JPH10293387A - Silver halide photosensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material and an image forming method by which a contrasty excellent image can be easily and quickly formed and a preserving characteristic can also be improved. SOLUTION: A silver image is formed on a silver halide photosensitive material by performing ageing development under the existence of a silver halide solvent, a reducing agent and water by superposing the silver halide photosensitive material, which has a photosensitive silver halide emulsion, a hydrophilic binder and a basic metallic compound slightly soluble to water on a support body and contains a hydrazine dielectric, on a sheet containing a complex forming compound and physical development nucleus to a metallic ion to constitute the basic metallic compound after an image-like exposure or simultaneously with the image-like exposure.

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 recent years, a method for forming an image on a photosensitive material using silver halide has been changed from a conventional wet process to an instant system incorporating a developing solution, and a dry development process by heating or the like. Have been developed from the viewpoint of environmental protection.
Japanese Patent Application Laid-Open No. 8-137 discloses one such image forming method.
No. 073, a silver halide light-sensitive material having a light-sensitive silver halide emulsion, a hydrophilic binder and a water-insoluble basic metal compound on a support, after or after imagewise exposure. At the same time, a sheet containing a complex forming compound for a metal ion constituting the basic metal compound and a physical development nucleus are superimposed and thermally developed in the presence of a silver halide solvent, a reducing agent and water to thereby provide the photosensitive material. An image forming method for forming a silver image on a material is known, but this method has a problem that the halftone dot quality of a printing material is not sufficient.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a high-contrast, easy-to-use and excellent image formation method, and at the same time, have a high storage stability. Another object of the present invention is to provide an excellent silver halide photosensitive material and an image forming method.

[0004]

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

(1) A silver halide light-sensitive material having a photosensitive silver halide emulsion, a hydrophilic binder and a basic metal compound which is hardly soluble in water and containing a hydrazine derivative on a support is prepared by image-forming. After the exposure or simultaneously with the imagewise exposure, the complex forming compound for the metal ion constituting the basic metal compound and the sheet containing the physical development nucleus are superimposed, and the silver halide solvent, the reducing agent and water are present. A silver halide photosensitive material used in an image forming method for forming a silver image on the silver halide photosensitive material by thermal development.

(2) A silver halide photosensitive material having a photosensitive silver halide emulsion, a hydrophilic binder and a poorly water-soluble basic metal compound on a support, and containing a hydrazine derivative, is prepared by an image-forming method. After the exposure or simultaneously with the imagewise exposure, the complex forming compound for the metal ion constituting the basic metal compound and the sheet containing the physical development nucleus are superimposed, and the silver halide solvent, the reducing agent and water are present. A silver halide photosensitive material used in an image forming method for forming a silver image on an image receiving sheet having physical development nuclei by performing silver salt diffusion transfer development.

(3) The silver halide photosensitive material as described in (1) or (2) above, wherein the hydrazine derivative is contained as a solid dispersion.

(4) The silver halide photosensitive material as described in (1) or (2) above, wherein the hydrazine derivative is dispersed in a high boiling point solvent.

(5) The silver halide photosensitive material as described in any one of (1) to (4) above, wherein a film surface pH of the silver halide photosensitive material is 6 or less.

(6) The silver halide photosensitive material as described in any one of (1) to (5) above, wherein the hydrazine derivative is added to a non-photosensitive layer other than the silver halide emulsion layer.

(7) The silver halide photosensitive material as described in any one of (1) to (6) above, wherein the silver halide photosensitive material contains a nucleation accelerator.

(8) An image forming method comprising forming a hard silver image having a γ of 10 or more using the silver halide photosensitive material as described in any one of 1 to 7 above.

Hereinafter, the present invention will be described in detail. The hydrazine derivative used in the silver halide photographic light-sensitive material of the present invention is preferably a compound represented by the following formula [H].

[0014]

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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].

[0017]

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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, for example, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, such as 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 both are preferably 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.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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

The above hydrazine derivative can be synthesized by a known method. For example, US Pat.
No. 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 in the dispersion obtained as described above can be in the range conventionally obtained by this method, and is generally about 0.05 to about 0.05.
It is 1.5 μm, preferably between 0.1 and 1.0 μm.

In 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 point 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.

[0040]

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Film surface pH of the silver halide light-sensitive 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 that can be volatilized during coating and drying, for example, lower amines such as ammonia and methylamine are preferably used.

As the compound that 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.

[0046]

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The locations 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.

In the present invention, the effect is exhibited when the film surface pH is 6 or less, but pH 5.5 or less is particularly preferred.

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 may be added to a layer other than the silver halide emulsion layer. preferable.

From the viewpoint of increasing sensitivity, a nucleation accelerator for accelerating nucleation development of hydrazine can be contained. The following general formulas [Na], [Nb] and (P) are used as the nucleation accelerator used in the present invention.

[0051]

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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.

[0053]

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Further, R _{1 to} R ₄ may be linked to each other to form a ring.

As the substituent represented by R _{1 to} R ₄ , an alkyl group (methyl group, ethyl group, propyl group, butyl group,
Hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (piperidinyl group, piperazinyl group) , Morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group,
Sulfolanyl group), an amino group and the like. R ₁ ~
Examples of the ring which R ₄ can form by connecting to each other include a piperidine ring, a morpholine ring, a piperazine ring, a quinuclidine ring,
Examples include a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring. The groups represented by R _{1 to} R ₄ may have a substituent such as a hydroxyl group, an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group, and an aryl group.

As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

Examples of the anion represented by X ⁻ include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion and a p-toluenesulfonic acid ion.

Specific examples of these nucleation accelerators [Na] are shown below.

[0059]

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[0060]

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[0061]

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[0062]

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In the general 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 examples of the compound represented by the general formula [Nb] include the following.

[0065]

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[0066]

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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 compound represented by the general formula (P) is more preferably a compound represented by the following general formula (Pa), (Pb) or (Pc), and a compound represented by the following general formula [T]. .

[0068]

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetallic atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. 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, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. A ¹ , A ² ,
Preferred examples of A ³ , A ⁴ and A ⁵ include 5- to 6-membered rings (rings such as pyridine, imidazole, thiazole, oxazole, pyrazine and pyrimidine), and a more preferred example is a pyridine ring. .

B _P represents a divalent linking group, m is 0 or 1
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ¹⁶ ) — (R ¹⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferably as B _p
An alkylene group and an alkenylene group.

R ¹¹ , R ¹² and R ¹⁵ each represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ¹¹ and R ¹² may be the same or different. As the substituent,
The substituents are the same as those described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ . Preferred examples of R ¹¹ , R ¹² and R ¹⁵ are each an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0072] X _p ^- is a counter ion necessary to balance the charge of the whole molecule, for example chloride, bromide,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate and the like. n _p represents the number of counter ions required to balance the charge of the entire molecule, and n _p is 0 in the case of an internal salt.

[0073]

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The phenyl substituent R ₂₁ of the triphenyltetrazolium compound represented by the above general formula [T],
R ₂₂ and R ₂₃ are preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating electron-withdrawing degree.

The Hammett's sigma value at the phenyl group has been reported in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, vol. 304, p. As a group having a particularly preferable negative sigma value, for example, a methyl group (σP = −0.17 or less, all of which can be seen in reports by C. Hansch et al.)
P value), ethyl group (-0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-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 has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Specific examples of the quaternary onium salt compound are shown below, but are not limited thereto.

[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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The above quaternary onium salt compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemical Reviews 55 p.
335-483 can be referred to.

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

Examples of the reducing agent that can be used in the present invention include, for example, US Pat.
Nos. 761, 270, 3,764, 328, 3, 3
42,599, 3,719,492, Research Disclosure 12146, 15108
No. 15,127, and JP-A-56-27132,
Nos. 53-135628 and 57-79035, p-phenylenediamine-based and p-aminophenol-based developing agents, phosphate amidophenol-based developing agents, sulfonamidoaniline-based developing agents, and hydrazone-based developing agents, Phenols, sulfonamide phenols,
There are polyhydroxybenzenes, naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the above various reducing agents.

Two or more reducing agents may be used in combination.
A combination of -aryl-3-pyrazolidone or a derivative thereof with a hydroquinone derivative is preferred. The amount of the reducing agent to be used is from 0.01 to 20 mol, particularly preferably from 0.1 to 10 mol, per mol of silver.

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 Cl-is 70%.
More preferably, it is more preferably 80% or more. Especially C
l ^- the content of preferably 90% or more or silver chloride.

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 multilayer structure in which the composition changes stepwise or continuously. It may be silver halide.

Further, 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 distinctive 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. 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-50-8,524 and JP-A-50-38,525.
Nos. 52-15,661 and 55-127,549
Internal latent image type silver halide emulsions whose grain surfaces are not fogged in advance as described in JP-A Nos. 2000-163, and 1988 can be used.

The photosensitive silver halide can 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 photosensitive silver halide emulsion has a particle size of 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 obtained 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 photosensitive material.
Preferably, it is used in the range of 0.05 to 25 g.

In the photothermographic 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 the sensitivity and improving the 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.

The basic metal compound insoluble in water used in the present invention includes zinc or aluminum oxides, hydroxides and basic carbonates, particularly preferably zinc oxide, zinc hydroxide and basic carbonate. Zinc. The basic metal compound which is hardly soluble in water is used by dispersing it in a hydrophilic binder as solid fine particles. The average particle size of the fine particles is 0.01 to 2 μm
And preferably 0.05 to 1 μm. The content in the photosensitive material is 0.1 to 5 g / m ² , preferably 0.1 to 5 g / m ² .
05 to 2.5 g / m ² .

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 .

As the binder that can be used in the photothermographic material and the complexing agent sheet of the present invention, hydrophilic binders are preferable, for example, ethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol (molecular weight of about 2,000 or more), gelatin , Gelatin derivatives such as phthalated gelatin, cellulose derivatives, and synthetic or natural polymer substances such as starch, agar, and gum arabic.
More than one species can be used in combination.

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.

According to the image forming method of the present invention, a silver image can be formed on a photosensitive material and a complexing agent sheet. Whether to use the image of the photosensitive material or the image of the complexing agent sheet may be selected depending on the application.

Examples of the silver halide solvent of the present invention include:
Examples include compounds containing the general formula described in JP-B-7-120023. In the present invention, thiosulfates (eg, sodium thiosulfate, ammonium thiosulfate), imide compounds (eg, uracil, 5-methyluracil, 6
-Methyluracil, 6-butylthiouracil), 4-substituted thiourea compounds, organic thioether compounds, thione compounds, active methylene compounds, and mesoionic compounds are preferably used. Preferably, sodium thiosulfate, ammonium thiosulfate, uracil, 5-methyluracil, 6-
Methyluracil and 6-butylthiouracil are used. Particularly, sodium thiosulfate is preferable. In the present invention, the silver halide solvent is contained in the photosensitive material and the complexing agent sheet, and may be supplied from the outside during development. It is particularly preferable that the complexing agent sheet contains a silver halide solvent. The content of the silver halide solvent is 0.01 mol to 10 mol, preferably 1 mol, per mol of silver halide.
0.1 to 5 mol.

The physical development nucleus of the present invention comprises zinc, mercury, lead,
Cadmium, iron, chromium, nickel, tin, cobalt,
Conventionally known physical development nuclei such as heavy metals such as copper, noble metals such as palladium, platinum, silver, and gold, and sulfides, selenides, and tellurides of these metals can be used. Among them, zinc, silver, sulfide of palladium and silver are preferred as physical development nuclei, and zinc sulfide and palladium sulfide are particularly preferred. These physical development nuclei may be used in combination. These physical development nuclei reduce the corresponding metal ions to form a metal colloidal dispersion, or mix a metal ion solution with a soluble sulfide, selenide or telluride solution to form a water-insoluble metal sulfide. , Metal selenide or metal telluride to obtain a colloidal dispersion. These physical development nuclei are contained in the complexing agent sheet, 10 ^-6 to 1
g / m ^2, preferably included 10 ^-5 ~0.1g / m ^2.

In the photothermographic material and the complexing agent sheet 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.

[Base Precursor] Compounds that decarboxylate upon heating to release a basic compound (such as guanidine trichloroacetic acid), and compounds that decompose by an intramolecular nucleophilic substitution reaction to release amines, and the like. For example, JP-A-56-130745 and JP-A-59-15763
No. 7, No. 59-166943, No. 59-180537
Nos. 59-174830 and 59-195237
No. 62-108249, No. 63-97942,
No. 63-96159 and JP-A-1-68746.

[Heat Solvent] The heat solvent used in the photothermographic material and the complexing agent sheet for promoting the transfer of image dyes and for other purposes is liquefied at the time of thermal development to promote thermal development and transfer of the soluble silver complex. It is preferable that the compound is in a solid state at normal temperature.

Examples of the thermal solvent which can be used in the present invention include, for example, US Pat. Nos. 3,347,675 and 3,663.
No. 7,959, No. 3,438,776, No. 3,66
No. 6,477, Research Disclosure (No.
17643, JP-A-51-19525 and 53-2
No. 4829, No. 53-60223, No. 58-1186
No. 40, No. 58-198038, No. 59-22955
No. 6, No. 59-68730, No. 59-84236,
Nos. 60-191251, 60-232525, 60-14241, 61-52643, and 62-
No. 78554, No. 62-42153, No. 62-47
No. 37, No. 63-53548, No. 63-161446
And compounds described in JP-A Nos. 1-222451 and 2-863.

[Development accelerator] For example, JP-A-59-177
No. 550, No. 59-111636, No. 59-1243
No. 33, No. 61-72233, No. 61-236548
And JP-A-1-152454 are useful, and compounds disclosed in JP-A-61-159542 and JP-A-1-159454 are useful.
No. 04645 and JP-A-1-110767 can also be used.

[Anti-fogging agent] In the present invention, an anti-fogging agent generally used for photography 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 photothermographic material and the complexing agent sheet of the present invention. Examples thereof include a filter dye, a fluorescent brightener, an antistatic agent, and a surfactant. Agents (anionic, cationic, nonionic, fluorine-containing anions, etc.), inorganic and organic matting agents,
It can contain an ultraviolet absorber and a mordant. These are specifically described in RD (Research Disclosure) Magazine No. No. 17029, the same No. 29963
And JP-A-62-135825 and 64-135.
No. 46, each publication. As mordant, 3
Polymers containing a quaternary amine or a quaternary ammonium salt are preferably used. For example, JP-A-48-75237, JP-A-50-61228, JP-A-50-80132, JP-A-50-73440, and JP-A-53-12903.
No. 4, No. 54-145529, No. 55-14
Nos. 2339, 56-161410, 59
Polymer mordants having a quaternary ammonium group described in JP-A-219745, JP-A-62-30249, and JP-A-62-34159, such as U.S. Pat.
No. 249,393, JP-A-60-23851 and the like, for example, polyvinyl pyridine mordants such as U.S. Pat. No. 4,115,124 and British Patent 2,056,101.
No. 2,093,041, JP-A-59-55436.
Gazettes, JP-A-60-23854 and JP-A-60-3964
No. 4, No. 60-60643, No. 60-118
834, 60-122941, 60-
No. 235124, a polyvinyl imidazole-based mordant, a mordant having a group having a mordant ability described in JP-A-47-3689, to which a group is grafted,
Combinations of tertiary amine mordants and quaternary ammonium mordants described in JP-A-60-57836, JP-A-63-198051, JP-A-2-32335.
And the like. 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 complexing agent sheet used in combination with the photothermographic material of the present invention comprises a support and a physical developing layer provided thereon for developing a soluble silver complex. The layer is a complexing agent sheet containing a physical development nucleus in a hydrophilic binder.

The support of the complexing agent sheet may be either a transparent support or a reflective support. More specifically, polyethylene phthalate, polypropylene, and a support obtained by adding a white pigment such as barium sulfate or titanium dioxide to a support thereof, or a paper support coated with a thermoplastic resin containing a white pigment (eg, polyethylene). Laminated paper can be used.

When a paper support is used, a support in which both sides of the paper support are coated with polyethylene is particularly preferred.
In this case, it is preferable that titanium oxide is contained in polyethylene on at least one side (particularly preferably on the side of the complexing agent-containing layer).

Various known additives can be added to the complexing agent sheet. Such additives include, for example, a stain inhibitor and an ultraviolet absorber (for example,
Benzophenone-based compounds, benzotriazole-based compounds, and the like described in JP-A-130735 and JP-A-61-153638, etc., fluorescent whitening agents (for example,
Diaminostilbene compounds described in JP-A-143752, compounds described in JP-A-63-147166, etc.), image stabilizers (for example, JP-A-5959 / 1988).
Nos. 182785 and 61-159644, development accelerators, antifoggants (KBr, NaCl,
KI, benzotriazole derivatives and 1-phenyl-5-
Nitrogen-containing heterocyclic compounds such as mercaptotriazole derivatives, etc.), pH regulators (acid and acid precursors, base precursors, etc.), thermal solvents, organic fluorine compounds, oil droplets,
Examples thereof include a surfactant, a hardener, a polymer latex (for example, described in JP-A-61-156045), a matting agent, and various transition metal ions.

The above-mentioned complexing agent sheet may have a so-called back layer in order to balance the curl and improve the slipperiness. The back layer can use either a hydrophilic binder or a hydrophobic binder,
It can be appropriately selected according to the application and configuration.

The photothermographic material of the present invention may optionally have a non-photosensitive layer such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer, and a release layer, in addition to the photosensitive layer. .

The photothermographic material of the present invention can be exposed by known exposure means suitable for the color sensitivity of the photosensitive material.

The exposure light sources that can be used include 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.

The photothermographic material of the present invention is preferably used after imagewise exposure or simultaneously with exposure, preferably at 60 to 100 ° C, more preferably at 70 to 100 ° C, preferably for 1 to 100 seconds, preferably for 2 to 60 seconds. Heat development is performed to form a silver image on the photosensitive material or the complexing agent sheet.

In the image forming method of the present invention, a very small amount of water may be supplied to the light-sensitive material or the complexing agent sheet immediately before the heat development, and the two may be adhered to each other for the heat development. In this case, the water may be simple water, or may be an alkaline aqueous solution, water containing a surfactant, the above-mentioned heat solvent, or sulfite ion. The amount of supply of water is preferably within the range of the maximum swelling film thickness of the photosensitive material or the image receiving material to be supplied. In addition, this water may contain a known antifungal agent, a development accelerator or an antifoggant, a fluorescent whitening agent, and the like, in addition to the additives.

In the photothermographic material of the present invention, a known heating means can be used for thermal development. For example, the photothermographic material may be brought into contact with a heated heat block or a surface heater, or may be heated with a heat roller or a heat drum. A method of passing through an atmosphere maintained at a high temperature, a method of using a high-frequency heating method, or a method of applying a heat-generating conductive substance such as a carbon black layer on the back surface of a photosensitive material or an image receiving member, and applying a current. A known thermal development method such as a method utilizing Joule heat generated by the above method can be applied.

The heating pattern at the time of thermal development is not particularly limited, and a method of performing at a constant temperature, a method of performing early development at a high temperature state and performing the latter half of the development at a low temperature state, or a converse method, and further, increasing the temperature in three or more steps Any method such as a method of changing the area or a method of continuously changing the temperature can be used. In particular, JP-A-63-250646.
As described in the above publication, in the dye release system, it is also possible to carry out silver development to some extent and then heat development in advance so that silver development occurs preferentially prior to the dye release reaction.

[0134]

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 AgCl particles having an average particle size of 0.12 μm were added to an aqueous gelatin solution, and this emulsion was used as a core emulsion. A monodispersed cubic silver chloride emulsion (average particle size 0.25 μm) was prepared by simultaneously adding a 10 ⁻⁸ mol aqueous solution of K ₂ [RhCl ₅ (H ₂ O)] while controlling the pAg. In the course of grain formation, 10 ^-8 mol of potassium iridium (IV) hexachloride was added per mol of silver halide when the grain diameter became 0.20 μm.

After desalting according to a conventional method, pAg =
Adjusted to 7.5, pH = 5.8. Next, 3.5 mg of sodium thiosulfate was added per 1 mol of silver halide, and the mixture was chemically ripened to an optimum point at 60 ° C., and then 0.9 g of ST-1 was added as a stabilizer to 1 mol of silver halide. Sensitization has ended. At 40 ° C. after completion of the chemical sensitization, sensitizing dye-1 was added as a methanol solution in an amount of 150 mg per mol of silver halide to obtain a silver halide emulsion.

[0137]

Embedded image

1-phenyl-4,4'-dimethyl-3-
Preparation of Pyrazolidone Dispersion A mixed water component of 22 g of 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 120 ml of a 3.7% aqueous gelatin solution and 0.7 g of a surfactant (SU-1), and further having a diameter of 0.1 g. Approximately 180 g of 8 mm glass beads is crushed with a sand grinder (BSG-1 / 16, manufactured by IMEX Co., Ltd.).
Dispersed at time 2200 revolutions. After the dispersion, the glass beads were separated by filtration, washed with 25 ml of water, and the washing water was mixed with the dispersion. The particle size of the dispersion was about 0.5 μm.

A light-sensitive material 101 was prepared using the above emulsion, a dispersion of the compound of the present invention, and the like. A layer having the following structure was coated on a 100 μm-thick polyethylene terephthalate with a gelatin undercoat. Here, the addition amount of each material is shown in an amount (g) per 1 m ^{2 of the} photothermographic material, and the photosensitive silver halide emulsion is shown in terms of silver.

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 Hydroquinone 0.66 g Hydroquinone Potassium sulfonate 0.46 g Dye-1 0.05 g Third layer ( Agent layer) Alkali-treated gelatin 1.60 g Photosensitive silver halide emulsion 1.75 g 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 PMMA latex (size 3 μm) 0.01 g

[0141]

Embedded image

As shown in Table 1, photographic materials 102 to 115 were prepared in the same manner as photographic material 101 except that hydrazine derivative and nucleation promoter were added.

Preparation of Complexing Agent Sheet A paper support having a thickness of 120 μm and laminated on both sides with polyethylene (complexing agent-containing layer side
An image receiving layer having the following composition was coated on the surface of the toner (containing titanium dioxide by weight of 2% by weight) to prepare a complexing agent sheet 101. (The amount of addition is represented by the amount per m ² of the image receiving material.) First layer gelatin 2.0 g Surfactant (SU-1) 0.02 g Surfactant (SU-2) 0.01 g Liquid paraffin 0.5 g Sodium benzyliminodiacetate 2.8 g Second layer gelatin 2.0 g Surfactant (SU-1) 0.08 g Surfactant (SU-2) 0.03 g Diisodecyl phthalate (DIDP) 0.4 g Polyvinyl alcohol (PVP) 0.4 g sodium benzyliminodiacetate 2.8 g sodium thiosulfate 0.71 g mixture of palladium sulfide and silver sulfide 1: 1 (weight) 0.01 g polymer (1) 0.35 g third layer gelatin 0.45 g polyvinyl alcohol 08g Surfactant (SU-1) 0.09g Hardener (1) 0.08g

[0144]

Embedded image

Preparation of Addition Solution of Hydrazine Derivative A: 20 g of hydrazine derivative was dissolved in methanol
L finished.

B: 20 g of hydrazine derivative and 3.7
% Gelatin aqueous solution 200ml and surfactant (SU-1)
0.6 g of the mixed water component and about 240 g of glass beads having a diameter of 0.8 mm were further added to a sand grinder (BSG-1-1).
6 (made by IMEX Co., Ltd.) for 1 hour at 2200 rpm. After the dispersion, the glass beads were separated by filtration, and the glass beads were washed with 50 ml of water. The wash water was mixed with the dispersion and stirred to obtain a uniform dispersion. The particle size of the dispersion is about 0.5μ
m.

C: 20 g of a hydrazine derivative, 50 g of a high boiling solvent O-8 and 50 ml of ethyl acetate were mixed and dissolved, added to 2 L of a 12% gelatin solution containing 1 g of a surfactant (SU-1), dispersed by an ultrasonic homogenizer, and then decompressed. The vinegar was distilled off underneath. The particle size of the high boiling solvent dispersion was about 0.4 μm.

Evaluation of photosensitive material The obtained silver halide photosensitive material was treated with He-N
The wedge was exposed using an e-laser, immersed in pure water for 2 seconds, and the surface of the complexing agent-containing layer of the complexing agent sheet and the surface of the photosensitive layer were overlapped, and then heated at 70 ° C. for 20 seconds. Then
When the complexing agent sheet was peeled off, a silver image was obtained on the photosensitive material and the complexing agent sheet.

Sensitivity The obtained developed photosensitive material sample was measured for blackening density 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.

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.

Forced deterioration treatment The obtained photothermographic material was treated at 40 ° C. and 60% relative humidity for 2 hours.
After immersion in pure water for 2 seconds, the complexing agent-containing layer surface of the complexing agent sheet and the photosensitive layer surface were overlapped,
After heating at 20 ° C. for 20 seconds to perform development processing, the sensitivity, γ, and black spot were evaluated in the same manner.

[0152]

[Table 1]

From Table 1, it can be seen that the sample of the present invention is a silver halide light-sensitive material having a high contrast, capable of forming an excellent image easily and quickly, and having excellent storage stability.

Example 2 A method for producing a photosensitive silver halide emulsion will be described. Solution (I) and solution (II) shown below are simultaneously added to a well-stirred aqueous gelatin solution having the following composition for 10 minutes, and 3 minutes later, solution (III) and solution (IV) are added. 18 at the same time
Minutes.

Composition of aqueous gelatin solution 800 cc H ₂ O lime-processed gelatin 20 g NaCl 4.2 g Silver halide solvent (1) 0.015 g Antifoggant (1) 0.011 g Citric acid (10%) 9 cc Temperature 40 ° C. (I ) Solution AgNO ₃ 75 g Total amount (with H ₂ O added) 240 cc (II) Solution NaCl 90 g KBr 1.5 g (NH ₄ ) ₃ RhCl ₆ 1.8 × 10 ^-4 Citric acid (10%) 0.1 cc Total amount ( H ₂ O was added) 24.0cc (III) solution AgNO ₃ added to 125g total _{(H 2 O) 400cc (IV} ) solution _{NaCl 14.0g KBr 2.5g K 3 IrCl 6} 7 × 10 -4 citrate (10%) 0.1cc Total (with H ₂ O) 400cc

[0156]

Embedded image

After desalting was performed by a conventional method, 50 g of demineralized gelatin was added to adjust the pH to 5.6 and the pAg to 7.6, followed by chemical sensitization at 60 ° C. For chemical sensitization, 0.005 g of hypo as a sulfur sensitizer, 0.012 g of chloroauric acid as a gold sensitizer were added, and 70 minutes later, 0.1 g of a preservative benzoisothiazolone and 0 g of a stabilizer ST-1 were added. 0.05g was added to obtain a silver chlorobromide emulsion. The average grain size of the obtained silver halide was 0.21 μm.

To 100 g of this emulsion, 20 mg and 30 mg of sensitizing dyes 2 and 3 were added per 1 ml of silver, respectively.
2.5% of a 1% methanol solution of 4'-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid sodium salt was added.
13 mg of l, 3- (2-propenyl) -benzothiazolium bromide was added, and a solution of 1-phenyl-5-mercaptotetrazole in 0.1% methanol was dissolved in 1.5 m
and 160 mg of the surfactant p-sodium dodecylbenzenesulfonate and 150 mg of the water-soluble polymer were added to obtain a solution of the emulsion layer, and the amount of silver was 1.3 g / m 2.
² was applied.

[0159]

Embedded image

Method for Preparing 1,5-Diphenyl-3-pyrazolidone Dispersion 10 g of 1,5-diphenyl-3-pyrazolidone and 0.2 g of Demol manufactured by Kao were added to 90 cc of 5.7% lime-treated gelatin.
Was added and dispersed in a mill using glass beads having an average particle size of 0.75 mm for 30 minutes. The glass beads were separated to obtain a gelatin dispersion of a reducing agent. A solid dispersion of the antihalation dye was also prepared according to the method described above to obtain a gelatin dispersion of the antihalation dye.

Method for Preparing a Dispersion of Zinc Hydroxide 12.5 g of zinc hydroxide having an average particle size of 0.2 μm,
1 g of carboxymethylcellulose and 0.1 g of sodium polyacrylate as a dispersant were added to a 4% gelatin aqueous solution 100
In addition to cc, the mixture was dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

A light-sensitive material 201 was prepared by using the above emulsion, a dispersion of the compound of the present invention, and the like, according to the structure shown in Table 2 below.

[0163]

[Table 2]

[0164]

Embedded image

As shown in Table 3, photographic materials 202 to 209 were prepared in the same manner as for photosensitive material 201, except that a hydrazine derivative and a nucleation promoting agent were added.

Preparation of Complexing Agent Sheet Next, a complexing agent sheet 201 having the structure shown in Table 3 was prepared.

[0167]

[Table 3]

[0168]

Embedded image

The obtained photosensitive materials 201 to 209 and the complexing agent sheet 201 were evaluated in the same manner as in Example 1, and the results are shown in Table 4. However, the exposure of the photosensitive material was performed by 780 nm laser exposure.

[0170]

[Table 4]

From the results shown in Table 4, it can be seen that the sample of the present invention is a silver halide light-sensitive material which is hard, can form an excellent image easily and quickly, and has excellent storage stability.

Example 3 Using the photosensitive materials 201 and 202 and the complexing agent sheet 201 prepared in Example 2, a developing process was performed in the same manner as in Example 2 to obtain an image on the image receiving sheet (complexing agent sheet). Evaluation was performed in the same manner as in Method 1.

[0173]

[Table 5]

From Table 5, it can be seen that the image of the complexing agent sheet obtained from the light-sensitive material of the present invention is excellent in sensitivity and γ.

[0175]

According to the present invention, a silver halide light-sensitive material and a method for forming an image, which can form an excellent image with high contrast, easily and quickly, and have excellent storage stability, can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/76 501 G03C 1/76 501 8/28 8/28

Claims (8)

[Claims] An imagewise exposure method comprising the steps of: image-wise exposing a silver halide photosensitive material having a photosensitive silver halide emulsion, a hydrophilic binder and a basic metal compound which is hardly soluble in water, and containing a hydrazine derivative on a support. After or simultaneously with the imagewise exposure, the complex forming compound for the metal ion constituting the basic metal compound, a sheet containing a physical development nucleus is superimposed,
A silver halide light-sensitive material which is used in an image forming method for forming a silver image on the silver halide light-sensitive material by thermal development in the presence of a silver halide solvent, a reducing agent and water. 2. A method for imagewise exposing a silver halide photosensitive material having a photosensitive silver halide emulsion, a hydrophilic binder and a basic metal compound which is hardly soluble in water and containing a hydrazine derivative on a support. After or simultaneously with the imagewise exposure, the complex forming compound for the metal ion constituting the basic metal compound, a sheet containing a physical development nucleus is superimposed,
A silver halide photosensitive material, which is used in an image forming method of forming a silver image on an image receiving sheet having physical development nuclei by performing silver salt diffusion transfer development in the presence of a silver halide solvent, a reducing agent and water. 3. The silver halide photosensitive material according to claim 1, wherein the hydrazine derivative is contained as a solid dispersion. 4. The silver halide light-sensitive material according to claim 1, wherein the hydrazine derivative is dispersed in a high boiling point solvent. 5. The silver halide light-sensitive material according to claim 1, wherein a film surface pH of said silver halide light-sensitive material is 6 or less. 6. The silver halide light-sensitive material according to claim 1, wherein said hydrazine derivative is added to a non-light-sensitive layer other than the silver halide emulsion layer. 7. The method according to claim 1, wherein the silver halide photosensitive material contains a nucleation accelerator.
Item. 8. An image forming method using the silver halide light-sensitive material according to claim 1 to form a hard silver image of γ10 or more.