JPH1138565A - Silver halide photosensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior development stability and to form a high density and low Dmin black-and-white image excellent in discrimination and image preservability in a short time. SOLUTION: A silver halide photosensitive material holding a photosensitive silver halide emulsion, a hydrophilic binder and a slightly water-soluble basic metallic compd. on the substrate and contg. a developing agent capable of developing >=50% of the silver halide emulsion is developed with a processing soln. contg. a compd. forming a complex with a constituent metallic ion of the basic metallic compd. after or while it is imagewise exposed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black-and-white image forming method using a silver halide light-sensitive material and a silver halide light-sensitive material used therefor. The present invention also relates to an image forming method capable of obtaining a black-and-white image having excellent image storability.

[0002]

2. Description of the Related Art In a method of forming an image on a photosensitive material using silver halide, sensitivity changes due to air oxidation of a developing solution or a composition change due to the developing process during development processing, and it is necessary to control the developing solution. There is a demand for an image forming method capable of quickly, simply and stably obtaining an image.

As one of such image forming methods, a silver halide photosensitive material containing a developing agent as described in JP-A-56-1936 is treated with an alkaline aqueous solution having a pH of 11.5 or more. A method for forming a high-contrast image is known. However, in such a method, the pH of the processing solution is high and there is a problem in the handling safety of the solution. JP-A-63-101846 discloses that a light-sensitive material contains a metal compound which is hardly soluble in water and a developer which contains a compound which forms a complex with a metal salt which is hardly soluble in water.
Although a method for suppressing the fluctuation of H is described, there are problems in stability against air oxidation and simplicity of the processing solution. Further, not only the development processing but also the simplification of the fixing and washing steps and the reduction of waste liquid are required.

[0004] In printing photographic materials and the like, it is required to form a high-contrast image excluding halftones. Conventionally, for a high-contrast image, nucleation and development using hydrazine is used. There is a demand for a method of forming a stable and high-contrast image using a simple and stable processing solution, which is susceptible to fluctuations caused by oxidation of the developer and the developing solution.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method using a silver halide photographic material.
An object of the present invention is to provide an image forming method which is excellent in development stability, is excellent in discrimination of high density and low Dmin in a short time, and is capable of obtaining a black and white image excellent in image storability.

[0006]

The above objects of the present invention have been attained by the following constitutions.

(1) Development in which a photosensitive silver halide emulsion, a hydrophilic binder and a basic metal compound which is hardly soluble in water are provided on a support, and at least 50% of the silver halide emulsion can be developed. An image forming method in which a silver halide light-sensitive material containing a main ingredient is developed after or simultaneously with imagewise exposure with a processing solution containing a complex forming compound for a metal ion constituting the basic metal compound.

(2) The image forming method according to (1), wherein the immersion time in the treatment liquid is 20 seconds or less.

(3) The developing agent has a carbon number of 20 or less, and is subjected to a heat treatment after immersion. (1)
Or, the image forming method according to (2).

(4) The silver halide emulsion described in the sixth
The image forming method according to any one of (1) to (3), wherein a silver halide photosensitive material containing a transition metal of Group 10 to Group 10 is used.

(5) The image forming method according to any one of (1) to (4), wherein the silver halide photosensitive material contains an organic contrast agent.

(6) Any one of (1) to (5), characterized in that the processing solution containing the complex forming compound for the metal ions constituting the basic metal compound contains a fixing agent.
Item.

(7) The image forming method according to (6), wherein the treatment liquid contains a compound represented by the following general formula (1).

[0014]

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In the formula, Q represents an atomic group necessary for forming a 5- or 6-membered imide ring.

(8) The image forming method according to any one of (1) to (7), wherein after the development processing, processing is performed with a stabilizing solution.

(9) The silver halide photosensitive material used in the image forming method as described in (1) above, wherein the developing agent has 20 or less carbon atoms.

(10) The silver halide light-sensitive material according to (9), wherein the silver halide emulsion is a silver halide light-sensitive material containing a transition metal belonging to Groups 6 to 10 of the periodic table.

(11) The silver halide photosensitive material as described in (9) or (10), further comprising an organic contrast agent.

Hereinafter, the present invention will be described in detail.

Developing Agent As the developing agent of the present invention, an appropriate one can be selected from conventionally known ones. The developing agent referred to here includes a developing agent precursor that releases the developing agent during development.

Examples of the developing agent which can be used in the present invention include, for example, US Pat. Nos. 3,351,286, 3,761,270, 3,764,328, and 3,342,599. No. 3,719,492, Research Disclosure 12146, No. 1
Nos. 5108 and 15127 and JP-A-56-271.
No. 32, No. 53-135628, No. 57-79035
P-phenylenediamine and p-aminophenol-based developing agents, phosphoramidophenol-based developing agents, sulfonamidoaniline-based developing agents, and hydrazone-based developing agents, phenols, sulfonamidophenols, polyhydroxy Benzenes, naphthols, hydroxybisnaphthyls, methylenebisphenols,
There are ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the above various developing agents.

In the present invention, the developing agent is preferably incorporated in a light-sensitive material (hereinafter also referred to as a light-sensitive material). Therefore, the number of carbon atoms of the developing agent is preferably 20 or less in view of the content and the efficiency of developable Ag. And particularly preferably 15 or less carbon atoms.

Two or more developing agents may be used in combination, and 1-aryl-3-pyrazolidone or a derivative thereof and a hydroquinone derivative are particularly preferred.

The developing agent contained in the light-sensitive material of the present invention must contain a silver halide emulsion contributing to image formation in an amount capable of developing 50% or more, preferably 80% or more, particularly preferably 150% or more. Preferred amounts are preferred. The term "developable amount" as used herein refers to the number of moles of silver that can be reduced when the developing agent reacts theoretically to the maximum with respect to the silver halide emulsion contained in the light-sensitive material.

These developing agents can be contained in the silver halide emulsion layer and other hydrophilic colloid layers. Preferably, the same side of the support as the silver halide emulsion layer is used, and more preferably, a hydrophilic colloid layer other than the silver halide emulsion layer is used. Particularly preferred is any layer between the support and the silver halide emulsion layer.

It is preferred that the developing agent used in the present invention is contained in a solid dispersion state from the viewpoint of the storage stability of the light-sensitive material. As a method of dispersion, an aqueous solution containing a developing agent substantially free of an organic solvent such as ethyl acetate, methanol, methyl ethyl ketone and the like and a high boiling point organic solvent and optionally containing one or more stabilizers or pulverizers may be used. Or a method of removing the organic solvent under reduced pressure after mixing with water, or repeatedly subjecting the solid of the developing agent to a hard inorganic grinding medium in an aqueous solution which may contain one or more stabilizers or grinding agents Prepared. Hard inorganic grinding media include sand, silica spheres, stainless steel, silicon carbide, glass, zirconium, zirconium oxide,
Use beads such as alumina and titanium. These bead sizes range from 0.25 to 3.0 mm. Ball mill, media mill, attritor mill, jet mill,
A method of reducing the particle size using a vibration mill or the like is also often used.

The average particle size of the dispersion obtained as described above can be in the range conventionally obtained by this method, and is generally about 0.05 to 1.5 μm, preferably 0 to 1.5 μm. 0.1 to 1.0 μm.

For the dispersion used in the present invention, a stabilizer or a dispersion aid is used. As the stabilizer or the dispersing aid, a surfactant or a hydrophilic colloid is preferable.

As the surfactant, known anionic, cationic, nonionic, betaine surfactants and fluorine surfactants can be used.

Examples of the organic toning agent used in the present invention include the printing society of Japan, 24 , 299 (1987), Ima.
ging Sci. Technology 40 , 70 (1
996), and a compound exhibiting a selective development mechanism as described in The Journal of the Printing Society of Japan, 24 , 307 (1987).

Specific examples of these compounds include hydrazine derivatives, 5- to 6-membered nitrogen-containing heterocyclic compounds, tetrazolium compounds and the like, and it is preferable to use a nucleation accelerator together with these compounds.

As the hydrazine derivative, a compound represented by the following general formula [H] is preferable.

[0034]

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In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents-
(CO) _n -group, sulfonyl group, sulfoxy group, -P
(＝ O) represents a R ₁₂ — group or an iminomethylene group, n represents an integer of 1 or 2, and both A ₁ and A ₂ are a hydrogen atom or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl. R represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a heterocyclic oxy group, an amino group. A carbamoyl group or an oxycarbonyl group. R ₁₂ represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group, amino group and the like.

Among the compounds represented by the general formula [H], more preferred are the compounds represented by the following general formula [Ha].

[0037]

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In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, thienyl group, Furyl group),
These groups are preferably further substituted with an appropriate substituent. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples thereof include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [Ha], X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4,
Is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meanings as A ₁ and A ₂ in the general formula [H], and preferably both are hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes —COOR ₁₃ group and —CON
(R ₁₄₎ (R ₁₅₎ group (R ₁₃ represents an alkynyl group or a saturated heterocyclic group, R ₁₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₁₅ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but the present invention is not limited thereto.

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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Specific examples of other preferable hydrazine derivatives are described in US Pat. No. 5,229,248, columns 4 to 60 (1) to (252).
Can be mentioned.

The above hydrazine derivative can be synthesized by a known method. For example, US Pat.
No. 9,248, column 59 to column 80, can be synthesized by the method as described.

In the present invention, the optimum amount of the hydrazine derivative varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like. The range is preferably from 10 ^-6 to 10 ^-1 mol, and particularly preferably from 10 ^-5 to 10 ^-2 mol. The hydrazine derivatives used in the present invention may be used alone or in combination of two or more.

It is preferable that the hydrazine derivative used in the present invention is contained in a solid dispersion state from the viewpoint of storage stability of the light-sensitive material. As a method of dispersion, the hydrazine derivative is substantially free of an organic solvent such as ethyl acetate, methanol, and methyl ethyl ketone and a high-boiling organic solvent.
A method of removing an organic solvent by depressurization after mixing with an aqueous solution which may contain one or more kinds of stabilizers or crushing agents, or a method of removing one or more kinds of stabilizers or crushing agents from a solid of a hydrazine derivative In an aqueous solution that may contain
It is prepared by repeated collisions with a hard inorganic grinding media. As the hard inorganic grinding medium, beads such as sand, silica spheres, stainless steel, silicon carbide, glass, zirconium, zirconium oxide, alumina, and titanium are used. These bead sizes are between 0.25 and 3.0.
mm. A method of reducing the particle size using a ball mill, a media mill, an attritor mill, a jet mill, a vibration mill, or the like is often used.

The average particle size of the hydrazine derivative of the dispersion obtained as described above can be in the range usually obtained by the conventional method, and is generally about 0.05 to 0.05.
It is 1.5 μm, preferably between 0.1 and 1.0 μm.

For the dispersion used in the present invention, a stabilizer or a dispersion aid is used. As the stabilizer or the dispersing aid, a surfactant or a hydrophilic colloid is preferable.

As the surfactant, known anionic, cationic, nonionic, betaine surfactants and fluorine surfactants can be used. For example, surfactants include alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyltaurine, sulfosuccinic acid Carboxyl groups, such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates,
Anionic surfactants containing an acidic group such as a sulfonic acid group, a phosphoric acid group, a sulfate ester group, and a phosphate ester group, or alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium, imidazolium, etc. Cationic activators such as heterocyclic quaternary ammonium salts and aliphatic or heterocyclic-containing phosphonium or sulfonium salts, or saponins (steroids), alkylene oxide derivatives, glycidol derivatives, fatty acid esters of polyhydric alcohols, sugars Nonionic surfactants such as alkyl esters of the above can be used.

The hydrophilic colloid is a known water-soluble polymer,
For example, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polystyrene sulfonate, gelatin, derivative gelatin (phthalated gelatin, phenylcarbamoylated gelatin),
Synthetic or natural polymer substances such as cellulose derivatives (cellulose ether, cellulose ester, etc.), starch, gum arabic, pullulan, dextran, dextrin and the like are used.

A form in which the hydrazine derivative is emulsified and dispersed in a high-boiling solvent is also preferably used from the viewpoint of the preservability of the light-sensitive material. The method of dissolving and emulsifying and dispersing the hydrazine derivative in a high boiling point solvent is the same as the method conventionally used for oil-soluble couplers and oil-soluble ultraviolet absorbers. That is, the hydrazine derivative is dissolved in a high boiling organic solvent together with a low boiling organic solvent if necessary, mixed with a gelatin aqueous solution containing a surfactant, and emulsified and dispersed by a colloid mill or the like. Examples of the high boiling organic solvent used at this time include carboxylic esters, phosphoric esters, carboxylic amides, and hydrocarbons. For reference, specific examples of the high-boiling organic solvent advantageously used in the present invention are shown below.

[0060]

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Film surface pH of silver halide photosensitive material of the present invention
The pH of the film surface is preferably 6 or less. The term “film surface pH” as used herein refers to an aqueous solution (3.3 mol in the case of GS-5013F) having the same concentration and composition per 1 cm ² on the surface of the light-sensitive material to be measured per 1 cm ^2. / L of KCl) is added dropwise in an amount of 0.5 cc.
% RH atmosphere for 5 minutes and then a silver chloride electrode (AgCl
/ KCl) as a reference electrode, and a value measured 5 minutes after an integrally formed planar glass electrode (flat composite electrode) was brought into contact with the measurement surface. As a specific example of the flat composite electrode, a flat composite electrode GS-501 manufactured by Toa Denpa Kogyo KK
3F etc.

In the present invention, in order to adjust the film surface pH, a method of adding an acid, a method of adding a volatile alkali during coating and drying of a film, or a compound that releases an acid by a reaction after coating and drying is used. Various methods, such as a method using, are used.

As the acid used in the method of adding an acid, various organic and inorganic acids are preferably used. Specific examples include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, acetic acid, citric acid, phthalic acid, and benzoic acid. As the acid, a high molecular compound having an acid group with a pKa of 5.8 or less is preferably used in addition to the above low molecular compound. p
As those having an acid group of Ka 5.8 or less, acrylic acid, methacrylic acid, AMPS (2-acrylamido-2-methylpropane-sulfonic acid), maleic acid, fumaric acid, itaconic acid, cinnamic acid and the like as monomer components. Are preferably used. In addition, those containing a carboxyl group, a sulfonyl group, an acid salt of an aromatic amine or the like in the polymer chain are also preferably used.

As the alkali which can be volatilized during coating and drying, for example, lower amines such as ammonia and methylamine are preferably used.

As the compound which releases an acid in the reaction after coating and drying, acid halides such as acid chloride, and active halides such as benzyl bromide and NBS are preferably used. Specific examples of such compounds include:
The following are mentioned.

[0066]

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The positions where these compounds are added are the undercoat layer,
It can be added to any layer such as an emulsion layer and a non-emulsion layer.

The hydrazine derivative of the present invention can be contained in any layer of the silver halide light-sensitive material. However, from the viewpoint of storage stability of the light-sensitive material, it can be added to a layer other than the silver halide emulsion layer. preferable.

Next, as the 5- or 6-membered nitrogen-containing heterocyclic derivative which is preferably used in the present invention, a compound represented by the following general formula [Pa], [Pb] or [Pc] is particularly preferable. preferable.

[0070]

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In the general formulas [Pa], [Pb] or [Pc], A ₁ , A ₂ , A ₃ , A ₄ and A ₅ are nonmetallic groups for completing a 5- to 6-membered nitrogen-containing heterocycle. Represents a group of atoms,
The hetero ring may contain an oxygen atom, a nitrogen atom and a sulfur atom, and the hetero ring may be condensed with a benzene ring. _{A 1, A 2, A 3} , A 5~ composed of ₄ and A ₅
The 6-membered nitrogen-containing heterocyclic ring may have a substituent, and examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group. ,
Sulfo group, carboxy group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group,
Represents a carbamoyl group, a ureido group, an amino group, a sulfonamide group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group, or an arylthio group.

Examples of the 5- or 6-membered nitrogen-containing heterocyclic ring composed of A ₁ , A ₂ , A ₃ , A ₄ and A ₅ include pyridine,
Imidazole, thiazole, oxazole, pyrazine,
Examples thereof include a pyrimidine ring, and a pyridine ring is preferable.

In the general formulas [Pa] and [Pb], Bp
Represents a divalent linking group, a divalent linking group is an alkylene,
Arylene, _{alkenylene, -SO 2 -, - SO -} , -
O -, - S -, - CO -, - N (R 6) -, represents what is configured alone or in combination (R ₆ represents an alkyl group, an aryl group, a hydrogen atom). A preferred example is Bp
Represents an alkylene group, alkenylene group, or alkyleneoxy group.

In the general formulas [Pa] and [Pc],
R ₁ , R ₂ and R ₅ each represent a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, R ₁ and R ₂ may be the same or different, and the substituents are A ₁ and A ₂ , A ₃ , A ₄ and A ₅ may be the same as those mentioned above.

In a preferred example, R ₁ , R ₂ and R ₅ each represent an alkyl group having 4 to 10 carbon atoms, and more preferably, a substituted or unsubstituted aryl group or substituted alkyl group.

[0076] Formula [Pa], the [Pb] or [Pc], X _p ^- is a counter ion necessary to balance the charge of the whole molecule, such as chlorine ions, bromine ions, iodine ions, nitrate ions, represents sulfate ion, p- toluenesulfonate, oxalate, n _p represents the number of counter ions needed to balance the charge of the whole molecule, in the case of intramolecular salt n _p is 0. Specific examples of the compounds are shown below.

[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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In the present invention, the hydrazine compound or 5
It is preferable to use a nucleation accelerator in order to effectively promote hardening by a 6 to 6-membered nitrogen-containing heterocyclic derivative.

As a preferable nucleation accelerator, a compound represented by the following general formula [Na] or [Nb] is preferably used.

[0084]

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In the general formula [Na], R ₃₁ , R ₃₂ , R
₃₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group, and R ₃₁ , R ₃₂ and R ₃₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is particularly preferable. Preferred adsorbing groups include a heterocyclic ring, a mercapto group, a thioether group,
Examples include a selenoether group, a thione group, and a thiourea group. Particularly preferred as the general formula [Na] are compounds having at least one thioether group as a halogen adsorbing group in the molecule.

Specific examples of the nucleation accelerator [Na] will be described below.

[0087]

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[0088]

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[0089]

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[0090]

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In the above formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group. R ₃₄ is a hydrogen atom, an alkyl group, an alkynyl group, an aryl group,
Ar and R ₃₄ may be linked by a linking group to form a ring.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Preferred examples of the silver halide adsorption group include groups having the same meaning as the silver halide adsorption group of the compound represented by the formula [H].

Specific compounds of the general formula [Nb] include the following.

[0093]

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[0094]

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Specific examples of other preferable nucleation promoting compounds are the compounds (2-1) to (2-20) and 6-2587 described in JP-A-6-258571.
No. 51, (3-1) to (3-6), JP-A-7-27
No. 0957, onium salt compounds described in JP-A-7-104
No. 420, a compound of the formula I, JP-A-2-103536.
No. 19, page 19, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5;
No. 8 thiosulfonic acid compound.

The nucleation accelerator used in the present invention can be used in any photographic constituent layer on the side of the silver halide emulsion layer, but is preferably used in the silver halide emulsion layer or a layer adjacent thereto. Is preferred. The optimum amount to be added depends on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, etc., but is generally 10 ^-6 to 10 ^-1 per mol of silver halide. It is preferably in the range of mol, particularly preferably in the range of 10 ^-5 to 10 ^-2 mol.

As the tetrazolium compound, a compound represented by the following general formula [T] is preferable.

[0098]

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In the triphenyltetrazolium compound represented by the general formula [T], the substituents R ₁ , R ₂ ,
R ₃ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

For the Hammett's sigma value in the phenyl substitution, see, for example, Journal of Medical Chemistry.
hemistry) Volume 20, page 304, 1977,
C. of the description. As a group having a particularly preferable negative sigma value, for example, a methyl group (σP = −0.17 or less, all σP values) and an ethyl group (−0) can be seen in reports such as C. Hansch. .15), cyclopropyl group (-0.21), n-propyl group (-0.13), i
So-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which is useful as a substituent of the compound of the general formula [T] of the present invention.

N represents 1 or 2, and the anion represented by X _T ^n- includes, for example, chloride ion, bromide ion,
Halogen ions such as iodide ions; acid radicals of inorganic acids such as nitric acid, sulfuric acid and perchloric acid; acid radicals of organic acids such as sulfonic acid and carboxylic acid; anionic activators, specifically p-toluenesulfonic acid anion Lower alkylbenzene sulfonate anions, higher alkylbenzene sulfonate anions such as p-dodecylbenzene sulfonate, higher alkyl sulfate anions such as lauryl sulfate anion, borate anions such as tetraphenylboron, di-2-ethylhexyl sulfo. Dialkyl sulfosuccinate anions such as succinate anions, polyether alcohol sulfate anions such as cetyl polyethenoxy sulfate anion, higher aliphatic anions such as stearic acid anion, and polymers such as polyacrylic acid anion. With ones, and the like can be given.

Hereinafter, specific examples of the compound represented by the general formula [T] are shown below, but the tetrazolium compound is not limited thereto.

[0103]

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The above tetrazolium compound can be easily synthesized, for example, according to the method described in Chemical Reviews, vol. 55, pp. 335-483.

As the tetrazolium compound represented by the general formula [T], one kind may be used, or two or more kinds may be used in combination at an appropriate ratio.

These organic contrasting agents may be used alone or in combination of two or more.

In the silver halide emulsion containing a transition metal used in the present invention, a silver halide emulsion is prepared in a silver halide grain of the periodic table No. 6;
A transition metal selected from elements of Groups 10 to 10 can be introduced into the silver halide in the form of a complex. As the transition metal complex used in the present invention, a six-coordinate complex represented by the following general formula is preferable.

[ML ₆ ] ^{m In the} formula, M is a transition metal selected from elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, and m is 0, -1, -2 or -3.
Represents Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), osmium (Os) and iridium (Ir).

Specific examples of the transition metal coordination complex are shown below.

1: [RhCl ₆ ] ^3- , 2: [RuCl ₆ ] ^3- , 3: [ReCl ₆ ] ^3- , 4: [RuBr ₆ ] ^3- , 5: [OsCl ₆ ] ^3- , 6: [CrCl ₆ ] ⁴⁻ , 7: [Ru (NO) Cl ₅ ] ²⁻ , 8: [RuBr ₄ (H ₂ O) ₂ ⁻ , 9: [Ru (NO) (H ₂ O) Cl ₄ ] ⁻ , 10: [RhCl ₅ (H ₂ O) ²⁻ , 11: [Re (NO) Cl ₅ ] ²⁻ , 12: [Re (NO) CN ₅ ] ²⁻ , 13: [Re (NO) ClCN ₄ ] ^{2 -} , 14: [Rh (NO) ₂ Cl ₄ ] ^- , 15: [Rh (NO) (H ₂ O) Cl ₄ ] ^- , 16: [Ru (NO) CN ₅ ] ² , 17: [Fe ( CN) ₆ ] ³ , 18: [Rh (NS) Cl ₅ ] ² , 19: [Os (NO) Cl ₅ ] ² , 20: [Cr (NO) Cl ₅ ] ² , 21: [Re (NO) Cl ₅ ] ^- , 22: [Os (NS) Cl ₄ (TeCN)] ²⁻ , 23: [Ru (NS) Cl ₅ ] ²⁻ , 24: [Re (NS) Cl ₄ (SeCN)] ²⁻ , 25: [Os ( NS) Cl (SCN) ₄ ] ^2- , 26: [Ir (NO) Cl ₅ ] ^2- Metal complex can be added to the silver halide when silver halide grains are prepared. The transition metal preferably used in the present invention may be Ru or Rh so as to be uniformly distributed over the whole silver halide grains or to be present in the inner shell of the silver halide grains. There is no particular limitation, but it is preferable to add at the time of particle formation.

The addition amount is 10 ^-8 per mol of silver halide.
10 ^-3 mol, preferably 10 ^-8 to 10 ^-6 mol.

The photothermographic material used in the image forming method of the present invention contains photosensitive silver halide as a constituent. Conventionally known photosensitive silver halides can be used, for example, silver chloride, silver bromide, silver iodobromide,
Silver chlorobromide and silver chloroiodobromide can be used. Among them, silver chloride and silver chlorobromide are preferable, and the content of silver chloride is 70%.
More preferably, it is more preferably 80% or more. In particular, a silver chloride content of 90% or more or pure silver chloride is preferred.

These silver halides have a uniform composition from the inside to the surface of the grains, and have a so-called core / shell type in which the composition differs between the inside and the surface, or a multilayered structure in which the composition changes stepwise or continuously. It may be silver halide.

The silver halide may be monodisperse having a relatively uniform grain size or polydisperse having a wide grain size distribution.

The shape of silver halide is cubic, spherical,
Either octahedral, dodecahedral, or tetrahedral ones having a distinct crystal habit or those having no clear crystal habit can be used. Further, for example, JP-A-58-111933 and JP-A-58-11
No. 1934, Research Disclosure 22534
And two parallel crystallographic planes, each of which is a particle having a larger area than the other crystallographic planes and having a particle diameter to thickness ratio of about 5 : 1
The above tabular silver halides can also be used.

Further, for example, US Pat. No. 2,592,25
No. 0, 3,220,613, 3,271,257
No. 3,317,322 and 3,511,622
Nos. 3,531,291 and 3,447,927
Nos. 3,761,266 and 3,703,584
Nos. 3,736,140 and 3,761,276
No., JP-A-50-8524, JP-A-50-38525,
Internal latent image type silver halide emulsions in which the grain surface is not fogged in advance described in JP-A Nos. 52-15661 and 55-127549 can also be used.

The photosensitive silver halide may be formed at any stage of the grain formation by using iridium, gold, rhodium, iron,
Metal ion species such as lead can be added in the form of a suitable salt. In this case, these metal ions are generally added in a range of 10 ^-7 to 10 ^-5 mol per mol of silver.

The grain size of the above-mentioned photosensitive silver halide emulsion is about 0.05 to 2 μm, preferably about 0.1 to 1.0 μm.
μm. Further, for the purpose of gradation adjustment, it is possible to use silver halides having different average grain sizes in the same photosensitive layer in combination.

The photosensitive silver halide emulsion is prepared by chemically sensitizing the surface of silver halide grains with a known sensitizer (eg, active gelatin, inorganic sulfur, sodium thiosulfate, thiourea dioxide, sodium chloroaurate, etc.). Is preferred. Chemical sensitization can also be performed in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing heterocyclic compound.

The above-mentioned photosensitive silver halide can be appropriately subjected to spectral sensitization to blue, green, red and infrared light by a known spectral sensitizing dye. Representative sensitizing dyes are described in, for example,
JP-A-9-180553, JP-A-60-140335, JP-A-60-263937, JP-A-61-65232.
JP-A-61-153635, JP-A-61-153
No. 631, No. 62-32446, No. 63-6
Nos. 1242, 63-138343, JP-A-3-163440, 4-31854, 4-34547, 5-45833, and the like. Further, for example, JP-A-62-39846, JP-A-62-86360, and JP-A-62-89037
JP-A-62-147450, JP-A-62-147450
As described in JP-A-451-451, two or more sensitizing dyes may be used in combination with a single silver halide.

The use amount of these sensitizing dyes is 10 ^-5 to 10 ^-2 mol per mol of silver halide. The sensitizing dye may be added at any stage of the silver halide emulsion,
Specifically, it may be at the time of formation of silver halide grains, at the time of removal of soluble salts, before chemical sensitization, at the time of chemical sensitization, or after chemical sensitization.

These photosensitive silver halide and photosensitive silver salt-forming components are used in an amount of about 0.01 to 40 g per m ² of the light-sensitive material.
Preferably, it is used in the range of 0.05 to 25 g.

As the silver halide light-sensitive material used in the image forming method of the present invention, a known organic silver salt can be used, if necessary, for the purpose of increasing sensitivity and improving developability.

Preferred organic silver salts are silver salts of long-chain aliphatic carboxylic acids, silver salts of carboxylic acids having a heterocyclic ring, and silver salts of compounds having an imino group.

As the binder that can be used in the silver halide light-sensitive material of the present invention, hydrophilic binders are preferable, such as ethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol (having a molecular weight of about 2000 or more), gelatin, and phthalated gelatin. And synthetic or natural polymer substances such as cellulose derivatives, starch, agar, and gum arabic. These can be used alone or in combination of two or more.

In particular, gelatin is preferably used. As the gelatin, ordinary alkali-treated gelatin or acid-treated gelatin, or a gelatin derivative such as phenylcarbamoylated gelatin or phthalated gelatin is used. They can be used together. Also, a combination of the above-mentioned various gelatins and a water-soluble polymer other than gelatin is preferably used.

The amount of the binder to be used is generally 0.05 to 8 g, preferably 0.2 to 5 g, per m ^{2 of the} support in each constituent layer. The total amount of the binder in the photosensitive layer side of the photothermographic material support 1 m ² per 1
３０30 g, preferably 2-15 g.

The binder is preferably hardened with a known photographic hardener. Examples of the hardener include a vinyl sulfone hardener, an aldehyde hardener, an epoxy hardener, an N-methylol hardener, and a halogen-substituted -S- hardener.
And triazine-based hardeners. Further, the hardener may be a polymer hardener.

In the silver halide light-sensitive material used in the image forming method of the present invention, various additives other than those described above can be used, if necessary, as shown below.

Compounds which release a basic compound by decarboxylation upon heating (such as guanidine trichloroacetic acid) and compounds which decompose by an intramolecular nucleophilic substitution reaction to release amines are mentioned. JP-A-56-130
Nos. 745, 59-157637 and 59-1669
No. 43, No. 59-180537, No. 59-17483
No. 0, No. 59-195237, No. 62-108249
And JP-A-63-97942, JP-A-63-96159, and JP-A-1-68746.

The thermal solvent used in the photothermographic material and the complexing agent sheet for promoting the transfer of image dyes and for other purposes is a compound which liquefies during thermal development and has the function of promoting thermal development and the transfer of soluble silver complex. It is preferably in a solid state at normal temperature.

Examples of the thermal solvent that can be used in the present invention include, for example, US Pat. Nos. 3,347,675 and 3,6
67,959, 3,438,776, 3,66
No. 6,477, Research Disclosure No. 1
No. 7643, JP-A-51-19525 and JP-A-53-24
No. 829, No. 53-60223, No. 58-11864
No. 0, No. 58-198038, No. 59-229556
Nos. 59-68730, 59-84236, 60-191251, 60-232525, and 6
No. 0-14241, No. 61-52643, No. 62-7
No. 8554, No. 62-42153, No. 62-4473
No. 7, 63-53548, 63-161446
And compounds described in JP-A Nos. 1-222451 and 2-863.

For example, JP-A-59-177550 and JP-A-5-177550
Nos. 9-11636, 59-124333, 61
-72233 and 61-236548,
Compounds described in JP-A-152454 are useful, and JP-A-61-159842, JP-A-1-104645,
A development accelerator releasing compound described in JP-A-1-110767 can also be used.

In the present invention, an antifoggant generally known for photographic use can be used in combination. In addition, water-soluble halides (potassium bromide, potassium iodide, sodium chloride, etc.) can also be used for fog prevention and other purposes. The antifoggant can be added to any layer of the photothermographic material and the complexing agent sheet.

Various known photographic additives other than those described above can be used in the silver halide light-sensitive material of the present invention. , Nonionic, fluorine-containing anions, etc.), inorganic and organic matting agents, ultraviolet absorbers, and mordants. These are specifically described in RD (Research Disclosure) Magazine N
o. No. 17029, the same No. No. 29963, JP-A-62
No. 135825 and 64-13546. As the mordant, a polymer containing a tertiary amine or a quaternary ammonium salt is preferably used.
Nos. 1228, 50-80132 and 50-80
73440, 53-129034, 5
JP-A-4-145529, JP-A-55-142339, JP-A-56-161410, JP-A-59-21974.
No. 5, No. 62-30249, and No. 62-3
No. 4,249,39, which is a polymer mordant having a quaternary ammonium group described in, for example, US Pat.
No. 3, JP-A-60-23851, etc., polyvinyl pyridine-based mordants, for example, US Pat.
No. 5,124, British Patent Nos. 2,056,101, 2,093,041, JP-A-59-55436, JP-A-60-23854, JP-A-60-39644, and JP-A-60-60643. Publication No. 60-11883
No. 4, No. 60-122941, No. 60-23
No. 5124, a polyvinyl imidazole mordant described in JP-A No. 47-3689, a mordant having a group having a mordant ability grafted thereon described in JP-A-47-3689, and a mordant described in JP-A-60-57836. Combination of tertiary amine mordant and quaternary ammonium mordant,
Examples include mordants having an image stabilizing group described in JP-A-63-198051 and JP-A-2-32335. Further, as a binder used for holding these mordants, for example, a hydrophilic binder such as gelatin or polyvinyl alcohol is preferably used.

These various additives can be appropriately added not only to the photosensitive layer but also to any constituent layers such as an intermediate layer, an undercoat layer, a protective layer and a backing layer.

The silver halide light-sensitive material of the present invention comprises an undercoat layer, an intermediate layer, a protective layer, a filter layer,
A non-photosensitive layer such as a backing layer and a release layer can be optionally provided.

The silver halide light-sensitive material of the present invention can be exposed by known exposure means suitable for the color sensitivity of the light-sensitive material.

As the exposure light source that can be used, a tungsten lamp, a halogen lamp, a xenon lamp,
A mercury lamp, a CRT light source, a FO-CRT light source, a light emitting diode, a laser light source (for example, a gas laser, a dye laser, a YAG laser, a semiconductor laser, etc.) can be used alone or in combination. Further, a light source in which a semiconductor laser and an SHG element (second harmonic generation element) are combined can also be used.

In the present invention, examples of the basic metal compound which is hardly soluble in water include JP-A No. 62-129848 and European Patent 2
The one disclosed in 10660A2 can be used.
Preferred basic metal compounds are zinc or aluminum oxides, hydroxides and basic carbonates, particularly preferably zinc oxide, zinc hydroxide and basic zinc carbonate.

As a mode of adding the basic metal compound which is hardly soluble in water, it is preferable that the basic metal compound is contained in the light-sensitive material in the form of a fine particle dispersion. The preferred average particle size of the fine particles is 0.0
01 to 5 μm, particularly preferably 0.01 to 2 μm
It is. The content is preferably such that the base is released by the reaction with the complexing agent, so that the film surface pH becomes 10 or more, particularly preferably 11 or more.

The compound capable of forming a complex with the metal ion constituting the basic metal compound is contained in a sheet of a support separate from the light-sensitive material (hereinafter referred to as a complexing agent sheet). Preferred compounds capable of forming a complex with a metal ion are described in, for example, JP-A Nos. 62-174745, 62-187847, and 8-87097. In particular, guanidinium salts such as picolinic acid, EDTA, and benzyliminodiacetic acid, methylguanidinium salts, tetraalkylammonium salts, and alkali metal salts are preferable. The content in the complexing agent sheet is 0.01 to 15 g / m ² , preferably 0.1 to 10 g / m ² .

The specific amount of addition is preferably 0.1.
01 to 5 g / m ² , particularly preferably 0.05 to ² g / m ^2.
g / m ² .

Compounds capable of forming a complex with a metal ion constituting a basic metal compound are described in JP-A-62-174745.
Compounds disclosed in JP-A Nos. 62-187847 and JP-A-8-87097 can be used. In particular, guanidinium salts such as picolinic acid, EDTA, and benzyliminodiacetic acid, methylguanidinium salts, tetraalkylammonium salts, and alkali metal salts are preferable.

These compounds of the present invention are contained in a processing solution and react with a poorly soluble basic metal compound to develop a light-sensitive material. The preferred content is 0.1.
1 to 500 g / liter, particularly preferably 0.5 g to 1 g
It is a concentration of 00 g / liter.

In these processing solutions, various additives such as those shown below which are usually used in a developing solution for a silver halide light-sensitive material can be used.

Developing agents Paragraph Nos. [0067] to [0076] of JP-A-8-220703 Silver sludge inhibitor JP-A-8-220703 Paragraph Nos. [0077] to [0087] Preservatives Paragraph No. of JP-A-8-220703 [018
7] Development accelerator JP-A-8-220703, paragraph number [01
90] development inhibitor JP-A-8-220703, paragraph number [01
91] Other additives JP-A-8-220703, paragraph numbers [0188] to [0189] paragraph numbers [0192] to [0194] From the viewpoint of the stability of the processing solution, the developing agent contained in the processing solution of the present invention is preferably Less is preferred, preferably 10 g /
Liter or less, particularly preferably 5 g / liter or less.

In the image forming method of the present invention, the silver halide light-sensitive material may be immersed in a processing bath filled with the above-mentioned processing solution, or after immersion in the processing bath, excess processing solution is squeezed and developed under certain conditions. A method, a method of applying a processing solution to a light-sensitive material and developing the same is used, but in order to prevent diffusion of the released alkali, the immersion time in the processing solution is preferably 20 seconds or less, and preferably 5 seconds or less. Time is more preferred.
After immersion in the processing solution, it is preferable to perform development processing with various developing devices. In the photosensitive material of the present invention, it is possible to apply a known heating means at the time of thermal development, for example, a method of contacting with a heated heat block or a surface heater, or a method of contacting with a heat roller or a heat drum, A system that passes through an atmosphere maintained at a high temperature, a system that uses a high-frequency heating system, or a heat-generating conductive substance such as a carbon black layer provided on the back surface of a photosensitive material or an image receiving member, and Joule heat generated by energization is reduced. A known thermal development system such as a system to be used can be applied. Preferred processing conditions are 30 to
Heat development is performed at 100 ° C., more preferably 40 to 80 ° C., preferably for 1 to 100 seconds, preferably 2 to 60 seconds. From the viewpoint of dimensional stability, it is preferable to heat at a temperature lower than the glass transition point of the photosensitive material.

In the image forming method of the present invention, it is preferable to perform a fixing process. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; and organic compounds capable of forming a soluble stable silver complex salt. Sulfur compounds are used.

The compound represented by the general formula (1) is particularly preferably used.

[0152]

Embedded image

In the formula, Q represents an atom group necessary for forming a 5- or 6-membered imide ring. The nitrogen atom and carbon atom constituting Q are, as branches, a hydrogen atom, an amino group,
To 4 alkyl groups, halogen atoms, keto oxygen atoms,
An aryl group or the like may be bonded.

The compound having an imide ring represented by the general formula (1) is at least 0.1 g, preferably 0.5 g, in 100 ml of an aqueous solution containing equimolar sodium hydroxide.
The above dissolves.

Specific examples of the compound having an imide ring represented by the general formula (1) include uracil, 5-bromouracil, 4-methyluracil, 5-methyluracil, 4-carboxyuracil, 4,5-dimethyl Uracil, 5-aminouracil, dihydrouracil, 1-ethyl-6-methyluracil, 5-carboxymethylaminouracil,
Barbituric acid, 5-phenylbarbituric acid, cyanuric acid, urazole, hydantoin, 5,5-dimethylhydantoin, glutarimide, glutaconimide, citrazinic acid, succinimide, 3,4-dimethylsuccinimide, maleimide and the like. However, it is not limited to these compounds. In the present invention, among compounds having an imide ring represented by the general formula (1), uracil, 5-bromouracil, 4-methyluracil, 5-
Uracils such as methyluracil, 4-carboxyuracil, 4,5-cimethyluracil, 5-aminouracil, dihydrouracil, 1-ethyl-6-methyluracil, and 5-carboxymethylaminouracil are particularly preferred.

In these fixing processes, the fixing process may be performed after the development, but may be added to the processing solution containing the chelating agent. In any case, the concentration of the fixing agent is preferably from 0.1 mol to 5 mol per liter. More preferably, it is 0.5 to 2.0 mol.

The fixing solution may contain a water-soluble aluminum salt acting as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum and the like.

The fixing solution may contain compounds such as a preservative (eg, sulfite and bisulfite), a pH buffer, a pH adjuster, and a chelating agent having a water softening action, if desired.

Washing / Stabilizing Bath In the processing of the photosensitive material of the present invention, after the fixing process, the photosensitive material is washed and / or processed in a stabilizing bath. As a stabilizing bath,
In order to stabilize an image, inorganic and organic acids and salts or alkali agents thereof (for example, borate, metaborate, borax, etc.) for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8). Phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid and the like are used in combination, and aldehydes (for example, Formalin, glyoxal, glutaraldehyde, etc., chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetate, polyphosphate, etc.), fungicides (eg, phenol, 4-chlorophenol, cresol, o-phenyl) Phenol, chlorophen, dichlorophen, formaldehyde, p-hydroxybenzoate, 2- (4-thiophene) (Zoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, etc.), color adjustment Agent and / or residual color improving agent (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent, specifically sodium 2-mercapto-5-sulfonate)
Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-mercapto-5-propyl-1,3,4-triazole,
2-mercaptohypoxanthine). Among them, the stabilizing bath preferably contains a fungicide. The replenishment amount is 50 to 40 per m ² of the photosensitive material.
0 ml.

Replenishment System In the present invention, the processing is performed while replenishing a fixed amount of the processing solution and the fixing solution in proportion to the area of the photosensitive material in response to a demand for reducing the amount of waste liquid. The replenishment amounts of the processing solution and the fixing solution are each 30 to 200 ml per 1 m ^{2 of the} photosensitive material. Here, the replenishing amount of the processing solution and the replenishing amount of the fixing solution refer to the amount of the solution supplied to the processing tank to be replenished or the amount directly applied to the photosensitive material.

The replenisher can be supplied in the form of a working solution, a concentrated solution, or a solid. In the case of a concentrated solution or a solid, the solution may be dissolved and diluted with water and supplied, or the concentrated solution, the solid and water may be separately supplied to a predetermined supply amount.

The processing solution in the image forming method of the present invention comprises:
It is preferable to perform continuous treatment using a solid treating agent. The solid processing agent referred to here is a solid processing agent such as a powder processing agent, a tablet, a pill, and a granule, which is subjected to moisture proof processing as necessary. Powder is an aggregate of fine-grained crystals.
It refers to particulate matter of 00 μm. A tablet means a powder or a granule obtained by compression molding into a certain shape.

To solidify the photographic processing agent, a concentrated liquid or a fine or granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is added to the surface of the temporarily formed photographic processing agent. Any means can be adopted such as forming a coating layer by spraying.

[0164] A preferred tablet production method is a method in which a powdery solid processing agent is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet.

As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation are used. Can be done.
For tablet formation, the average particle size of the obtained granulated product is 100 to 800 μm in that, when the granulated product is mixed and compressed under pressure, the components become non-uniform, so-called segregation is unlikely to occur.
It is preferred to use
７750 μm. Furthermore, the particle size distribution is
Preferably, 0% or more is within a deviation of ± 100 to 150 μm. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The solid processing agent obtained by pressurization and compression can take any shape, but from the viewpoint of productivity, handling properties or dust when used on the user side, cylindrical, so-called tablets are used. preferable.

More preferably, at the time of granulation, the above-mentioned effect becomes more remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative and the like.

The bulk density of the solid processing agent is 1.0 g / cm ³ or more in the case of a tablet from the viewpoint of solubility and effect.
2.5 g / cm ³ is preferred. When it is more than 1.0 g / cm ³ , the strength of the obtained solid is preferable,
When the diameter is smaller than ³ cm ³ , the solubility of the obtained solid is more preferable. When the solid processing agent is a granule or powder, the bulk density is preferably from 0.40 to 0.95 g / cm ³ .

The temperature for the development, fixing, washing and / or stabilizing treatment is preferably in the range of 10 to 70 ° C., and the respective temperatures may be separately adjusted.

In the present invention, processing is carried out using an automatic developing machine because of a demand for shortening the developing time. The processing time is preferably such that the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine until it comes out of the drying zone is 50 seconds or less and 10 seconds or more.

The term "total processing time" as used herein includes the total processing time required for processing a black-and-white photographic light-sensitive material, and specifically includes the processing, such as development, fixing, washing or stabilizing bath,
The time including all steps such as drying, that is, Dry t
o Dry time.

More preferably, the total processing time (Dry t
o Dry) is 15 seconds to 44 seconds. In order to stably process a large amount of photosensitive material of 10 m ² or more, the development time is preferably 18 seconds or less and 2 seconds or more.

[0172]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 Preparation of Silver Halide (Preparation of Silver Halide Emulsion A) Aqueous silver nitrate solutions A and N
The water-soluble halide B consisting of aCl and KBr is converted to a silver potential (E
Ag) at 120 mV, pH 3.0, 35 ° C. in liquid C for 7 minutes by the double-mixing method and 0.09 μm AgCl ₇₀ Br ₃₀
Nucleated. Thereafter, the silver potential was adjusted to 100 mV with NaCl.
The silver nitrate aqueous solution D and the water-soluble halide E were added again for 15 minutes, and the particle size was 0.20 μm (coefficient of variation 15%).
₇₀ Br ₃₀ was obtained. Then pH is adjusted with 1N-NaOH aqueous solution.
The temperature was adjusted to 5.6 and aged at 50 ° C. for 10 minutes. After this, unnecessary salts were removed by ultrafiltration, and then 15 g of gelatin was added per 1 mol of silver to adjust the pH to 5.7 and dispersed at 55 ° C. for 30 minutes. After the dispersion, 4 × 10 ⁻⁴ mol of chloramine T was added per 1 mol of silver. The silver potential of the completed emulsion was 190 mV (40 ° C.).

A: silver nitrate 116 g nitric acid 5% 5.3 ml ion exchange water 48 ml B: NaCl 3.8 g KBr 3.5 g ossein gelatin 1.7 g ion exchange water 48 ml C: NaCl 1.4 g ossein gelatin 7 g nitrate 5% 6.5 ml ion-exchanged water 700 ml D: silver nitrate 154 g nitric acid 5% 4.5 ml ion-exchanged water 200 ml E: NaCl 37 g KBr 33 g ossein gelatin 6 g Transition metal of the 6th to 10th groups of the periodic table Table 1 Amount of ion-exchanged water 200 ml obtained The emulsion thus obtained contained 4-hydroxy-6
Methyl-1,3,3a, 7-tetrazaindene is added to 1.5
× 10 ⁻³ mol and 8.5 × 10 ⁻⁴ mol of potassium bromide were added to adjust the pH to 5.6 and the EAg to 123 mV. Sulfur dispersed in fine particles is converted into sulfur atoms at 2 × 10 ^-5 mo
and 1.5 × 10 ⁻⁵ mol of chloroauric acid, and chemically ripened at a temperature of 60 ° C. for 80 minutes.
6 × methyl-1,3,3a, 7-tetrazaindene was used in an amount of 2 × 10 ⁻³ mol per mol of silver, 1 × phenyl-5-mercaptotetrazole was used in an amount of 3 × 10 ⁻⁴ mol, and potassium iodide was added. 5 × 10 ^-3 mol was added. After cooling to 40 ° C., sensitizing dye S-1 was added at 2 × 10 ⁻⁴ m 2 per mol of silver.
ol was added.

[0175]

Embedded image

First layer (basic metal compound layer insoluble in water) Alkali-treated gelatin 1.85 g Phenylcarbamoylated gelatin 0.35 g Polyvinylpyrrolidone (PVP) 0.30 g Zinc hydroxide 1.50 g Surfactant (SU -1) 0.09 g Surfactant (SU-2) 0.09 g Second layer (developer-containing layer) Alkali-treated gelatin 2.90 g Phenylcarbamoylated gelatin 0.10 g Polyvinylpyrrolidone (PVP) 0.10 g Polyethylene glycol ( Molecular weight 2000) 0.15 g 1-phenyl-4,4'-dimethyl-3-pyrazolidone 0.27 g Surfactant (SU-1) 0.05 g Surfactant (SU-2) 0.02 g Developing agent Table 1 Amount Na-21 0.05 g Dye-1 0.05 g Third layer (emulsion layer) Alkali-treated gelatin 1 .60 g Photosensitive silver halide emulsion 1.75 g Organic contrast agent Amount in Table 1 Phenylcarbamoylated gelatin 0.34 g Polyvinylpyrrolidone (PVP) 0.15 g Surfactant (SU-1) 0.09 g Surfactant (SU -2) 0.03 g Development inhibitor 0.06 g Dye-2 0.02 g Fourth layer (protective layer) Alkali-treated gelatin 0.24 g Phenylcarbamoylated gelatin 0.09 g Polyvinylpyrrolidone (PVP) 0.05 g Surfactant ( SU-1) 0.002 g Surfactant (SU-2) 0.010 g Hardener (1) 0.07 g Hardener (2) 0.04 g Polymethyl methacrylate (average particle size 3 μm) 0.01 g

[0177]

Embedded image

Evaluation of photosensitive material The obtained silver halide photosensitive material was treated with He-N of 633 nm.
Wedge exposure was performed using an e-laser, and the sample 101 was treated with the following developing solution and fixing solution, and then washed and dried.

Developer (per liter of working solution) Pure water 224 ml DTPA · 5Na 1.0 g Potassium sulfite 12.54 g Sodium sulfite 42.58 g KBr 4 g H ₃ BO ₃ 8 g Potassium carbonate 55 g Diethylene glycol 40 g 5-methylbenzotriazole 21 g 1-phenyl-5-mercaptotetrazole 0.03 g Dimezone S 0.85 g Na ascorbate 10 g Hydroquinone 20 g KOH 18 g According to the above-mentioned formulation, the solution was dissolved to make pure water 400 ml.
When used, 600 mL of pure water is mixed to make 1 L. The pH of the working solution was 10.40.

Fixer (per liter of working solution) Pure water 216 ml Ammonium thiosulfate 140 g Sodium sulfite 22 g Boric acid 10 g Tartaric acid 3 g Sodium acetate trihydrate 37.8 g Acetic acid (90% aqueous solution) 13.5 g Aluminum sulfate 18 hydrate 18 g According to the above formula, it was dissolved and finished to 400 ml with pure water. When used, 600 ml of pure water and the above-mentioned concentrated liquid are mixed and used. The pH of the working solution was 4.83.

(Processing conditions) (Process) (Temperature) (Time) Current image 35 ° C. 30 seconds Fixed 35 ° C. 20 seconds Rinse at room temperature 20 seconds Squeeze / Dry 45 ° C. 30 seconds Total 100 seconds 102-109 Then, the substrate was immersed in a processing solution for 2 seconds, and immediately after the immersion, the excess processing solution was removed and heat development was performed at 50 ° C. for 20 seconds. Thereafter, the mixture was treated with a stabilizing solution at 35 ° C. for 10 seconds and dried at 45 ° C. for 15 seconds.

Treatment solution (per liter of working solution) Sodium benzyliminodiacetate 50 g Sodium thiosulfate 100 g Sodium sulfite 22 g 2-mercapto-6-hydroxypurine 0.1 g Sodium hydroxide was adjusted to pH 8.2. It was adjusted.

Stabilizing solution (per liter of working solution) Ethylenediamine-N, N'-disuccinic acid 40 g Potassium sulfite 35 g Potassium carbonate 25 g 8-Mercaptoadenine 0.1 g Sanbac-P (manufactured by San-ai Oil Co., Ltd.) 20 g The blackening density of a sample of the developed photosensitive material was measured with a PDA-65 (Konica Digital Densitometer). 1
The reciprocal of the exposure amount giving a blackening density of 1.0 is defined as 100 and the relative sensitivity is defined as 100.

Dmax, Dmin: Dmax at the point where the highest density of the blackened portion was highest, and Dmin where the lowest density of the unexposed portion.

[Γ] γ = (3-1) / [Log (exposure amount giving D = 3) −
Log (exposure amount giving D = 1)] Black pot The non-image portion of the obtained sample is visually observed with a 40 × loupe, and is measured at 2 m.
The number of black spots of 5 μm or more in m squares was determined. Practically, it is preferable that the number is 10 or less.

Oxidation Fatigue Solution The same treatment was carried out using a solution obtained by bubbling 10 L of oxygen into 10 L of the developing solution and the processing solution.

[0187]

[Table 1]

[0188]

[Table 2]

Example 2 The sample 102 prepared in Example 1 was immersed in the following treatment solution at 50 ° C., and immediately after immersion, the excess treatment solution was removed.
Evaluation was performed by changing the immersion time and the heat development time in a processing method in which heat development was performed at 0 ° C., followed by processing with a stabilizing solution at 35 ° C. for 10 seconds and drying at 45 ° C. for 15 seconds. Thereafter, evaluation was made in the same manner as in Example 1.

Treatment solution (per liter of working solution) Sodium benzyliminodiacetate 50 g Sodium thiosulfate 100 g Potassium sulfite 22 g 2-mercapto-6-hydroxypurine 0.1 g Sodium hydroxide was adjusted to pH 8.5. It was adjusted.

Stabilizing solution (per liter of working solution) Ethylenediamine-N, N'-disuccinate 40 g Potassium sulfite 35 g Potassium carbonate 25 g 8-Mercaptoadenine 0.1 g

[0192]

[Table 3]

Example 3 Evaluation was performed in the same manner as in Example 1 except that the processing liquid of Example 1 was used.

[0194]

[Table 4]

[0195]

According to the present invention, a black-and-white image having excellent development stability, excellent high-density, low-Dmin discrimination, and excellent image storability can be obtained in a short time.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/38 G03C 5/38 11/00 11/00

Claims (11)

[Claims] 1. A developing agent having a photosensitive silver halide emulsion, a hydrophilic binder and a basic metal compound which is hardly soluble in water on a support, and capable of developing 50% or more of the silver halide emulsion. An image characterized in that a silver halide light-sensitive material having a built-in is developed with a processing solution containing a complex forming compound for a metal ion constituting the basic metal compound after or simultaneously with imagewise exposure. Forming method. 2. The image forming method according to claim 1, wherein the immersion time in the processing liquid is 20 seconds or less. 3. The developing agent has a carbon number of 20 or less, and is subjected to a heat treatment after immersion.
Or the image forming method according to 2. 4. A method according to claim 1, wherein said silver halide emulsion comprises
4. The image forming method according to claim 1, wherein a silver halide photosensitive material containing a Group 0 transition metal is used. 5. The image forming method according to claim 1, wherein the silver halide photosensitive material contains an organic contrast agent. 6. The image forming method according to claim 1, wherein a fixing agent is contained in a processing solution containing a complex-forming compound for a metal ion constituting a basic metal compound. 7. The image forming method according to claim 6, wherein the treatment liquid contains a compound represented by the following general formula (1). Embedded image [In the formula, Q represents an atom group necessary for forming a 5- or 6-membered imide ring. ] 8. The image forming method according to claim 1, wherein the development processing is followed by processing with a stabilizing solution. 9. The silver halide photosensitive material used in the image forming method according to claim 1, wherein the developing agent has 20 carbon atoms.
A silver halide photosensitive material characterized by the following. 10. The silver halide emulsion according to any one of claims 6 to
The silver halide light-sensitive material according to claim 9, which is a silver halide light-sensitive material containing a Group 10 transition metal. 11. The silver halide light-sensitive material according to claim 9, further comprising an organic contrast agent.