JPH1124214A - Developer for silver halide photographic sensitive material and method for processing the material with the developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent deterioration of pH of the developer in the case of replenishing the developer in a low rate by incorporating reductones and at least one of specified compounds in the developer. SOLUTION: This developer contains one of reductones and at least one of the compounds represented by the formula in which R<1> is an H atom or a methyl group, preferably, R<1> is an H atom in order to enhance effect; and each of R<2> -R<4> is, independently, an H atom or a 1-3C non-substituted alkyl, hydroxyalkyl, carboxyalkyl, sulfoalkyl, or carboxyl group, but when R<2> -R<4> are H, is not -SH group. The reductons to be used as a developer are embodied by types of endiol, enaminol, endiamine, thiolenol, or enamine-thiol, and each salts of lithium, sodium, and potassium, or the like as salts of the resuctones.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developing agent for a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a "light-sensitive material"). The present invention relates to a material developer and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, it has become an essential requirement to reduce development processing waste liquid for environmental protection.

[0003] Further, as for hydroquinones, which have been generally used as developing agents, conventionally, ascorbic acids and their derivatives (for example, reductones) are being studied as alternatives because of their insufficient safety.

[0004] However, ascorbic acids have the drawback of lowering the pH of the developing solution by air oxidation, thereby lowering the developing reaction and the developing activity. Therefore, it is technically difficult to maintain the pH to reduce the replenishment amount. Was included.

On the other hand, a developer is generally supplied as a concentrated solution or powder, and is prepared into a working solution by diluting or dissolving it in a certain amount of water before use. These concentrates or solid processing agents are easily oxidized by oxygen in the air during storage.

[0006] Oxidation lowers the concentration or pH of the developing agent or preservative, deteriorating the developability after storage over time. As described above, since the concentrated solution of the treating agent or the solid treating agent is deteriorated by long-term storage, there is a need for a technique that does not deteriorate the performance even after long-term storage. Further, there has been a demand for the development of a developer capable of obtaining stable photographic performance without processing fluctuation in a long-term running process.

Conventionally, techniques for preventing the oxidation of a developing solution include, for example, US Pat. No. 1,420,656 to which an amine compound is added as an antioxidant of a color developing agent, and Japanese Patent Application Laid-open No.
No. 3532 is disclosed.

However, a decrease in pH due to oxidation of a developer containing ascorbic acid (reductones) as a main agent is suppressed,
There was no disclosure of a technique for maintaining the development activity.

As a technique for maintaining the pH of the developer, it is known to use a large amount of a carbonate buffer. As a technique for maintaining the activity, it is conceivable to increase the amount of sulfite or add a preservative. However, these techniques are not preferable because the maintenance of the pH is insufficient and the salt concentration of the developer is increased to cause a decrease in developability.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a developer using reductones and derivatives thereof as a developing agent. Provided are a developer for a silver halide photographic light-sensitive material, which has excellent storage stability and running processability of a concentrated solution, and provides stable photographic performance without processing fluctuation, and a method for processing a silver halide photographic light-sensitive material using the same. It is in.

[0011]

The above object has been attained by the following constitutions.

A developer for a silver halide photographic material, comprising a reductone and at least one compound represented by the following general formula (1).

[0013]

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(Wherein R ¹ represents a hydrogen atom or a methyl group; R ² , R ³ and R ⁴ each independently represent a hydrogen atom,
Represents an unsubstituted alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group or a carboxyl group. 3. The developer for a silver halide photographic light-sensitive material according to claim ¹ , wherein R ^{1 in the} general formula (1) is a compound represented by a hydrogen atom.

The compound represented by the general formula (1) is
4. The developer for a silver halide photographic light-sensitive material according to claim 1, which is a compound represented by the following general formula (2).

[0016]

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(Wherein R ⁵ and R ⁶ represent a hydrogen atom or a methyl group. However, when one or both of R ⁵ and R ⁶ are a methyl group, the methyl group is substituted with a hydroxy group or a carboxyl group. M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n represents 0, 1 or 2
Represents The developer for a silver halide photographic light-sensitive material according to any one of Items 1 to 3, wherein the reductone is a compound represented by the following general formula (A).

[0018]

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Wherein R ⁷ and R ⁸ are each a hydroxy group,
Represents 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 each represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group, an aryl group, or are bonded to each other. Represents a group of non-metallic atoms forming a 5- to 8-membered ring.
Y represents ＝ O or ＮＲNR ⁹ , and R ⁹ is a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group,
Represents a sulfoalkyl group or a carboxyalkyl group. A method for processing a silver halide photographic light-sensitive material, comprising processing in the presence of a reductone and a compound represented by the above general formula (1) and / or the general formula (2). Material treatment method.

In the method for processing a silver halide photographic light-sensitive material, the processing is carried out using the developer for a silver halide photographic light-sensitive material described in any one of the above-mentioned items. Processing method.

A method for processing a silver halide photographic light-sensitive material processed by an automatic developing machine, wherein the following formula (L) is satisfied.

0.03 ≦ R / V ≦ 0.11 Formula (L) (where R represents a replenishing amount of developer per day (liter / day), and V represents a developing tank of an automatic developing machine. Hereinafter, the present invention will be described in detail.

In the developer of the present invention, reductones are used as a developing agent. Examples of the reductone include an enediol type, an enaminol type, an enediamine type, a thiol enol type and an enamine thiol type, and are preferably compounds represented by the above general formula (A).

In the general formula (A), R ⁷ and R ⁸ are each 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 group). , 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 R ⁷ and R ⁸ preferably include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are hydroxy, carboxyl, alkoxy (methoxy, ethoxy, butoxy, etc.), hydroxyalkyl (hydroxymethyl, hydroxyethyl, etc.), carboxyalkyl (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 an aryl group (phenyl, p-tolyl, naphthyl, etc.)
Or may be bonded to each other to form a 5- to 8-membered ring together with two vinyl carbon atoms substituted with R ⁷ and R ⁸ and a carbon atom substituted with Y. The ring may form a saturated or unsaturated fused ring.

Examples of the 5- to 8-membered ring include a dihydrofuranone ring, 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 ⁹ , R ⁹ is a hydrogen atom,
Represents a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group, and specific examples of each substituent are the same groups as those described above for R ⁷ , R ⁸ , P and Q Can be mentioned.

Hereinafter, specific examples of the compound represented by formula (A) are shown, but the present invention is not limited to these.

[0029]

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[0030]

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[0031]

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The salts of the reductones include, for example, lithium, sodium, potassium, ammonium and the like.

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

The amount of these reductones to be added to the developing solution is not particularly limited, but is practically 0.1 to 100 g, preferably 0.5 to 60 g, more preferably 1 to 30 g per liter of the processing solution. Is desirable in order to obtain the effect of suppressing the formation of a white precipitate.

The reductones may contain only one kind or two or more kinds.

Next, the compound represented by the general formula (1) according to the present invention used together with the above-mentioned reductones will be described.

In the general formula (1), R ¹ in the formula is selected from a hydrogen atom or a methyl group. R ² , R ³ , R ⁴
Is independently selected from a hydrogen atom, an unsubstituted alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group or a carboxyl group.

When R ² , R ³ and R ⁴ are alkyl groups, there is no --SH group as a substituent. R ² , R ³ and R ⁴ are
It is preferable to be substituted with a hydroxyalkyl group, a carboxyalkyl group or a sulfoalkyl group, respectively, in order to reduce odor. In order to exhibit the effects of the present invention, it is more preferable that R ¹ is a hydrogen atom.

In the present invention, the compound represented by the general formula (1) is more preferably the compound represented by the general formula (2).

In the general formula (2), R ⁵ and R ⁶ are selected from a hydrogen atom, a methyl group, a hydroxymethyl group and a carboxymethyl group. It should be noted that R ⁵ and R ⁶ in the general formula (2) each have-
SH groups are not substituted. M can take 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 developing solution to form an anion. Although n can take 0, 1, or 2, 0 is the highest effect of the present invention, and the effect is reduced as the number increases.

Specific examples of the compounds represented by the above general formulas (1) and (2) according to the present invention are shown below, but the present invention is not limited only to these.

[0042]

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[0043]

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[0044]

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Each of these compounds is a known compound and can be easily obtained by synthesis, extraction and the like. Among these, compounds (2-1), (2-2) and (2-5) are particularly preferred for the present invention.

The amount of the compound represented by the general formulas (1) and (2) of the present invention added to the developer is not particularly limited, but is practically 0.1 to 1 liter per actually used developer. 0
The amount may be 1 mol to 1.5 mol, and more preferably 0.05 mol to 1 mol.

In the developer of the present invention, the compound represented by the general formula (1) or (2) may be used alone, or the compound represented by the general formula (1) and the compound represented by the general formula (2) May be used in combination.

In the processing method of the present invention, it is preferable that the relationship between the replenishment amount of the developer and the capacity of the developing tank falls within the range of the following formula (L).

0.03 ≦ R / V ≦ 0.11 Equation (L) V: Liquid amount in developing tank of automatic developing machine (unit: liter) R: Replenishment amount of developing solution per day (unit: liter) The term "developing image tank" as used in the present invention refers to a tank in an automatic developing machine which contains a developing solution that is immersed when a photosensitive material is subjected to development processing. 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.

In the present invention, when the R / V value of the above formula is within the above range, the effect of the present invention is particularly excellent.

Next, the developer according to the present invention will be described in detail.

The compound used as a developing agent in the present invention may contain the following black-and-white developing agents in addition to the compounds of the general formula (A) which are reductones. For example, substituted dihydroxybenzenes (potassium hydroquinone monosulfonate, sodium hydroquinone monosulfonate, potassium hydroquinone disulfonate, sodium hydroquinone disulfonate, etc.); and 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); as aminophenols (o
-Aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.); (P-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-aminopyrazoline, 1-
(P-amino-m-methylphenyl) -3-aminopyrazoline, etc.); Examples of pyrazolones include (4-aminopyrazolone), or a mixture thereof.

Of the pyrazolidones, particularly, dimesone and dimesone S substituted at the 4-position are particularly preferable since they have little change over time in the water-soluble or solid processing agent itself.

The developer (liquid) of the present invention may further contain, if necessary, a preservative (sulfite, bisulfite, etc.), a buffer (carbonate, borate, borate, saccharide, phosphoric acid, etc.). ), Alkaline agents (such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, and potassium carbonate), dissolution aids (such as polyethylene glycols and esters thereof), and pH adjusters (such as citric acid and tartaric acid). Organic acids), sensitizers (quaternary ammonium salts, etc.), development accelerators,
Hardeners (dialdehydes such as glutaraldehyde),
A surfactant or the like can be contained. Further, as an antifoggant, an azole organic antifoggant (indazole, imidazole, benzimidazole, triazole, benzotriazole, tetrazole,
A thiadiazole type) or a masking agent (sodium hexametaphosphate, calcium hexametaphosphate, polyphosphate, etc.) for masking calcium ions mixed in tap water may be added. As the silver stain inhibitor, for example, the compounds described in JP-A-56-24347, JP-B-56-46585, JP-B-62-2849, JP-A-4-362942 and the like can be used. In addition, L.
F. A. Mason, Photographic Processing Chemistry, Published by Focal Press (196)
6 years) pp. 22-229, U.S. Pat. No. 2,193,015
No. 2,592,364, JP-A-48-64933.
No. described in the item may be used.

PH at the time of use of the developer used in the present invention
Is preferably in the range of 9 to 12, more preferably 9.5 to
10.5.

Next, the fixing solution used in the present invention will be described.

The fixing solution preferably contains a thiosulfate. Thiosulfates are usually used as lithium, potassium, sodium, ammonium salts,
Preferably, sodium thiosulfate and ammonium thiosulfate are 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 concentration of the thiosulfate is preferably 0.1 to 5 mol / l, more preferably 0.5 to 2 mol / l, and even more preferably 0.7 to 1.8 mol / l. In addition, iodide salts, thiocyanates and the like can also be used as fixing agents.

The fixing solution contains a sulfite, and the concentration of the sulfite is 0.2 mol / L 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 aluminum 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. The amount of the chromium salt or aluminum salt added is 0.2 to 3.0 g, preferably 1.2 to 2.5 g, per liter of the fixing solution.

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 after dissolution or dilution of the fixing solution is usually 3.8 or more, 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 solid. To solidify the processing agent, a concentrated liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. Any means such as forming a coating layer can be adopted (for details, see JP-A-4-29136 and JP-A-4-29136).
No. 85535, No. 4-85536, No. 4-85533
Nos. 4-85534 and 4-172341. In the present invention, when a developer or a fixer is supplied as a tablet, the binder is disclosed in JP-A-7-295161 (23).
To pp. 30) (monosaccharides, polysaccharides in which a plurality of monosaccharides are linked to each other, and their decomposed products), and dextrins and sugar alcohols are particularly preferably used. There is little change in shape during long-term storage, and trouble during addition and usability are improved.

The solid processing agents include a lubricant as disclosed in
It is preferable to use acylated amino acids described in JP-A-92624 (pages 9 to 15). By this method, a solid processing agent can be stably produced without impairing the strength, the solubility is less deteriorated, and the storage stability and dust generation are improved. Organic sulfur compounds described in Japanese Patent Application No. 8-4764 (pages 19 to 21) are also preferable.

The solid processing agents include coating agents such as hydroxylamines, phenylcarboxylic acids,
It is preferable to use phenylsulfonic acids, alkyl (or alkenyl) carboxylic acids into which a hydroxyl group or a carboxyl group has been introduced, sulfites, water-soluble polymers (polyalkylene glycol, methacrylic acid type betaine-type polymer, 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.

As the light-sensitive material which can be processed using the developer of the present invention, a photographic light-sensitive material containing a silver halide emulsion produced by a known method can be used. For example, Research Disclosure (RD) 17643
(December 1978), p. 22-23, 1 "Emulsion Preparation and Emulsion Preparation and
types) and (RD) 18716 (Jan. 1979)
January) page 648.
Also, for example, T.I. H. James "The theor
y of the photographic pro
cess "4th edition, published by Macmillan (1977)
Years), pages 38-104; F. Dauff
"Photographic Emulsion Chemistry", "Photographic"
emulsion Chemistry ", Focal
Press (1966), p. Glafkid
es, "Physics and Chemistry of Photography", Chimie et p.
hysque photographique "Pa
ul Montel (1967); L. Ze
"Manufacture and Coating of Photographic Emulsions", Maki
ng and Coating Photograph
A silver halide emulsion prepared by a method described in Ic Emulsion "Focal Press (1964) or the like may be used.

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. 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, Pho
t. 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 is
Tabular grains having an average aspect ratio of greater 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 and US Pat.
Nos. 520, 4,433,048 and 4,414,3
No. 10,434,226, JP-A-58-113
No. 927, No. 58-127921, No. 63-1383
No. 42, No. 63-284272, No. 63-30534
No. 3, etc., and 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 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 water washing method such as a noodle washing method or a flocculation sedimentation method to remove soluble salts. As a preferred 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.
In the emulsion, a hydrazine compound or a tetrazolium compound can be used as a high contrast agent. Further, a nucleation promoter can be used.

Other known additives for the emulsion include:
For example, (RD) 17643 (December 1978)
Pp. 23-29, 18716 (November 1979) 64
Pages 8 to 651 and 308119 (December 1989)
The compounds described on pages 996-1009 can be added.

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.

[0076]

Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 The following silver halide light-sensitive materials were prepared for evaluation of processability with the developer of the present invention.

<Preparation of Emulsion EM-1> Solution A High methionine gelatin (59.7 mg of methionine per 1 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 1135 g of silver nitrate 2000 ml with distilled water 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 is linearly accelerated over an additional 55 minutes (from start to finish 9.
8 times), during which time the entire amount of solution B was added. After 5 and 18 minutes 400 ml of a 4M sodium chloride solution and 2
0 mM 4,5,6-triaminopyrimidine solution 100
ml was added. During the addition of the above materials, the flow of silver was stopped for 1 minute and the additives were mixed homogeneously.

During this period, the pH was controlled to be constant by adding sodium hydroxide or nitric acid. After the addition,
Excess salts were precipitated and desalted by a conventional method.

When about 3000 particles of the obtained EM-1 were observed with an electron microscope, the average aspect ratio was 15
(Average circle equivalent diameter 1.80μm, average thickness 0.12μ
m), tabular silver chlorobromide grains containing 90 mol% of silver chloride.

<Preparation of photosensitive material> Emulsion EM-1 obtained
The following spectral sensitizing dyes (SD-1) and (SD
-2) was added at a weight ratio of 20: 1 to 400 mg per mol of silver halide.

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 4-hydroxy-6-methyl-1,3,3a, 7- as a stabilizer was added. Tetrazaindene (ST-1) was added in an amount of 3 × 10
^-2 mol was added and dispersed in an aqueous solution containing 70 g of gelatin.

Next, 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-triphenylphosphonium Chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 4.0 g Sodium 2-mercaptobenzimidazole-5-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

[0085]

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Further, 1.0 g of a dye emulsion dispersion shown below was used.
Was added to obtain an emulsion coating solution.

(Preparation of Dye Emulsion Dispersion) The following dye (F-
1) 10 kg 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, 9.3 containing 1.35 kg of sodium tri-i-propylnaphthalenesulfonate (SU-1) which is an anionic surfactant is contained.
% Gelatin solution 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. An appropriate amount of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane was added to the obtained dispersion, and the mixture was made up to 240 kg with water to obtain a finished dye emulsion dispersion.

[0089]

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The additives used in 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 DuPont) 30 g Glyoxal 40% aqueous solution (hardener) 1.5 ml (CH ₂ ＣＨCHSO ₂ CH ₂ ) ₂ O (hardener) 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 62 mg DI-1 (antifungal agent) 0.9 mg

[0092]

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Thickness of 175μ colored blue at 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. The amount of addition is shown in the amount of application per 1 m ² .

(Undercoat Layer Coating Solution) 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 (matting agent with an average particle size of 2.5 μm) 2 mg

[0095]

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[0096] 0 The emulsion coating solution on a support which has been subjected to the undercoating 1.8 g / m ² on one surface per terms of silver value, 1.6 g / m ² as a weight with a gelatin protective layer as weight with gelatin.
The emulsion layer and the protective layer were simultaneously coated on both sides at a speed of 90 m / min with two slide hopper coaters so as to obtain 9 g / m ^2, and dried for 2 minutes and 30 seconds to obtain a sample.

(Preparation of Developer and Processing Agent According to the Present Invention)
A developing solution and a fixing solution having the following compositions were prepared, and the storage stability of the developing concentrated solution, pH fluctuation in running of the developing solution, and photographic performance were evaluated.

<Preparation of Developing Concentrate> Diethylenetriaminepentaacetic acid 5 g Sodium sulfite 24 g Sodium carbonate monohydrate 87.5 g Potassium carbonate 97.5 g Sodium erythorbate 120 g N-acetyl-D, L-penicylamine 0.1 g 1-phenyl- 4-Methyl-4-hydroxymethyl-3-pyrazolidone 16.0 g 5-methylbenzotriazole 0.15 g Compound Table 1 Amount Glutaraldehyde (50 wt% aqueous solution) 8.0 g Water is added to make up to 1 liter.

The pH is adjusted to 10.20 with KOH.

The method of preparing the working solution was as follows: 400 ml of the developing concentrate was added to 600 ml of water to make 1 liter of the working solution.
Let it be 1.

<Preparation of Fixing Concentrate> Ammonium thiosulfate (70 wt / vol%) 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 Add water to make up to 1 liter. Adjust to 60.

The preparation method of the working solution was as follows. 500 ml of water was added to 500 ml of the fixing concentrate to make 1 liter of working solution, and the fixing solution-1 was used.
And

(Evaluation of Storage Concentration of Developed Concentrate) The developed concentrated solution was placed in a polyethylene container and stored at 60 ° C. for 2 months, and the pH and photographic performance after storage were evaluated. As a comparative compound of the compound represented by the general formula (1) or (2), a developing concentrate to which the following compound was added was similarly prepared and evaluated in the same manner.

[0104]

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The photographic performance was evaluated by diluting the stored concentrated developing solution and fixing concentrated solution at the above ratio, and using an automatic developing machine SRX.
-701 (manufactured by Konica Corporation) and developed in a 30-second mode under the following conditions.

For comparison, the developer immediately after preparation was evaluated.
Comparison before and after storage was performed. The developing temperature and the fixing temperature were both 35 ° C. The sensitivities in the table are shown as relative values with the reciprocal of the exposure amount that gives an optical density of fog density +1.0 in the developer immediately after the preparation (not stored) as 100. Fog indicates the optical density including the unexposed portion of the support, and Dm indicates the maximum density. The amount of liquid in the developing tank was adjusted to 13.5 liters. Table 1 shows the obtained results.

[0107]

[Table 1]

As is clear from Table 1, the developer of the present invention has a small fluctuation in pH when stored in a concentrated solution, and the photographic performance with respect to the sensitivity and the maximum density when diluted in a working solution. All were excellent.

Next, the running processability was evaluated using the film sample obtained above.

The above-prepared developer 1 and fixer 1 were placed in an automatic developing machine SRX-701, and a running test was conducted in the 30-second mode under the following conditions. The developing temperature and the fixing temperature were both 35 ° C.
The processing was carried out in the stated amounts, and running processing was carried out for 3 weeks at a processing amount shown in Table 2 while replenishing the developing solution and the fixing solution by 150 ml per 1 m ² of the photographic light-sensitive material.

At the start of running, acetic acid was added to the developing tank of the automatic developing machine as a starter to adjust the pH of the developing solution to 10.0.
An amount that became 0 and an amount that made potassium bromide a concentration of 12.2 g / l were added to obtain a new solution. Table 2 shows the results.

The sensitivity shown in the table is a new solution of a developing solution to which the compound represented by formula (1) or (2) of the present invention is added immediately after the preparation, and gives an optical density of fog density + 1.0. The reciprocal of the exposure amount was set to 100 and 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 13.5 liters, and the R / V values are shown in the table.

[0113]

[Table 2]

As is clear from Table 2, the sample of the present invention has improved running processing stability. Also, according to the present invention, it can be seen that the effect is large when the average number of stay days is large.

Example 2 The following solid developer and solid fixing agent were prepared, and the pH fluctuation and the photographic performance during running of the developer were evaluated.

<Preparation of Solid Developer-1> Granules (A) 500 g of 1-phenyl-3-pyrazolidone, 10 g of N-acetyl-D, L-penicillamine, 500 g of boric acid, glutaraldehyde sodium bisulfite adduct 1000g
Are ground in a commercially available bantam mill to an average of 10 μm.

To this fine powder, 300 g of DTPA · 5Na (diethylenetriaminepentaacetic acid · pentasodium), 300 g of dimezone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone), 400 g of ascorbic acid
0 g, 1600 g of sodium sulfite, 1-phenyl-5
-7.0 g of mercaptotetrazole, 400 g of binder mannitol, and the compound represented by the general formula (1) or (2) of the present invention were added in the amounts shown in Table 3 and mixed in a mill for 30 minutes, followed by commercial stirring granulation. 30m at room temperature for about 10 minutes
After granulation by adding 1 l of water, the granules are dried in a fluidized bed drier at 40 ° C. for 2 hours to remove almost completely the moisture of the granules.

Granulated product (B) 11000 g of potassium carbonate, 2000 of sodium bicarbonate
g are each ground in a commercially available bantam mill to an average of 10 μm. 800 g of binder mannitol is added to each fine powder, mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 15 minutes in a commercially available stirring granulator, and then granulating. The material is dried in a fluidized drier at 40 ° C. for 2 hours to almost completely remove the water content of the granulated material.

The granules (A) and (B) thus obtained were mixed with 100 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,
21,000 ascorbic acid-based developing tablets were prepared.

The method for preparing the working solution is to add water to 24 solid developers to make 1 liter of working solution.

<Preparation of Solid Fixing Agent> Granulated product (C) Ammonium thiosulfate / sodium thiosulfate (90/1
15000 g), 1500 g of β-alanine, and 4000 g of sodium acetate are pulverized in a commercially available bantam mill to an average of 10 μm.

To this fine powder were added 500 g of sodium sulfite, 750 g of sodium persulfate, and 1300 mannitol binder.
g, adding water to 50 ml and performing stirring granulation,
The granulate is dried at 40 ° C. in a fluidized bed drier to remove water almost completely.

Granules (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 adjusted to 0 ml and stirred and granulated, and the granulated product is dried at 40 ° C. using 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. In the preparation method of the working solution, water was added to 28 solid fixing agents to make 1 liter of the working solution to obtain a fixing solution-1.

The developer-1 and the fixer-1 prepared as described above were placed in an automatic developing machine TCX-201 (manufactured by Konica Corporation), and
The running process was performed in the 0 second mode under the following conditions.

The developing temperature and the fixing temperature are both 36 ° C.
The photographic light-sensitive material prepared in Example 1 was processed daily in the amounts shown in Table 3 below, and the developing solution and the fixing solution were treated with 1 m ² of the photographic light-sensitive material.
A running test was performed for three weeks while replenishing 150 ml per bottle. At the start of running, acetic acid was added to the developing tank of the automatic developing machine as a starter so that the developing pH was 10.0.
An amount that became 0 and an amount that made potassium bromide a concentration of 12.2 g / l were added to obtain a new solution.

Table 3 shows the obtained results. The sensitivities in the table indicate the exposure amount that gives an optical density of fog density +1.0 with a new developer solution immediately after the preparation, to which the compound represented by the general formula (1) or (2) of the present invention is not added. The reciprocal number was set to 100 and shown as a relative value. Fog and Dm are shown in the same manner as in Example 2. The liquid amount in the developing tank was adjusted to 7.8 liter.

[0128]

[Table 3]

As can be seen from Table 3, the sample of the present invention
It can be seen that, even under severe running processing conditions, the stability and the maximum concentration are not deteriorated even when the stability is excellent, the replenishment is low, and the average residence time of the processing solution is large.

Example 3 The following solid developer and solid fixing agent were prepared, and the pH fluctuation and photographic performance during the running of the developer were evaluated.

(Preparation of light-sensitive material) Preparation of silver halide photographic light-sensitive material sample for bright room reversal Using a double-mixing method, a silver chloride content of 98 mol% and a silver bromide content of 2 mol% were used. Monodisperse, cubic silver chlorobromide particles of 15 μm were prepared. K ₃ Rh (H ₂ O) during mixing
7 × 10 ⁻⁵ mol of Br ₅ was added per mol of silver. Before the desalting step of removing soluble salts by a conventional method, 0.6 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added per mol of silver (hereinafter, referred to as “the salt”). Unless otherwise specified, the amount is based on 1 mol of silver).

The temperature of this emulsion was raised to 60 ° C.
mg and 0.75 mg of sodium thiosulfate were added.
60 minutes after adding I, 600 mg of TAI was further added and the temperature was lowered and set.

Next, a coating solution was prepared by adding an additive so as to be in the following amount per 1 m ^{2, and the} following emulsion layer coating solution and protective layer lower layer solution were successively applied to one surface of the undercoated support. On the opposite side, the following backing coating solutions were simultaneously applied.

<Emulsion coating solution> NaOH (0.5 N solution) 4.39 ml / m ² compound b 6.53 mg / m ² quillajasaponin 107 mg / m ² compound b 18.5 mg / m ² compound c 9.8 mg / m ² Gelatin latex 480 mg / m ² Sodium polystyrene sulfonate 52.2 mg / m ² Colloidal silica 20 mg / m ² <Lower layer of protective layer> Gelatin 0.5 g / m ² Solid dispersion of dye D (average particle size 0.1 μm) 62.0 mg / m ² citric acid 4.1 mg / m ² formalin 1.2 mg / m ² hardener: K-1 0.6mg / m ² of sodium polystyrenesulfonate 11.0 mg / m ² <upper protective layer solution> gelatin 0.3 g / m ² compound e 18.0 mg / m ² dye d 48.4 mg / m ² compound f 105.0 mg / m ² compound DOO 1.25 mg / m ² Amorphous silica (average particle size 1.63 μm) 15.0 mg / m ² Amorphous silica (average particle size 3.5 μm) 21.0 mg / m ² Citric acid 4.5 mg / m ² Sodium polystyrene sulfonate 11.0 mg / m ² formalin 10 mg / m ² <backing coating solution> in-line addition compound Chi 170 mg / m ² dye d 30 mg / m ² compound Li 45 mg / m ² compound j 10 mg / m ² Quillaja saponin 111 mg / m ² compound le 200 mg / m ² colloidal silica 200 mg / m ² compound o 35 mg / ^{m 2} compound follower 31 mg / m ² compound Ca 3.1 mg / m ² of polymethyl methacrylate acid polymer (average particle size 5.6 [mu] m) 28.9 mg / m ² glyoxal 10. 1 mg / m ² citric acid 9.3 mg / m ² sodium polystyrene sulfonate 71.1 mg / m ² additive compound the following in-line Yo 81 mg / m ² Compound data 88.2Mg / m ² of calcium acetate 3.0 mg / m ² Hardener: K-1 10mg / ^{m 2}

[0135]

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[0136]

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[0137]

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The coating amount was 2.0 g / silver in the emulsion layer.
gelatin amount 1.2 g / m ² m ^{2, and} the amount of gelatin backing layer is uniformly coated so as to be 2.1 g / m ^2.

(Preparation of Solid Developer) <Preparation of Solid Processing Agent-E> 0.6 g of 8-mercaptoadenine and 5.5 g of 5-methylbenzotriazole were reduced to an average particle size of 10 μm in a commercially available hammer mill. Grind until it is. Add sodium erythorbate monohydrate 60
0 g, 24.2 g of Dimaison S, and 120 g of sodium metabisulfite were mixed in a hammer mill for 30 minutes, and the mixture was added to a commercially available stirring granulator by adding 20 ml of pure water and 100 g of an aqueous D-sorbite solution (64 wt%). After granulation, the mixture was dried with a fluidized bed dryer at 50 ° C. for about 1 hour and 30 minutes to reduce the water content of the granulated product to 1% or less, thereby obtaining a granulated product E. The granulated product E thus obtained was subjected to 25 ° C., RH
In a room conditioned to 40% or less, 1m with a commercial granulator
The resulting granulated product and the compound shown in Table 4 were mixed with a commercially available cross rotary mixer for 3 minutes, and then a tableting machine modified from Tough Press Collect HU manufactured by Kikusui Seisakusho Co., Ltd. The weight per tablet was adjusted to 10 g and compression tableting was performed to prepare a solid processing agent-E <Preparation of solid processing agent-F> Potassium carbonate and potassium bromide were averaged in a commercially available hammer mill. Grind to a particle size of 10 μm. An aqueous solution (b) is prepared by dissolving 0.5 g of LiOH.H ₂ O and 0.4 g of 1-phenyl-5-mercaptotetrazole in 21 ml of pure water.

30 g of DTPA.5H (diethylenetriaminepentaacetic acid), 20 g of the above-ground potassium bromide, 60 g of mannitol, 30 g of sorbitol, and 55 g of the above-ground potassium carbonate were mixed in a hammer mill for 30 minutes, and commercially available stirring was conducted. Pure water 4m for about 5 minutes in a granulator
After granulating by adding 1 and the above aqueous solution (b), the granulated product was dried with a fluidized bed drier at 60 ° C. until the water content became 2% or less to obtain a granulated product F. .

The granules F thus obtained were subjected to heating at 25 ° C.
In a room conditioned to H40% or less, 1
The resulting granulated product and the compound shown in Table 4 were mixed with a commercially available cross rotary mixer for 3 minutes, and then weighed to 10 g per tablet using the same tableting machine as described above. Compression tableting was performed to prepare a solid processing agent-F.

Combine 81 tablets of the solid processing agent-E prepared above and 53 tablets of the solid processing agent-F, dissolve in pure water, adjust to 10 liters, adjust the pH to 10.70, and develop. Used as mother liquor and replenisher.

<Preparation of Fixing Solution>
CFL-881 (manufactured by Konica Corporation) was used, and the following fixing replenisher was used.

(Preparation of Fixing Replenishment Tablet) Granulation A parts (for 1 liter of liquid used) Ammonium thiosulfate (10% Na salt: manufactured by Hoechst) 140 g Sodium metabisulfite 7.5 g Sodium acetate 40 g Pine flow (trade name: Matsutani Chemical) 11.8 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator. Granulated A dried for 2 hours
Got the parts.

Granulation B parts (for 1 liter of liquid used) 10 g of boric acid 3 g of tartaric acid 26.5 g of sodium hydrogen sulfate 15.8 g of aluminum sulfate / 18 hydrate D-mannitol (trade name: Kao) 4.4 g N-lauroyl taurine ( Trade name: Nikko Chemicals) 2 g Demol N (trade name: Kao) 5 g The above materials were mixed in a commercially available bantam mill for 30 minutes, and further granulated at room temperature for 10 minutes with a commercially available stirring granulator. Is dried in a fluidized-bed dryer at 40 ° C. for 2 hours to obtain granulated product B.
Got the parts.

The above A parts and B parts were thoroughly mixed for 10 minutes, and the resulting mixture was used in a Masina UD manufactured by Masina Co., Ltd.
・ Use a DFE 30/40 tableting machine.
25 tablets having a diameter of 30 mm and a thickness of 10 mm were obtained by compression tableting at 1.5 g / m ² with a filling amount of 6 g. When used, 25 tablets are dissolved in pure water so that the volume becomes 1 liter. The pH of the working solution is 4.20
Met.

Processing conditions Automatic developing machine: GR-26SR (manufactured by Konica Corporation) Developing 35 ° C. for 15 seconds Fixing 34 ° C. for 10 seconds Washing at room temperature for 10 seconds Drying 45 ° C. for 10 seconds A running test was performed using 26SR (manufactured by Konica Corporation) under the above conditions. That is, the photosensitive material was processed daily in the amount shown in Table 4, and the developing solution and the fixing solution were added in an amount of 100 ml per m ² of the photosensitive material.
A running test was performed for three weeks while replenishing each time. At the start of the 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 10.40, and potassium bromide was added in an amount to give a concentration of 12.2 g / l to obtain a new solution. Table 4 shows the obtained results. Here, the sensitivity is a new developer solution to which the compound represented by the general formula (1) or (2) of the present invention is added immediately after the preparation, and the fog density +
The reciprocal of the exposure amount giving an optical density of 1.0 is shown as a relative value with 100 being the reciprocal. Fog and Dm were shown in the same manner as in Example 2. The liquid amount in the developing tank was adjusted to be 27 liters.

[0148]

[Table 4]

Example 4 (Preparation of photosensitive material) <Preparation of silver halide emulsion A> An average thickness of 70 mol% of silver chloride and the balance of silver bromide was 0.05 by a double jet method.
μm, silver chlorobromide core particles having an average diameter of 0.15 μm were prepared. At the time of mixing the core particles, K ₃ RuCl ₆ was added in an amount of 8 × 10 ⁻⁸ mol per mol of silver. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was replaced with silver 1
3 × 10 ^-7 mol was added per mol. The obtained emulsion was silver / chloroiodobromide (90 mol% of silver chloride) having a core / shell type monodisperse (coefficient of variation: 10%) having a (100) plane as a main plane having an average thickness of 0.10 μm and an average diameter of 0.25 μm. , Silver iodide 0.2 mol%, the remainder being silver bromide).

Then, the modified gelatin described in JP-A-2-280139 (Example in which the amino group in the gelatin is substituted with phenylcarbamyl, for example, compound G-8 on page 287 (3) of JP-A-2-280139) is used. Use desalted.
The EAg after desalting was 190 mV at 50 ° C.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 1 × 10 ⁻³ mol per mol of silver, and potassium bromide and citric acid were added to adjust the pH to 5%. .6, adjust to EAg123mV,
After adding 2 × 10 ^-5 mol of chloroauric acid, 3 × of inorganic sulfur was added.
Chemical ripening was carried out at a temperature of 60 ° C. until the maximum sensitivity was obtained by adding 10 ⁻⁶ mol.

After ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 2 × 10 ^-3 mol per mol of silver, and 1-phenyl-5-mercaptotetrazole was added in an amount of 3 × 10 ^-4. Mole and gelatin were added.

<Preparation of Silver Halide Emulsion B> Using a double jet method, 60 mol% of silver chloride and 2.5 mol% of silver iodide, the balance being silver bromide having an average thickness of 0.05 μm and an average diameter of 0.1 mol / m.
15 μm silver chloroiodobromide core grains were prepared. At the time of mixing the core particles, K ₃ Rh (H ₂ O) Br ₅ was added in an amount of 2 × 1 per mole of silver.
^0-8 moles were added. The core particles were shelled using a double jet method. At that time, K ₂ IrCl ₆ was added in an amount of 3 × 10 ⁻⁷ mol per mol of silver. The resulting emulsion was a core / shell type monodisperse (coefficient of variation: 10%) silver chloroiodobromide (90 mol% silver chloride, 0.5 mol silver iodobromide) having an average thickness of 0.10 μm and an average diameter of 0.42 μm. %, The rest consisting of silver bromide)
The emulsion was a tabular grain emulsion. Then, JP-A-2-28013
No. 9 described in Japanese Unexamined Patent Publication (Kokai) No. 2-2 (the modified gelatin wherein the amino group in the gelatin is substituted with phenylcarbamyl).
Desalting was carried out using the exemplified compound G-8) of No. 80139, page 287 (3). The EAg after desalting was 180 mV at 50 ° C.

To the resulting emulsion, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was added in an amount of 1 × 10 ^-3 mol per mol of silver, and potassium bromide and citric acid were added to adjust the pH to 5%. .6, adjust to EAg123mV,
After adding 2 × 10 ⁻⁵ mol of chloroauric acid, N, N, N′-
3 × 1 of trimethyl-N′-heptafluoroselenourea
0 ^-5 mol added to up sensitivity out at a temperature 60 ° C. chemically ripened. After completion of ripening, 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene was used in an amount of 2 × 10 ^-3 mol, 1-phenyl-5-mercaptotetrazole and 3 × 10 ^-4 mol per mol of silver and gelatin. Was added.

(Preparation of a silver halide photographic light-sensitive material for a printing plate making scanner for a HeNe laser light source) On one undercoat layer of a support, a gelatin undercoat layer of the following formula 1 was coated with 0.5 g / m ^{2 of} gelatin. The silver halide emulsion layer 1 of Formulation 2 was further provided thereon with a silver content of 1.5 g / m ² and a gelatin content of 0.5 g / m ² as an intermediate protective layer. Formulation 3 coating solution with gelatin content of 0.3
g / m ² , and the silver halide emulsion layer 2 of Formula 4 as an upper layer further having a silver content of 1.4 g / m ² and a gelatin content of 0.4 g / m ^2. Was applied simultaneously so that the amount of gelatin became 0.6 g / m ² . On the other side of the undercoat layer, a backing layer of the following formulation 6 was further coated with a hydrophobic polymer layer of the following formulation 7 so that the amount of gelatin was 0.6 g / m ² , and further a further formulation of the following 8 with a gelatin content of 0.4
A sample was obtained by simultaneous multi-layer coating with the emulsion layer so as to give g / m ² .

Formulation 1 (Composition of gelatin undercoat layer) Gelatin 0.5 g / m ² Solid dispersed fine particles of dye AD-1 (average particle size 0.1 μm) 25 mg / m ² Sodium polystyrene sulfonate 10 mg / m ² S-1 (Sodium-iso-amyl-n-decylsulfosuccinate) 0.4 mg / m ² Prescription 2 (composition of silver halide emulsion layer 1) Silver halide emulsion A Dye AD so that the silver amount becomes 1.5 g / m ² -8 solid dispersion fine particles (average particle size: 0.1 μm) 20 mg / m ² cyclodextrin (hydrophilic polymer) 0.5 g / m ² sensitizing dye d-1 5 mg / m ² sensitizing dye d-2 5 mg / m ² hydrazine derivative H-7 20mg / m ² redox compound: RE-1 20mg / m ² compound e 100 mg / m ² latex polymer f 0.5 g / m ² hardener ^{g 5mg / m 2 S-1} 0. mg / m ² 2-mercapto-6-hydroxy purine ^{5mg / m 2 EDTA 30mg / m} 2 Colloidal silica (average particle size 0.05 .mu.m) 10 mg / m ² Formulation 3 (intermediate layer composition) Gelatin 0.3 g / m ² S -1 2 mg / m ² formulation 4 (silver halide emulsion layer 2 composition) silver halide emulsion B silver sensitizing dye to be ^{1.4g / m 2 d-1 3mg} / m 2 sensitizing dye d-2 3 mg / m ² Hydrazine derivative H-20 20 mg / m ² Nucleation promoter: Exemplified compound Nb-12 40 mg / m ² Redox compound: RE-2 20 mg / m ² 2-Mercapto-6-hydroxypurine 5 mg / m ² EDTA 20 mg / m ² latex polymer ^{f 0.5g / m 2 S-1} 1.7mg / m 2 formulation 5 (emulsion protective layer composition) solid dispersion of gelatin 0.6 g / m ² dye AD-5 (average particle size ^{.1μm) 40mg / m 2 S-} 1 12mg / m 2 Matting agent: average particle size 3.5μm monodisperse silica 25 mg / m ² nucleation accelerator: Example Compound Na-3 40mg / m ² 1,3- vinyl Sulfonyl-2-propanol 40 mg / m ² Surfactant h 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 10 mg / m ² Hardener: K-1 30 mg / m ² Formulation 6 (backing layer composition) Gelatin 0.6 g / m ² S-1 5 mg / m ² latex polymer f 0.3 g / m ² colloidal silica (average particle size 0.05 μm) 70 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² Compound i 100 mg / m ² formulation 7 (hydrophobic polymer layer composition) latex (methyl methacrylate: acrylic acid = 97: 3) 1.0g / m 2 hardener g 6 mg / m ² formulation 8 (aeration Grayed protective layer) Gelatin 0.4 g / m ² Matting agent: monodispersed polymethylmethacrylate 50 mg / m ² Sodium an average particle diameter of 5 [mu] m - di - (2-ethylhexyl) - sulfosuccinate 10 mg / m ² Surfactant h 1 mg / M ² dye k 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² Hardener: K-1 20 mg / m ²

[0157]

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[0158]

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[0159]

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[0160]

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<Preparation of Processing Solution> CDM-681 was used as a starting mother liquor as a developing solution, and a developing replenisher prepared according to the following formulation was used.

Development replenisher (formulation per liter) Pure water 327 g DTPA / 5Na. 40% aqueous solution 10.86 g sodium sulfite 66.58 g potassium bromide 2 g sodium carbonate 8 g potassium carbonate 44.58 g DEG 70 g 8-mercaptoadenine 0.2 g sodium erythorbate / H ₂ O 60 g benzotriazole 0.26 g dimezone S 1.1 g 1-phenyl-5-mercaptotetrazole 0.08 g KOH. 48.6% aqueous solution 14.6 g Finished to 1 liter with water Adjusted to pH 10.40 The fixer used was Konica Corporation's CFL-881 as the starting mother liquor, and the fixer replenisher used was prepared according to the following formulation. .

Fixing replenisher (prescription per liter) Ammonium thiosulfate 1.0 mol Pure water 242 g Sodium sulfite 22 g Boric acid 9.78 g Sodium acetate trihydrate 32.27 g 90% acetic acid aqueous solution 16.78 g Tartaric acid 3 g Aluminum sulfate 27% 32.93 g of aqueous solution Make up to 1 liter with water Salt concentration (mol / l) 1.78 mol / l pH 4.70 Processing conditions The automatic developing machine used was GR-680 (manufactured by Konica Corporation).

[0164] A running test was performed under the above conditions. The photosensitive material was processed in the amounts shown in Table 5 every day, and a running test was carried out for 3 weeks while replenishing 130 ml of the developing solution and 230 ml of the fixing solution per 1 m ^{2 of} the photosensitive material. At the start of the running, acetic acid was used as a starter in the developing tank of the automatic developing machine in an amount to make the developing pH 10.40, and potassium bromide was added in an amount of 1 to 40.
An amount of 2.2 g / l was added to obtain a new solution. Table 5 shows the results. The sensitivity in the table is the reciprocal of the exposure amount that gives an optical density of fog density +1.0 with a new developer of a developer to which the compound represented by formula (1) or (2) of the present invention is not added immediately after the preparation. Is shown as a relative value when 100 is taken. Fog and Dm are shown in the same manner as in Example 2. The capacity of the developing tank was adjusted to be 40 liters.

[0165]

[Table 5]

As is clear from Tables 4 and 5 above,
It can be seen that even if the silver halide photographic light-sensitive materials to be processed are different, the processing method of the present invention can provide stable running processability. In addition, it can be seen from the sensitometry results under the condition that the film was processed with a large amount of run and that the effect of the present invention was further enhanced.

[0167]

As demonstrated in the examples, according to the present invention, even if the replenishing amount is reduced with a developer using ascorbic acids, p
A developer capable of obtaining stable photographic performance without H reduction, excellent storage stability and running processability of the concentrated solution, and no process fluctuation, and a processing method using the same could be obtained.

Claims (7)

[Claims] 1. A developer for a silver halide photographic light-sensitive material, comprising a reductone and at least one compound represented by the following general formula (1). Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group; R ² , R ³
And R ⁴ each independently represent a hydrogen atom,
Represents an unsubstituted alkyl group, hydroxyalkyl group, carboxyalkyl group, sulfoalkyl group or carboxyl group. ) 2. The developer according to claim 1, wherein R ^{1 in the} general formula (1) is a compound represented by a hydrogen atom. 3. The compound represented by the general formula (1)
2. The developer for a silver halide photographic light-sensitive material according to claim 1, which is a compound represented by the following general formula (2). Embedded image (Wherein, R ⁵ and R ⁶ represent a hydrogen atom or a methyl group. However, when one or both of R ⁵ and R ⁶ are a methyl group, the methyl group may be substituted with a hydroxy group or a carboxyl group. M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n represents 0, 1 or 2.) 4. The developer for a silver halide photographic light-sensitive material according to claim 1, wherein the reductone is a compound represented by the following general formula (A). Embedded image (Wherein R ⁷ and R ⁸ are each a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group,
Represents a mercapto group or an alkylthio group. P and Q are each a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group,
It represents an alkyl group or an aryl group, or a non-metallic atomic group which forms a 5- to 8-membered ring by bonding to each other. Y represents ＝ O or ＮＲNR ⁹ , and R ⁹ represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. ) 5. A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed in the presence of a reductone and a compound represented by the general formula (1) and / or the general formula (2). Processing method of silver halide photographic light-sensitive material. 6. A method for processing a silver halide photographic light-sensitive material, wherein the processing is carried out using the developer for a silver halide photographic light-sensitive material according to any one of claims 1 to 4. Processing method of silver photographic photosensitive material. 7. The processing method of a silver halide photographic light-sensitive material according to claim 5 or 6, wherein the processing method of the silver halide photographic light-sensitive material processed by an automatic developing machine satisfies the following formula (L). . 0.03 ≦ R / V ≦ 0.11 Formula (L) (where R represents the replenishing amount of the developer per day (liter / day), and V is the amount of the solution in the developing tank of the automatic developing machine) (Represents liter)