JP3131660B2 - Processing method for silver halide black and white photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide black-and-white photographic material, and more particularly to a processing method using a solid processing agent and a processing method suitable for processing a super-high contrast photographic material.

[0002]

2. Description of the Related Art A silver halide black-and-white photographic material is usually processed with a processing solution such as a developing solution or a fixing solution using an automatic developing machine after image exposure. In the process, each processing solution is added to a start solution by a photosensitive material,
In order to compensate for evaporation, oxidation by oxygen in air, deterioration due to processing, and the like, a replenishing agent is replenished.

[0003] The starting solution and the replenishing solution are supplied to the user in the form of a concentrated liquid in a plastic bottle (liquid type), and the user dilutes the concentrated liquid with water and uses it in the form of a powder. There are two general forms in which the powder is packaged (solid type) and provided to the user, and the user dissolves the powder in water. The concentrated liquid generally contains an acid or an alkali for the purpose of improving the treatment activity, and a pH buffer for the purpose of reducing the pH fluctuation.

[0004] In the liquid type, some components of the treating agent cause a chemical reaction in the treating agent when it moves from a set pH to a significantly acidic or alkaline condition, thereby causing precipitation. In particular, if the developer is a photosensitive material containing a tetrazolium compound or a hydrazine derivative for the purpose of significantly improving the sharpness (sharpness), deterioration of the concentrated solution until the preparation of the solution may cause sharpness, maximum density, fog, etc. Performance is greatly affected.

On the other hand, as a solid-type technology, there is a technology of granulation as a technology for solving the problem that fine powder soars up and is sucked by an operator or mixed into another processing agent to contaminate it. Nos. 109042, 2-09043, 3-39735 and U.S. Pat. No. 2,843,484.

[0006]

However, in the conventional liquid-type treating agent, since the treating agent component is stored in the form of a concentrated solution, it is affected by storage conditions such as the storage temperature during aging. However, the activity of the processing solution changes,
The use of such a processing solution may cause precipitation of the active ingredient or the like, and as described above, there is a problem that the stability of photographic performance is impaired. The solid processing agent is slightly better in stability in packaging than the concentrated liquid type except for the developing agent and the fixing agent, but the degree of deterioration during storage of the developing agent and the fixing agent is the concentrated liquid type. There is a worse problem. Under such circumstances, there is a strong demand for the development of a processing method capable of always obtaining stable performance.

Accordingly, it is an object of the present invention to firstly provide a processing agent for a silver halide black-and-white photographic light-sensitive material having excellent stability in a packaging form, and secondly, a sharpness (sharpness) The object of the present invention is to provide a method for processing a silver halide black-and-white photographic light-sensitive material in which the fluctuation of maximum density and fog is improved.

[0008]

The first object of the present invention is to provide a black-and-white silver halide photographic material having a photosensitive silver halide emulsion layer coated on a support by a solid processing method containing a cyclodextrin compound. This is achieved by a method for processing a silver halide black-and-white photographic light-sensitive material, characterized by processing with a chemical. Further, the first and second objects are achieved in the above-mentioned processing method, wherein the light-sensitive material contains a tetrazolium compound or a hydrazine derivative in a light-sensitive silver halide emulsion layer.

Hereinafter, the present invention will be described in detail.

The solid of the solid processing agent in the present invention refers to a general solid, and includes powders, granules, tablets, pastes (viscosity of 5 p or more), and the like, and mixtures thereof. You may.

The components contained in the solid processing composition of the present invention are described below.

First, a solid processing agent (solid developer) for a developer will be described.

The combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is the most preferable, since good performance is easily obtained as a developing agent contained in a solid developer for a black-and-white developer. Needless to say, a p-aminophenol-based developing agent may also be contained.

Examples of dihydroxybenzene developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethyl. There are hydroquinone and the like, but hydroquinone is particularly preferred.

The developing agents for 1-phenyl-3-pyrazolidone or derivatives thereof include 1-phenyl-4,4-dimethyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3
-Pyrazolidone.

As p-aminophenol-based developing agents, N-
Methyl-p-aminophenol, p-aminophenol, N-
(β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-amino Phenol is preferred.

The developing agent is usually used in an amount of 0.01 to 1.2 in the working solution.
It is preferably used in an amount of mol / l.

In a solid developer, preservatives such as sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Sulfites such as formaldehyde sodium bisulfite can be included. Sulfite is used at 0.
It is preferable to contain it in an amount of 2 mol / l or more, particularly 0.4 mol / l or more. The upper limit is preferably up to 2.5 mol / l.

The solid developer may contain an alkali agent and a pH moderator as a pH adjuster for the developer. pH
Alkali agents used for the setting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Compounds such as sodium tribasic phosphate and potassium tribasic phosphate are included. The effects of the present invention, especially the improvement of black spots and sharpness when processing a photographic material containing hydrazine and the improvement of pinholes and sharpness when processing a photographic material containing a tetrazolium compound, are particularly remarkable when the pH is 10 or more. .

Solid developers include JP-A-61-28708 (borate), JP-A-60-93439 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates and the like. May be contained.

In addition to the above components, solid developers include development inhibitors such as sodium bromide, potassium bromide and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol; Organic solvents such as ethanol and methanol; 1-phenyl-5-mercaptotetrazole, mercapto-based compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole-based compounds such as 5-nitroindazole, 5-methylbenzotriazole It may contain an antifoggant such as a benzotriazole-based compound such as a colorant, a surfactant, an antifoaming agent, a water softener, and an amino compound described in JP-A-56-106244, if necessary. May be.

The solid developer may contain a silver stain inhibitor such as the compounds described in JP-A-56-24347. Further, an amino compound such as an alkanolamine described in JP-A-56-106244 can be contained.

In addition, L. F. A. Meson, Photographic Processing Chemistry, Focal Press (1966), pp. 226-229, U.S. Patent No. 2,19
Nos. 3,015, 2,592,364 and JP-A-48-64933 may be contained.

Next, the solid processing agent (solid fixing agent) for the fixing solution will be described.

The components contained in the solid fixing agent include the following components.

(A) Fixing agents such as sodium thiosulfate and ammonium thiosulfate. From the viewpoint of the fixing speed, ammonium thiosulfate is preferred.

(B) a hardener such as aluminum chloride,
Water-soluble aluminum salts such as aluminum sulfate and potassium alum.

(C) such as tartaric acid, citric acid or derivatives thereof (specifically, potassium tartrate, sodium tartrate, potassium sodium acid tartrate, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, etc.) Organic acids and their salts.

(D) Preservatives such as sulfites and bisulfites.

(E) pH buffers such as acetic acid and nitric acid.

(F) pH adjusters, such as sulfuric acid.

(G) A chelating agent capable of softening water.

The amounts of these components are as follows:
The amount of (a) is about 0.1 to 6 mol / l, and the amount of (c) is 0.05 mol / l or more, particularly 0.01 to 0.03 mol / l.

Next, the cyclodextrin compound contained in the solid processing agent will be described.

In the present invention, the cyclodextrin compound means cyclodextrin, cyclodextrin derivative, branched cyclodextrin, cyclodextrin polymer and the like.

The above cyclodextrin is represented by the following general formula [I].

[0037]

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Among them, those particularly useful in the present invention are those in which n ₁ =
4 of α- cyclodextrin, n ₁ = 5 of β- cyclodextrin, a γ- cyclodextrin n ₁ = 6.

The cyclodextrin moiety performs an inclusion function to form an inclusion compound. In the present invention, the inclusion compound can be used. The cyclodextrin inclusion compound is described, for example, by F. Kramer (F.
r), “Einshuls Verbindungen” (Ein
Schlus Verbindungen) Springer (1954) or M. Hagan (M. Hagan) "Clathrate Inclusion Compound"
nde) As described in Reinheld (1962), there is a hole of an appropriate size inside a three-dimensional structure formed by bonding atoms or molecules, in which other atoms or molecules have a fixed composition ratio. Substances that form a specific crystal structure by entering
Means

Citations for the production examples of the inclusion compound of cyclodextrin are described below, but these are merely a few examples and, of course, the invention is not limited thereto.

◎ Journal of the American Chemica
l Society) Vol. 71, p. 354, 1949.

◎ Chemische Berchte
ichte) 90: 2572, 1957.

◎ 90, 2561, 1957.

Next, the cyclodextrin derivative will be described.

Examples of the cyclodextrin derivative used in the present invention include known derivatives in which the hydroxyl group of the cyclodextrin represented by the above general formula [I] is changed to an ether, ester, amino group or the like. Regarding these cyclodextrins, ML vendor, M. Komiyama, Cyclodextrin Chemistr.
y) The details are described in Springer-Verlag, published in 1978.

The cyclodextrin derivative used in the present invention includes a compound represented by the following general formula [II] or [III].

[0047]

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In the general formula [II], R _{1 to} R ₃ may be the same or different and represent a hydrogen atom, an alkyl group or a substituted alkyl group. Particularly, those in which R ₁ and R ₃ are alkylated are preferable.

As an example, heptakis-2,6-dimethyl-β
-Cyclodextrin, hexakis-2,6-dimethyl-α-cyclodextrin, octakis-2,6-dimethyl-γ-cyclodextrin and the like.

General formula [III] CD- (OR) _{l In} general formula [III], R represents a hydrogen atom, -R ² CO ₂ H, -R
² SO ₃ H, -R ² NH ₂ or -N (R ³ ) ₂ (R ² represents a linear or branched alkylene group having 1 to 5 carbon atoms, and R ³ represents a linear chain having 1 to 5 carbon atoms. Or represents a branched alkyl group), and l is 1
Represents an integer of from 5 to 5.

Specific examples of the compound represented by the general formula [III] are shown in the following table, but are not limited thereto.

[0052] Exemplified Compound _{No. R l m-1 -CH 2} COOH 3 m-2 -CH 2 COOH 5 m-3 - (CH 2) 4 SO 3 H 1 m-4 - (CH 2) 4 SO 3 H _{3 m-5 -N (C 2} H 5) 2 2 will be described next branch cyclodextrins used in the present invention.

The branched cyclodextrin used in the present invention is a known cyclodextrin obtained by branching or binding a water-soluble substance such as a monosaccharide such as glucose, maltose, cellobiose, lactose, sucrose, galactose or glucosamine or a disaccharide to a known cyclodextrin. Preferably, maltosyl cyclodextrin in which maltose is bound to cyclodextrin (the number of binding molecules of maltose may be one, two, or three), or glucosyl in which glucose is bound to cyclodextrin Cyclodextrin (The number of binding molecules of glucose is 1 molecule, 2 molecules,
Or any of three molecules).

Specific methods for synthesizing these branched cyclodextrins are described, for example, in Starch Chemistry, Vol. 33, No. 2, p.
-126 (1986), P.127-132 (1986), Starch Chemistry, No.3
Vol. 0, No. 2, pp. 231 to 239 (1983) can be synthesized by a known synthesis method. For example, maltosyl cyclodextrin is obtained by using cyclodextrin and maltose as raw materials and isoamylase and pullulanase. It can be produced by a method of binding maltose to cyclodextrin using an enzyme. Glucosylcyclodextrin can be produced in a similar manner.

In the present invention, examples of the branched cyclodextrin preferably used include the following specific compounds.

Illustrative Compounds D-1 α-cyclodextrin with one molecule of maltose bound, D-2 β-cyclodextrin with one molecule of maltose bound, D-3 γ-cyclodextrin with one molecule of maltose bound, D-4 Α-cyclodextrin with two molecules of maltose bonded, D-5 β-cyclodextrin with two molecules of maltose bonded, D-6 γ-cyclodextrin with two molecules of maltose bonded, D
-7 α-cyclodextrin with three molecules of maltose bound, D-8 β-cyclodextrin with three molecules of maltose bound, γ with three molecules of D-9 maltose bound
-Cyclodextrin, α-cyclodextrin with one molecule of D-10 glucose bound, β-cyclodextrin with one molecule of D-11 glucose bound, γ-cyclodextrin with one molecule of D-12 glucose bound, D-1
3 α-cyclodextrin with two glucose molecules bound, β-cyclodextrin with two D-14 glucose molecules bound, γ-cyclo with two D-15 glucose molecules bound
Α-cyclodextrin in which three molecules of cyclodextrin and D-16 glucose are bonded, and three molecules of D-17 glucose
The structures of β-cyclodextrin with molecular bonds, γ-cyclodextrin with three molecules of D-18 glucose, and the structures of these branched cyclodextrins are described by HPLC, NM
R, TLC (thin layer chromatography), INEPT method (Insensi
Although various methods have been studied for measurement methods such as tive nuclei enhanced by polarization transfer), it has not yet been determined even with current science and technology and is in the stage of estimation structure. However, the fact that each monosaccharide or disaccharide or the like is bound to cyclodextrin is that there is no error in the above measurement method. Therefore, in the present invention, when multiple molecules of a monosaccharide or a disaccharide are bonded to cyclodextrin, for example, as shown in the following figure, when they are individually bonded to each glucose of cyclodextrin, It includes both those linked linearly to two glucoses.

[0057]

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Since the ring structure of the existing cyclodextrin is kept as it is, it exhibits the same inclusion function as that of the existing cyclodextrin, and is added with highly water-soluble maltose or glucose, so that the solubility in water is increased. The feature is that it has been improved.

The branched cyclodextrin used in the present invention can be obtained as a commercial product. For example, maltosyl cyclodextrin is commercially available as Isoelite (registered trademark) manufactured by Shimizu Minato Seika.

Next, the cyclodextrin polymer used in the present invention will be described.

The cyclodextrin polymer used in the present invention is preferably a polymer represented by the following general formula [IV].

[0062]

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The cyclodextrin polymer used in the present invention can be produced by subjecting cyclodextrin to a cross-linking polymerization with, for example, epichlorohydrin.

The water solubility of the cyclodextrin polymer, that is, the solubility in water is preferably at least 20 g per 100 ml of water at 25 ° C., and for this purpose, the polymerization degree n ₂ in the general formula [I] is preferably 3 to 3. The water solubility of the cyclodextrin polymer itself and the effect of solubilizing the substance are higher as this value is smaller.

These cyclodextrin polymers are described, for example, in JP-A-61-97025 and German Patent 3,544,842.
It can be synthesized by a general method described in the specification and the like.

The cyclodextrin polymer may be used as an inclusion compound of the cyclodextrin polymer as described above.

The amount of the cyclodextrin, cyclodextrin derivative, branched cyclodextrin or cyclodextrin polymer used in the present invention is defined as
The amount is preferably in the range of 0.1 to 100 g per 00 ml, more preferably 0.5 to 50 g / 1.

Next, a method for producing the solid processing agent will be described.

In order to produce a solid processing agent for a developer and a solid processing agent for a fixing solution, the components to be contained in the solid processing agent are mixed, kneaded, and then granulated by extrusion granulation. Known techniques such as a tableting method can be applied.

In order to form granules or tablets, it is preferable to use generally used granulating auxiliaries, and water-soluble or alkali- or acid-soluble polymers are used. Specifically, gelatin, pectin, polyacrylic acid, polyacrylate, polyvinyl alcohol, polyvinylpyrrolidone, vinyl acetate copolymer, polyethylene oxide, sodium carboxymethylcellulose, hydroxypropylcellulose, methylcellulose, ethylcellulose, alginate, chitanic acid Gum, gum arabic, tragacanth gum, karaya gum, carrageenan, methyl vinyl ether, maleic anhydride copolymer, polyoxyethylene alkyl ether such as polyoxyethylene ethyl ether and polyoxyethylene stearyl ether, polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol Polyoxyethylene alkylphenol ether such as ether, or Japanese Patent Application No. 2-203165 It can be used in combination of one or more kinds selected from among the water-soluble binder.

The packaging form of the solid processing agent may be encapsulated with the processing agent in two or more separate forms in the kit in order to increase the preservability in the kit.

Next, a method for preparing a processing solution using a solid processing agent will be described. As a method for dissolving the solid processing agent,
Similar to the usual liquid preparation method, it may be performed manually or mechanically, and even if the replenishment tank is inside the automatic developing machine,
It may be outside. The method of supplying the treating agent may be any method as long as each component of the treating agent is not scattered.For example, a method in which a solid treating agent is wrapped with a water-soluble polymer film and charged as it is, or the surface is treated with a material such as polyethylene. There is a method in which the powder is wrapped in paper to prevent the dust from scattering and remaining, and is added to the tank. In consideration of the solubility of the processing agent in water, as a solid form, granules or tablets are preferable, but the components of the photographic processing agent often include those that are hardly soluble in water. Poorly soluble substances may precipitate in the processing solution. In order to avoid this, there is a method of adding a solvent separately.

The processing method using the processing solution prepared using the solid processing agent can be in accordance with a known method.

Next, the silver halide black-and-white photographic light-sensitive material according to the present invention will be described.

The silver halide photographic light-sensitive material according to the present invention contains a tetrazolium compound or a hydrazine compound.

First, the tetrazolium compound used in the present invention will be described.

The tetrazolium compound has the following general formula [T]
Can be indicated by

General formula [T]

[0079]

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In the present invention, the substituents R ₁ , R ₂ and R ₃ of the phenyl group of the triphenyltetrazolium compound represented by the above general formula [T] are each a hydrogen atom or a Hammett's sigma value indicating an electron-withdrawing degree. (σP) is preferably negative or positive. In particular, those having a negative sigma value are preferred.

The Hammett's sigma value for phenyl substitution is described in many literatures, for example, the Journal of Medical.
Chemistry (Journal of Medical Chemistry) No. 20
Vol., P. 304, C. Hansch et al., 1977, etc., and a particularly preferred group having a negative sigma value is, for example, a methyl group (σP = −0.17 or less). ΣP value), ethyl group (-0.15), cyclopropyl group (-0.21), propyl group (-0.13), isopropyl group (-0.15).
5), cyclobutyl group (-0.15), butyl group (-0.16), isobutyl group (-0.20), pentyl group (-0.15), cyclohexyl group (-0.22), amino group (-0.66), acetylamino group (- 0.15), hydroxyl group (-0.37), methoxy group (-0.2
7), an ethoxy group (-0.24), a propoxy group (-0.25), a butoxy group (-0.32), a pentoxy group (-0.34), and the like. These are all compounds of the general formula [T] of the present invention. Useful as a substituent.

Specific examples of the compound of the general formula [T] used in the present invention include, for example, JP-A-2-226143, pages (8) to (8).
(9) IV-1 to IV-18 described on page 9, but the compound of the present invention is not limited thereto. The following are representative examples.

[0083]

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The hydrazine derivative contained in the light-sensitive material according to the present invention is preferably a compound represented by the following general formula [H].

[0085]

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In the present invention, among these, the following general formulas [Ha], [Hb], [Hc] or [H-
The compound represented by d] is preferred.

[0087]

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In the general formulas [Ha] and [Hb],
A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents 1 or 2.
When n = 1, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Represents a heterocyclic oxy group, and R ₁ and R ₂ may form a ring together with a nitrogen atom. When n = 2, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, or an alkynyloxy group. , An aryloxy group or a heterocyclic oxy group. However, when n = 2, at least one of R ₁ and R ₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or a heterocyclic oxy group. It is. R ₃ represents an alkyl group or a saturated heterocyclic group.

The compound represented by the general formula [Ha] or [Hb] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.

The details of A, R ₁ and R ₂ are the same as those described in Japanese Patent Application No. 2-222,638.

-NH in the general formulas [Ha] and [Hb]
H of NH—, that is, the hydrogen atom of hydrazine is a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg, acetyl, trifluoroacetyl,
Ethoxycarbonyl, etc.) and oxalyl groups (eg, ethoxylyl, pyruvoyl, etc.), and may be substituted. The compounds represented by the general formulas [Ha] and [Hb] are compounds such as these. Including.

More preferred compounds in the present invention are compounds of the general formula [Ha] when n = 2 and compounds of the general formula [Hb].

In the compound of the formula [Ha] wherein n = 2, R ₁ and R ₂ are a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group or a hydroxy group. Or a compound in which at least one of R ₁ and R ₂ is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group.

Representative compounds represented by the above general formulas [Ha] and [Hb] include the exemplified compound (I-1) described on page 3 to page 6 of JP-A-2-120852. -(I-59), H-1 to H- described in Japanese Patent Application No. 2-222638, pages 20 to 44.
130 and below. However, needless to say, the general formulas [Ha] and [H-
Specific compounds of b) are not limited to these compounds.

Specific examples of compounds

[0096]

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[0097]

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In the above general formula [Hc], R ₃ and R ₄ are
A hydrogen atom, a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a butyl group, a dodecyl group,
2-hydroxypropyl group, 2-cyanoethyl group, 2-chloroethyl group) or substituted or unsubstituted phenyl group, naphthyl group, cyclohexyl group, pyridyl group or pyrrolidyl group (for example, phenyl group, p-methylphenyl group, naphthyl) Group, α-hydroxynaphthyl group, cyclohexyl group, p-methylcyclohexyl group, pyridyl group,
4-propyl-2-pyridyl group, pyrrolidyl group, 4-methyl-2-
R ₅ represents a hydrogen atom, a substituted or unsubstituted benzyl group, an alkoxy group or an alkyl group (eg, benzyl group, p-methylbenzyl group, methoxy group, ethoxy group, ethyl group, butyl group). R ₆ and R ₇ each represent a divalent aromatic group (for example, a phenylene group or a naphthylene group), Y represents a sulfur atom or an oxygen atom, and L represents a divalent linking group (for example, —SO ₂ CH _2). CH
_{2 NH -, - SO 2 NH} -, - OCH 2 SO 2 NH -, - O -, - CH = N
-), And R ₈ represents -NR'R "or -OR ₉ ;
R ′, R ″ and R ₉ each represent a hydrogen atom, a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a dodecyl group), a phenyl group (eg, a phenyl group, a p-methylphenyl group, a p-methoxyphenyl group) ), A naphthyl group (for example, α-naphthyl group, β-naphthyl group) or a heterocyclic group (for example, unsaturated heterocyclic group such as pyridine, thiophene, furan or saturated heterocyclic group such as tetrahydrofuran, sulfolane), R ′ and R ″ may form a ring (eg, piperidine, piperazine, morpholine, etc.) together with the nitrogen atom.

M and n each represent 0 or 1.
When R ₈ is —OR ₉ , Y is preferably a sulfur atom.

[0100]

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In the above formula [Hd], R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom, an alkyl group (for example, a methyl group, an ethyl group, a butyl group, a 3-aryloxypropyl group), a substituted or unsubstituted group. Substituted phenyl, naphthyl,
Represents a cyclohexyl group, a pyridyl group, a pyrrolidyl group, a substituted or unsubstituted alkoxy group (eg, methoxy group, ethoxy group, butoxy group) or a substituted or unsubstituted aryloxy group (eg, phenoxy group, 4-methylphenoxy group).

In the present invention, R ₁₂ is preferably a hydrogen atom or an alkyl group.

R ₁₃ represents a divalent aromatic group (for example, a phenylene group or a naphthylene group), and Z represents a sulfur atom or an oxygen atom.

R ₁₄ is a substituted or unsubstituted alkyl group,
Represents an alkoxy group or an amino group, and examples of the substituent include an alkoxy group, a cyano group, and an aryl group.

The hydrazine derivative can be easily synthesized by a known method.
Compounds can be synthesized according to the descriptions in JP-A Nos. 2-47646 and 2-12237.

Representative compounds represented by the above formulas [Hc] and [Hd] are shown below.

[0107]

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Specific compounds other than those described above are described in
Examples of compounds described on pages 542 (4) to 546 (8) of 2-841
There are (1) to (61) and (65) to (75).

The above hydrazine derivative is disclosed in JP-A-2-841 / 546.
It can be synthesized by the method described on pages (8) to 550 (12). In the light-sensitive material according to the present invention, the hydrazine derivative is added to the silver halide emulsion layer and / or the adjacent layer. The addition amount is 1 × 10 ^-6 to 1 × 10 ^-1 per mol of silver.
Moles, more preferably 1 × per mole of silver.
It is 10 ⁻⁵ mol to 1 × 10 ⁻² mol.

The hydrazine derivative [Ha]
Or when [Hb] is contained, at least one nucleation promoting compound described in Japanese Patent Application No. 2-234,203, page 68, line 1 to page 144, line 12, is coated with a silver halide emulsion layer. as well as/
Alternatively, it is preferably contained in a non-photosensitive layer on the side of the silver halide emulsion layer on the support.

Representative examples of the nucleation accelerator include compounds of N-1 to N-11 described in paragraphs 0054 to 0055 of Japanese Patent Application No. 4-39,673 filed by the present applicant. Is mentioned.

The hydrazine derivatives contained in the silver halide photographic light-sensitive material according to the present invention are also described in paragraphs [0057] to [0097] of Japanese Patent Application No. 4-39,673 filed by the present applicant.
May be a redox compound represented by the general formula [R].

In the silver halide emulsion layer of the present invention, photosensitive silver halide grains having an average grain size of preferably 0.05 to 0.3 μm are used. Here, the average particle size, in the case of spherical particles,
In the case of particles having a shape other than spherical, the diameter indicates a diameter when the projected image is converted into a circular image having the same area.

It is preferred that 60% or more of the total number of particles have a particle size in the range of ± 10% of the average particle size.

The silver halide emulsion (hereinafter also referred to as silver halide emulsion or simply emulsion) used in the silver halide emulsion layer of the present invention includes, for example, silver bromide, silver iodobromide, Any of the usual silver halide emulsions such as silver iodochloride, silver chlorobromide, and silver chloride can be used. Preferably, a 60% by mole or more of a negative silver halide emulsion is used. Silver chlorobromide containing silver or silver chlorobromide, silver bromide or silver iodobromide containing silver chloride or 10 mol% or more of silver bromide as a positive silver halide emulsion.

The silver halide grains used in the silver halide emulsion may be obtained by any of an acidic method, a neutral method, an ammonia method and the like. The particles may be grown at a time, or may be grown after the seed particles have been made. The method of producing the seed particles and the method of growing may be the same or different.

In the silver halide emulsion, a halide ion and a silver ion may be mixed at the same time, or one of them may be mixed in a liquid in which one of them is present. Alternatively, it may be formed by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and pAg in the mixed solution while considering the critical growth rate of silver halide crystals. According to this method, silver halide grains having a regular crystal form and a nearly uniform grain size can be obtained. After the growth, the halogen composition of the grains may be changed using a conversion method.

In the production of a silver halide emulsion, the grain size, grain shape, grain size distribution and grain growth rate of silver halide grains can be controlled by using a silver halide solvent, if necessary. it can.

As the silver halide solvent, ammonia,
Examples thereof include thiourea derivatives such as thioether, thiourea, and 4-substituted thiourea, and imidazole derivatives. Regarding thioethers, U.S. Patent Nos. 3,271,157 and 3,7
Nos. 90,387 and 3,574,628 can be referred to.

When the solvent is other than ammonia, the amount of the solvent used is preferably 10 ^{-3 to} 1.0% by weight, particularly preferably 10 ^-2 to 10 ^-1 % by weight. In the case of ammonia, it can be arbitrarily selected.

The silver halide grains used in the silver halide emulsion are formed during the formation and / or growth of the grains by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium. Salt (including complex salt)
And at least one selected from iron salts (including complex salts) to add a metal ion to allow these metal elements to be contained inside the particles and / or on the surface of the particles, and particularly to contain a water-soluble rhodium salt. It is preferred that In addition, by placing it in an appropriate reducing atmosphere, a reduction sensitizing nucleus can be provided inside the grains and / or on the surface of the grains. When adding a water-soluble rhodium salt, the amount added is 1 × 10 ⁻⁷ to 1 × 10 ⁻⁴ mol /.
AgX is preferably 1 mol.

In the silver halide emulsion, unnecessary soluble salts may be removed after the completion of the growth of the silver halide grains.
Alternatively, it may be kept contained. To remove the salts, use Research Disclosure
closure) can be performed based on the method described in 17643.

The silver halide grains used in the silver halide emulsion may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. There may be.

The silver halide grains used in the silver halide emulsion may be grains whose latent image is mainly formed on the surface or grains whose latent image is mainly formed inside the grain.

The silver halide grains used in the silver halide emulsion may have a regular crystal form such as a cubic, octahedral or tetradecahedral form, or an irregular form such as a sphere or plate. It may have a crystal form. In these particles, the ratio between the {100} plane and the {111} plane can be arbitrarily used. Further, those having a composite form of these crystal forms may be used, and particles of various crystal forms may be mixed.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, sulfur sensitization, selenium sensitization,
A reduction sensitization method, a noble metal sensitization method using gold or another noble metal compound, or the like can be used alone or in combination.

Silver halide emulsions are described, for example, in British Patent No. 61
No. 8,061, No. 1,315,755, No. 1,396,696, Tokiko 44-15
No. 748, U.S. Patent Nos. 1,574,944, 1,623,499, 1,6
73,522, 2,278,947, 2,399,083, 2,410,68
9, 2,419,974, 2,448,060, 2,487,850,
2,518,698, 2,521,926, 2,642,361, 2,6
94,637, 2,728,668, 2,739,06, 2,743,18
No. 2, No. 2,743,183, No. 2,983,609, No. 2,983,610,
3,021,215, 3,026,203, 3,297,446, 3,2
97,447, 3,361,564, 3,411,914, 3,554,75
7, 3,565,631, 3,565,633, 3,591,385,
3,656,955, 3,761,267, 3,772,031, 3,8
57,711, 3,891,446, 3,901,714, 3,904,41
No. 5, 3,930,867, 3,984,249, 4,054,457,
No. 4,067,740, Research Disclosure (Resea
rch Disclosure) 12008, 13452, 13654, The
Theory of the Photographic Processes (THJames Chopsticks)
s. 4th. Ed. Macmillan. 1977) It is preferable to sensitize using a chemical sensitizer or a sensitization method described in pp. 67 to 76 and the like.

Other constitutions of the silver halide black-and-white photographic light-sensitive material according to the present invention and an image forming method using the light-sensitive material include a known silver halide black-and-white photographic light-sensitive material containing a tetrazolium compound or a hydrazine derivative and the use thereof. The technology of the image forming method can be applied,
Paragraph Nos. 0083 to 0083 of Japanese Patent Application No. 4-8685 by the present applicant.
The description in [0151] can be applied.

[0130]

EXAMPLES Examples of the present invention will be specifically described below, but it goes without saying that the present invention is not limited to these examples.

Example 1 Preparation of Photosensitive Material 1 (Synthesis of Latex Lx-1)
7.5 g of sodium dodecylbenzenesulfonate was added to a solution containing 0.05 kg of ammonium persulfate and 0.05 kg of ammonium persulfate, and a mixture of the following (a) to (c) or (d) was added under a nitrogen atmosphere while stirring the solution at 50 ° C. The solution was added over 1 hour, and after stirring for 3 hours, 0.05 kg of ammonium persulfate was added and stirred for 1.5 hours. At the end of the reaction, the remaining monomer was removed by steam distillation for 1 hour, and then cooled to room temperature. The pH was adjusted to 6.0 using water and finished to 80.5 kg with water.

(A) Ethyl acrylate 5.0 kg (A) Methyl methacrylate 1.4 kg (C) Styrene 3.0 kg (D) Acrylamido-2-methylpropanesulfonic acid 0.6 kg (Preparation of silver halide emulsion A) A solution obtained by adding a rhodium hexachloride complex to an aqueous solution of sodium chloride and potassium bromide at a concentration of 8 × 10 ⁻⁵ mol / Agmol was simultaneously added to the gelatin solution while controlling the flow rate. A cubic silver chlorobromide emulsion containing 1 .mu.m and 1 mol% of silver bromide was obtained.

This emulsion was subjected to sulfur sensitization by a conventional method, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and the following additives were added to the emulsion. A coating solution was prepared, and then an emulsion protective layer coating solution, a backing layer coating solution, and a backing protective layer coating solution were prepared according to the following composition.

(Preparation of Emulsion Coating Solution) Gelatin 1.2 g / m ² Compound (a) 1 mg / m ² NaOH (0.5N) Adjusted to pH 5.6 Compound (b) 40 mg / m ² Compound (c) 30 mg / m ² Saponin (20%) 0.5 ml / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² Compound (d) 2 mg / m ² Compound (e) 10 mg Compound (f) 6 mg / m ² latex Lx-1 0.5 g / m ² Styrene-maleic acid copolymerizable polymer (thickener) 90 mg / m ²

[0135]

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(Emulsion protective layer coating solution) Gelatin 1.1 g / m ² compound (g) (1%) 25 ml / m ² compound (h) 120 mg / m ² spherical monodisperse silica (8 μm) 20 mg / m ² 3 [mu] m) 10 mg / m ² compound (i) 100mg / m ² latex Lx-1 0.5g / m ² adjusted to citric acid pH 6.0 (backing layer coating solution) gelatin 1.0 g / m ² compound (j) 100mg / m ² Compound (k) 18 mg / m ² Compound (l) 100 mg / m ² Saponin (20%) 0.6 ml / m ² Latex (m) 300 mg / m ² 5-Nitroindazole 20 mg / m ² Styrene-maleic acid copolymerizable polymer (thickener) 45 mg / m ² glyoxal 4 mg / m ² compound (o) 150 mg / m ² (backing protective layer coating solution) gelatin 0.5 g / m ² compound (g) (1%) 2ml / m 2 spherical polymethyl Methacrylate (4 μm) 25 mg / m ² Sodium chloride 70 mg / m ² Glyoxal 22 mg / m ² Compound (n) 10 mg / m ²

[0137]

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[0138]

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[0139]

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Each coating solution prepared as described above was used in JP-A-5
On a polyethylene terephthalate base having a thickness of 100 μm and subjected to undercoating described in No. 9-19941, 10 W / (m ² · m
After applying a corona discharge in in), the composition was applied using a roll fit coating pan and an air knife with the following composition. The drying was 90 ° C and the overall heat transfer coefficient was 25 Kcal (m ²
(r.degree. C.) for 30 seconds and then at 140.degree. C. for 90 seconds. The thickness of this layer after drying was 1 μm, and the surface resistivity of this layer was 1 × 10 ⁸ Ω at 23 ° C. and 55%.

[0141]

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Ammonium sulfate 0.5 g / l Polyethylene oxide compound (average molecular weight 600) 6 g / l Hardener 12 g / l

[0143]

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On the base, the emulsion layer side and the emulsion protective layer were coated simultaneously in the order of the emulsion surface side and the emulsion protective layer while adding a hardener solution by a slide hopper method while maintaining the temperature at 35 ° C. After passing through the zone (5 ° C.), the backing layer and the backing protective layer were also applied by a slide hopper while adding a hardening agent, and set in a cold air (5 ° C.). At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions.
In addition, after coating both sides of the backing, the film was conveyed in a state of non-contact with a roller and other parts until winding. At this time, the coating speed was 100 m / min.

(Drying conditions) After setting, the film was dried with a drying air at 30 ° C. until the weight ratio of H ₂ O / gelatin became 800%.
0% is dried with 35 ° C (30%) drying air, and the air is blown as it is to reach the surface temperature of 34 ° C (assuming the drying is completed)
After 30 seconds, drying was performed for 1 minute at 48 ° C. and 16% air.

Preparation of Developer Developing agents No. 1-3, 1-5, 1-7, 1-9, 1-11 According to the following composition A and composition B, each was extruded to a particle size of about 2 mm. To obtain a granule developer. The following compositions A and B are shown in amounts corresponding to the developer formulation for 1 liter of the working solution.

Composition A Hydroquinone 15 g 1-Phenyl-3-pyrazolidone 0.5 g Water (as a granulating binder) 0.4 g Composition B KBr 4.5 g EDTA · 2Na 1.0 g KHCO _{3 3} g K ₂ SO ₃ 49.5 g Cyclodextrin clathrate ( (See below) Amount shown in Table 1 Water (as a granulating binder) 3.5 g Cyclodextrin inclusion complex Cyclodextrin compound Amount shown in Table 1 K ₂ CO ₃ 66 g 5-Nitroindazole 0.15 g 1-phenyl-5-mercaptotetrazole 0.02 g 0.16 g of 5-methylbenzotriazole The above compound was dissolved in 100 ml of water, homogenized at 5000 rpm for 10 minutes, dried by spray drying, and used in the above composition B.

Each of the granular developers of the composition A and the composition B was blended so as to have the above-mentioned ratio, and the developer Nos. 1-3, 1-5 and
Granular developers 1-7, 1-9 and 1-11 were obtained.

Comparative developer Nos. 1-4, 1-6, 1-
8, 1-10, 1-12 A comparative developer was prepared using each of the compositions A and B as one liquid having a volume of 1 liter.

Comparative Developer No. 1-1 (Comparative (a)) Instead of the cyclodextrin clathrate in the composition B,
Except for removing the cyclodextrin compound in the composition of the cyclodextrin clathrate, a developer was used in the same manner as the developer No. 1-3 except that a comparative composition prepared in the same manner as the cyclodextrin clathrate was used. Comparative developer (powder)
Was manufactured.

Comparative developer No. 1-2 (comparison (b)) Instead of water (granulating binder) in compositions A and B, 1.0 g of polyethylene glycol (molecular weight: 600) was used in composition A and 4.0 g was used in composition B. g except for developer No. 1-1 (Comparative
Comparative developer No. 1-2 (solid) was produced in the same manner as in (a)).

Comparative developer Nos. 1-13 to 1-15 (comparative
(c), (d) and (e)) except that the composition of the developer was changed as follows.
Comparative developer Nos. 1-13 to 1-15 in the same manner as in 1-4.
(Comparative (c), (d) and (e)) were prepared.

Composition of developer (per liter of working solution) Hydroquinone 15 g 1-phenyl-3-pyrazolidone 0.5 g KBr 4.5 g EDTA · 2Na 1.0 g KHCO _{3 3} g K ₂ SO ₃ 49.5 g K ₂ CO ₃ 66 g 5-nitroindazole 0.15 g diethylene glycol (Table 1) The amount shown in Table 1 1-phenyl-5-mercaptotetrazole 0.02 g 5-methylbenzotriazole 0.16 g The pH of the working solution of the developing solution prepared using the above developer was 10.40. Was.

[0154]

[Table 1]

In Table 1, (1) DEG represents diethylene glycol, PEG represents polyethylene glycol, and the number following DEG or PEG represents the molecular weight.

(2) In the column of the type of cyclodextrin compound, “α-CD” represents “α-cyclodextrin”, and “Iso-Elite” is a trademark of a cyclodextrin compound manufactured by Saltwater Port Refining Co., Ltd. .

(3) The amount of the clathrate of cyclodextrin
Developer Nos. 1-1, 1-2, 1-13, 1-14 and 1-1
The amounts in column 5 are the total amount of K ₂ CO ₃ , 5-nitroindazole, 1-phenyl-5-mercaptotetrazole and 5-methylbenzotriazole.

(4) “g / l” means grams per liter of working solution.

Evaluation method of developer The same day as when the developer was prepared (storage condition 1), and 30 l of each of the above-mentioned developers was placed in a polyethylene terephthalate bottle (container capacity: 30 l), and after purging with nitrogen, the temperature was reduced to 50 ° C. 23 days in a thermo machine at 48% relative humidity (storage condition 2), 23
After storage in a refrigerator at -5 ° C for 7 days at a relative humidity of 18% (storage condition 4) for 7 days (storage condition 3) and at a relative humidity of 18% for 7 days (storage condition 4), dissolution rate during liquid preparation and visual observation of the treatment agent Evaluation of observation and photographic performance were evaluated.

The dissolution rate was 1 liter of water in a 1.5 liter beaker.
(25 ° C.), and using a stirrer (diameter: 7 mm, length: 50 mm) at a rotation speed of 500 rpm, the dissolution time was evaluated from the introduction to the dissolution. In the evaluation of the liquid preparation, water was added to the liquid preparation to make the total amount 1 liter.

In the visual evaluation of the treating agent, the degree of discoloration from the above-mentioned storage condition 1 to the above-mentioned storage conditions 2 to 4 was evaluated in five levels of 1 to 5. 5 is the best when there is no discoloration, 3 is the degree of slight discoloration, and 1 is the worst level of discoloration.

The photographic performance was determined by measuring the transmission density of the photosensitive material 1 processed by an automatic processor GR-27 (manufactured by Konica Corporation) using each developer sample under the storage conditions 1 to 4 described above with a digital densitometer P.
The sensitivity, fog and maximum density were measured using DA-65 (manufactured by Konica Corporation). The sensitivity is represented by a reciprocal of an exposure amount required to obtain a density of 1.0 as a relative value. Sharpness was evaluated by visual sensory evaluation on a scale of 1 to 5. 5 is the best, 1 is the worst level, and 3 or more is a practically usable level.

The running stability was evaluated as follows. The photographic performance on the 14th day was evaluated in the same manner as described above by continuously processing 100 sheets of the entire size (blackening ratio: 20%) per day. Was evaluated. The results are shown in Tables 2 to 4.

[0164]

[Table 2]

[0165]

[Table 3]

[0166]

[Table 4]

Example 2 (Preparation of silver halide emulsion B) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by a double jet method. During this mixing, K ₂ IrCl ₆ was added in an amount of 8 × 10 ⁻⁷ mol per mol of silver. The obtained emulsion was a cubic monodispersed emulsion having an average particle size of 0.20 μm (the coefficient of variation of the particle size distribution was 9%). Washing and desalting were carried out in a conventional manner. The pAg at 40 ° C. after desalting was 8.0.
Subsequently, the following sensitizing dye D-1 was added to this emulsion per mole of silver.
Was added, and 10 mg of D-2 was added. Further, a mixture of the following compounds [A], [B] and [C] was added thereto, and then sulfur sensitization was performed to obtain a silver halide emulsion B.

[0168]

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Preparation of photosensitive materials 2 to 5 A photosensitive silver halide emulsion layer of the following formula (1) was coated on one side of a subbed polyethylene terephthalate support with a gelatin content of 2.0 g / m ² and a silver content of 3.2. by coating so as to become a g / m ^2,
Further, an emulsion protective layer having the following formula (2) was coated thereon so that the amount of gelatin became 1.0 g / m ² , and the surface of the support opposite to the emulsion layer (subbed) was coated with the following. The backing layer of formula (3) is coated so that the amount of gelatin is 2.4 g / m ^2, and the backing protective layer of formula (4) below is further coated so that the amount of gelatin is 1 g / m ^2. Established.

The pH of each layer was adjusted with sodium carbonate and / or citric acid, and the film surface pH of the outermost layer was adjusted.
The light-sensitive materials 2 to 5 containing the hydrazine derivatives shown in the following were prepared.

Formulation (1) (Composition of photosensitive silver halide emulsion layer) Gelatin 2.0 g / m ² Silver halide emulsion A Silver amount 3.2 g / m ² Stabilizer: 4-methyl-6-hydroxy-1,3, 3a, 7-tetrazaindene 30 mg / m ² Antifoggant: 5-nitroindazole 10 mg / m ² 1-phenyl-5-mercaptotetrazole 5 mg / m ² Surfactant: sodium dodecylbenzenesulfonate 0.1 g / m ²

[0172]

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Hydrazine derivative (shown in Table 5) 7 × 10 ⁻⁵ mol / m ²

[0174]

[Table 5]

[0175]

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Formulation (3) (backing layer composition)

[0177]

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Gelatin 2.4 g / m ² Surfactant: sodium dodecylbenzenesulfonate 0.1 g / m ² Surfactant: S-16 mg / m ² colloidal silica 100 mg / m ² Hardener: E 55 mg / m ²

[0179]

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Formulation (4) (Composition of backing protective layer) Gelatin 1 g / m ² Matting agent: Monodispersed polymethyl methacrylate having an average particle size of 5.0 μm 50 mg / m ² Surfactant: S-2 (described above) 10 mg / m ² Hardener: glyoxal 25 mg / m ² Hardener: HA-1 (described above) 35 mg / m ² Preparation of developer Developer No. 2-3, 2-5, 2-7 to 2-12 Composition C below The resulting mixture was granulated by extrusion granulation so as to have a particle size of about 2 mm according to the composition D and the composition, respectively, to obtain a granular developer. In addition, the following compositions C and D are shown in amounts corresponding to the developer formulation of 1 liter of the working solution.

Composition C Hydroquinone 29 g N-methyl-p-aminophenol sulfate 350 mg EDTA · 2Na 1 g Water (as a granulating binder) 0.4 g Composition D NaCl 5 g KBr 1.2 g Na ₃ PO ₄ 75 g 5-methylbenzotriazole 250 mg 2 -Mercaptobenzothiazole 23mg benzotriazole 83mg diisopropylaminoethanol 2.3ml water (as a granulating binder) 3.5g H ₂ N-CH (CH ₃ ) -CH _2- [OCH ₂ CH (CH ₃ )] _x -NH ₂ (x = 2.6 (average)) 0.5 ml The amount of KOH used solution to make pH 11.6 Cyclodextrin compound (shown in Table 6) 4.7 g Each of the granular developers of composition C and composition D is blended so as to have the above-mentioned ratio. Developer No. 2-3, 2-5, 2-7 to 2-1
2 granular developer was obtained.

Comparative developer Nos. 2-1 (Comparative a ') and 2
-2 (Comparative b ') Except for the cyclodextrin compound, polyethylene glycol (molecular weight: 600) was added to the granulating binder water No. 2-1.
g / l, No. 2-2 was dissolved at 5 g / l, and the developer N
A comparative granule developer was prepared in the same manner as in o.2-3.

Comparative Developer Nos. 2-4 and 2-6 Comparative developers were prepared using the above compositions C and D as one liquid in a volume of 1 liter.

Comparative developer No. 2-13 (Comparative c ') Comparative developer No. 2-13 (Comparative c') The same procedure as in Comparative developer No. 2-4 except that the cyclodextrin compound was omitted to make a 1-liter solution of Comparative example Developer was prepared.

[0185]

[Table 6]

The storage stability of the photosensitive material was tested in the same manner as in Example 1 using the developer. Tables 7 and 8 show the combinations of the photosensitive material and the developer and the results.

[0187]

[Table 7]

[0188]

[Table 8]

Tables 7 and 8 show that the solid processing agents of the present invention have remarkably good storage stability.

[0190]

According to the present invention, the following effects (1) and (2) can be obtained.

(1) A developer for a silver halide black-and-white photographic material having excellent stability in a package form is provided.

(2) A processing method is provided for improving the sharpness, maximum density and fog fluctuation of a silver halide black-and-white photographic material containing a tetrazolium compound or a hydrazine derivative.

Continuation of the front page (56) References JP-A-53-48735 (JP, A) JP-A-63-276050 (JP, A) JP-A-1-128066 (JP, A) JP-A-5-204100 (JP) JP-A-64-88452 (JP, A) JP-A-4-85535 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 5/26 520

Claims (3)

(57) [Claims] 1. A silver halide black-and-white photographic material characterized in that a silver halide black-and-white photographic material having a photosensitive silver halide emulsion layer coated on a support is treated with a solid processing agent containing a cyclodextrin compound. Processing method of photosensitive material. 2. The processing method according to claim 1, wherein the light-sensitive silver halide emulsion layer contains a tetrazolium compound. 3. The processing method according to claim 1, wherein the photosensitive silver halide emulsion layer contains a hydrazine compound.