JP2663069B2 - Image forming method by silver salt diffusion transfer method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming an image by silver salt diffusion transfer and a film unit used therefor.

[0002]

2. Description of the Related Art The diffusion transfer method is currently well known in the art, and the details thereof will be omitted. For more information,
A.Rott, E.Weyde, "Photographic Silver Halide Diffusio (PhotographicSilver Halide Diffusio)
n Processes) ”, published by Focal Press
ss, 1972); J. Sturge, V. Walworth, A. Sh
epp), "Imaging Processes and Materials: Nebulette 8th Edition (Imaging Processes and Materi
als: Neblete's Eighth Edition) ”, published by Van Nostrand Reinhold 19
89), Chapter 6, Instant photography and Related Reprographic Processings
prographic Processes; G. Hais
t), “Modern Photographic Processing (M
odernPhotographic Processing Vol. 2), published by John Wiley And Sons 19
79), Chapter 8, Diffusion Transfer, etc.

In this diffusion transfer method, many kinds of photographic materials can be produced. As an example, a photosensitive element in which a silver halide emulsion is coated on a support and an image receiving element in which an image receiving layer containing silver precipitation nuclei is coated on another support are overlapped with each other to form a processing element, an alkaline processing. A transferred image can be obtained by developing a composition such as a high-viscosity or low-viscosity alkaline processing composition containing a developing agent and a silver halide solvent between the two elements.

[0004]

In the silver salt diffusion transfer method, in recent years, obtaining a transferred image in a shorter time has become an important issue in simplifying handling. For this purpose, it is necessary to fundamentally develop a technology for obtaining an image with higher sensitivity and higher maximum density by accelerating the development reaction between the photosensitive element and the image receiving sheet.

In order to obtain an image with higher sensitivity, it is necessary to make the silver halide emulsion in the light-sensitive element higher in sensitivity. In recent years, a method using a tabular emulsion has been developed as a technique for improving the sensitivity of a silver halide emulsion used for a color photographic light-sensitive material. The use of tabular emulsions as silver halide grains in photosensitive elements used in the silver salt diffusion transfer method is an important breakthrough in achieving the above problems of high sensitivity and high density.

On the other hand, in the case of performing development processing by the silver salt diffusion transfer method, in a photosensitive element, a reaction in which silver halide particles in an exposed portion are developed (reduced) by a developing agent and a silver halide particle in an unexposed portion are halogenated. The reaction of dissolving while forming a silver complex solvent and a silver complex salt proceeds simultaneously. Particularly, in the silver halide grains in a portion given an intermediate exposure amount, these two reactions proceed competitively. However, if the latter dissolution reaction proceeds faster than the former development reaction, the development reaction The silver halide grains are dissolved and disappear before the occurrence of the phenomenon, and the amount of silver halide grains to be developed is substantially reduced, that is, the photographic sensitivity of the photosensitive element is reduced. Especially when tabular silver halide grains are used, when compared with cubic grains, etc.
Since the surface area per unit volume becomes larger, the progress of the development reaction and the dissolution reaction becomes faster simply. Therefore, when tabular silver halide grains are used, 2
Competition between the two reactions becomes more intense, and it is very important to develop more silver halide grains given an intermediate exposure dose by a technology that promotes the development reaction without suppressing the dissolution reaction. . Therefore, development of such a high sensitivity technique has been strongly demanded.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver salt diffusion transfer method capable of obtaining a transferred silver image having a high sensitivity and a high maximum density in a shorter time in the silver salt diffusion transfer method.

[0008]

In order to solve the above-mentioned problems, the present inventor has proposed a method of using a tabular silver halide emulsion for a light-sensitive element without suppressing the dissolution of silver halide grains, and furthermore, without using a silver halide emulsion. The study of compounds that promote the development of silver halide emulsions was advanced. When a mercapto compound, which has been conventionally used for the purpose of preventing development fogging of silver halide grains, is added to a processing solution, the dissolution of silver halide grains is suppressed. I knew it would. On the other hand, when a specific compound having no mercapto group such as benzotriazole is added to the processing solution, it is possible to obtain a transferred image with high photographic sensitivity without lowering the maximum density when developed in a short time. I found that. Regarding compounds such as benzotriazole, British Patent No. 772,027 describes a method for obtaining a black silver image by adding the compound to a silver salt diffusion transfer treatment solution together with 2-mercaptothiazoline. U.S. Pat. No. 3,390,998
The specification describes a method of adding a benzotriazole as a method for improving the preservation of a silver salt diffusion transfer treatment solution containing a specific surfactant. JP 6
In the specification of Japanese Patent Application No. 2-279332, metal salt particles are selectively dissolved and transferred by a dissolving agent released by a reaction between an oxidized developing agent produced by a developing reaction and a dissolving agent releasing compound of non-photosensitive metal salt particles. In the method for obtaining a transferred image by performing the method, a method in which treatment is performed in the presence of benzotriazole as an antifoggant is described. JP-A-60-1132
No. 38 describes a method for obtaining a high-contrast silver image by processing in the presence of a compound such as a triazole in a silver salt diffusion transfer method using a silver chloroiodobromide or silver chlorobromide emulsion. Have been described. JP-A-2-14654
No. 2 describes a method for improving the storability of a product comprising an image receiving sheet, a photosensitive element and a processing solution by adding a triazole or the like to a photosensitive element in a silver salt diffusion transfer method.

However, the above technique does not disclose or suggest a sensitizing effect obtained when a photosensitive element containing tabular silver halide grains is processed with a processing solution containing benzotriazoles. Nor. Therefore, the fact that a benzotriazole conventionally known as a development inhibitor was added to a processing solution to obtain a high-sensitivity transfer image was completely surprising.

That is, the objects of the present invention are to develop a photosensitive element containing an image-exposed photosensitive silver halide emulsion layer by using an alkali processing composition containing a silver halide solvent, and At least a portion of the unexposed silver halide of the silver emulsion layer is a transferable silver complex salt, and at least a portion of the transferable silver complex salt is transferred to an image receiving layer containing silver precipitation nuclei, and an image is formed on the image receiving layer containing silver precipitation nuclei. And forming an image by separating the silver precipitate nucleus-containing image-receiving layer from the photosensitive element after image formation, whereby the photosensitive silver halide emulsion layer contains all grains. At least 50% of the projected area contains tabular silver halide grains having an average aspect ratio of 3 or more, and the alkaline processing solution contains at least one compound selected from the group consisting of compounds represented by the following general formula (I). It was achieved by the image forming method according to the silver salt diffusion transfer process, characterized in that it allowed to contain a compound. General formula (I)

[0011]

Embedded image

In the formula, Q represents at least one atom selected from the group consisting of carbon, nitrogen, oxygen and sulfur.
Represents an atom group necessary for forming a 6-membered or 6-membered heterocyclic ring. This heterocyclic ring may be condensed with a carbon aromatic ring or a heteroaromatic ring. Further, the heterocyclic ring may have a substituent, but does not have a mercapto group as a substituent.

Specific examples of the heterocyclic ring formed by Q include an indazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazole ring, a benzthiazole ring, an imidazole ring, a thiazole ring, an oxazole ring, a triazole ring, a tetrazole ring, Examples include an azaindene ring, a pyrazole ring, an indole ring, a triazine ring, a pyrimidine ring, a pyridine ring, and a quinoline ring.

These heterocycles include a nitro group, a halogen atom (eg, a chlorine atom and a bromine atom), a cyano group, and a substituted or unsubstituted alkyl group (eg, a methyl group, an ethyl group, a propyl group, a t-butyl group, Cyanoethyl group,
Methoxyethyl group, methylthioethyl group, etc.), aryl group (eg, phenyl group, 4-methanesulfonamidophenyl group, 4-methylphenyl group, 3,4-dichlorophenyl group, naphthyl group, etc.), alkenyl group (eg, allyl group, etc.) ), Aralkyl groups (eg, benzyl group, 4-methylbenzyl group, phenethyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group, etc.), aryloxy groups (eg, phenoxy group, 4-methoxyphenoxy group, etc.), alkylthio groups (Eg, methylthio group, ethylthio group, methoxyethylthio group, etc.), arylthio group (eg, phenylthio group, etc.), sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, p-toluenesulfonyl group, etc.), carbamoyl group (eg, unsubstituted) Carbamoyl group,
Methylcarbamoyl group, phenylcarbamoyl group, etc.),
Sulfamoyl group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), carbonamide group (eg, acetamido group, benzamide group, etc.), sulfonamide group (eg, methanesulfonamide group, benzenesulfonamide group) , P-toluenesulfonamide group, etc.), acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), sulfonyloxy group (eg, methanesulfonyloxy group, etc.), ureido group (eg, unsubstituted ureido group, methylureido group,
An ethylureido group, a phenylureido group, etc.), a thioureido group (eg, an unsubstituted thioureido group, a methylthioureido group, etc.), an acyl group (eg, an acetyl group, a benzoyl group, etc.), a heterocyclic group (eg, a 1-morpholino group, 1-
Piperidino group, 2-pyridyl group, 4-pyridyl group, 2-
Thienyl group, 1-pyrazolyl group, 1-imidazolyl group,
2-tetrahydrofuryl group, tetrahydrothienyl group, etc.), oxycarbonyl group (eg, methoxycarbonyl group, phenoxycarbonyl group, etc.), oxycarbonylamino group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, 2-ethylhexyloxycarbonylamino group Etc.), an amino group (for example, an unsubstituted amino group, a dimethylamino group, a methoxyethylamino group, an anilino group), a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, and a hydroxy group.

M is a hydrogen atom, an alkali metal atom (eg, sodium atom, potassium atom, etc.), a quaternary ammonium group (eg, trimethylammonium group, dimethylbenzylammonium group, tetrabutylammonium group, tetramethylammonium group, etc.), and alkali M under conditions
Can be a hydrogen atom or an alkali metal atom (eg, acetyl, cyanoethyl, methanesulfonyl, etc.)
And n represents 0 or 1.

Preferred among the heterocycles represented by the general formula (I) are benzotriazoles, indazoles,
Benzimidazoles, and benzotriazoles are particularly preferred.

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited to these.

[0018]

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[0019]

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[0020]

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The compound used in the present invention is Berichte der Deutsche Chen Hemischen Geselshaft (Be
richte der DeutschenChemischen Gesellschaft) 2
2, 77 (1895), JP-A-50-37436, JP-A-51-3231, U.S. Pat. Nos. 3,295,976 and 3,376,310, Berichte der Deutschen Cheng Hemischen Gesellschaft (Berichte) der Deuts
chen Chemischen Gesellschaft) 22, 568 (188
9), ibid., 29, 2483 (1896), Journal of Chemical Society (J. Chem. Soc.) 32, 18
06, Journal of the American Chemical
Society (J. Am. Chem. Soc.) 71, 4000 (194
9), U.S. Pat. Nos. 2,585,388 and 2,541,
No. 924, Advances in Heterocyclic Chemistry
9, 165 (1968), Organic Synthesis (O
rganic Synthesis) IV, 569 (1963), Journal of the American Chemical Society
(J. Am. Chem. Soc.) 45, 2390 (1923), Chemische Brichte 9, 465 (187)
6), JP-B-40-28496, JP-A-50-890
No. 34, U.S. Pat. Nos. 3,106,467 and 3,42.
0,760, 2,271,229, 3,13
7,578, 3,148,066, 3,51
No. 1,663, No. 3,060,028, No. 3,27
Nos. 1,154, 3,251,691, 3,59
8,599, 3,148,066, JP-B-43-
No. 4135, U.S. Pat. Nos. 3,615,616 and 3,4
20,664, 3,071,465, 2,44
No. 4,605, No. 2,444,606, No. 2,44
Nos. 4,607 and 2,935,404;
Nos. 202,531, 57-167,023, 57
164,735, 60-80839, 58-
152, 235, 57-14836, 59-1
62,546, 60-130,731, 60-
138,548, 58-83852, 58-1
Nos. 59, 529, 59-159, 162, 60-
No. 217,358, No. 61-80238, Tokiko No. 60
No. 29390, No. 60-29391, No. 60-13
Compounds can be synthesized by the methods described in JP-A Nos. 3,061 and 60-1431.

The amount of the compound of the present invention to be added to the processing solution is preferably 1 × 10 ^-4 to 1 × 110 ^-1 mol, more preferably 5 × 10 ^-4 to 1 × 10 ^-2 mol per kg of the processing solution. The compound of the present invention may be added to the treatment liquid by one kind alone, or two or more kinds may be added.

The image receiving element, photosensitive element and processing composition of the present invention are described below. The image receiving element in the present invention is coated on a support carrying an image receiving layer containing silver precipitation nuclei, for example, baryta paper, cellulose triacetate or a polyester compound. Such image-receiving elements can be prepared by coating, if necessary, an undercoated support with a coating solution of a suitable cellulose ester having dispersed therein silver precipitation nuclei, for example, cellulose diacetate. The obtained cellulose ester layer is subjected to alkaline hydrolysis to convert at least a part of the cellulose ester in the depth direction to cellulose. In a particularly useful embodiment, the unhydrolyzed portion of the silver precipitation nucleus layer and / or the underlying unhydrolyzed cellulose ester, for example, the cellulose ester layer containing cellulose diacetate, is replaced by a silver transfer layer. It contains one or more mercapto compounds suitable for improving the hue, stability or other photographic performance of the image. Such a mercapto compound is utilized during diffusion by diffusing from the position where it was originally placed. An image receiving element of this type is described in U.S. Pat. No. 3,711,283.

[0024] The mercapto compound is disclosed in
No. 20,634, JP-B-56-44418, British Patent 1,276,961, JP-B-56-21140, JP-A-59-231537, JP-A-60-122939.
Are preferred.

As specific examples of the silver precipitation nucleus, specific examples of the non-photosensitive silver precipitation nucleus of the present invention include heavy metals such as iron, lead, zinc, nickel, cadmium, tin, chromium, copper, cobalt, and noble metals, such as Gold, silver (including fine colloidal silver), platinum, palladium and the like. Heavy metals, and sulfide salts of noble metals, the same selenide salts, for example, sulfide salts such as copper, aluminum, zinc, cobalt, nickel, silver, lead, antimony, bismuth, cerium, magnesium, gold, platinum, palladium, Alternatively, selenide salts such as lead, zinc, antimony, and nickel can also be preferably used. Silver halide grains which have been previously fogged are also reduced by development, and can be preferably used as silver precipitation nuclei as metallic silver.

It is preferable to provide an acidic polymer layer for neutralization (alkali neutralized layer) between the unsaponified layer (timing layer) and the support. For the alkali neutralizing layer used in the present invention, for example, a polymer acid described in U.S. Pat. No. 3,594,164 is used. Preferred polymer acids are maleic anhydride copolymers (eg, styrene-maleic anhydride copolymer, methyl vinyl ether-maleic anhydride copolymer, ethylene-maleic anhydride copolymer, etc.) and (meth) acrylic acid (Co) polymers (for example, acrylic acid-alkyl acrylate copolymer, acrylic acid-alkyl methacrylate copolymer, methacrylic acid-alkyl acrylate copolymer, methacrylic acid-alkyl methacrylate copolymer, etc.) No. In addition, polymers containing sulfonic acids such as polyethylene sulfonic acid and acetalized products of benzaldehyde sulfonic acid and polyvinyl alcohol are also useful. Further, the neutralization layer may contain a mercapto compound used in the timing layer. Further, for the purpose of improving the physical properties of the membrane, these polymer acids may be mixed with a hydrolyzable alkali non-permeable polymer (particularly preferably the above-mentioned cellulose ester) or an alkali-permeable polymer.

The image receiving sheet preferably has an image stabilizing layer for improving image storability, and a cationic polymer electrolyte is preferable as the stabilizing agent. In particular, JP-A-59-166940 discloses US Patent 3,958,
No. 995, JP-A-55-142339 and JP-A-54-12.
No. 6027, No. 54-155835, No. 53-303
No. 28, the polyvinylpyridinium salts described in U.S. Pat. Nos. 2,548,564, 3,148,061 and 3,756,814; U.S. Pat. No. 3,709,690 Or a water-soluble quaternary ammonium salt polymer described in US Pat.
The water-insoluble quaternary ammonium salt polymer described in No. 088 is preferred as the cationic polyelectrolyte. As the binder for the image stabilizing layer, cellulose acetate is preferred, and cellulose diacetate having an acetylation degree of 40 to 49% is particularly preferred. This image stabilizing layer is preferably provided between the neutralizing layer and the timing layer.

Further, the timing layer is provided with an acid polymer (for example, methyl vinyl ether and methyl vinyl ether) for the purpose of preventing the timing time from being lengthened by the change of the cellulose ester during the long-term storage or shortening the timing time. Copolymer of maleic anhydride or copolymer of methyl vinyl ether and half ester of maleic anhydride)
Can be included. Furthermore, white pigments (for example, titanium dioxide, silicon dioxide, kaolin, zinc dioxide, barium sulfate) may be added to the timing layer and the neutralization layer in order to prevent light from penetrating from the cross-sectional direction of the sheet to the inside (light piping). ) Can be included. Further, an intermediate layer may be provided between the image receiving layer and the timing layer. As the intermediate layer, a hydrophilic polymer such as gum arabic, polyvinyl alcohol, and polyacrylamide can be used.

It is preferable to provide a release layer on the surface of the image receiving layer in order to prevent the processing liquid from adhering to the surface of the image receiving layer at the time of release after the development of the processing liquid. Preferred as such a release layer are, in addition to gum arabic, hydroxyethylcellulose, carboxymethylcellulose, polyvinyl alcohol, polyacrylamide and sodium alginate, U.S. Pat. Nos. 3,772,024, 3,820,999 and British Patent 1,360,65
No. 3 can be mentioned.

As a method of shading, a method of including a shading agent (for example, carbon black or an organic black pigment) in the paper of the support or a method of coating the shading agent on the back surface of the support and further applying It is preferable to apply a white pigment (for example, titanium dioxide, silicon dioxide, kaolin, zinc dioxide, barium sulfate) for whitening. For the purpose of improving curling and brittleness, a moisture absorbent such as glycerin or a film quality improving agent such as polyethyl acrylate latex may be included. It is preferable to provide a protective layer on the uppermost layer. The protective layer can be made to contain a matting agent to improve the adhesiveness or to provide writing properties. Gelatin, cellulose ester, polyvinyl alcohol, or the like is used as a binder for the light-shielding layer and the protective layer.

In the present invention, a photosensitive silver halide emulsion layer is provided on one side of a support having an undercoat layer on both sides of a polyethylene terephthalate film containing titanium dioxide or carbon black, and a protective layer is provided on the other side. A photosensitive element having a carbon black layer and a protective layer thereon is preferably used. In addition to the above-mentioned layer constitution, a support having an undercoat layer on both sides of a polyethylene terephthalate film containing titanium dioxide or carbon black, a titanium dioxide layer on one side, a photosensitive silver halide emulsion layer thereon, and a protective layer thereon And a photosensitive element provided with a carbon black layer on the other surface and a protective layer thereon. A colored dye may be used instead of or in addition to the above-described carbon black. When polyethylene terephthalate contains carbon black and / or a colored dye, it is not necessary to provide a layer of carbon black and / or a colored dye on one surface. Further, the titanium dioxide may be replaced with another white pigment. As the support, in addition to the polyester compound, paper laminated with polyethylene, baryta paper, and cellulose triacetate are used. The above-mentioned photosensitive silver halide emulsion layer, protective layer, carbon black layer and the like usually contain a hydrophilic binder such as gelatin.

The light-sensitive silver halide emulsion according to the present invention includes silver iodobromide (including pure silver bromide) and silver chloroiodobromide (including chloroodor) having an average silver iodide content of 10 mol% or less. Silver iodide) or silver chloroiodide (including silver chloride), particularly from 2.0 to 10 silver iodide in order to reduce fluctuations in photographic performance when the processing solution is stored over time. It is preferably 0.0 mol% of silver iodobromide, silver chloroiodobromide, or silver chloroiodide. In the silver halide emulsion used in the present invention, tabular grains having an average aspect ratio of 3 or more occupy at least 50% of the total projected area of the silver halide grains. As used herein, "aspect ratio" refers to the ratio of diameter to particle thickness. Here, the "diameter" of a grain indicates the diameter of a circle having an area equal to the projected area of the grain when the silver halide grain is observed with an optical microscope or an electron microscope. From the shaded electron micrograph of the particle sample, the thickness and diameter of each particle can be measured, and the spectral ratio of each particle can be measured.

The average aspect ratio of the silver halide emulsion grains used in the present invention is determined as follows. That is, of all silver halide grains present in the emulsion, a diameter of 0.1 to 1
0 μm and a thickness of 0.3 μm or less are selected, and tabular grains having a large aspect ratio are collected as necessary so that the sum of the projected areas exceeds 50%, and the average aspect ratio of the grains thus collected is selected. May be calculated so that the value becomes 3 or more.

The average grain diameter of the silver halide emulsion grains is 4
μm or less, more preferably 3 μm or less, and particularly preferably 0.2 to 2 μm. The particle size distribution may be narrow or wide. The thickness of the particles is 0.
Preferably it is 3 μm or less. The average aspect ratio is preferably 3 or more and 30 or less, particularly 4 or more and 11 or less.
It is preferably 0 or less.

The size distribution of the tabular silver halide grains used in the present invention may be narrow or wide, but is preferably monodisperse grains, and the grain size distribution indicating the degree of monodispersion is a statistical standard. The ratio (s / d) between the deviation (s) and the average particle size (d) is 0.25 or less, preferably 0.2
3 or less.

The silver halide emulsion used in the present invention contains the above-mentioned tabular silver halide grains, but also contains silver halide grains having an equiaxed crystal form such as cubic or octahedral. It may be one having an irregular crystal form such as a sphere or a complex form of these crystal forms.

Regarding the halogen composition distribution of the silver halide grains, there is a so-called uniform type grain having the same composition in any part of the silver halide, a core inside the silver halide grain, and a shell surrounding the core. ) (One or more layers), so-called laminated structure grains having a different halogen composition, or a structure having a non-layered portion having a different halogen composition inside or on the surface of the grains (when the grains are on the grain surface, edges, corners, or faces of the grains) Particles having a structure in which portions having different compositions are joined together) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. It is also possible to employ a structure in which a continuous structural change is positively provided. Further, the latent images need not be localized in any of them. In particular, particles whose latent image is mainly formed on the surface are more preferable.
The thickness of the silver halide emulsion layer is 0.5 to 8.0 µm, particularly 0.6 to 6.0 µm, and the coating amount of silver halide grains is 0.1 to 3 g / m ² as silver amount, preferably. Is 0.2 ~
1.5 g / m ² .

The light-sensitive silver halide emulsion layer can contain various compounds for the purpose of preventing fogging during the production process, storage, or photographic processing of the photographic material and stabilizing photographic performance. . These compounds include:
Azoles (eg, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles , Nitrobenzotriazoles, benzotriazoles), mercaptopyrimidines, mercaptotriazines, thioketo compounds, azaindenes (eg, triazaindenes, tetrazaindenes, pentaazaindenes), benzenesulfonic acids, benzenesulfine Well-known antifoggants and stabilizers such as acids, benzenesulfonic amides and α-lipoic acid are preferably used. Representative examples include 1-phenyl-2-mercaptotetrazole,
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 2-mercaptobenzothiazole, 5-carboxybutyl-1,2-dithiolane and the like. For more detailed examples of these and how to use them,
For example, US Pat. No. 3,982,947, Japanese Patent Publication No.
No. 28660 can be used.

Further, a spectral sensitizer can be added to the silver halide emulsion layer of the present invention. The sensitizing dye used is preferably a cyanine dye, a merocyanine dye, a composite cyanine dye, a composite merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxanol dye. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Also, JP-A-59-114533,
As described in JP-A-61-163334, a plurality of sensitizing dyes can be used in combination.

The photosensitive element of the present invention can contain an inorganic or organic hardener. For example, chromium salts (chrom alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methylol dimethylhydantoin, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, etc.), mucohalic acids (mucochloric acid, mucophenoxycyclolic acid) And the like can be used alone or in combination. Coating aids can be used in the silver halide emulsion layer and other hydrophilic colloid layers of the light-sensitive element of the present invention. As a coating aid, Research Disclos
176) 176, 17643, p. 26 (1978.1).
2), "Coating aids", and the compounds described in JP-A-61-20035. In the silver halide emulsion layer and other hydrophilic colloid layers of the photosensitive element of the present invention, for the purpose of increasing sensitivity, increasing contrast or promoting development, for example, polyalkylene oxide or its derivatives such as ethers, esters and amines, thioether compounds Thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. Examples of such compounds include U.S. Pat. Nos. 2,400,532 and 2,42.
No. 3,549, No. 2,716,062, No. 3,61
7,280, 3,772,021, 3,80
No. 8,003 and the like can be used.

The silver halide emulsion layer and other hydrophilic colloid layers of the light-sensitive element of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene alone or in combination, or acrylic acid, methacrylic acid, A polymer having a combination of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid and the like as a monomer component can be used.

A protective layer can be provided on the silver halide emulsion layer used in the light-sensitive element of the present invention. The protective layer is made of a hydrophilic polymer such as gelatin.
Matting agents or sliding agents such as polymethyl methacrylate latex and silica as described in JP-A-47946 and JP-A-61-75338 can be contained. In the light-sensitive element of the present invention, a dye or an ultraviolet absorber may be contained in the silver halide emulsion layer and other hydrophilic colloid layers for the purpose of preventing a filter or irradiation. In addition, the photosensitive element of the present invention includes an antistatic agent,
Plasticizers and antifoggants may be included.

The treatment composition used in the present invention includes:
The processing composition contains a developing agent, a silver halide solvent and an alkali agent. Further, depending on the purpose, a developing agent and / or a silver halide solvent may be contained in the light-sensitive element and / or the image-receiving element. The developing agent used in the present invention has at least 2
Benzene derivatives in which two hydroxyl and / or amino groups have been substituted in the ortho or para position of the benzene nucleus (eg hydroquinone, amidol, methol,
Glycine, p-aminophenol, pyrogallol) and hydroxylamines, especially primary aliphatic N-substituted,
Secondary aliphatic N-substituted, aromatic N-substituted or β-hydroxylamines, which are soluble in aqueous alkalis, such as hydroxylamine, N-methylhydroxylamine, N-ethylhydroxylamine, US Pat. No. 2,857,276 and the N-alkoxyalkyl-substituted hydroxylamines described in U.S. Pat. No. 3,293,034. Further, a hydroxylamine derivative having a tetrahydrofurfuryl group described in JP-A-49-88521 can also be used. In addition, West German Patent Application (OLS) 2,
009,054, 2,099,055, 2,0
Aminoreductones described in JP 09,078 and heterocyclic aminoreductones described in US Pat. No. 4,128,425 are also used. Further, a tetraalkyl reductic acid described in U.S. Pat. No. 3,615,440 can also be used. Phenidones, p-aminophenols and ascorbic acid can be used in combination with the above developing agents as auxiliary developing agents, and it is preferable to use phenidones in combination.

The fixing agent (silver halide solvent) used in the present invention includes ordinary fixing agents (for example, uracil and derivatives thereof, sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate and the above-mentioned US Pat. No. 2,543, 181), thioether compounds described in Japanese Patent Application No. 3-99107, combinations of cyclic imides and nitrogen bases, and U.S. Pat. No. 2,857,274. Such a combination is used. Also, 1,1-bissulfonylalkanes and derivatives thereof are known and can be used as the silver halide solvent of the present invention. The amount of the silver halide solvent to be added is preferably 1 × 10 ^-4 to 5 × 10 ^-1 mol, more preferably 1 × 10 ^-3 to 2 × 10 ^-2 mol, per 100 g of the alkali composition. .

The treatment composition (treatment liquid) of the present invention contains an alkali, preferably an alkali metal hydroxide, for example, sodium hydroxide or potassium hydroxide. If applied to developing the processing composition as a thin layer between a superposed photosensitive element and an image receiving element, the processing composition will include a polymer film former, a thickener or a thickener. Is preferable. Hydroxyethylcellulose and sodium carboxymethylcellulose are particularly useful for this purpose and are incorporated into the treatment composition by known techniques of diffusion transfer photography at concentrations effective to provide the appropriate viscosity. The processing composition may further comprise other auxiliaries known in silver salt diffusion transfer processes, for example,
An antifoggant, a toning agent, a stabilizer and the like may be contained. As these auxiliaries, for example, compounds described in JP-A-2-146542 and the like can be used.

It is preferable to add iodide ions to the alkaline processing liquid of the present invention from the viewpoint of reducing the influence of fluctuation in photographic performance when the processing liquid is stored. The amount of iodide ion added is preferably from 1 × 10 ^-4 mol to 1 × 10 ^-2 mol, and particularly preferably from 5 × 10 ^-4 mol to 1 × 10 ^-2 mol per liter of the processing solution.
It is preferably from × 10 ⁻⁴ mol to 5 × 10 ⁻³ mol. The iodide ion is usually added in the form of an alkali metal salt or an alkaline earth metal salt. Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

[0047]

【Example】

Embodiment 1 FIG. 1. Preparation of Image Receiving Sheet The following layers were sequentially provided on a support polyethylene laminated paper to prepare an image receiving sheet. The values in parentheses indicate the amount of coating in g /
m ² . (1) Neutralization layer Cellulose acetate (55% acetylation degree) (6), methyl vinyl ether-maleic anhydride copolymer (4), Uvitex OB (trade name of Ciba Geigy)
(0.04) 1- (4-hexylcarbamoylphenyl) -2,3-dihydroxyimidazole-2-thione (0.25) (2) Image stabilizing layer Cellulose acetate (46% acetylation degree) (4) The following polymer A (2) Polymer A

[0048]

Embedded image

(3) Timing layer Cellulose acetate (55% acetylation degree) (8) (4) Image receiving layer Cellulose acetate (55% acetylation degree) (2), palladium sulfide (7.5 × 10 ^-4 ), 1- (4-hexylcarbamoylphenyl) -2,3-dihydroimidazole-2-thione (1.0 × 10 ^-2 ) (5) Saponification A surface obtained by mixing 12 g of sodium hydroxide, 24 g of glycerin and 280 ml of methanol. And then washed with water. (6) Release layer Butyl methacrylate-acrylic acid copolymer (molar ratio 15:85) (0.1) (7) Back layer A light-shielding layer, a white layer, and a protective layer are applied to the back surface of the support. . (7-1) Light-shielding layer Carbon black (4), gelatin (8), polyacrylate spherical particles (average diameter 0.05 μm) (0.2) (7-2) White layer titanium dioxide (6), gelatin (0 .7) (7-3) protective layer polymethyl methacrylate (average diameter 0.05 μm)
(0.2), gelatin (1.6)

2. Preparation of photosensitive element The following layers were coated on a support (polyethylene terephthalate) to prepare a photosensitive element. Numerical values in parentheses indicate the coating amount in g / m ² . (1) Photosensitive layer Silver iodobromide (AgI content: 3.0 mol%) having an average particle size of 1.8 μm and an aspect ratio of 5.0 (silver equivalent: 0.60);
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (0.012), sensitizing dye A (4.1 × 1
^-4 ), sensitizing dye B (4.1 × 10 ^-4 ), sensitizing dye C (1.4 × 10 ^-4 ), gelatin (3.6) sensitizing dye A

[0051]

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Sensitizing dye B

[0053]

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Sensitizing dye C

[0055]

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(2) Protective layer Gelatin (0.7), polymethyl methacrylate particles (average diameter 4.7 μm) (0.1) (3) Back layer (3-1) Light-shielding layer Carbon black (4.0) , Gelatin (2.0) (3-2) protective layer gelatin (0.7), polymethyl methacrylate particles (average diameter 0.05 μm) (0.1)

The photosensitive element was designated as (2A), and the average aspect ratio of the silver iodobromide grains in the photosensitive layer was changed as shown in Table 2, and the other conditions were the same as for photosensitive element (2A). Elements (2B) to (2E) were created.

3. Preparation of treatment element A treatment liquid was prepared in a nitrogen stream according to the following recipe. After preparation, each pod is placed in a plurality of cleavable containers (pods).
A processing element (1A) was prepared by filling 7 g of the processing liquid. The composition amount of titanium dioxide 5 g potassium hydroxide 280 g uracil 90 g tetrahydropyrimidine thione 0.2 g 1-phenyl-2-mercaptoimidazole 0.2 g zinc nitrate · 9H ₂ O 40 g triethanolamine 6 g 1-hydroxy Ethylidene-1,1-diphosphonic acid (60% aqueous solution) 15 g Hydroxyethyl cellulose 45 g Potassium iodide 1 g N, N-bis (methoxyethyl) hydroxylamine (17% aqueous solution) 220 g 4-methyl-4-hydroxy Methyl-1-phenyl-3-pyrazolidinone 10 g Water 1300 ml

Next, as shown in Table 1, the exemplary compounds of the present invention or the following comparative compounds A and B were added to the processing solution prepared by the processing element (1A) in an amount of 5 per 2,000 g of the processing solution.
The processing elements (1B) to (1L) were prepared in the same manner as in (1A), except that ^{x10 -3} mol was added. Comparative compound A: 3-phenyl-5-mercaptotetrazole Comparative compound B: 2-methylthio-5-mercapto-1-
Thia-3,5-diazole

4. Developing process 16 lu through the optical wedge through the photosensitive element (2A)
x, exposure for 0.01 second, and after developing each sample combined with the image receiving sheet and the processing elements (1A) to (2A) at 25 ° C. so as to have a liquid thickness of 35 μm, peeled off in 15 seconds. Thus, a transfer image for sensitometry was obtained on the image receiving sheet. The maximum density and density of the transferred image are 1.
The exposure amount (photographic sensitivity) at which the value becomes 0 was measured. Photosensitive element (2
Based on the maximum density and photographic sensitivity when A) and the processing element (1A) were combined, the difference from the reference value was determined for the measured values for other combinations. The results obtained are shown in Table 1. Table 1

[0061]

[Table 1]

As is apparent from Table 1, the processing elements (1B) to (1H) containing the additive of the present invention and the light-sensitive element (2A) containing silver halide grains having an aspect ratio of 5.0.
When the developing process was performed in combination with the above, an image having high photographic sensitivity was obtained without lowering the maximum density as compared with the case where the developing process was performed using the processing element containing no additive (1A). In particular, when benzotriazoles are used as additives (processing elements (1B) to (1E)), the photographic sensitivity is higher.
More favorable results were obtained. In contrast, when comparative compounds A and B were added (treatment element (1I), (1
In J)), unfavorable results such as low maximum density and low photographic sensitivity were obtained.

Embodiment 2 FIG. Embodiment 1 FIG. Each of the photosensitive elements (2A) to (2E) prepared in the above, the image receiving sheet, and the processing elements (1A) and (1B) were combined, and the maximum density and photographic sensitivity were measured in the same manner as in Example 1. The results obtained are shown in Table 2.

[0064]

[Table 2]

As is clear from Table 2, the processing element (1B) containing the additive of the present invention and the light-sensitive elements (2A) to (2A) containing silver halide grains having an aspect ratio of 3.0 or more.
When development processing is performed in combination with D), the processing element (1A) containing no additives and the photosensitive elements (2A) to (2D)
As compared with the case where the combination was used, an image was obtained without a decrease in the maximum density and at a high photographic sensitivity. In particular, when the photosensitive elements (2A) to (2C) containing silver halide grains having an aspect ratio of 4 or more and 10 or less were used, more favorable results with higher photographic sensitivity were obtained. In contrast, when the photosensitive element (2E) containing silver halide grains having an aspect ratio of 2.5 was used, the processing element (1E) was used.
No image having high photographic sensitivity was obtained by combining any of A) and (1B).

[0066]

The maximum density is reduced when a processing element containing the additive represented by the general formula (I) of the present invention is combined with a photosensitive element containing an emulsion comprising silver halide grains having an aspect ratio of 3 or more and an image receiving sheet. Without this, favorable results with high photographic sensitivity can be obtained.

Claims (1)

(57) [Claims] A photosensitive element containing a photosensitive silver halide emulsion layer that has been image-exposed is developed using an alkali processing composition containing a silver halide solvent, and the unexposed halogen in the photosensitive silver halide emulsion layer is developed. At least a portion of the silver halide is formed into a transferable silver complex salt, and at least a portion of the transferable silver complex salt is transferred to an image-receiving layer containing silver precipitation nuclei to form an image on the image-receiving layer containing silver precipitation nuclei. In a method for forming an image by silver salt diffusion transfer in which an image is later obtained by separating the image-receiving layer containing silver precipitation nuclei from the light-sensitive element, at least 50% of the total projected area of the grains is contained in the light-sensitive silver halide emulsion layer. Specifically, tabular silver halide grains having an average aspect ratio of 3 or more are contained, and at least one compound selected from the group of compounds represented by the following general formula (I) is contained in the alkaline processing solution. An image forming method by a silver salt diffusion transfer method. General formula (I) In the formula, Q represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring composed of at least one atom of a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom; May have a substituent, but does not have a mercapto group as a substituent. M represents a hydrogen atom, an alkali metal atom, a quaternary ammonium group, and a group in which M can be a hydrogen atom or an alkali metal atom under alkaline conditions, and n represents 0 or 1.