydroxybenzene compound in the developer is desirably 0.0001 mol / liter or less, and most preferably, it is not contained at all.

On the other hand, dihydroxybenzene-based developing agents include hydroquinone, hydroquinone monosulfonic acid, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone,
2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,
Although there are 5-dimethylhydroquinone and the like, hydroquinone is particularly preferred.

In the present invention, it is particularly preferable to use an auxiliary developing agent such as 1-phenyl-3-pyrazolidone or p-aminophenol together with the above ascorbic acid-based developing agent. In particular, in the present invention, it is preferable to use an ascorbic acid-based developing agent in combination with such an auxiliary developing agent.

The 1-phenyl-3-pyrazolidones include 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 and the like.

Examples of p-aminophenols include N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, and 2-methyl-p-aminophenol. There are aminophenol and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferred. In the present invention, the developing agent in the developer is usually 0.01 mol /
It is preferably used in an amount of from 1 to 0.8 mol / l, particularly preferably in an amount of from 0.05 to 0.4 mol / l.

When an ascorbic acid-based developing agent is used in combination with an auxiliary developing agent such as 1-phenyl-3-pyrazolidone or p-aminophenol, the former is defined as 0.
05 mol / l to 0.5 mol / l, the latter being 0.001 to 0.06 mol / l (particularly 0.003 mol / l
〜0.06 mol / liter).

The developer or developer of the present invention preferably contains a sulfite as a preservative. Examples of the sulfite include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite. The sulfite in the developer is preferably at least 0.03 mol / l. The upper limit is 1.0
It is preferably up to mol / l, especially up to 0.8 mol / l.

The developer or developer of the present invention may contain an amino compound for accelerating the development. Especially JP
Amino compounds described in JP-A-56-106244, JP-A-61-267759, and JP-A-2-208652 may be used.

The pH of the developer used in the present invention is 8.0 to 13.0.
, Preferably from 8.3 to 12, more preferably from 8.5 to 10.5.

The developer or developer of the present invention preferably contains a carbonate (for example, sodium carbonate or potassium carbonate) as a pH buffer for setting a pH value. The amount of the carbonate used in the present invention is preferably 0.1 mol / L or more, particularly preferably 0.3 mol / L or more and 2 mol / L or less, and more preferably 0.4 mol / L or more and 1 mol / L. The following are most preferred.

The alkaline agent used for setting the pH of the developer or the developing solution of the present invention may be a conventional water-soluble inorganic alkali metal salt (for example, sodium hydroxide,
Potassium hydroxide) can also be used.

When the developing agent in the developer or the developer of the present invention is an ascorbic acid derivative, a boron compound such as boric acid or sodium metaborate is not preferred because it may react with the ascorbic acid derivative and inactivate it. .

The developer or developer according to the present invention further includes
Boric acid, borax, sodium phosphate dibasic, potassium phosphate dibasic, sodium phosphate monobasic, pH buffering agents such as potassium phosphate monobasic, and the pH described in JP-A-60-93433
Buffering agents can be used. Further, development inhibitors such as potassium bromide and potassium iodide, organic solvents such as dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol, benzotriazole derivatives, and nitroindazole can be used. Benzotriazole derivatives include 5-methylbenzotriazole, 5-bromobenzotriazole,
-Chlorobenzotriazole, 5-butylbenzotriazole, benzotriazole and the like, among which 5-methylbenzotriazole is particularly preferred. Examples of nitroindazole include 5-nitroindazole, 6-nitroindazole, 4-nitroindazole, 7-nitroindazole, 3-cyano-5-nitroindazole, and the like.
Particularly, 5-nitroindazole is preferred.

Further, if necessary, a color tone agent, a surfactant and the like may be contained.

The developer or the developer may contain a chelating agent, and specific examples of the compound include the following compounds. That is, ethylenediamine diorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid,
Nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid Acetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, nitrilotrimethylenephosphonic acid,
-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, Examples thereof include sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. Particularly preferred are, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanoltetraacetic acid, glycol etherdiaminetetraacetic acid, and hydroxyethylethylenediaminetriacetic acid. 2-phosphonobutane-1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydro Shipuropiriden 1,1-diphosphonic acid, 1-amino-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and salts thereof.

The total cation contained in the developer of the present invention is preferably such that potassium ion is 10 mol% or more and 90 mol% or less, sodium ion is 10 mol% or more and 90 mol% or less. It is more preferable that the content is 20 mol% or more and 50 mol% or less, and the sodium ion content is 50 mol% or more and 80 mol% or less.

The developer of the present invention can also be used as a concentrate for reducing transportation costs and storage space. When a concentrated solution is used, the concentration is preferably 3 times or less, more preferably 2 times or less, for the purpose of preventing precipitation of the developer components at low temperatures. In addition, components having different solubilities may be stored in several parts, and mixed and diluted at the time of use. At this time, the storage container has an oxygen permeability at 20 ° C. and 65% RH of 50 ml / m ² · atm · day or less, usually 1.0 to 50 ml.
/ m ² · atm · day is preferable.

The developer of the present invention is preferably of a working solution type, but most preferably one-concentration two-fold.

The developer of the present invention can be supplied as a solid chemical, that is, a powder.

The replenishment amount of the developing solution of the present invention is 25 ml or more and 250 ml or less per 1 m ² of a photosensitive material as a diluted developing solution.
Preferably it is 30 ml or more and 230 ml or less, more preferably 60 ml or more and 200 ml or less.

The development processing temperature and development processing time in the development processing of the present invention are each at 20 ° C. to 50 ° C. for 5 to 60 seconds, preferably at 25 ° C. to 40 ° C. for 10 to 45 seconds, more preferably. Are 15 to 32 ° C to 38 ° C respectively
30 seconds.

The total processing time (Dry to Dry) is from 20 seconds to
Preferably, it is 100 seconds.

In the present invention, the processing of the silver halide photographic material is carried out using an automatic developing apparatus. The opening ratio of the developing tank is 0.04 cm ^-1 or less, usually 0.01 to 0.0
It is preferably 4 cm ^-1 . Further, each replenisher of the developing solution and the fixing solution is preferably supplied by a mixed dilution method immediately before being supplied from each of these concentrated solutions diluted with water in each of the tanks to be used, and each of the concentrated solutions is It preferably comprises one part. Further, it is preferable that the containers for the concentrated developing solution and the concentrated fixing solution are an integrated packaging material.

When a chemical mixer is incorporated in the automatic developing apparatus, it is preferable to have a mechanism in which the cartridges for the developing solution and the fixing solution can be used simultaneously. When the developer is of the working liquid type, it is preferable to use the fixing solution of the working liquid type.

As the automatic developing device, it is preferable to use an automatic developing machine provided with a rinsing tank and a rinsing roller (crossover roller) between the developing tank and the fixing tank and between the fixing tank and the washing tank. Further, it is preferable that a stock tank for water to be supplied with various water rust preventive agents (antibacterial agents) is installed in the washing tank and the rinsing tank. Further, it is preferable that an electromagnetic valve is installed at the drain of the washing tank.

Further, it is preferable that the rinsing tank of the automatic developing apparatus is a multi-chamber tank or that a multi-stage countercurrent rinsing system is employed.

Further, it is preferable to provide a roller section in contact with the photosensitive material at a stage preceding the drying section of the automatic developing apparatus.
As described above, the temperature is more preferably set to 70 to 110 ° C.

The photographic light-sensitive material developed using the developer of the present invention is not particularly limited, and a general black-and-white light-sensitive material is mainly used. In particular, photographic materials for laser light sources and photosensitive materials for printing, as well as X-ray photosensitive materials for direct medical photography,
Medical indirect X-ray photosensitive materials, CRT image recording photosensitive materials, microfilms, general photographing photosensitive materials, and the like can also be used.

Next, emulsion grains in a silver halide light-sensitive material which is developed using the developer of the present invention will be described. The silver halide composition is preferably silver chloride, silver chlorobromide, silver bromide, silver chloroiodobromide, and the like. Silver chloride 10 to 100 mol%, silver bromide 10 to 100 mol%, silver iodide 0 to 5 Molar% is preferred. As the particle size, the diameter of a sphere having the same volume as the emulsion particles (hereinafter referred to as a sphere-equivalent average particle size) is 0.1.
It is preferably 2 μm or more and less than 2.0 μm, particularly preferably 1.
Preferably it is less than 5 μm. The narrower the particle size distribution, the better. The silver halide grains in the emulsion were cubic, 8
It may have a regular crystal form such as a tetrahedron or a tetrahedron, or may have an irregular crystal form such as a sphere, plate, potato, or the like. It may consist of a mixture of particles of different crystal forms. Further, tabular grains whose grains are at least 5 times the grain thickness are preferably used in the present invention. (For details, RESEARCH DISCLOSURE Volume 225, Item
22534 pages 20 to 58, January, 1983, and JP-A-58-127921 and JP-A-58-113926. The tabular silver halide grains can be produced by appropriately combining methods known in the art. Tabular silver halide emulsions are described in JP-A-58-127921, JP-A-58-113927, JP-A-58-113928, U.S. Pat.
It can be easily prepared by referring to the method described in 39520. The projected area diameter of the tabular emulsion of the present invention is from 0.3 to 2.0.
μm, particularly preferably 0.5 to 1.2 μm. The distance between the parallel planes (particle thickness) is 0.05 μm
Of 0.3 to 0.3 μm, especially 0.1 to 0.25 μm.
Those having a value of at least 8 and less than 8 are preferred. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 2 or more exist in an amount of 50% (projected area) or more, particularly 70% or more of all grains, and the average aspect ratio of the tabular grains is 2 or more. 3 or more,
Particularly, it is preferably from 4 to 8.

The size distribution of the silver halide grains may be wide or narrow, but the so-called monodisperse emulsion is better in photographic characteristics such as latent image stability and pressure resistance and processing stability such as developer pH dependency. preferable. The value S / d obtained by dividing the standard deviation S of the diameter distribution when the projected area of the silver halide grains is converted into a circle by the average diameter is preferably 20% or less, more preferably 15% or less.

In the present invention, it is particularly preferable to use a cubic monodispersed emulsion, in which the size of silver halide grains is 0.4 μm or less, more preferably 0.15 to 0.4 μm.
It is preferable that

Emulsions such as silver chloride, silver chlorobromide, silver bromide or silver chloroiodobromide emulsions used in the silver halide photographic light-sensitive material used in the present invention are described in "Photographs" by P. Glafkides (Graffide). Chemistry and Physics "(Paul Montell, 1967
), GF Duffin, "The Chemistry of Photographic Emulsions" (Focal Press, 1966), VL Ze
It can be prepared by applying a method described in "Preparation and Coating of Photographic Emulsion" by likman et al. (Focal Press, 1964). That is,
Acid method, neutral method, any of ammonia method, etc.,
In particular, the acidic method and the neutral method are preferred in the present invention from the viewpoint of reducing fog. In order to obtain a silver halide emulsion by reacting a soluble silver salt with a soluble halogen salt, any one of a so-called single-sided mixing method, a double-sided mixing method, and a combination thereof may be used. A so-called back-mixing method in which grains are formed under conditions of excess silver ions can also be used. In order to obtain an emulsion of monodisperse grains which is preferable for the present invention, it is preferable to use a double jet method. As one type of the double jet method, it is more preferable to use a method in which the silver ion concentration in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method. By using this method, a silver halide emulsion having a regular silver halide crystal shape and a narrow grain size distribution can be obtained.

In order to form high silver chloride grains, a method described in
No. 32, No. 3-137632, No. 4-6546, Japanese Patent Application No. 3-36632,
No. 3-236880, etc., using a bispyridinium compound described in JP-A-62-293536, JP-A-1-155332, JP-A-63-2043, JP-A-63-25643, U.S. Pat.
And the methods described in Japanese Patent No. 5061617 and the like can be preferably used.

In the course of such silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, or an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or an iron salt as described above. Alternatively, a complex salt thereof may coexist.

During or after grain formation, a silver halide solvent (for example, as known ones, ammonia, thiocyanate, US Pat. No. 3,271,157, JP-A-51-12360)
No., JP-A-53-82408, JP-A-53-144319, JP-A-54
Thioethers and thione compounds described in JP-A-100717 or JP-A-54-155828, etc., and when used in combination with the above-mentioned method, a halogenated silver halide having a regular silver halide crystal shape and a narrow grain size distribution. A silver emulsion can be obtained.

The silver halide solvents used in the present invention are described in US Pat. Nos. 3,271,157, 3,531,289, 3,574,628, JP-A-54-1019 and JP-A-54-158917. a) Organic thioethers, JP-A-53-824
Nos. 08, 55-77737, 55-2982, etc. (b) Thiourea derivatives, and (c) Oxygen or sulfur atoms and nitrogen atoms described in JP-A-53-144319 Silver halide solvent having a sandwiched thiocarbonyl group
(D) imidazoles described in -100717, (e)
Sulfite, (f) thiocyanate and the like. Particularly preferred solvents include thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind. For example, in the case of thiocyanate, the preferred amount is 1 × 10 ^-4 mol or more per mol of silver halide.
10 ^-2 mol or less.

In order to effectively use the effects of the present invention,
It is preferable to use a selenium sensitizer. As the selenium sensitizer, a selenium compound disclosed in a conventionally known patent can be used. Non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-344.
Compounds described in No. 92 and JP-B No. 52-34491 are used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethione and derivatives thereof.

The silver halide photographic emulsion developed with the developer of the present invention can achieve higher sensitivity and lower fog by using sulfur sensitization and / or gold sensitization in chemical sensitization. . Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain period of time. Gold sensitization is usually carried out by adding a gold sensitizer at a high temperature, preferably 40 ° C.
This is carried out by stirring the emulsion at a temperature of not less than ° C for a certain period of time.
Known sulfur sensitizers can be used for the above sulfur sensitization. For example, thiosulfates, thioureas, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like can be mentioned. In addition, U.S. Patent Nos. 1574944, 2410689, 2278947
Nos. 2,728,668, 3,501,313, 3,569,055, German Patent 1,422,869, JP-B-56-24937,
Sulfur sensitizers described in JP-A-55-45016 and the like can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc., but is not less than 1.times.10.sup.- ⁷ mol and 5.times.10.sup.- ⁴ per mol of silver halide. Molar or less is preferred.

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 or +3, and gold compounds usually used as gold sensitizers can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acidide, ammonium aurothiocyanate, pyridyl trichlorogold, and the like. Although the amount of the gold sensitizer to be added varies depending on various conditions, the standard is preferably 1 × 10 ⁻⁷ mol to 5 × 10 ⁻⁴ mol per mol of silver halide.

In order to effectively utilize the effects of the present invention,
During chemical sensitization during the emulsion preparation process as described in JP-A-2-68539, it is preferred that 0.5 mmol or more of a silver halide-adsorbing substance is present per 1 mol of silver halide.
The silver halide-adsorbing substance may be added at any time such as during grain formation, immediately after grain formation, or before or after the start of post-ripening. However, addition of a chemical sensitizer (for example, gold or sulfur sensitizer) It is preferably added before the chemical sensitizer or at the same time as the chemical sensitizer, and it must be present at least during the course of chemical sensitization. As a condition for adding the silver halide-adsorbing substance, the temperature may be any temperature of 30 ° C to 80 ° C, but is preferably in the range of 50 ° C to 80 ° C for the purpose of enhancing the adsorptivity. The pH and pAg may be arbitrarily set, but are preferably 5 to 10 and pAg 7 to 9 at the time of chemical sensitization.

Here, the silver halide-adsorbing substance means a sensitizing dye or a photographic performance stabilizer. That is, azoles {eg, benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc .; mercapto compounds {eg, mercaptothiazoles, Mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines and the like; Thioketo compounds; azaindenes {eg, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) Tiger aza indene), pentaazaindenes such like); known as antifoggants or stabilizers, such as, a number of compounds may be mentioned as the silver halide adsorptive materials. Further, purines or nucleic acids, or JP-B-61-36213, JP-A-59-90844
, Etc. are also adsorptive substances that can be used.

As a silver halide-adsorbing substance, a sensitizing dye can realize a preferable effect. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention are described, for example, in U.S. Patent Nos. 3,352,052, 3,619,197, 3,713,828, and 36.
15643, 3615632, 3617293, 3628964
No. 3703377, No. 3666480, No. 3667960, No. 36
79428, 3672897, 3769026, 3556800
Nos. 3615613, 3615638, 3615635, 37
05809, 3632349, 3677765, 3770449
Nos. 3770440, 3769025, 3745014, 371
3828, 3567458, 3625698, 2526632
No. 2503776, JP-A-48-76525, Belgian Patent No.
It is described in 691807 and the like.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material to be developed using the developer of the present invention may have coating aids, antistatic properties, improved slipperiness, improved emulsification and dispersion, improved adhesion and improved photographic properties ( For example, various surfactants may be included for various purposes such as development acceleration, hardener, and sensitization.

As a binder or protective colloid which can be used in the emulsion layer, intermediate layer and surface protective layer of the light-sensitive material, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate, dextran and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone; Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole can be used. As the gelatin, besides lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and hydrolyzate or enzyme-decomposed product of gelatin can also be used. Among these, it is preferable to use dextran or polyacrylamide having an average molecular weight of 50,000 or less together with gelatin. The methods described in JP-A-63-68837 and JP-A-63-149641 are also effective in the present invention.

The photographic emulsion and the non-photosensitive hydrophilic colloid may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ),
Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β-
(Vinylsulfonyl) propionamide] and other active halogen compounds (2,4-dichloro-6-hydroxy-s
-Triazines), mucohalogenic acids (mucochloric acid, mucophenoxycyclolic acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-41221 and JP-A-53-41221
Preferred are the active vinyl compounds described in U.S. Pat. Nos. 3,57,287 and 60-80846 and the active halides described in U.S. Pat. No. 3,325,287.

The hydrophilic colloid layer in the photographic light-sensitive material is preferably hardened by these hardeners so that the swelling ratio in water is 280% or less. The swelling ratio in water in the present invention is measured by a freeze-drying method. That is, the swelling ratio of the hydrophilic colloid layer is measured when the photographic material is aged at 25 ° C. and 60% RH for 7 days. The dry thickness (a) is determined by a scanning electron microscope of the section. The swelling film layer (b)
The photographic material is immersed in distilled water at 21 ° C. for 3 minutes, freeze-dried with liquid nitrogen, and then observed with a scanning electron microscope. The swelling ratio is a value (%) obtained by dividing the value of {(b)-(a)} by (a) and multiplying by 100. The swelling ratio is preferably 150% or more.

The emulsion layer of the photographic light-sensitive material may contain a plasticizer such as a polymer or an emulsion in order to improve pressure characteristics. For example, British Patent No. 738618 discloses a heterocyclic compound and No. 738637 discloses an alkyl phthalate.
No. 2,960,404, a polyhydric alcohol, U.S. Pat.No. 3,121,060, a carboxyalkyl cellulose, JP-A-49-5017, paraffin and carboxylate, No. 28086 discloses a method using an alkyl acrylate and an organic acid. Other constitutions of the emulsion layer of the silver halide photographic light-sensitive material of the present invention are not particularly limited, and various additives can be used as needed. For example, ResearchDisclosure 1
76, pp. 22-28 (December 1978), binders, surfactants, other dyes, coating aids, thickeners, and the like can be used.

The thickness of the emulsion layer of the silver halide photographic light-sensitive material in the present invention is preferably about 2 to 10 μm as the thickness existing on one side of the support.

A silver halide photographic light-sensitive material having a photographic emulsion layer on both sides has a problem that the image quality is easily deteriorated by crossover light. The crossover light is emitted from the respective intensifying screens disposed on both sides of the photosensitive material, passes through a support of the photosensitive material (usually, a thick one having a thickness of about 170 to 180 μm is used), and is exposed to light on the opposite side. Visible light that reaches the layer and reduces the image quality (especially sharpness). The silver coating amount of the photographic emulsion layers on both sides of such a light-sensitive material is preferably 3.5 g or less, more preferably 1.0 to 3.5 g per 1 m ² .

The smaller the crossover, the sharper the image. Although there are various methods for reducing the crossover, the most preferable method is to fix a decolorable dye between the support and the photosensitive layer by a development treatment. The use of microcrystalline dyes, taught in U.S. Pat.No. 4,803,150, provides good fixation, good decolorization, can contain a large amount of dyes, and is very useful for reducing crossover. Preferred. According to this method, there is no desensitization due to improper fixation, the dye can be decolorized by rapid processing, and the crossover can be reduced to 15% or less.

The dye layer for reducing crossover is more preferably a layer in which dyes are arranged as densely as possible. It is preferable that the amount of gelatin used as a binder is reduced and the thickness of the dye layer is 0.5 μm or less. However, an extremely thin layer tends to cause poor adhesion, and the most preferable thickness of the dye layer is 0.05 μm to 0.1 μm.
3 μm.

In addition to the above, the black-and-white photographic light-sensitive material may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styrine dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As a support for a photographic light-sensitive material,
It must have a thickness of 250 μm. This is indispensable from the viewpoint of handleability when observing on a medical shakasten. The material is preferably a polyethylene terephthalate film, particularly preferably colored blue.

The surface of the support is preferably subjected to a corona discharge treatment, a glow discharge treatment or an ultraviolet irradiation treatment in order to improve the adhesion to the hydrocolloid layer. Alternatively, an undercoat layer made of styrene-butadiene-based latex, vinylidene chloride-based latex, or the like may be provided, and a gelatin layer may be further provided thereon.

An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided.

The undercoat layer may be further subjected to a surface treatment to further improve the adhesion to the hydrocolloid layer.

As various additives used in the photographic light-sensitive material, those described in the following applicable places can be used.

Items The present section 1) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16, JP-A-5-313282. 2) Antifoggant, JP-A-2-68539, page 10, lower left column, line 17 to stabilizer Stabilizer, page 11 upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column .

3) Color tone improver From page 7, lower left column, line 7 of JP-A-62-276538 to page 10, lower left column, line 20; JP-A-3-94249, page 6 lower left column, line 15 To page 11, upper right column, line 19.

4) Surfactant, JP-A-2-68539, page 11, upper left column, line 14 to antistatic agent, page 12, upper left column, line 9.

5) Matting Agent, Sliding JP-A-2-68539, page 12, upper left column, line 10 Agents and plasticizers Same upper right column, line 10, page 14, lower left column, line 10 to lower right column 1, Line.

6) Hydrophilic colloids JP-A-2-68539, page 12, upper right column, line 11 to lower left column, line 16;

7) Hardener From page 17, lower left column, line 17 to page 13, upper right column, line 6 of JP-A-2-68539.

8) Polyhydroxyl JP-A-3-39948, page 11, upper left column to page 12, benzenes, lower left column, EP Patent No. 452772A.

9) Layer Configuration JP-A-3-19841

The preferred embodiments of the present invention are as follows. 1. The developer according to claim 1, which is a one-part concentrate.

2. A processing method for developing a silver halide photographic material having a swelling ratio of 150% or more using the developer according to claim 1.

3. A processing method for developing a silver halide photographic light-sensitive material having a silver amount applied to both sides of the photographic light-sensitive material of 3.5 g or less per 1 m ² using the developer according to claim 1.

4. A processing method for developing a cubic monodispersed silver halide photographic material having silver halide grains of 0.4 μm or less using the developer of claim 1.

5. The silver halide grains have a silver chloride content of 10 to 1
00 mol%, silver bromide 10 to 100 mol%, silver iodide 0
2. A silver halide photographic light-sensitive material having a content of from 5 to 5 mol%.
A processing method of developing using a developer.

6. A processing method using the developer according to claim 1, wherein the total processing time (Dry to Dry) is 20 seconds to 100 seconds.

7. A processing method in which the temperature of the heating means of the roller portion in contact with the photosensitive material before the drying section of the automatic developing apparatus using the developing solution of claim 1 is 70 ° C. or higher.

8. A processing method which is an automatic developing apparatus having a mechanism in which a developer and a fixing liquid cartridge are simultaneously used when a chemical mixer is incorporated in the automatic developing apparatus.

9. A processing method according to claim ^{1, wherein} the opening ratio of the developing tank of the automatic developing apparatus using the developer is 0.04 cm ^-1 or less.

10. A processing method in which a developing concentrated solution and a fixing concentrated solution are composed of one part, and each concentrated solution and water are diluted into a working solution in each tank and supplied as a replenisher (just before mixing and dilution method).

11. A processing method wherein the container for the concentrated developing solution and the concentrated concentrated fixing solution according to claim 1 is an integrated packaging material.

12. A processing method using an automatic developing machine provided with a rinsing tank and a rinsing roller (crossover roller) between the developing tank and the fixing tank and between the fixing tank and the washing tank using the developer according to claim 1.

13. A processing method using an automatic developing machine provided with a stock tank for water in which various water-stain inhibitors (antibacterial agents) are supplied to a washing tank and a rinsing tank.

14. A processing method using an automatic developing machine in which a solenoid valve is installed at a drain port of a washing tank.

15. The developer according to claim 1, wherein the developer is a powder.

16. A processing method in which the developer and the fixing agent are of a working liquid type.

17. A processing method in which the washing tank of the automatic developing apparatus has a multi-chamber tank and a multi-stage counter-current washing tank.

18. Oxygen permeability is 50 ml / m ² · atm · day (2
A method for storing and processing the liquid developer of claim 1 in a container having a temperature of 0 ° C. and 65% RH or lower.

[0130]

Next, the present invention will be described in more detail with reference to examples, but the examples of the present invention are not limited to these examples.

Example 1 Preparation of Developing Solution Developing Solution A Sodium sulfite 10.0 g Potassium carbonate 55.2 g Diethylene glycol 25.0 g Diethylenetriaminepentaacetic acid 2.0 g Sodium bromide 1.0 g 5-Methyl-benzotriazole 0.1 g 4- Hydroxymethyl-4-methyl-1-phenyl 6.6 g -3-pyrazolidone L-ascorbic acid 30.0 g

Add water to make up 1 liter and bring to pH = 10.3 with potassium hydroxide.

The developer A, to which the respective compounds were added, was used as a mother liquor developer B, C, D, E, F, G, H,
Developers as shown in Table 1 were prepared as J, K, L, M, N, P, and Q. Starters prepared by adding 7.4 g of potassium bromide and 7.2 g of acetic acid respectively corresponding to the developing solutions A to Q were prepared.

[0134]

[Table 1]

Using a Fuji Medical Xray Film Super HR-S30 and a Fuji Medical Film Processor CEPROS-S, a film was processed at a rate of 10 m ² per day, and each developer was added at a rate of 200 ml / m ² without a starter. A 2-month running test was carried out while replenishing with the use of. The development at this time was performed at 35 ° C. for 29 seconds, and the total processing time (Dry to Dr.
y) was 100 seconds. Table 2 shows the obtained results.

The sensitivities in the table are shown as relative values with the reciprocal of the amount of exposure necessary for obtaining a blackening density of 1.0 in the developing solution A being 100. The silver stain was visually evaluated for the processed film and the developing tank of the automatic developing machine by running for two months. In this case, “1” corresponds to a failure due to partial adhesion of silver stain on the film, and “3” indicates no silver stain on the film, but silver on the bottom of the developing tank of an automatic developing machine, a wall rack, or the like. There is a possibility that a stain may occur on the film after running for a long time, and the developing tank and the rack need to be cleaned at this point. "5" indicates a silver stain on the bottom wall rack of the developing tank. And there is no need to wash the developing tank, rack, etc. of the automatic developing machine, and it can be continued as it is, and those between "1" and "3" are "2", "3" and "5" The score in the middle of "4" was visually evaluated on a scale of 5 as "4".

[0137]

[Table 2]

As can be seen from the results in Table 2, compounds 11-1, 12-1, and 13- of known silver stain preventive agents are known.
Developers B, C, D containing 1, 14-1, 15-1, etc.
E, F, G, H, J, K, and L improved silver stain on developer A but were insufficient. Among these, developer B was prepared in the same manner as in JP-A-58-169147.
Is used in combination with a benzotriazole compound, but the effect of preventing silver staining is insufficient. Surprisingly, the developers M, N, P, of the present invention using the compound represented by the formula (6) in combination with any one of the compounds represented by the formulas (7) to (10):
In the case of Q, the silver stain was remarkably improved. Incidentally, the developers M, N, P, and Q use two kinds of compounds in combination, so that the total amount of the developers is 1.0 mM. However, the developers C, E, G,
Even when the amount of addition is 1.0 mM alone as in the cases of J and L, such an effect of preventing silver stain cannot be obtained. It is considered that the use of the compound represented by Chemical Formula 6 and the compounds represented by Chemical Formulas 7 to 10 effectively prevented the effect of preventing silver stain which had not been considered until now.

In the above description, a working solution type developer is used. However, similar results were obtained when the solution was diluted with a compact concentrated solution type developer and used.

[0140]

According to the present invention, the generation of silver stain can be remarkably suppressed even in a long running with a low replenishing amount.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-123943 (JP, A) JP-A-7-77781 (JP, A) JP-A-57-26848 (JP, A) 53257 (JP, A) JP-A-62-296140 (JP, A) JP-A-63-33744 (JP, A) JP-A-7-56286 (JP, A) JP-A-6-186690 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 5/29-5/305

Claims (3)

(57) [Claims] 1. An ascorbic acid-based developing agent, and
And a compound represented by the following formulas 2, 3, 4, and 5
A developer for a silver halide photographic material containing at least one compound selected from the group consisting of: Embedded image Embedded image Embedded image Embedded image Embedded image [Wherein R ₁ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aminoalkyl group, a dialkylaminoalkyl group or a carboxyalkyl group each having an alkyl portion having 1 to 6 carbon atoms. Wherein R ₂ and R
₃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. However, R ₂ and R ₃ are not simultaneously hydrogen atoms. R ₄ and R ₅ each represent a hydrogen atom or a group having 1 to 3 carbon atoms.
R ₆ represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms. R ₇ and R ₈ each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an acyl group having 18 or less carbon atoms, or a —COOM ₁₀ group. Here, M ₁₀ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group or having 15 or less of the aralkyl group having a carbon. However, R ₇ and R ₈ are not simultaneously hydrogen atoms. M ₁ represents a hydrogen atom, an alkali metal atom or an ammonium group. k is 0, 1 or 2. In chemical formula 3, X
Represents a hydrogen atom, a hydroxy group, a lower alkyl group, a lower alkoxy group, a halogen atom, a carboxyl group or a sulfo group. M ₂ and M ₃ may be the same or different and each represents a hydrogen atom, an alkali metal atom or an ammonium group. In Chemical Formula 4, D ₁ and B ₁ each independently represent an alkylene group. E ₂ and A ₂ are each independently —COOM, —SO ₂ M, —OM, —SZ, —SO ₂ N
(X ₁ ) (Y ₁ ) or —CO (X ₁ ) (Y ₁ ). Where M is 1
Represents a valent cation. X ₁ and Y ₁ are each a hydrogen atom,
Represents an alkyl group or a phenyl group which may be substituted by a hydroxy group, a sulfonic acid or a carboxylic acid, or a sulfonyl group which may be substituted by an alkyl group or a phenyl group. Z has the same meaning as X ₁ and Y ₁ , but is not a hydrogen atom. p is 1-2 and m and n are each an integer of 1-3. In formula 5, R ₉ and R ₁₀ are each a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a hydroxy group, a mercapto group, a carboxy group, a sulfo group,
Represents a phosphono group, an amino group, a nitro group, a cyano group, a halogen atom, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, or a heterocyclic group. R ₉ and R ₁₀ may be linked to each other to form a ring. ] 2. A method for processing a silver halide photographic light-sensitive material, comprising developing the silver halide photographic light-sensitive material imagewise exposed using the developer of the silver halide photographic light-sensitive material according to claim 1. 3. A photosensitive material 1 in which a replenishing amount of a developing solution is processed.
3. The method for processing a silver halide photographic light-sensitive material according to claim ² , wherein the amount is 25 to 250 ml / m < ² > per m < ² >.