JP2000047355A - Developing solution for silver halide photographic sensitive material and processing method for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a developing soln. which stably gives photographic performance even under low replenishment, suppresses the generation of silver sludge and imparts good preservability to an image after development by incorporating at least two specified compds. SOLUTION: The developing soln. contains a compd. of formula I and a compd. arbitrarily selected from the group consisting of compds. of formula II, etc. In formula I, R11 is a branched alkyl, an aryl or a branched alkoxy, R12 is a 1-5C alkyl group, an alkoxy group or a cyano group, X is a carboxy group, a sulfonate group, a sulfate group, a phosphate group or a 1-4C alkyl group or alkenyl group with these groups substd., (m) is 0-3, (n) is 1-4 and m+n=4. In formula II, R1 is H, a 1-6C alkyl, an aminoalkyl having a 1-6C alkyl part, a dialkylaminoalkyl having a 1-6C alkyl part or a carboxyalkyl having a 1-6C alkyl part.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a developer for a silver halide photographic light-sensitive material and a method for processing a silver halide photographic light-sensitive material. The present invention provides stable photographic performance even with low replenishment, and suppresses the generation of silver sludge.
An object of the present invention is to provide a developer for a silver halide photographic light-sensitive material capable of obtaining an image after development processing having good storage stability, and a method for processing a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, interest in the global environment has increased, and in the field of photographic processing, for example, marine dumping of disposal of processing agents has been regulated. For this reason, for example, in the field of medical photography, there is a demand for a reduction in the amount of processing agents used.

In order to reduce the amount of replenishment, the concentration of the components contained in the developer may be increased by the amount corresponding to the reduced amount of replenishment. The amount of the substance of the treating agent to be used can be adjusted so that the amount before the reduction and the amount after the reduction are equal. However, when the replenishment amount is reduced, the time during which the developer stays in the storage unit, for example, the developing tank, becomes longer, the tendency of the developer to be oxidized by air is increased, and the activity of the developer may be reduced. A problem has arisen.

[0004] On the other hand, sulfurous acid used as an antioxidant in a developer has solubility in silver halide. Therefore, the eluted silver ions are reduced by the developing agent, and accumulate deposited silver called silver sludge. When continuous processing is performed by an automatic developing machine, the silver sludge floats in a developing solution and adheres to a photosensitive material film, or adheres to a roller or a belt of the automatic developing machine. For this reason, serious obstacles such as generation of yellow-brown streak-like stains and scratches on the conveyed film are not eliminated.

Further, it is desired that the photosensitive material has good image storability. Particularly, for example, a medical diagnostic image may need to be stored for a long period of time in order to monitor the progress of a medical condition. The requirement for storage stability is particularly important.

The storability of an image varies depending on the constitution of the photosensitive material, development processing conditions, and storage conditions after development processing. For example, if the fixation and washing with water during the development process are insufficient, silver sulfide may be generated during storage, and the silver image may change to yellow (sulfur discoloration).

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art. The problem to be solved by the present invention is, first, to process a silver halide photographic material. The present invention provides a developer for a silver halide photographic light-sensitive material capable of stably obtaining photographic performance even when replenishing at a low level, and a method for processing a silver halide photographic light-sensitive material.
The second object is to provide a developer for a silver halide photographic light-sensitive material in which the generation of silver sludge is suppressed even when the replenishment is low, and a method for processing a silver halide photographic light-sensitive material.
Another object of the present invention is to provide a developing solution for a silver halide photographic light-sensitive material and a method for processing a silver halide photographic light-sensitive material, which have good preservability of an image after development even if the replenishment is low.

[0008]

The above objects of the present invention have been attained by the following. The compounds will be described later. At least one compound represented by the general formula (1);
General formula (A), (B), (C), (D), or (E)
And at least one arbitrarily selected from the group consisting of compounds represented by the formula: At least one compound represented by the general formula (2);
General formula (A), (B), (C), (D), or (E)
And at least one arbitrarily selected from the group consisting of compounds represented by the formula: At least one kind of reductone compound, at least one kind of compound represented by the following general formula (3), and at least one compound represented by the following general formulas (A), (B), (C), (D), or (E) A developer for a silver halide photographic light-sensitive material, comprising at least one arbitrarily selected from the group consisting of the compounds represented by the formula (I). The developer for a silver halide photographic material as described above, wherein the compound represented by the general formula (3) is represented by the general formula (4). In the formula (3), R ²¹ is a hydrogen atom, wherein the developer for a silver halide photographic material is as described above. A method for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, comprising: A method for processing a silver halide photographic light-sensitive material. A method for processing a silver halide photographic material as described above, characterized by satisfying the following relational expression (L). Relational expression (L) 0.03 ≦ R / V ≦ 0.11, where capacity of developing tank: V (liter) Replenishment amount of developer per day: R (liter / day)

Hereinafter, the present invention will be described in more detail. First, the compound represented by the general formula (1) will be described.
The general formula (1) is as follows.

[0010]

Embedded image

R ¹¹ is a group selected from branched alkyl, aryl and branched alkoxy. R ¹² : each independently an alkyl group having 1 to 5 carbon atoms;
It is a group selected from a substituted alkyl group, an alkoxy group, a substituted alkoxy group, and a cyano group. X: carboxyl group, sulfonic group, sulfate group,
It is a group selected from alkyl and alkenyl having 1 to 4 carbon atoms in which at least one of a phosphate group, a carboxyl group, a sulfonic group, a sulfate group and a phosphate group is substituted. m = 0-3, n = 1-4 (where m + n = 4)

R ¹¹ and R ¹² are preferably an alkyl group having 3 or 4 carbon atoms, a substituted alkyl group, an alkoxy group, or a substituted alkoxy.

X is preferably a carboxyl group, a sulfonic group, a sulfate group or a phosphate group.

Further, a compound represented by the following general formula (5) among the general formula (1) is more preferably used.

[0015]

Embedded image

The compounds represented by the general formulas (1) and (5) can be synthesized by a generally known method, and the preferable addition amount is 0.001 mol / L or more and 0.1 mol / L or less. Is preferably used. More preferably, it is 0.1 mol / L or more and 0.07 mol / L or less.

Hereinafter, specific examples of the compound represented by the general formula (1) will be shown, but it should not be construed that the invention is limited thereto.

[0018]

Embedded image

[0019]

Embedded image

Next, the compound represented by formula (2) will be described. The general formula (2) is as follows.

[0021]

Embedded image

M is a monovalent or divalent atom. k: 2 when M is monovalent, and 1 when M is bivalent. A: An atom selected from P, Sb, and Bi.

A represents an atom selected from P, Sb and Bi, and P is particularly preferably used. The compound represented by the general formula (2) can be synthesized by a generally known method. The preferable addition amount is 0.01 mol / L or more and 1 mol / L or less. More preferably, it is 0.05 mol / L or more and 0.5 mol / L or less.

Hereinafter, specific examples of the compound represented by the general formula (2) will be given, but it should not be construed that the invention is limited thereto.

[0025]

Embedded image

Next, the compound represented by formula (3) will be described. The general formula (3) is as follows.

[0027]

Embedded image

In the formula, R ²¹ is a group selected from a hydrogen atom and a methyl group. R ²² , R ²³ and R ²⁴ are each independently a group selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a carboxyl group. However, when each of R ²² , R ²³ and R ²⁴ is an alkyl group, each may be independently substituted with a hydroxyl group, a carboxyl or a sulfo group. In the case where each of R ²² , R ²³ and R ²⁴ is an alkyl group, the —SH group is not substituted.

When R ²² , R ²³ and R ²⁴ are alkyl, it is preferable to substitute them with a hydroxyl group, a carboxyl group or a sulfo group from the viewpoint of reducing odor.

Hereinafter, specific examples of the compound represented by the formula (3) will be shown, but the invention is not limited thereto.

[0031]

Embedded image

[0032]

Embedded image

The amount of the compound represented by the general formula (3) of the present invention to be added to the developer is not particularly limited, but practically 0.01 mol or more per 1 liter of a developer actually used. It is used in an amount of 5 mol or less, more preferably 0.05 mol or more and 1 mol or less.

In the present invention, the compound represented by formula (3) may be used alone or in combination.

Next, the compound represented by formula (4) will be described. The general formula (4) is as follows.

[0036]

Embedded image

R ²⁵ and R ²⁶ each independently represent a hydrogen atom,
Selected from methyl groups. However, when one or both of R ²⁵ and R ²⁶ is a methyl group, the methyl group is —COO
It may be substituted with M ', -OH. In the general formula (4) of the present invention, R ²⁵ and R ²⁶ are not substituted with a —SH group. M '
Can be a hydrogen atom, an alkali metal atom, or an ammonium salt, but is actually a carboxylic acid, and is considered to be dissociated in a developer in an anion form. 1 is 0, 1.
Although 2 can be taken, 0 is the highest effect of the present invention, and the effect decreases as the number increases. Specific examples of the compound represented by the general formula (4) are shown below, but it should not be construed that the invention is limited thereto.

[0038]

Embedded image

[0039]

Embedded image

These compounds are all known compounds and can be easily obtained by synthesis, extraction, and the like.
Of these, (4-1), (4-2),
(4-5).

In the present invention, the amount of the compound represented by the general formula (4) to be added to the developer is not particularly limited, but is practically 0.01 mol or more per liter of the developer actually used. It is used in an amount of 0.5 mol or less, more preferably 0.05 mol or more and 1 mol or less.

In the present invention, the compound represented by formula (4) may be used alone or in combination. Similar effects can be obtained by using the compound represented by the general formula (1) and the compound represented by the general formula (4) in the present invention in combination.

Next, the general formulas (A), (B), (D),
The compounds represented by (D) and (E) will be described.

[0044]

Embedded image

In the general formula (A), 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 moiety having 1 to 6 carbon atoms. Represent.

In the general formula (B), R ² and R ³ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Where R ²
And R ³ do not simultaneously become hydrogen atoms. R ⁴ and R ⁵ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁵ 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 alkyl group 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 the general formula (C), 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 the general formula (D), D ¹ and B ¹ each independently represent an alkylene group. E ² and A ² independently of one another, respectively, -COOM, -SO ₃ M, -CM,
^{_{-SZ, -SO 2 N (X 1}} ) (Y 1) or -CO (X
¹ ) represents (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 1-3.

In the general formula (E), R ³ and R ¹⁰ each represent 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, Represents 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 ³ and R ¹⁰ may be linked to each other to form a ring.

Specific examples of the compound represented by formula (A) are shown below. Among them, A-1 is most preferred.

[0051]

Embedded image

In the compound represented by the general formula (B), R
² and R ³ represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl, propyl). Where R ² and R
³ is not simultaneously a hydrogen atom, and both are preferably alkyl groups. R ⁴ and R ^{5 each} represent a hydrogen atom or 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 are 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, an acetyl group, propionyl) or a —COOM ¹⁰ group Represents 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 alkyl group having usually 7 to 15. Where R ⁷ and R ⁸
Cannot be hydrogen atoms at the same time. M ¹ is a hydrogen atom,
Represents an alkali metal atom or an ammonium group. k is 0, 1
Or 2 is represented.

Specific examples of the compound represented by formula (B) are shown below.

[0054]

Embedded image

In the compound represented by the general formula (C), 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.

Specific examples of the compound represented by formula (C) are shown below. Among them, C-1 is most preferred.

[0057]

Embedded image

In the compound represented by the general formula (D),
D ¹ and B ¹ each independently represent an optionally substituted alkylene group (for example, methylene, ethylene, dimethylmethylene, dimethylethylene, phenylethylene, methylphenylmethylene). E ² and A ² are each independently of the other —COOM, —SO ₂ M, —O
_{M, -SZ, -SO 2 X (} X 1) (Y 1), - CO (X
¹ ) represents (Y ¹ ). Here, M represents a monovalent cation (for example, H ⁺ ). Each X ¹ and Y ¹ represents a hydrogen atom, a hydroxy group, a sulfonic acid or carboxylic acid substituted optionally also an alkyl group or a phenyl group or an alkyl group or optionally a sulfonyl group optionally substituted 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 integers of 1-3.

Specific examples of the formula (D) are shown below.

[0060]

Embedded image

In the compound represented by the general formula (E),
R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group (which may have a substituent, for example, methyl, ethyl, propyl, morpholinomethyl, 4-methylpiperazylmethyl, diaminomethyl), an aryl group (for example, phenyl), Aralkyl groups,
Represents 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, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, and a heterocyclic group . R ⁹ and R ¹⁰ may be linked to each other to form a ring (for example, cyclohexene).

Specific examples of the compound represented by formula (E) are shown below.

[0063]

Embedded image

The compounds represented by formulas (A) to (E) 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 compounds represented by formulas (A) to (E) 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 relational expression (L) in the present invention is defined as follows. 0.03 ≦ R / V ≦ 0.11 Relational expression (L) Capacity of developer tank; V (liter) Replenishment amount of developer per day; R (liter / day) A tank containing a developer immersed when a silver halide photographic material is developed. The replenishing amount of the developing solution means an amount of a new developing solution to be replenished to a developing tank containing a developing solution that has become tired during the developing process. The present invention is particularly effective when the R / V value is within the above range. Next, the developer used in the present invention will be described. The developing solution for a silver halide photographic light-sensitive material referred to in the present invention is a general term for those used as a developing solution when developing a silver halide photographic light-sensitive material.
Includes those which are supplied as concentrated liquids, powders, granules, tablets and the like, and which are prepared and used as developing solutions by diluting or dissolving in a certain amount of water. Further, it may be directly supplied to a developing tank of an automatic developing machine together with water as a concentrate, a powder, a granule, a tablet or the like. In the developer used in the present invention, reductones are preferably used as a developing agent. As the reductones, enediol type, enaminol type, enediamine type, thiol enol type and enamine thiol type are generally known as compounds. Examples of these compounds are described in U.S. Pat. No. 2,688,549, JP-A-62-237.
443, etc. Methods for synthesizing these reductones are also well known, and are described in, for example, Yuji Nomura and Hirohisa Omura, "Chemistry of Reductone" (Uchida Roizuruhoshinsha 1969)
Year). Among them, preferred reductones for use in the present invention are compounds represented by the following general formula (X).

[0067]

Embedded image

(Wherein, R ^a and R ^b each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group. P and Q. Is a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group,
Represents an aminoalkyl group, an alkyl group, or an aryl group, or is bonded to each other to form 5 to 5 together with two vinyl carbon atoms substituted with R ^a and R ^b and a carbon atom substituted with Y.
Represents a group of non-metallic atoms forming an 8-membered ring. Y represents = 0 or = NR ^c , and R ^C represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. )

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

P and Q are each a hydroxy group, a carboxyl group, an alkoxy group (methoxy, ethoxy, butoxy, etc.), a hydroxyalkyl group (hydroxymethyl, hydroxyethyl, etc.), a carboxyalkyl group (carboxymethyl, carboxyethyl, etc.), Sulfo group (including salt), sulfoalkyl group (sulfoethyl, sulfopropyl, etc.), amino group (including alkyl substitution), aminoalkyl group (aminoethyl, aminopropyl, etc.), alkyl group (methyl, ethyl, propyl, butyl) , Pentyl, etc.)
Or ^a 5- to 8-membered aryl group (phenyl, p-tolyl, naphthyl, etc.), or two vinyl carbon atoms bonded to each other and substituted by R ^a and R ^b and a carbon atom substituted by Y; Represents a group of non-metallic atoms forming a ring. The 5- to 8-membered ring may form a saturated or unsaturated condensed ring.

Examples of the 5- to 8-membered ring include a dihydrofuranone group, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring,
Examples thereof include an azacyclohexenone ring, a uracil ring, a cycloheptenone ring, a cyclohexanone ring, an azepine ring, and a cyclooctenone ring, and a 5- to 6-membered ring is preferable. Among them, preferred examples of the 5- to 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexanone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

When Y represents ＮＲNR ^c , R ^C represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. The above R ^a , R
^{The same} groups as those described for ^b , P and Q can be mentioned.

Specific examples of the compound represented by formula (X) are shown below, but it should not be construed that the invention is limited thereto.

[0074]

Embedded image

[0075]

Embedded image

[0076]

Embedded image

These salts include salts of lithium, sodium, potassium, ammonium and the like.

Of these, ascorbic acid or erythorbic acid (stereoisomer) (X-1) is preferred.

The amount of the compound of the present invention to be added to the processing solution is not particularly limited, but is practically 0.1 to 100 g, preferably 0.5 to 60 g, more preferably 1 to 100 g per liter of the processing solution. A range of 30 g is desirable for obtaining the effect of suppressing the formation of a white precipitate.

The developer or developer of the present invention may contain only one compound of the present invention or two or more compounds.

Examples of the black-and-white developing agent other than the reductones of the developing solution of the present invention include the following.

Substituted dihydroxybenzenes (potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, potassium hydroquinone disulfonate, sodium hydroquinone disulfonate); 3-
Pyrazolidones (1-phenyl-3-pyrazolidone, 1
-Phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-
5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-
Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1- (2-benzothiazole)- 3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc.); aminophenols (o-aminophenol, p
-Aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol and the like; 1-allyl-3-aminopyrazolidones (1- (p-hydroxyphenyl) ) -3-Aminopyrazolidone, 1- (p-methylaminophenyl) -3
-Aminopyrazolidone, 1- (p-amino-m-methylphenyl) -3-aminopyrazolidone and the like; pyrazolones (4-aminopyrazolone and the like), or a mixture thereof. Of the pyrazolidones used, those in which the 4-position is particularly substituted (dimesone, dimesone S, etc.) are particularly preferred since they have little change over time in the water-soluble or solid processing agent itself.

The developing solution may further contain a preservative (sulfite, bisulfite, etc.), a buffer (carbonate, borate, saccharide, phosphoric acid, etc.), an alkali agent (sodium hydroxide, Potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, etc.), dissolution aids (polyethylene glycols and esters thereof), pH adjusters (organic acids such as citric acid and tartaric acid), sensitizers (4 Quaternary ammonium salt), a development accelerator, a hardening agent (dialdehydes such as glutaraldehyde), a surfactant and the like. Further, as an antifoggant, an azole-based organic antifoggant (indazole type, imidazole type, benzimidazole type, triazole type, benzotriazole type, tetrazole type, thiadiazole type) and for masking calcium ions mixed in tap water. Hiding agents (sodium hexametaphosphate, calcium hexametaphosphate, polyphosphates, etc.) may be added. As the silver stain inhibitor, for example, compounds described in JP-A-56-24347, JP-B-56-46585, JP-B-62-2849 and JP-A-4-362942 can be used.

The pH of the developer used in the present invention is 9-1.
2 is preferable, and more preferably 9.5 to 10.5.
It is.

In addition, L. F. A. Mason, "Photographic Processing Chemistry," Focus Press, 1966, pp. 22-229, U.S. Pat. Nos. 2,193,015 and 2,592,364,
Those described in JP-A-48-64933 may be used.

Next, the fixing solution that can be used in the present invention will be described. The fixing solution preferably contains a thiosulfate. The thiosulfate is usually used as a lithium, potassium, sodium, or ammonium salt, and preferably, sodium thiosulfate or ammonium thiosulfate is used. More preferably, a fixing solution having a high fixing speed can be obtained by using an ammonium salt, but a sodium salt is preferable from the viewpoint of storage stability and the like.

The thiosulfate concentration is preferably 0.1 to 5
Mol / l, more preferably 0.5 to 2 mol / l, even more preferably 0.7 to 1.8 mol / l.

In addition, iodide salts and thiocyanates can also be used as fixing agents.

The fixing solution contains a sulfite, and the concentration of the sulfite is 0.2 mol / liter or less when the thiosulfate and the sulfite are dissolved and mixed in an aqueous solvent. As the sulfite, a solid lithium, potassium, sodium, ammonium salt or the like is used, which is dissolved and used together with the solid thiosulfate.

The fixing solution used in the present invention may contain a water-soluble chromium salt or a water-soluble ammonium salt.
Examples of the water-soluble chromium salt include chromium alum, and examples of the water-soluble aluminum salt include aluminum sulfate, potassium aluminum chloride, and aluminum chloride. These chromium salts or aluminum salts are added in an amount of 0.2 to 3.0 g per liter of the fixing solution.
And it is preferably 1.2 to 2.5 g.

Further, the fixing agent may include acetic acid, citric acid, tartaric acid, malic acid, succinic acid, phenylacetic acid and optical isomers thereof. These salts include, for example, potassium citrate, lithium citrate, sodium citrate, ammonium citrate, lithium hydrogen tartrate, potassium hydrogen tartrate, potassium tartrate, sodium hydrogen tartrate, sodium tartrate, ammonium hydrogen tartrate, ammonium potassium tartrate, tartaric acid Sodium potassium, sodium malate, ammonium malate,
Preferred examples include lithium, potassium, sodium, and ammonium salts represented by sodium succinate, ammonium succinate, and the like.

Among the above compounds, more preferred are acetic acid, citric acid, isocitric acid, malic acid, phenylacetic acid and salts thereof. The amount of compound added is 0.2 to
0.6 mol / l is preferred. Examples of the acid include inorganic acids and salts such as sulfuric acid, hydrochloric acid, nitric acid, and boric acid, and organic acids such as formic acid, propionic acid, oxalic acid, and malic acid, and preferably boric acid and aminopolycarboxylic acids. Acids and salts. Particularly preferred aminocarboxylic acids include β-alanine and piperidine acid.
The preferred addition amount of the acid is 0.5 to 40 g / liter.

Examples of the chelating agent include aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, and salts thereof.

Examples of the surfactant include anionic surfactants such as sulfated and sulfonated compounds, nonionic surfactants such as polyethylene glycol and ester, and amphoteric surfactants described in JP-A-57-6840. Is mentioned. As a fixing accelerator, for example,
5-35754, JP-B-58-122535, 5
Thiourea derivative, alcohol having a triple bond in the molecule, U.S. Pat. No. 4,126,45
Thioether described in JP-A No. 9 and a meso-ion compound described in JP-A-4-229860.

The pH of the fixing solution after dissolution or dilution is usually 3.8 or higher, preferably 4.2 to 5.5.

The developer of the present invention and the fixing solution used in the present invention are preferably provided to the user in the form of a concentrated solution or a solid. In order to solidify the photographic processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. Or any other means such as forming a coating layer (see JP-A-4-29136 and JP-A-4-8136).
No. 5535, No. 4-85536, No. 4-85533
Nos. 4-85534 and 4-172341).

In the present invention, when the developing solution and the fixing solution are supplied as tablets, a binder is disclosed in JP-A-7-29516.
The saccharides described in No. 1 (pages 23 to 30) (monosaccharides, polysaccharides in which a plurality of monosaccharides are linked to each other, and glycoside bonds thereof and their decomposed products) are preferable, and among them, those selected from dextrins and sugar alcohols are particularly preferable. It is preferably used. There is little change in shape during long-term storage, and trouble during addition and usability are improved.

[0098] The solid processing agent includes a lubricant as disclosed in
It is preferable to use acylated amino acids described in No. 92624 (pages 9 to 15). The solid processing agent can be manufactured stably without impairing the strength, the solubility is less deteriorated, and the storage stability and dust generation are improved. In addition, Japanese Patent Application Hei 8
Organic sulfur compounds described in U.S. Pat. No. 4,767,464 (pages 19 to 21) are also preferred.

The solid-state treating agent includes, as a coating agent, hydroxylamines, phenylcarboxylic acids, phenylsulfonic acids, and alkyl (or hydroxyl group- or carboxyl-group-introduced) described in JP-A-7-261337 (pages 14 to 33). It is preferable to use (alkenyl) carboxylic acids, sulfites, water-soluble polymers (polyalkylene glycol, methacrylic acid-based betaine-type polymers, etc.), and saccharides. The generation of fine powder is small, the deterioration of solubility is small, and excellent storability can be maintained and stable photographic performance can be maintained.

The emulsion used in the light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) 17643 (December 1978) 22
1 to 23 "Emulsion production method (Emulsion Pre
(parties and types) and (RD)
18716 (November 1979), p. 648. Also, for example, T.I. H. Jam
es, "The theory of the pho
graphical process, 4th edition, Mac
The method described in Millan Co. (1977) pp. 38-104, G.I. F. "Photographic Emulsion Chemistry" by Dauffin
“Photographic emulation Ch
Emistry ", published by Focal Press (19
66), p. "The Physics and Chemistry of Photography" by Glafkids, "Chimie et physique pho
"Making and Coat", VL Zelikman et al., "Manufacture and Coating of Photographic Emulsions", published by Paul Montel, Inc. (1967).
ing Photographic Emulsio
It is prepared by the method described in n "Focal Press" (1964) and the like.

Examples of preferably used silver halide emulsions include those described in JP-A-59-177535 and JP-A-61-8.
No. 02237, No. 61-132943, No. 63-49
No. 751 and JP-A-2-85846. Further, silver chlorobromide or silver chloride having a silver chloride content of 50 mol% or more is also preferable.

The crystal structure of silver halide is preferably a core / shell type monodisperse emulsion having a two-layer structure comprising a high iodine core portion and a low iodine shell layer. The silver iodide content of the high iodine part is 20 to 40 mol%, particularly preferably 20 to 30 mol%. Examples of these include, for example, Photo
o. Sic. 12, 242 to 251 (1963), JP-A-48-36890, JP-A-52-16364, and 5
Nos. 5-142329, 58-49938, British Patent 1,413,748, U.S. Patent 3,574,628
No. 3,655,394, British Patent 1,027,1
No. 46, U.S. Pat. Nos. 3,505,068 and 4,44
4,877 and JP-A-60-14331.

The silver halide emulsion preferably used in the present invention is tabular grains having an average aspect ratio of more than 1. The advantage of such tabular grains is that they can improve spectral sensitization efficiency, improve graininess and sharpness of an image and the like, for example, British Patent No. 2,112,157, US Pat.
439,520, 4,433,048, 4,4
14,310, 4,434,226, JP-A-58
-113927, 58-127921, 63-
No. 138342, No. 63-284272, No. 63-3
The emulsions can be prepared by the methods described in these publications.

These emulsions can be prepared by using a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. Good. The emulsion may be subjected to a washing method such as a noodle washing method or a flocculation sedimentation method in order to remove soluble salts. As a preferred water washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or an agglomerated polymer agent described in JP-A-63-158644 (exemplified G3, G8) And the like. Particularly preferred is a desalting method. As the method of chemical ripening of the silver halide emulsion, gold sensitization, sulfur sensitization, reduction sensitization, sensitization with a chalcogen compound, and a combination thereof are preferably used.

In the emulsion, various photographic additives can be used before and after physical ripening or chemical ripening. A hydrazine compound can be added.
Compounds of the formula (134) are preferred, and compounds of the formula (5) and compounds of the formulas (7) and (8) are particularly preferred as the nucleation promoting agent. A tetrazolium salt can be added, and those described in JP-A-2-25050 are particularly preferred. Other known additives include, for example, RD described above.
17643 (December 1978), pp. 23-29, 18
716 (November 1979) pages 648 to 651 and 3
08119 (December 1989), pp. 996-1009.

Examples of the support usable for the light-sensitive material include RD17643, page 28 and RD3081.
19, page 1009.
A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, or the like in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided.

An emulsion layer may be present on both sides of the support.
Only one side may be used. In the case of both sides, both sides may have the same performance or different performances.

[0108]

Embodiments of the present invention will be described below. However, needless to say, the present invention is not limited to the embodiments described below.

Example 1 A silver halide photosensitive material was prepared for running evaluation. (Preparation of Emulsion EM-1) Solution A High methionine gelatin (59.7 g of methionine per g of gelatin) 30 g 4,5,6-triaminopyrimidine 100 g Sodium chloride 1054 g Sodium bromide 68.7 g Distilled water 6000 ml Solution B Silver nitrate 1135 g Distilled water at 2000 ml At 40 ° C., the pH of solution A in a reaction vessel having a mixing stirrer described in JP-B-58-58288 was adjusted to 5.6, and 6 ml of solution B was added over 1 minute. . The addition rate was linearly accelerated (9.8 times from the start to the end) over a further 55 minutes, during which the entire amount of solution B was added.
After 5 minutes and 18 minutes, 400 g of 4M sodium chloride solution
And 100 g of a 20 mM 4,5,6-triaminopyrimidine solution. During the addition of the above materials, the inflow of silver
Stopped for minutes and the additives were mixed homogeneously. During this time, the pH was controlled to be constant by adding sodium hydroxide or nitric acid. After completion of the addition, excess salts were precipitated and desalted by a conventional method. Approximately 3000 particles of EM-1 were observed and estimated by an electron microscope, and the shape was analyzed. As a result, an aspect ratio of 15 (average equivalent circle diameter 1.80 μm, average thickness 0.12 μm) and 90 mol% of silver chloride were contained. It was tabular silver chlorobromide grains. (Preparation of photosensitive material sample)
The following spectral sensitizing dyes (SD-1) and (SD-2) were added in a weight ratio of 20: 1 at 400 ° C. per mole of silver halide.
mg was added. SD-1: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt SD-2: Anhydro-5,5'-di- ( (Butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-
Sulfobutyl) benzimidazolocarbocyanine sodium salt After 10 minutes, an appropriate amount of ammonium thiocyanate, chloroauric acid and sodium thiosulfate, and a dispersion of triphenylphosphine selenide were added, followed by chemical ripening. Forty minutes before the completion of ripening, a silver iodide fine grain emulsion of 0.06 μm was added in an amount of 6 × 10 ⁻⁴ mol per mol of silver, and then the following stabilizer (ST-1) was added in an amount of 3 × 10 ⁻² per mol of silver. Mole,
It was dispersed in an aqueous solution containing 70 g of gelatin. ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Strazaindene The following additives were added to this emulsion. The amount of addition is shown in an amount per mole of silver halide. 1,1-dimethylol-1-bromo-1-nitromethane 70 mg t-butylcatechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonyl chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 4.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate 15 mg 1-phenyl-5-mercaptotetrazole 10 mg Trimethylolpropane 10 g C ₄ H ₉ OCH ₂ CH (CH ₃ ) CH ₂ N (CH ₂ COOH) ₂ 1 g Compound A 60 mg Compound B 35 mg

[0110]

Embedded image

Further, 1.0 g of a dye emulsified dispersion shown below was used.
Was added to obtain an emulsion coating solution. (Preparation of dye emulsion dispersion) 10 kg of the following dye (F-1)
Was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresyl phosphate and 85 liters of ethyl acetate. This is called an oil-based solvent. On the other hand, an anionic surfactant (S
U-1) A 9.3% gelatin aqueous solution containing 1.35 kg is referred to as an aqueous solvent.

Next, an oil-based solvent and an aqueous-based solvent were placed in a dispersion vessel and dispersed while maintaining the liquid temperature at 40 ° C. To the obtained dispersion, an appropriate amount of phenol, 1,1′-dimethylol-1-bromo, and 1-nitromethane were added, and the mixture was added with water at 240 k.
g. SU-1: sodium tri-i-propylnaphthalenesulfonate

[0113]

Embedded image

The additives used for the protective layer are as follows. The amount of addition is indicated by the amount per liter of the coating solution. (Coating solution for protective layer) Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Polymethyl methacrylate (matting agent having an average particle size of 5.0 μm) 1.1 g Silicon dioxide particles (matting agent having an average particle size of 3.0 μm) 0.5 g Ludox AM (colloidal silica manufactured by Dubon Co.) 30 g Grioxal 40% aqueous solution (hardening agent) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 500 mg C ₁₂ H ₂₅ CONH (CH ₂ CH _{2) O) 5 H 2.0g SU-2} ( surfactant) 20mg SU-3 (surfactant) 7mg SU-4 _{(surfactant) 7mg C 12 H 25 CONH (} CH 2 CH 2 O) 6 H 62mg DI -1 (mold inhibitor) 0.9mg

[0115]

Embedded image

Thickness 175μ colored blue with a concentration of 0.15
On both surfaces of the polyethylene terephthalate support of m, a coating solution prepared such that the coating amount per one surface was the following composition was applied to form an undercoat layer. Shown in the amount of coating per 1 m ² . (Coating solution for undercoat layer) Dye (F-2) 30 mg Gelatin 0.5 g p-nonylphenoxypolyethylene oxide (degree of polymerization = 10) 6 mg 1-morphonylcarbonyl-3- (pyridinio) methanesulfonate 80 mg polymethyl methacrylate (average) 2.5mg particle size matting agent) 2mg

[0117]

Embedded image

The emulsion coating solution was 1.8 g / m ^{2 in} terms of silver per side, 1.6 g / m ² in gelatin, and 0.9 g in gelatin in the protective layer on one side of the undercoated support. / m ² and comprising as at a speed per minute 90m by two slide hopper type coaters, emulsion layer, a protective layer was dual-side coated to obtain a photosensitive material sample was dried in 2 minutes 30 seconds.

(Preparation of Development Concentrate) <Development Concentrate 1> Diethylenetriaminepentaacetic acid 5 g Sodium sulfite 24 g Sodium carbonate monohydrate 87.5 g Potassium carbonate 97.5 g Sodium erythorbate 120 g 1-phenyl-4-methyl-4- Hydroxymethyl-3-pyrazolidone 16.0 g 5-methylbenztriazole 0.15 g Any of the compounds represented by the general formulas (1), (2), (3) and (4) (or comparative compound) described in Table 1. Amount (indicated by the concentration when used as a solution) Any of the compounds represented by the general formulas (A), (B), (C), (D), and (E). 8.0 g water and adjust the pH to 10.20 with 1 liter KOH

In the preparation method after use, 600 ml of water was added to 400 ml of the concentrated developing solution to make 1 liter of working solution, and this was used as developer 1.

[0121]

Embedded image

(Preparation of Fixing Concentrate) <Fixing Concentrate> Ammonium thiosulfate (70 wt / vol 1%) 400 ml Sodium sulfite 40 g boric acid 16 g β-alanine 36 g glacial acetic acid 60 g tartaric acid 5 g aluminum sulfate 20 g Adjust to 4.60

The method for preparing the working solution is to add 500 ml of water to 500 ml of the fixing concentrated solution to make 1 liter of the working solution to obtain the fixing solution 1.

The developer 1 and the fixer 1 were placed in SRX-701 manufactured by Konica Corporation and a running test was performed in a 30-second mode under the following conditions. Both development temperature and fixing temperature are 3
The above photographic material exposed to a temperature of 5 ° C. and having a chemical concentration of 1.0 was processed daily in the amounts shown in Table 1, and the developing solution and the fixing solution were run for 3 weeks while replenishing the photographic material with 150 ml / m ^2. Tested. At the start of running, acetic acid was added to the developing tank of the automatic developing machine as a starter in such an amount that the developing pH became 10.00, and potassium bromide was added in an amount to give a concentration of 12.2 g / liter to obtain a new solution. The results are shown in Table 1. Here, the sensitivity means the fog test 1 with a new developer solution to which none of the compounds represented by formulas (1), (2), (3) and (4) of the present invention is added immediately after the preparation. The reciprocal of the amount of exposure that gives an optical density of 0.0 is shown as a relative value with 100 being the reciprocal. Fog indicates the optical density including the unexposed portion of the support. Dm indicates the maximum concentration. The capacity of the developing tank was adjusted to 13.7 liters.

<Evaluation of Silver Sludge> The degree of silver sludge generation after the running was evaluated according to the following criteria. 5: No adhesion of silver sludge was observed on both sides and bottom of the developing tank of the automatic developing machine. 4: Slight adhesion of silver sludge was observed on both sides and bottom of the developing tank of the automatic developing machine. Adhesion of silver sludge is observed on both sides and bottom of the tank. 2: Silver sludge adheres everywhere in the developing tank of the automatic processor. 1: A large amount of silver sludge adheres in the developing tank of the automatic processor. Then it adheres to the film

<Evaluation of preservability of image of processed film> The above-mentioned film developed and processed using an automatic developing machine running for 3 weeks under the above conditions was stored under the following conditions.
The film was exposed to an optical density of 1.0 and then developed. Storage conditions: put 60g cobalt chloride saturated aqueous solution (CoC ₁₂ · 6H ₂₀ in sealable pressure vessel (1), pure water 1
4 ml was added), and the developed film was placed on a mesh plate so as not to come into contact with the above-mentioned aqueous solution of cobalt chloride. Close the lid, replace the oxygen until the internal oxygen concentration becomes 90 vol% or more, set the pressure in the container to 2.3 kgw / cm ^2, and at 65 ° C (heating),
Stored tightly for one year.

The above preserved film was visually evaluated on a Shakasten according to the following criteria. 4: No discoloration is observed 3: Discoloration is slightly observed 2: Discoloration is clearly observed 1: Discoloration is considerably observed

The results are shown in Tables 1 to 5. As is clear from the description in the table, the present invention has excellent running characteristics, suppresses silver sludge, and has good storage stability of the processed film. The effect of the present invention is as follows: 0.003 ≦ R / V ≦ 0.
It can be seen that the effect is significantly exhibited in the eleven regions.

[0129]

[Table 1]

[0130]

[Table 2]

[0131]

[Table 3]

[0132]

[Table 4]

[0133]

[Table 5]

Example 2 The following solid developers and fixing agents were prepared, and the photographic performance, silver sludge, and the preservability of the processed film in running the developer were evaluated. <Solid developer 1> Granules (A) 500 g of 1-phenyl-3-pyrazolidone, a compound of the formula (A), (B), (D), (D) or (E) Either (described in Table 2), the amount described in Table 2, boric acid 500
g, glutaraldehyde sodium bisulfite adduct 10
00 g in an average of 10 μm each in a commercially available bandam mill.
pulverize to m.

To this fine powder, 300 g of DTPA · 5Na, 300 g of dimezone S, 4000 g of ascorbic acid, 1600 g of sodium sulfite, 7.0 g of 1-phenyl-5-mercaptotetrazole, 400 g of binder mannitol,
One of the compounds represented by the general formulas (1), (2), (3) and (4) is added in the amount shown in Table 1, mixed in a mill for 30 minutes, and placed in a commercial stirring granulator at room temperature. After granulating by adding 30 milliliters of water for about 10 minutes, the granulated substance is dried at 40 ° C. for 2 minutes with a fluidized bed drier to almost completely remove the moisture of the granulated substance. . DTPA · 5Na: diethylenetriaminepentaacetic acid · pentasodium Dimezone S: 1-phenyl-4-hydroxymethyl-4
-Methyl-3-pyrazolidone (Eastman Kodak Company, registered trademark) Granulated product (B) 11000 g of potassium carbonate, 2000 of sodium bicarbonate
g are each ground in a commercial vandam mill to an average of 10 μm. 800 g of binder mannitol was added to each fine powder, mixed in a mill for 30 minutes, and granulated by adding 30 ml of water for about 15 minutes at room temperature in a commercially available stirring granulator. Granulate 4 with fluidized dryer
After drying at 0 ° C. for 2 hours, the water content of the granulated material is almost completely removed.

(Preparation of solid developer) The granules (A) and (B) thus obtained were mixed with sodium lauryl sulfate 1
After mixing uniformly for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less, the obtained mixture was mixed with Kikusui Seisakusho's Tough Presto Collect 1527HU.
Was subjected to compression tableting using a modified tableting machine at a filling amount of 10 g per tablet to produce 21,000 ascorbic acid-based developing tablets. The method of preparing the working solution is to add water to 24 solid developers to make 1 liter of the working solution.

The method for producing the solid fixing agent is described below. <Solid fixing agent> Granulated product (C) Ammonium thiosulfate / sodium thiosulfate (90/1
15000 g, 0,500 g of β-alanine, and 4000 g of sodium acetate are pulverized in a commercially available bandam mill until the average becomes 10 µm. To this fine powder, 500 g of sodium sulfite, 750 g of sodium persulfate, and 1300 g of mannitol binder were added, and the amount of water added was 50 ml, and the mixture was stirred and granulated. Almost completely removed. Granulated material (D) 700 g of boric acid, aluminum sulfate / 18-hydrate 1500
g, 1200 g of succinic acid are ground as in (A). 200 g of sodium hydrogen sulfate was added to this fine powder, and the amount of water added was 3
The mixture is stirred at 0 ml and granulated with stirring, and the granulated product is dried at 40 ° C. with a fluidized bed drier to completely remove water.

The granules (C) and (D) thus obtained were mixed with 150 g of sodium lauryl sulfate at 25 ° C.
Using a mixer in a room conditioned to 40% RH or less
After uniformly mixing for 1 minute, the obtained mixture was subjected to compression tableting with a tableting machine modified from Kikusui Seisakusho's Tough Presto Collect 1527HU to a filling amount of 10 g per tablet,
26000 fixing tablets were produced.

The method for preparing the working solution is to add water to 28 solid fixing agents to make 1 liter of working solution.

The developer 1 and the fixer 1 were placed in TCK-201 manufactured by Konica Corporation and a running test was conducted in the 60-second mode under the following conditions. Both development temperature and fixing temperature are 36
Example 1 exposed to an optical density of 1.0 ° C. and an optical density of 1.0
In the prepared photographic material were treated daily Table 2 wherein the amount were performed 3 weeks running test while replenishing the developer and fixer each 150 ml per photosensitive material 1 m ^2. At the start of running, acetic acid was added to the developing tank of the automatic developing machine as a starter in such an amount that the developing pH became 10.00, and potassium bromide was added in an amount to give a concentration of 12.2 g / liter to obtain a new solution. The results are shown in Table 2. Here, the sensitivity refers to the general formulas (1), (2), and
The reciprocal of the amount of exposure that gives an optical density of fog plus 1.0 with a new developer solution to which none of the compounds represented by (3) and (4) is added is shown as a relative value. Fog indicates the optical density including the unexposed portion of the support. Dm indicates the maximum concentration. The capacity of the developing tank was adjusted to 7.8 liters.

<Evaluation of Silver Sludge> The degree of silver sludge generation after the above-mentioned running was evaluated according to the following criteria. 5: No adhesion of silver sludge was observed on the side and bottom surfaces of the developing tank of the automatic developing machine. Little adhesion of silver sludge is observed on both sides and bottom of the developing tank of the developing machine. 3: Adhesion of silver sludge is observed on both sides and bottom of the developing tank of the automatic developing machine. 2: Everywhere in the developing tank of the automatic developing machine. 1: Silver sludge adheres to the film in the developing tank of the automatic processor.

<Evaluation of preservability of image of processed film> The above-mentioned film developed and processed using an automatic developing machine running for 3 weeks under the above conditions was stored under the following conditions.
The film was exposed to an optical density of 1.0 and then developed. Storage conditions: (put 60g of CoCl ₁₂ · 6H _20, adding deionized water 14 ml) cobalt chloride saturated aqueous solution in a sealable pressure vessel (1) Place the petri-dishes and,
The developed film was placed on a mesh plate so as not to come into contact with the aqueous cobalt chloride solution. Close the lid and replace with oxygen until the internal oxygen concentration becomes 90 vol% or more, the pressure in the container is set to 2.3 kgw / cm ^2, and 65 ° C. (heating)
And stored tightly for one year.

The above preserved film was visually evaluated on Shakasten according to the following criteria. 4: No discoloration is observed 3: Discoloration is slightly observed 2: Discoloration is clearly observed 1: Discoloration is considerably observed

The above results are shown in Tables 6 to 10. As is clear from the description in the table, the present invention has excellent running characteristics, suppresses silver sludge, and has good storage stability of the processed film. The effect of the present invention is as follows: 0.003 ≦ R / V ≦
It can be seen that the effect is significantly exhibited in the region of 0.11.

[0145]

[Table 6]

[0146]

[Table 7]

[0147]

[Table 8]

[0148]

[Table 9]

[0149]

[Table 10]

[0150]

As will be understood from the above-described embodiments, according to the present invention, photographic performance can be stably obtained even when the replenishment is low in processing a silver halide photographic light-sensitive material. Further, even if the replenishment is low, the generation of silver sludge is suppressed. Further, it is possible to provide a developing solution for a silver halide photographic light-sensitive material and a method for processing a silver halide photographic light-sensitive material having good storage stability of an image after development even if the replenishment is low.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a pressure-resistant container used in an example.

[Explanation of symbols]

1 ... Metal body part, 2 ... Metal lid part, 3 ...
・ Oxygen gas inlet / outlet, 4 ・ ・ ・ Oxygen gas inlet / outlet, 5 ・ ・ ・ Sealing valve, 6 ・ ・ ・ Sealing valve, 7 ・ ・ ・ Sealing screw, 8 ・ ・ ・ Bottom, 9 ・ ・ ・ Sample , 10 ... net board,
11 ... barometer, 12 ... packing, 13 ...
Humidifier, 14 ... Petri dish.

Claims (7)

[Claims] 1. A compound represented by the following general formula (1) and at least one compound represented by the following general formula (A), (B), (C)
A developer for a silver halide photographic light-sensitive material, which comprises (D) or at least one arbitrarily selected from the group consisting of the compounds represented by (E). Embedded image Here, R ¹¹ is a group selected from branched alkyl, aryl, and branched alkoxy. R ¹² : each independently an alkyl group having 1 to 5 carbon atoms;
It is a group selected from a substituted alkyl group, an alkoxy group, a substituted alkoxy group, and a cyano group. X: carboxyl group, sulfonic group, sulfate group,
It is a group selected from alkyl and alkenyl having 1 to 4 carbon atoms in which at least one of a phosphate group, a carboxyl group, a sulfonic group, a sulfate group and a phosphate group is substituted. m = 0-3, n = 1-4 (where m + n = 4) In the general formula (A), 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 moiety having 1 to 6 carbon atoms. In the general formula (B), 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 ⁵ 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,
Represents the following acyl group or -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 alkyl group 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 the general formula (C), 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 the general formula (D), D ¹ and B ¹
Each independently represents an alkylene group. E ² and A ² independently of one another, respectively, -COOM, -SO
₃ represents _{M, -CM, -SZ, -SO 2} N (X 1) a (Y ¹⁾ or ^{-CO (X 1) (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 1-
It is an integer of 3. In the general formula (E), R ³ 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 ³ and R ¹⁰ may be linked to each other to form a ring. 2. A compound represented by the following general formula (2) and at least one compound represented by the following general formula (A), (B), (C):
A developer for a silver halide photographic light-sensitive material, which comprises (D) or at least one arbitrarily selected from the group consisting of the compounds represented by (E). Embedded image General formula (2): MkHAO ₃ where M is a monovalent or divalent atom. k: 2 when M is monovalent, and 1 when M is divalent. A: An atom selected from P, Sb, and Bi. (3) at least one reductone compound;
Any compound selected from the group consisting of at least one compound represented by the following general formula (3) and a compound represented by the above general formula (A), (B), (C), (D) or (E) A developer for a silver halide photographic light-sensitive material, comprising at least one selected from the group consisting of: Embedded image However, in the formula, R ²¹ is a group selected from a hydrogen atom and a methyl group.
R ²² , R ²³ and R ²⁴ are each independently a group selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and a carboxyl group. However, when each of R ²² , R ²³ and R ²⁴ is an alkyl group, each may be independently substituted with a hydroxyl group, a carboxyl or a sulfo group. Also,
When each of R ²² , R ²³ and R ²⁴ is an alkyl group,
The -SH group is not substituted. 4. The developing solution for a silver halide photographic light-sensitive material according to claim 3, wherein the compound represented by the general formula (3) is represented by the following general formula (4). Embedded image However, R ²⁵ and R ²⁶ are each independently selected from a hydrogen atom and a methyl group. However, when one or both of R ²⁵ and R ²⁶ is a methyl group, the methyl group is —COOM ′, —OH
May be substituted. R ²⁵ and R ²⁶ are not substituted with a —SH group. M 'can take a hydrogen atom, an alkali metal atom, or an ammonium salt. l can be 0, 1.2. 5. The developing solution for a silver halide photographic light-sensitive material according to claim 3, wherein in the general formula (3), R ²¹ is a hydrogen atom. 6. A processing method for processing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide according to claim 1. A method for processing a silver halide photographic light-sensitive material, which is developed with a developer for a photographic light-sensitive material. 7. The method for processing a silver halide photographic material according to claim 6, wherein the following relational expression (L) is satisfied. Relational expression (L) 0.03 ≦ R / V ≦ 0.11, where capacity of developing tank: V (liter) Replenishment amount of developer per day: R (liter / day)