JPH0934084A - Silver salt diffusion transfer method and film unit to be used for it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel film unit capable of obtaining high density safely in a short time by using substantially only water but no developing solution. SOLUTION: A photosensitive material having a support at least (a) an image receiving layer containing a silver precipitator, (b) a strippable layer, (c) an antihalation layer having a light-shielding function, and (d) a silver halide emulsion layer containing photosensitive silver halide grains having a high silver chloride content of >=50mol%, is imagewise exposed and brought into close contact with the film surface of a processing sheet having a hydrophilic colloidal layer containing a silver halide solvent on a support, and subjected to the silver salt diffusion transfer development in the presence of a small amount of water, a developing agent, and a base and/or its precursor, and then, the strippable layer and the upper layer and the processing sheet are stripped off and a positive image is obtained in the image receiving layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method suitable for a monochromatic image such as a film for printing plate making, a medical film and the like by a silver salt diffusion transfer method, and a film unit used therefor.

[0002]

2. Description of the Related Art An image forming method by diffusion transfer using a silver salt such as silver halide is well known. Explaining the method in detail, for example, an imagewise exposed light-sensitive silver halide emulsion is treated with an alkaline aqueous solution containing a developer, a silver halide solvent and a film-forming agent (thickener) to obtain an exposed halogen. The silver halide particles are reduced to silver by a developer, while
The remaining unexposed silver halide grains are made into a transferable silver complex salt by a silver halide solvent, and this silver complex salt is diffused and transferred by penetration into a silver precipitating agent-containing layer (image receiving layer) superimposed on the emulsion layer. , Where the silver complex salt is reduced with a developer with the aid of a silver precipitant to obtain development.

In carrying out this method, for example, a light-sensitive element in which a light-sensitive silver halide emulsion layer is usually provided on a support, an image-receiving element in which an image-receiving layer containing a silver precipitating agent is provided on a support, and a developer are used. , A film unit comprising a combination of processing elements consisting of an active alkali aqueous solution containing a silver halide solvent and a film forming agent is used. First, the emulsion layer of the light-sensitive element is imagewise exposed, and then the light-sensitive element is superposed so that the emulsion layer and the image-receiving layer of the image-receiving element face each other, while a pair of viscous aqueous alkali solutions of the processing element is developed therebetween. Pass between the rollers. Then, after leaving the image receiving element for a predetermined period of time and peeling the image receiving element from the photosensitive element, a print having a desired image formed on the image receiving layer can be obtained.

Further, in the light-sensitive material using this silver salt diffusion transfer method, a film unit having a peeling layer provided between the image receiving layer and the emulsion layer for the purpose of peeling and removing the emulsion layer containing the processing composition. Are described in JP-A-2-205845. However, in JP-A-2-205845, since a viscous and highly alkaline liquid is used as the treatment liquid, the handling risk is high. Further, as a release layer having a similar release layer, there is a release layer between the image receiving layer and the photosensitive layer, hydrophilic layers are provided on both sides of the release layer, and one layer contains a granular substance (US Patent 4499174), having a light opaque layer between the image receiving layer and the photosensitive layer (US Pat. No. 373).
0718), two release layers (a layer containing gelatin and a layer containing a hydrophilic polymer not containing gelatin) are provided between the image-receiving layer and the photosensitive layer, and at least the two layers adjacent to the release layer are provided. One layer contains no pigment (JP-A-60-
No. 42755), etc., but all of them use a viscous and highly alkaline treatment liquid, and thus have problems in handling.

High silver chloride emulsion grains are usually (100)
Although cubic crystal particles having an outer surface are likely to be formed, the presence of a particle formation control agent makes it possible to form particles having a (111) outer surface. JP-A-63-20
Japanese Patent No. 43 discloses a method of forming tabular high silver chloride grains having a (111) plane as a principal plane by forming grains in the presence of a compound containing a sulfur atom in a heterocycle.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel film unit which is safe and can obtain a high density in a short time by using substantially only water without using a developing solution. .

[0007]

The above object of the present invention is to provide an image-receiving layer containing at least a) a silver precipitating agent on a support,
Imagewise exposure of a light-sensitive material having b) a peeling layer, c) an antihalation layer having a light-shielding function, and d) a silver halide emulsion layer containing photosensitive silver halide grains having a silver chloride content of 50 mol% or more. After the application, a treatment sheet having a hydrophilic colloid layer containing a silver halide solvent on the support is brought into close contact with the film surface, and a silver salt is added in the presence of a small amount of water and a developing agent, a base and / or a base precursor. This is achieved by a silver salt diffusion transfer method characterized in that after performing diffusion transfer development, the layers above the release layer are peeled off together with the treated sheet to obtain a positive image on the image receiving layer.

The emulsion of the present invention will be specifically described below. The silver halide emulsion used in the present invention must be an emulsion consisting of silver chloride, silver chlorobromide or silver chloroiodobromide and having an average silver chloride content of 50 mol% or more. The above is more preferable. The crystal habit of the silver halide grains of the present invention is not particularly limited, and those having an equiaxed crystal system such as a cube, octahedron, and tetrahedron, and deformed crystals such as spherical and tabular Any of those having a shape or those having a composite form of these crystal forms may be used, but cubic grains or tabular grains are preferable. More preferably, it is a tabular grain having the (100) plane as the main plane.

The silver halide grains may be composed of different phases in the inside and the surface layer, or may be composed of a uniform phase. Further, the particles may be such that the latent image is mainly formed on the surface, or the particles may be mainly formed inside the particles, and the latent image may not be localized on any of them. . In particular, particles in which the latent image is formed as a seed on the surface are more preferable.

A tabular silver halide grain having a (100) plane as a main plane and a silver chloride content of 50% or more is disclosed in European Patent No. 534,395A1, page 7, line 53 to line 19.
It can be prepared by the method described on page 35, line or paragraphs (0006) to (0024) of Japanese Patent Application No. 4-214109. The silver halide grains of the present invention are preferably tabular silver halide grains in which 35% or more of the total projected area of all silver halide grains has a (100) plane as a main plane. It is more preferably 60% or more, still more preferably 80% or more. The aspect ratio of the tabular silver halide grains is preferably 2 to 20 and 4
10 is more preferable. The average projected grain size of the tabular silver halide grains is preferably 10 μm or less, and is 0.2 to 5 μm.
m is more preferred. Here, the aspect ratio refers to (diameter / thickness) of the tabular grain, and the diameter refers to the diameter of a circle having an area equal to the projected area of the grain when the grain is observed with an electron microscope. The thickness means the distance between the main planes of tabular grains. The average aspect ratio means the average value of the aspect ratios of all the tabular grains. The average projected grain size refers to the arithmetic mean value of the diameters of all the tabular grains. The principal plane refers to two parallel maximum outer surfaces in one tabular grain. The particle size distribution of the tabular grains is preferably monodisperse, and the coefficient of variation is preferably 40% or less, more preferably 20% or less.

The halogen composition of the emulsion may be different or the same between the grains, but it is preferable to use an emulsion having the same halogen composition between the grains because it is easy to make the properties of each grain uniform.

In the present invention, the bromine ion needs to be localized on the surface of the particle, and the bromine ion content on the particle surface is at least twice the average bromine ion content on the entire particle. It is preferable that it is 3 times or more and 200 times or less, and it is particularly preferable that it is 5 times or more and 100 times or less. The surface defined in the present invention means a surface in a range measured by the XPS (X-ray Photoerectron Spectroscopy) method. This measuring method is specifically described by Someno and Yasumorii "Surface Analysis" Kodansha (19
Published in 1977).

The high silver chloride emulsion grains preferably have a structure in which the silver bromide localized phase is layered or non-layered on the surface of the silver halide grain. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%.
These localized phases can be present on the edges, corners or planes of the grain surface, and one preferable example is a grain epitaxially grown on the corner portion of the grain. The high bromine ion concentration on the surface of the grain means that a sparingly soluble bromide such as silver bromide or a water-soluble bromide such as potassium bromide, or US Pat. This is accomplished by adding a bromide ion donating compound, such as a bromide ion sustained release agent as described in No. 615.

The average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodispersed coefficient of variation coefficient (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% by weight of all grains as a projected area is also preferably used. You can The silver chlorobromide emulsion used in the present invention is a Chimie et Phisi by P. Glafkides.
que Photographique (Published by PaUl Montel, 1967
), GF Duffin Photographic Emulsion Chemist
ry (Focal Press, 1966), VL Zelikman e
t al by Making and Coating Photographic Emulsion
(Focal Press, Inc., 1964) and the like. That is, the acidic method,
Any method such as a neutral method or an ammonia method may be used, and as a method for reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof may be used. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one type of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

A preferred film unit embodiment is shown below. Photosensitive material Protective layer: containing at least gelatin Silver halide emulsion layer: containing at least one silver halide emulsion Antihalation layer: containing at least one pigment having absorption at the wavelength of exposure light source Release layer: at least one release Receptor layer containing agent: At least one silver precipitant Support: Film or paper Treatment sheet Treatment layer: At least one silver halide solvent,
A base precursor and a developing agent are included, and at least gelatin is used as a binder. Support: film or paper processing solution No development processing component is contained, and it is substantially water. However,
A small amount of antibacterial agent for the purpose of preventing water stain may be contained.

As the layer structure, an image receiving layer is provided on a support. A release layer is provided adjacent to the image receiving layer, but a protective layer containing gelatin may be provided between the image receiving layer and the release layer for the purpose of improving the scratch resistance of the image after processing. An antihalation layer, a silver halide emulsion layer, and a protective layer are provided in this order on the release layer. Specific examples of silver precipitants contained in the image-receiving layer include heavy metals such as iron, lead, zinc, nickel, cadmium, tin, chromium, copper, cobalt, and particularly noble metals such as gold, silver, platinum and palladium. Other useful silver precipitants are sulfides and selenides of heavy and noble metals, especially mercury, copper, aluminum, zinc, cadmium, cobalt, nickel, silver, lead, antimony, bismuth, cerium, magnesium, gold, platinum and palladium. And the selenides of lead, zinc, antimony and nickel. Particularly, gold, platinum, palladium or their sulfides are preferable. The addition amount of physical development nuclei cannot be specified because the effect depends greatly on the type and size of nuclei, but 1 g
/ M ² or less, preferably 0.1 g / m ² or less.

A mercapto compound is used for the purpose of improving the color tone of the transferred silver image. Such a mercapto compound may be added to the image-receiving layer, or may be used by diffusing it from another layer or a treatment sheet. As the mercapto compound, JP-A-49-120634 and JP-B-56-
44418, British Patent 1276961, Japanese Patent Publication No. 56-2.
1140, JP-A-59-231537, JP-A-60-1
The compounds described in 22939 are preferred.

The peeling layer must have a function of keeping the image-receiving element and the light-sensitive element in close contact with each other when untreated and peeling off cleanly after the treatment. Preferred examples of such a release agent include those disclosed in JP-A-47-8237 and JP-A-56-6.
5133, ibid. 59-220727, ibid. 59-22955
5, JP-B-49-4334, 49-4653, 45
-24075, U.S. Patents 3,220,835 and 43,595.
18, the same 3227550, the same 2759825, the same 440
1746 and 4366227. Specific examples include water-soluble (or alkali-soluble) cellulose derivatives. Examples include hydroxy cellulose, cellulose acetate phthalate, plasticized cellulose, carboxymethyl cellulose and the like. Also,
There are various natural polymers such as alginic acid, pectin, and gum arabic. Also, various modified gelatins, for example, acetylated gelatin, phthalated gelatin and the like can be used. Furthermore, water-soluble synthetic polymers can also be used. For example, polyvinyl alcohol, polyacrylate, polymethacrylate, butyl methacrylate, or a copolymer thereof may be used. The release layer may be a single layer or may be composed of a plurality of layers. Examples thereof are disclosed in JP-A-59-220727 and JP-A-60-60642.
Etc.

The antihalation layer may be formed using a known dye or pigment. Further, it is advantageous to use an infrared absorber or carbon black for providing the antihalation layer on the infrared photosensitive layer. It is particularly advantageous to use carbon black for preventing halation. As a specific embodiment, those described in Japanese Patent Application No. 61-18963 can be used.

In the present invention, as a base precursor in the image forming reaction system, for a basic metal compound which is poorly soluble in water and a metal ion which constitutes this basic metal compound,
It is preferable to contain a compound capable of forming a complex by using water as a medium (hereinafter, referred to as a complex forming compound), and to raise the pH of the reaction system by a reaction between these two compounds in the presence of water. The image forming reaction system in the present invention means a region where an image forming reaction occurs. Specifically, for example, it refers to a layer belonging to both the photosensitive material and the processing sheet.

In the present invention, water used as a medium is
Water can be supplied by a method of supplying water from the outside, a method of preliminarily including a capsule containing water in the image forming reaction system, and destroying the capsule by heating to supply water. Examples of the water-insoluble basic metal compound used in the present invention include 2
Carbonates, phosphates, silicates, borates, aluminates, hydroxides, oxides having a solubility in water at 0 ° C. (the number of grams of a substance soluble in 100 g of water) of 0.5 or less, And double salts of these compounds such as basic salts. And what is represented by Formula TmXn is preferable. Here, T represents a transition metal, for example, Zn, Ni, Co, Fe, Mn, or the like, or an alkaline earth metal, for example, Ca, Mg, Ba, or the like, and X represents a complex forming compound described later in water. M coming out
Capable of being a counter ion of and exhibiting alkalinity, for example, carbonate ion, phosphate ion, silicate ion,
Borate ion, aluminate ion, hydroxy ion,
Represents an oxygen atom. m and n each represent an integer such that the valences of T and X are balanced.

Preferred specific examples are listed below. Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate (CaMg (Co ₃ ) ₂ ), magnesium oxide, zinc oxide, tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide,
Magnesium hydroxide, calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide, manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, Calcium aluminate, basic zinc carbonate (2ZnCO ₃・ 3Zn (OH) ₂・ H ₂ O), basic magnesium carbonate (3MgCO ₃・ Mg (OH) ₂・ 3H ₂ O), basic nickel carbonate
(NiCO ₃・ 2Ni (OH) ₂ ), basic bismuth carbonate (Bi ₂ (CO ₃ ) O ₂
・ H ₂ O), basic cobalt carbonate, (2CoCO ₃・ 3Co (OH) ₂ ),
Aluminum magnesium oxide Among these compounds,
Those which are not colored are particularly preferable.

The complex-forming compound used in the present invention forms a complex salt having a stability constant of 1 or more in log K with the metal ion constituting the water-insoluble basic metal compound. Examples of these complex-forming compounds include AE Martel and AE Martel.
l. RM Smith) Co-authored “Critical Stability Constants, No. 1-
5 ", Plenum Press. Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, anilinecarboxylic acids, pyridinecarboxylic acids, aminophosphoric acids, carboxylic acids (mono, di,
Compounds having substituents such as tri, tetracarboxylic acid and phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino), alkali metals such as hydroxamic acids, polyacrylates, polyphosphoric acids, guanidines, Examples thereof include salts such as amidines and quaternary ammonium salts.

As a preferred specific example, picolinic acid,
2,6-Pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 4-dimethylaminopyridine-2,6-dicarboxylic acid, quinoline-2-carboxylic acid, 2-pyridylacetic acid, oxalic acid, citric acid, tartaric acid, isocene Alkali metal salts of acids, malic acid, gluconic acid, EDTA, NTA, CyDTA, hexametaphosphoric acid, tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, salts of guanidines,
Examples thereof include salts of amidines and quaternary ammonium salts. Of these, an aromatic heterocyclic compound having at least one —CO ₂ M and one nitrogen atom in the ring is preferable. The ring may be a single ring or a condensed ring, and examples thereof include a pyridine ring and a quinoline ring. And -C
The position at which O ₂ M is bonded to the ring is particularly preferably the α position with respect to the N atom. M is any of alkali metal, guanidine, amidine and quaternary ammonium ions. As the poorly soluble basic metal compound and complex forming compound, those described in JP-A-64-13546 can be used.

In the present invention, the basic metal compound which is poorly soluble in water and the complex-forming compound must be added to at least another layer in order to prevent the reaction from occurring before the development processing.
A more preferred form is a form in which a basic metal compound and a complex-forming compound that are hardly soluble in water are contained in at least one layer on separate supports. For example, it is preferable that a basic metal compound which is poorly soluble in water is contained in a light-sensitive material and a complex-forming compound is contained in a processing sheet. When a basic metal compound which is hardly soluble in water is added to the light-sensitive material, the layer to be added may be any of an emulsion layer, an antihalation layer and a protective layer. Further, it may be added dividedly in multiple layers, or may be added concentratedly in one layer. Basic metal compounds are described in JP-A-59-174830,
It is desirably contained as a fine particle dispersion prepared by the method described in JP-A-53-102733 and the like, and the average particle size is preferably 50 μm or less, particularly preferably 5 μm or less.

In the present invention, when the basic metal compound or the complex-forming compound which is poorly soluble in water is contained in the layer on the support, the addition amount is the compound species, the particle size of the poorly-soluble metal compound, and the complex formation reaction rate. It is suitable to use the coating film in an amount of 50% by weight or less in terms of weight, more preferably 0.01% by weight to 40% by weight, depending on factors such as the above. Further, in the present invention, the content of the complex-forming compound in the reaction system is 1/100 to 100 times, and particularly 1/10 times as much as the content of the sparingly soluble metal compound.
Double is preferred.

In the present invention, a light-sensitive silver halide emulsion layer is provided on the peeling layer, and a protective layer is provided thereon. The silver halide emulsion may be one kind or a mixture of a plurality of kinds. The silver halide emulsion layer may be a single layer or a multilayer of two or more layers. Even if the silver halide emulsion contains a heavy metal compound such as an iridium compound, a rhodium compound, a divalent or trivalent iron ion-containing compound, a rhenium compound, a ruthenium compound or an osmium compound described in JP-A-7-043844. good. Only one kind of these compounds may be contained, or two or more kinds thereof may be contained. General additives can be used in the silver halide emulsion. Examples thereof include chemical sensitizers, reciprocity law failure property improving agents such as platinum group compounds, spectral sensitizers, post-ripening terminators such as tetrazaindenes, and antifoggants such as heavy metal compounds and organic compounds. The thickness of the silver halide emulsion layer is 0.5 to 8.0 .mu.
6 to 6.0 μ, and the coating amount of silver halide grains is 0.1 to 3 g / m ² as silver amount, preferably 0.2 to 2.0 g
/ M ² .

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloids, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; Vinyl alcohol, polyvinyl alcohol partial acetal,
A wide variety of synthetic hydrophilic polymeric substances such as poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used. In addition to lime-processed gelatin, acid-processed gelatin and Bulletin Soc. Sci. Phot. Japan (Bull. Soc. Sci. Phot. Japan), No. 1
6, oxygen-treated gelatin as described in P.P. 30 (1966) may be used, and a hydrolyzate or an enzymatic hydrolyzate of gelatin may also be used. As the photographic gelatin, lime-processed bone gelatin is preferably used. For general information on photographic gelatin and the content of impurities, see “Basics of Photographic Engineering-Silver Salt Photographs”, 1980, 1979.
It is described in detail on pages 116-150 of Corona Publishing Co., Ltd.

The photographic emulsion used in the present invention may be chemically sensitized. For chemical sensitization, for example, H. Frieser Die Grundlagen der Photographis
hen Prozesse mit Silderhalogeniden) (Akademische Verlag
sgesellschaft), 1968] pp. 675-734, the sulfur sensitization method, reduction sensitization method, selenium sensitization method, tellurium sensitization method, noble metal sensitization method and the like can be used alone or in combination. For example, in sulfur sensitization, sulfur sensitizers, that is, compounds containing sulfur obtained by reacting with active gelatin or silver include, for example, thiosulfates, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p -Toluenethiosulfonate, Rhodan, mercapto compounds and the like are used. In addition, U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, and 2,728,668,
Those described in No. 3,656,955 and the like can also be used. The addition amount of these sulfur sensitizers varies over a considerable range under various conditions, but is usually preferably about 10 ^-7 to 10 ^-2 mol per mol of silver.

In gold sensitization, the gold sensitizer may have an oxidation number of gold of +1 or +3, and specific examples thereof include chloroauric acid, potassium chloroaurate, auric trichloride and potassium auric thiocyanate. , Potassium iodoaurate, tetracyanoauric acid and the like are used. The addition amount of these gold sensitizers varies over a considerable range under various conditions, but is usually preferably about 10 ^-9 to 10 ^-2 mol per mol of silver. It is particularly preferred that 80% or more of the gold sensitizer be present in the silver halide grain phase as described in Japanese Patent Application No. 61-79687. In the present invention, Japanese Patent Application No. 7-1031
The selenium sensitization or tellurium sensitization described in 66 can also be used. The addition amount of the selenium sensitizer and the tellurium sensitizer is selected from a wide range, but usually 10 ^-7 to 1 per mol of silver.
0 ^-2 mol is preferred.

In addition to the above-mentioned sulfur sensitization, gold sensitization, selenium sensitization and tellurium sensitization, a reducing substance (eg, primary tin salt, amines, hydrazine derivative, formamidinesulfinic acid, silane compound) is used. Reduction sensitization method: A noble metal sensitization method using a noble metal compound (for example, a complex salt of a metal of Group VIII of the periodic table such as Pt, Ir, and Pd in addition to a gold complex salt) can be used together. U.S. Pat. Nos. 2,983,609, 2,419,974, 4,054,458 and the like for reduction sensitization, and U.S. Pat. No. 2,399,083 for noble metal sensitization. , No. 2,448,06
No. 0, US Pat. No. 618,061 and the like. Typical combinations of sensitizers are gold / sulfur sensitization, gold / selenium sensitization, and gold / sulfur / selenium sensitization, but other combinations are also possible. In gold / sulfur sensitization, the use ratio of both sensitizers varies depending on the aging conditions and the like, but usually 1 to 1000 mol of the sulfur sensitizer is used per 1 mol of the gold sensitizer. For gold / selenium sensitization and gold / sulfur / selenium sensitization, usually gold sensitizer 1
It is preferable to use the selenium sensitizer in an amount of about 1 to 1000 mol per mol. In gold / sulfur sensitization and gold / selenium sensitization, the gold sensitizer may be added at the same time as the sulfur sensitizer or the selenium sensitizer, the sulfur or selenium sensitizer, or after the end. Good.

In the present invention, these chemical sensitizers are added to the silver halide photographic emulsion by a conventional method. That is, the water-soluble compound is added as an aqueous solution, and the compound soluble in an organic solvent is added as a solution of an organic solvent that is easily mixed with water, such as methanol or ethanol. The conditions such as pH, pAg and temperature during chemical sensitization are not particularly limited, but the pH value is preferably 4-9, particularly 5-8, p
The Ag value is preferably kept at 5 to 11, particularly preferably 7 to 10. The temperature is 40 to 90 ° C., and particularly 45 to
75 ° C is preferred.

The photosensitive emulsion layer includes a photographic material manufacturing process,
Various compounds can be contained for the purpose of preventing fogging during storage or photographic processing or stabilizing photographic performance. That is, azoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, nitrobenzotriazoles, benzotriazoles and the like are preferable. For example, 1-phenyl-5-
Mercaptotetrazole is typical. Further, mercaptopyrimidines, mercaptotriazines, for example thioketo compounds such as oxadrine thione, azaindenes, for example triazaindenes, tetrazaindenes,
Pentaazaindenes are preferred. For example, 4-hydroxy-6-methyl and 1,3,3a, 7-tetrazaindene are typical. In addition, well-known antifoggants and stabilizers such as benzenesulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides, α-lipoic acid, and a combination use of a tetrazaindene compound and an imidazole compound are used. For more specific examples and methods of using them, those described in, for example, U.S. Patents 3,954,474 and 3,982,947 and JP-B-52-28660 can be used. The light-sensitive element used in the present invention may contain a developer, for example, a hydrophobic compound such as a pyrizolidone compound or a hydroxylamine compound, and a silver halide solvent, for example, a uracil compound or a thiosulfate compound, for the purpose of increasing the developing speed.

The silver halide emulsion is described in Japanese Patent Application No. 7-1031.
66, the spectral sensitizing dye described in Japanese Patent Application No. 7-103250 can be used. Cyanine dye as a spectral sensitizing dye,
Preferred are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

The photosensitive element and the processing sheet of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chrome alum, chromium acetate, etc.) aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.) , Active vinyl compounds (such as 1,3,5-triacryloyl-hexahydro-s-triazine) and mucohalic acids (such as mucochloric acid and mucophenoxycyclolic acid) can be used alone or in combination.

A coating aid can be used in the hydrophilic colloid layer of the photosensitive element and the processing sheet of the present invention. As a coating aid, Research Disclosure (Research
Disclosure) Volume 176, 17643, page 26 (197)
The compounds described in the section of "coating aids" (issued in 8.12) and the compounds described in JP-A-61-20035 can be used.

The silver halide emulsion layer and other hydrophilic colloid layers of the light-sensitive element of the present invention may contain, for example, polyalkylene oxide or its ether, ester, amine, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. Compounds such as derivatives of bisphenol, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane derivatives, urea derivatives, imidazole derivatives, and 3-pyrazolidones. Examples of such compounds are described in U.S. Pat.
6062, 3617280, 37702021, 3
Compounds described in 808003 and the like can be used.

The hydrophilic colloid layer of the light-sensitive element and the processing sheet of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth)
Acrylamide, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth). It is possible to use a polymer having a combination of acrylate, styrene sulfonic acid, etc. as the short-mer component.

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 and is disclosed in JP-A-61-161.
Matting agents or sliding agents such as polymethyl methacrylate latex and silica as described in 47946 and 61-75338 can be included. In the light-sensitive element of the present invention, the light-sensitive silver halide emulsion layer and other hydrophilic colloid layers may contain a dye or an ultraviolet absorber as a filter dye or for the purpose of preventing irradiation. In addition, the photosensitive element of the present invention may contain an antistatic agent, a plasticizer and an air fogging inhibitor.

The developer may be present in the light-sensitive material and / or the processing sheet. As the developer, for example, hydroquinone, tert-butylhydroquinone, a benzene or naphthalene-based organic compound having a hydroxy group at a para or ortho position is used. Further, reductic acid as described in US Pat. No. 3,615,440 and α, β-ene diol as described in US Pat. No. 770716 are preferably used. Further, a hydroxyamine developer as described in U.S. Pat. Nos. 3,287,125 and 3293034 is preferably used. Also, 1-aryl-3 described in JP-B-49-13580 as a developer is used.
-A pyrazolidinone compound or an alkyl-substituted p-aminophenol may be used in combination with the above hydroxylamine developer. The amount of the developer used is 0.5 mol to 3.0 mol, preferably 0.6 mol to 2.0 mol, per 1 mol of the coated silver.
0 mol. More preferably, the developer is added to the processing sheet. The developers can be used in combination of two or more kinds. Particularly, a combination of a hydroquinone-based developing agent and another developing agent is preferable.

The silver halide solvent may be present in the light-sensitive material and / or the processing sheet. Among them, the processing sheet is most preferable. US Patents 2,857,274 and 2,857,727
The cyclic compounds described in Nos. 5 and 2857276 are suitable, and among them, uracil and 6-methyluracil are preferred examples. Further, alkali metal thiosulfates, particularly sodium or potassium salts, are preferred. U.S. Pat. Nos. 3,958,992, 3,976,647, and 40
09167, 4032538, 4046568, 4047954, 4047955, 41071176
And disulfonylmethane compounds disclosed in JP-A-47-330 and U.S. Patents 4,126,459, 4,150,228 and 42.
Dihydroxypyrimidine compounds having a thioether group described in US Pat.
51617, 4267254 and 4267256.
From aminothioethers.

The method of applying water as a solvent to the photographic material is described in, for example, the roller coating method or the wire bar coating method described in JP-A-59-181353, which is described in JP-A-59-181354. A method of applying water to a photographic material by using such a water-absorbing member, as described in JP-A-59-181348, forming a bead between a water-repellent roller and a photographic material to apply water. In addition to the above, various methods such as a dip method, an extrusion method, a method of ejecting as a jet from pores and applying, and a method of applying in a crushing manner of a pod can be used. The water as the solvent is not limited to so-called “pure water”, but includes water in a widely and conventionally used sense.

The amount of water used is at least 0.1 times, preferably 0.1 times or more the weight of the total coating film of the light-sensitive material and the processing sheet, and the solvent corresponding to the maximum swelling volume of the total coating film. Or less (particularly less than or equal to the weight of the solvent corresponding to the maximum swelling volume of the entire coated film minus the weight of the entire coated film). The state of the film at the time of swelling is unstable. Depending on the conditions, local bleeding may occur. Less than the amount is preferred.
Specifically, the range is preferably 1 g to 50 g, particularly 2 g to 35 g, and more preferably 3 g to 25 g per square meter of the total area of the photosensitive material and the processing sheet. The method described in JP-A-61-147244 can be applied to the pressure condition and the method of applying pressure when the light-sensitive material and the processing sheet are superposed and brought into close contact with each other.

[0045]

EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Example 1. Preparation of Light-Sensitive Material A light-sensitive material was prepared by sequentially providing the following layers on a support PET film. (1) Image Receptor Layer Preparation of Silver Precipitating Agent (Palladium Sulfide) Used for Image Receptor Layer Solution A; Palladium chloride 3.3 g Concentrated hydrochloric acid 20 ml Add 500 ml of water after dissolving the above solution Solution B; Na ₂ S.9H ₂ O 4.5 g Gelatin 140 g H ₂ O 2400 ml Solution B is heated to 70 ° C. and solution A is added with stirring. After addition of solution A, the temperature is lowered to 40 ° C. and the pH is adjusted to 5.0 with NaOH. Vinyl sulfone hardener CH ₂ = CHSO ₂ CH ₂ CONH (CH ₂ ) ₂ NHCOCH ₂ SO ₂ CH = CH ₂ 0.4g was added to make a coating solution, and the silver precipitant was applied at 2g / m ² . did.

(2) Image Protecting Layer For the purpose of protecting the processed image, gelatin was coated on the image receiving layer so that the coating amount was 0.3 g / m ² . (3) Release layer Hydroxyethyl cellulose (HEC SP-800
Daicel Co., Ltd.) was applied so as to be 0.15 g / m ² . (4) Antihalation layer Carbon black CB # 10B (Mitsubishi Kasei Co., Ltd.)
A gelatin dispersion prepared in (1) was prepared and coated so that the solid content of carbon was 0.15 g / m ² and the gelatin was 0.3 g / m ² .

(5) Silver Halide Emulsion Layer Emulsions A to E were prepared as follows. (Preparation of Emulsion A) A 1.0 M silver nitrate aqueous solution and 3 × 10 ⁻⁷ mol of (NH ₄ ) ₃ RhCl ₆ per 1 mol of silver, 0.7 M potassium bromide and 0.34 M sodium chloride are contained. An aqueous solution of a halogen salt containing
To the aqueous gelatin solution containing 1,3-dimethyl-2-imidazolinethione, the mixture was added with stirring by the double jet method at 45 ° C. for 30 minutes, and the average particle size was 0.28 μm.
m, and silver chlorobromide grains having a silver chloride content of 70 mol% were obtained. After that, it is washed with flocculation according to the usual method,
40 g of gelatin was added to adjust pH to 5.5 and pAg to 7.5, and sodium thiosulfate was 3.0 per mol of silver.
mg, triphosphine selenide 3.0 mg, chloroauric acid 6.0
mg, sodium benzenethiosulfonate 4 mg, and sodium benzenethiosulfinate 1 mg were added, and chemical sensitization treatment was performed at 65 ° C. to obtain the optimum sensitivity.
150 mg of -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. The obtained grains were silver chlorobromide cubic grains having an average grain size of 0.25 μm and a silver chloride content of 30 mol%. (Variation coefficient 10%)

(Preparation of Emulsion B) Except that the halogen composition of silver halide grains was 50 mol% in silver chloride content, the same preparation as in Emulsion A was carried out.

(Preparation of Emulsion C) The same preparation as Emulsion A was carried out except that the halogen composition of the silver halide grains was 70 mol% in silver chloride.

(Preparation of Emulsion D) The same preparation as Emulsion A was carried out except that the halogen composition of the silver halide grains was 95 mol% in silver chloride.

(Preparation of Emulsion E) An aqueous gelatin solution [H ₂ O 1200 cc, empty gelatin 6 g, NaCl was placed in a reaction vessel.
0.5 g, pH 9.0] was added, the temperature was raised to 65 ° C., (AgNO ₃ 0.1 g / cc) and ammonium hexabromorhodium (III) and potassium hexachloroiridium (III) were added with stirring. NaCl solution (NaCl
0.0345 g / cc) was co-added at 15 cc / min for 6 minutes. Next, gelatin solution (H ₂ O 100cc, empty
Containing 19 g of gelatin and 1.3 g of NaCl] and added HNO ₃
1N liquid was added to adjust the pH to 4.0. Next, the temperature was raised to 70 ° C. and ripening was performed for 16 minutes, and then a fine grain emulsion described below was added in an amount of 0.1 mol in terms of silver halide. After ripening for 15 minutes, 0.15 mol of a fine grain emulsion was added and ripening for 15 minutes was repeated twice. After aging for 2 minutes, increase the temperature to 4
The temperature was lowered to 5 ° C. and a NaOH solution was added to adjust the pH to 5.2. A precipitating agent was added, the temperature was lowered to 27 ° C., the pH was adjusted to 4.0, and the emulsion was washed with water by a precipitation washing method according to a conventional method. An aqueous gelatin solution was added, the temperature was raised to 40 ° C., the pH of the emulsion was 6.4, and pCl was 2.
Adjusted to 8. Next, the temperature was raised to 50 ° C., 0.005 mol of a silver bromide fine grain emulsion having a side length of 0.05 μ was added to this emulsion, and then a sulfur sensitizer and a gold sensitizer were added to optimally perform chemical sensitization. . The emulsion thus prepared has Rh and Ir of 3.8 × 10 ⁻⁷ and 6.1 × 10 ⁻⁸ per mol of silver.
Molar content, 80% of all silver halide grains as observed by an electron microscope (TEM) were tabular grains having a [100] plane as a main plane, and the average grain size was 1.4 μm and the average aspect ratio was 6. 5. The average particle volume measured by a Coulter counter manufactured by Coulter Co. was 0.13 μm ³ . The fine grain emulsion was prepared as follows. Aqueous gelatin solution in the reaction vessel [H ₂ O 1200 cc, average molecular weight 30,000 gelatin (M3) 24 g, comprises NaCl 0.5 g,
pH 3.0] and AgN with stirring at a temperature of 23 ° C.
O ₃ liquid (AgNO ₃ 0.2g / cc, (M3) 0.01g
/ Cc, including HNO ₃ 1N 0.25 cc / 100 cc) and NaCl solution (NaCl 0.07 g / cc, (M3) 0.
(01 g / cc, containing 0.25 cc / 100 cc of KOH 1N solution) was simultaneously added at 90 cc / min for 3 minutes and 30 seconds. 1
After stirring for 1 minute, the pH was adjusted to 4.0 and pCl 1.7.

The characteristics of Emulsions A to E are summarized in Table 1 above.

[0053]

[Table 1]

The following sensitizing dyes were added to these emulsions in an amount of 160 mg per mol of Ag, and as stabilizers, 280 mg of sodium 3- (5-mercaptotetrazole) -benzenesulfonate and 280 mg of thioctic acid were added. Sensitizing dye

[0055]

Embedded image

The above emulsion was coated so that the coating amount of silver was 1.0 g / m ² and the coating amount of gelatin was 0.8 g / m ² . (6) Protective layer 1.4 g of gelatin / protective layer on top of the light-sensitive material
It was coated so as to become a m ^2. In this protective layer, 1.3 g / m ² of Zn (OH) ₂ was used as a base precursor, and a polymethylmethacrylate particle of 0.1 g / m ^{2 was} used as a matting agent.
It was contained at 1 g / m ² . 2. Preparation of a treatment sheet A treatment sheet was prepared by coating the following on a support PET film. Gelatin 7.6 g / m ² Guanidium picolinate 2.3 g / m ² Sodium picolinate 2.1 g / m ² Hypo 0.5 g / m ² Hydroquinone 0.4 g / m ² 4-Hydroxymethyl-4-methyl-1- Phenyl-3-pyrazolidone 0.1 g / m ² vinyl sulfone type hardener 0.15 g / m ² vinyl sulfone type hardener is the same as that used in the light-sensitive material.

3. Sensitometric processing The light-sensitive material thus obtained was subjected to 670n from the emulsion film surface side.
Exposure was performed with xenon flash light with an emission time of 10 ⁻⁵ seconds through an interference filter having a transmitted light peak at m and a continuous wedge. Using a processing machine E-380 manufactured by Agfa Co., Ltd., 1000 cc of water was put in the water tank, the exposed light-sensitive material sheet was passed through the water tank, and immediately overlaid and pressure-bonded so that the processing sheet and the film surface were in contact with each other. did. After that, the temperature was kept at 40 ° C. for 30 seconds, and then the processed sheet was peeled off, and peeled off from the release layer of the light-sensitive material, and the punch halation layer, silver halide emulsion layer and the like were all transferred to the side of the processed sheet.

The results of the sensitometry treatment are shown in Table 2. Experiment No. of the present invention. 2 to 5 are sensitivity and transfer Dm
ax is good. Experiment No. 1 using the tabular silver halide emulsion E among them. 5 showed particularly good performance.

[0059]

[Table 2]

Claims (4)

[Claims] 1. A support having at least a) an image-receiving layer containing a silver precipitating agent, b) a peeling layer, c) an antihalation layer having a light-shielding function, and d) photosensitivity having a silver chloride content of 50 mol% or more. After imagewise exposure of a light-sensitive material having a silver halide emulsion layer containing silver halide grains, a support sheet having a hydrophilic colloid layer containing a silver halide solvent on a support is brought into close contact with the film surface. After performing silver salt diffusion transfer development in the presence of a small amount of water and a developing agent, a base and / or a base precursor, the layer above the release layer is peeled off together with the processing sheet to obtain a positive image on the image receiving layer. A silver salt diffusion transfer method characterized in that 2. The silver salt diffusion transfer method according to claim 1, wherein the silver halide emulsion grain according to claim 1 is a tabular photosensitive silver halide grain having a (100) plane as a main plane. . 3. A developing agent and a base and / or a base precursor are contained in a light-sensitive material and / or a processing sheet during the development processing, and substantially only water is added to a coating film of the light-sensitive material and / or the processing sheet. 3. The silver salt diffusion transfer method according to claim 1, wherein the silver salt diffusion transfer method is performed before closely adhering. 4. A film unit comprising a photosensitive material and a processing sheet used in the silver salt diffusion transfer method according to claim 1.