JPS62283332A - Image forming method - Google Patents

Abstract

PURPOSE:To easily and quickly obtain a silver image of high sensitivity with a high concn. by increasing pH by the reaction of a basic metallic compd. hardly soluble in water and compd. which make reaction to form complex with the metallic ions thereof with water as a medium. CONSTITUTION:The pH is increased by the reaction of the basic metallic compd. hardly soluble in water and the compd. which can form the complex with the metallic ions constituting the basic metallic compd. hardly soluble in water with water as a medium at the time of processing. An example of the basic metallic compd. hardly soluble in water to be used includes calcium carbonate, etc., and the uncolored compd. is more particularly preferable. The complex forming compd. to be used forms the complex exhibiting a complex salt having >=1 logK value of stability constant with the metallic ions constituting the basic metallic compd. and a preferred example includes a picolinic acid, etc.

Description

[Detailed description of the invention] 3. Detailed description of the invention Background of the invention Conventional field The present invention relates to an image forming method using a silver salt diffusion transfer method.

Prior art and its problems The silver salt diffusion transfer process is described in U.S. Patent No. 2.352,014 etc.

This method generally consists of a light-sensitive material and an image-receiving material.
With the exposed emulsion side of the photosensitive material facing the surface of the image-receiving material, insert the photosensitive material into the developer solution, squeeze out the liquid from the overlapping area, and leave it in the device for a short while. The fully exposed parts of the silver are developed, while the unexposed parts of the silver halide are solubilized by the action of a silver halide solvent, diffused onto the image-receiving material, and reduced in the presence of physical development nuclei. It becomes a silver 9-positive image.

This method uses a developer containing alkali, which stains hands and clothes and causes corrosion of the machine.

In addition, a considerable amount of P8 is required for handling processing chemicals and maintenance of the developing solution, making management complicated.

To solve these problems, many methods have been proposed for forming positive images by heating.

However, it is quite difficult to solubilize silver halide using only heat and a halide MW agent, and therefore, as described in Japanese Patent Publication No. 18667/1983, silver halide has a chloride content of at least 80 mol% or more. This problem has been solved by incorporating silver, but emulsions mainly containing silver chloride generally have low sensitivity and lack applicability.

Furthermore, since it takes time to transfer the solubilized silver salt onto an image-receiving material using only heat, a hydrophilic hot solvent is used to transfer the mobile silver salt, as described in JP-A-60-194448. is promoting.

However, hydrophilic thermal solvents tend to volatize when heated to high temperatures, causing a problem in that they contaminate the environment, processing equipment, and the like.

■ Purpose of the Invention The purpose of the present invention is to be able to easily obtain high-density, high-sensitivity silver images in a short time, and to do so in a short time! An object of the present invention is to provide an image forming method that allows easy management of machines and processing liquids.

■Disclosure of invention These objects are achieved by the present invention below.

That is, the present invention comprises a photosensitive silver halide photosensitive material,
In an image forming method in which a photographic material containing an image receiving material containing physical development nuclei is subjected to silver salt diffusion transfer treatment in the presence of a reducing agent and a silver halide solvent, a basic metal compound that is sparingly soluble in the water removed during this treatment is used. This image forming method is characterized in that the pH is increased by a reaction between metal ions constituting the basic metal compound that is dissolvable in water and a compound that can undergo a complex formation reaction using water as a medium.

■Specific structure of the invention Hereinafter, a specific configuration of the present invention will be explained in detail.

In the image forming method using silver salt diffusion transfer processing of the present invention, an image forming reaction system includes a basic metal compound that is sparingly soluble in water, metal ions constituting the basic metal compound that is sparingly soluble in water, and water as a medium. A compound (hereinafter referred to as a complex-forming compound) that can undergo a complex-forming reaction as a compound is added, and the pH of the reaction system is increased by the 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, examples thereof include layers existing on a support of a light-sensitive material, and, when a photographic element includes a light-sensitive element and an image-receiving element, layers belonging to both elements. When two or more layers are present, all or one layer may be used.

In the present invention, the water used as a medium can be supplied by a method of supplying water from the outside, a method of pre-existing a capsule containing water in the image forming reaction system, and a method of destroying the capsule by heating etc. and supplying water. can.

Examples of water-dissolvable basic metal compounds used in the present invention include those having a solubility in water at 20°C (number of grams of substance dissolved in 100 g of water) of 0.5 or less and represented by the formula Trn preferable.

Here, T is a transition metal such as Zn, Ni, Co, Fe,
Mn etc., or alkaline earth metals 1 such as Ca, Mg,
represents Ba, etc., and X can serve as a counter ion for M, which will appear in the explanation of complex-forming compounds described later in water,
It also represents something that is alkaline, such as carbonate ion, phosphate ion, silicate ion, borate ion, aluminate ion, hydroxyl ion, and oxygen atom. m and n represent integers such that the valences of T and X are balanced, respectively.

Preferred specific examples are listed below.

Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate.

Magnesium calcium carbonate <CaMg(CO3) 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 (2ZnCOz ・3Zn(
OH) 2 ・)I 20), basic magnesium carbonate (3MgCO3・Mg (OH) 2 ・3) 12
0), basic nickel carbonate (NiCO3.2Ni(oH
) 2), basic bismuth carbonate (Bi 2 ((:
03 )02 ・H2O), basic cobalt carbonate (2
GoCO3.3Co(OH) 2 ), magnesium aluminum oxide Among these compounds, uncolored compounds are particularly preferred.

The complex-forming compound used in the present invention has a stability constant of j! with the metal ion constituting the basic metal compound. 1 in ogK
This produces a complex salt that exhibits the above values.

These complex-forming compounds are described, for example, by N.E. Martill and R.M. Smith.
ell, R.M., Sm1th), “Critical
Stability Constance (Critical Sta.
bility Con5tants),'fs 1~
51-, Plenum Press
).

Specifically, aminocarboxylic acids, iminodiacetic acid and its derivatives, aniline carboxylic acids, pyridine carboxylic acids, aminophosphoric acids, carboxylic acids (mono, di, tri,
Tetracarboxylic acids and compounds with substituents such as osphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio, and phosphino), alkali metal compounds such as hydroxamic acids, polyacrylates, and polyphosphoric acids, guanidines, Examples include amidines and salts such as quaternary ammonium salts.

Preferred specific examples include picolinic acid, 2゜6-pyridinedicarboxylic acid, 2.5-pyridinedicarboxylic acid, 4-pyridinedicarboxylic acid,
dimethylaminopyridine-2,6-dicarboxylic acid, quinoline-2-carboxylic acid, 2-pyridylacetic acid, succinic acid,
Citric acid, tartaric acid, isocitric acid, malic acid, gluconic acid, EDTA, NTA, CDTA, hexametaphosphoric acid,
Tripolyphosphoric acid, tetraphosphoric acid, polyacrylic acid, HD2 (:CH20(12C820C82co2H.

HO2CCH20CI(2(,021(.

Examples include alkali metal salts such as CH3H2Q3P-C)l-PO3)12, salts of guanidines, salts of amidines, and quaternary ammonium salts.

Among these, aromatic heterocyclic compounds containing at least one -002M atom and having one nitrogen atom in the ring are preferred. The ring may be a j# ring or a fused ring, such as a pidgin ring or a quinoline ring. And -
The position where CO2M is bonded to the ring is particularly preferably α-position relative to the N atom; M is any one of an alkali metal, guanidine, amidine, and a quaternary ammonium ion.

Particularly preferred compounds include those represented by the following formula.

Formula In the above formula, R represents any one of a hydrogen atom, an aryl group, a halogen atom, an alkoxy group, -CO2M, a hydroxycarbonyl group, and an electron-donating group such as an amine group, a substituted amino group, and an alkyl group. Two R's may be the same or different.

Zl and 22 are each the same as defined in R,
Further, zl and 22 may be combined to form a ring condensed to a pidgin ring.

Next, the most preferred examples of combinations of basic metal compounds and complex-forming compounds are listed (here, M is an alkali metal ion, a substituted or unsubstituted guanidinium ion,
represents an amidinium ion or a quaternary ammonium ion).

Basic magnesium carbonate - Basic zinc carbonate - Basic magnesium carbonate - Calcium carbonate - Zinc oxide - Calcium carbonate - Calcium carbonate - Magnesium oxide - Zinc hydroxide - H3 (: Tin hydroxide - H3CCH3 Salt & calcium acid - Basic Magnesium carbonate - ee ee MO2C-C02M, calcium dodecate - basic zinc carbonate - combinations of these can be used alone or in combination of two or more.Also, they can be used in combination with a known base or base precursor. Can be done.

Here, the mechanism for increasing the pH of the reaction system in the present invention will be explained using a combination of potassium picolinate and zinc hydroxide as an example.

The reaction between the two is shown, for example, by the following formula.

That is, when water is present as a medium, picolinate ions undergo a complex formation reaction with zinc ions, and the reaction represented by the above formula proceeds, resulting in high alkalinity.

The progress of this reaction is due to the stability of the complex formed, but the progress of this reaction is due to the stability of the complex formed, and
ML generated from ML2. The stability number of the complex represented by ML3 is very large as shown below and explains the progress of this reaction well.

ML ML2 ML3 uogK 5.30 9.62 12.92 In the present invention, the water-dissolvable basic metal compound and the complex-forming compound may react through water during diffusion transfer development.

In the present invention, it is desirable that the slightly water-soluble basic metal compound and the complex-forming compound be contained in at least one layer on separate supports.

For example, it is preferable that a basic metal compound that is sparingly soluble in water is contained in a light-sensitive material, and a complex-forming compound is contained in an image-receiving material.
The complex-forming compound may also be supplied dissolved in the water involved.

Furthermore, as another bad practice, a basic metal compound that is sparingly soluble in water is placed in a bag that allows the solution to pass through but not insoluble materials (solids) and is immersed in the processing solution. Alternatively, it can be used by being included in an image-receiving material. Basic metal compounds that are sparingly soluble in water are described in JP-A-59-174830.
It is desirable to contain it as a fine particle dispersion prepared by the method described in No. 53-1027.33, etc., and the average particle size thereof is preferably 50 μm or less, particularly 5 μm or less.

In the present invention, when a basic metal compound or a complex-forming compound that is sparingly soluble in water is contained in the layer on the support, the amount added is as follows:
Although it depends on the type of compound, the particle size of the basic metal compound in 5 dll water, the rate of complex formation reaction, etc., it is appropriate to use each coating film in an amount of 50% by weight or less, more preferably 0% by weight. A range of .01% to 40% by weight is useful. When the complex-forming compound is dissolved in water and supplied, the amount is 0,005 moj2/1 to 5 mol/1. A concentration of 0.05 mol/1 to 2 moλ/It is particularly preferred. Furthermore, in the present invention, the content of the complex-forming compound in the photographic material is 1/100 to 100 times, particularly 171 times, in molar ratio to the content of the basic metal compound that is poorly soluble in water.
0 times to 20 times is preferable.

In the image forming method of the present invention, a photographic material having a photosensitive silver halide photosensitive material and an image receiving material containing physical development nuclei is subjected to silver salt diffusion transfer treatment in the presence of a reducing agent and a silver halide solvent.

The silver salt diffusion transfer process is usually carried out using a silver salt diffusion transfer method at a high temperature.

This silver salt diffusion transfer method is described in U.S. Patent No. 2.352.
, No. 014, etc.

That is, in the silver salt diffusion transfer method, an imagewise exposed silver halide emulsion layer is placed in contact with, or brought into contact with, an image-receiving layer in the presence of a developing agent and a silver halide solvent. , converting the unexposed silver halide to a soluble silver complex.

In the exposed portions of the silver halide emulsion layer, the silver halide is developed to silver so that it cannot be further dissolved and therefore cannot be diffused.

In the unexposed parts of the silver halide emulsion layer, the silver halide is converted to soluble silver complex salts, which are transferred to the image-receiving layer, where they form a silver image, usually in the presence of physical development nuclei. .

In a direct positive silver halide emulsion, the effects of silver halide in exposed and unexposed areas are reversed.

Further, treatment by heat development is also possible.

That is, by heating the photosensitive material in the presence of a reducing agent after exposure, a silver portion and a silver halide portion are generated on the image, and this silver halide reacts with a silver halide solvent, resulting in a silver image. A silver salt that is mobile at high temperatures is formed in a positive relationship with

By diffusing this mobile silver salt into an image-receiving layer that grows physical development nuclei and making the silver salt visible, an image having a negative relationship to the silver image can be obtained.

Among these, a preferred method is to heat a photosensitive material containing a photosensitive silver halide and a g3-containing silver salt at high temperature in the presence of a reducing agent and a silver halide solvent to form a mobile silver salt that has a negative relationship with respect to a silver image. This is a method of forming an image, and then diffusing this mobile silver salt into a silver salt fixed layer containing physical development nuclei under high temperature to form a silver image on this image receiving layer, which is the same as the image formed by the mobile silver salt.

In this case, the image-receiving material containing the image-receiving layer may be provided on a separate sheet from the photosensitive material containing the photosensitive layer containing silver halide, or may be provided on the same sheet with an intermediate layer or a reflective layer such as titanium oxide interposed therebetween. It may be provided on the sheet.

Further, the movement of the mobile silver salt may be carried out in the same process as the formation of the silver salt, or may be carried out by heating the photosensitive material and the image-receiving material in a stacked state after the formation of the mobile silver salt.

The photographic emulsion layer of the photographic light-sensitive material used in the present invention may contain one or more emulsions; in this case, the silver halides include silver bromide, silver iodobromide, silver chlorobromoiodide, and silver chloride. Either silver bromide or silver chloride may be used.

The average grain size of silver halide grains in a photographic emulsion (the grain diameter is used for spherical or approximately spherical grains, and the principal grain size is used for cubic grains, and expressed as an average based on the projected area) is There is no particular limitation, but it is preferably 3μ or less.

The particle size may be narrow or wide.

In addition, in order to obtain an image with particularly good sharpness and high contrast, the silver halide composition is preferably silver chlorobromide or silver chlorobromoiodide when an organic silver salt is not used in combination, and the bromide content is approximately 0.1 mol. % to about 9 mol%, preferably about 0.5 mol%
to about 5 mole percent, with 0 to about 0.2 mole percent iodide, preferably 0 to 01 mole percent, and the balance being chloride.

When an organic silver salt is used in combination, the silver halide composition is not particularly limited.

The grain size of the silver halide in this case is not particularly limited, but is preferably 0.1 to 1.5 microns, particularly 0.1 to 0.5 microns.
5μ is desirable.

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a hexagonal, or may have a spherical or hexagonal shape.
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of five times or more the grain thickness occupy 50% or more of the total projected area. The silver halide grains may have different layers inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particle.

The photographic emulsion used in the present invention is B. Grafkide (P,
Chimie et Physi Photography (GIafkides)
que・Photographique) [Published by Paul Montel, 19
1967], G.F. Duffin
in) Photographic by Emulsion Chemis
Photographic Emulsio
n Chemistry) [Published by The Focal Press, 1966], by V.L.
ikman et al) Making and Coating Photographic Emulsion (Makin
g and coating photography
cεmulsion) [The 7r-Culbreth (Th
eFocal Press, 1964. That is, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as a method of reacting the soluble root salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination of straws, etc. may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As a type of simultaneous mixing method, P in the liquid phase in which silver halide is produced is
It is also possible to use a method of keeping Ag constant, ie, the so-called Chondrold double jet method.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical annealing,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

After the emulsion is formed with a precipitate or after physical ripening, salts are usually removed from the emulsion, but the long-known maple water washing method, which involves gelatin gelatin, may be used. Inorganic salts consisting of anions, such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A sedimentation method (flocculation) may also be used.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, Bar-Friesel () 1. Fr1
Die Grundlagen de
rPhotographischenProzess
a mit Silberhalogeniden)
[Akademitsushie Verlagsgesellschaft (
Akademische Verlagsgesel
Ischaft), 1968] 675-73
The method described on page 4 can be used.

Namely, sulfur sensitization using compounds containing sulfur that react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, Reduction sensitization method using amines, dorazine derivatives, formamidine sulfinic acid, silane compounds; noble metal compounds (e.g., total complex salts, pt, I
A noble metal sensitization method using complex salts of metals of group (1) of the periodic table such as r, Pd, etc. can be used alone or in combination.

In the present invention, when a normal negative emulsion is used, a silver image that is in a positive relationship with the exposed image can be obtained, and when a direct positive emulsion is used, a silver image that is in a negative relationship with the exposed image can be obtained. be able to.

The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include
Cyanine pigment, merocyanine pigment, complex cyanine 0 element,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline nucleus, oxazole nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, hylysine nucleus, etc.: A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei; i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxadol nucleus, benzothiazole nucleus, naphthothiazole cylindrical, benzoselenium Sol nucleus, benzimidazo-2-hydrogen, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes having a ketomethylene structure include pyrazolin-5-one, thiohydantoin, 2-thioxazolidine-2,4-dione, thiazolidine-2,4-dione, Rhodanines and thiobarbyl ring can be used.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat. Nos. 2,933,390 and 3.635)
, No. 721), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like.

It is also effective to sensitize to the infrared region (700 mμ or more).

As a particularly effective sensitizing dye for the present invention, Japanese Patent Application No. 58-55
It is described in No. 694.

Ari! used in the present invention! When the salt is heated to 60° C. or higher, preferably 80° C. in the presence of photosensitive silver halide, it is reduced to silver.

There is something like this! Examples of IU silver salts include the following.

It is a silver salt of an organic compound having a carboxyl group, and representative examples include silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids.

Examples of aliphatic carboxylic acids are silver salts of behenic acid, silver salts of stearic acid, and silver salts of oleic acid.

Silver salt of lauric acid, silver salt of capric acid, silver salt of myristic acid, silver salt of palmitic acid, silver salt of maleic acid, silver salt of fumaric acid, silver salt of tartaric acid, silver salt of furoic acid, silver salt of linoleic acid. Examples include silver salts, silver salts of oleic acid, silver salts of adipic acid, silver salts of sebacic acid, silver salts of succinic acid, silver salts of acetic acid, silver salts of butyric acid, and silver salts of camphoric acid. Also effective are these silver salts which have been converted to rt with a halogen atom or a hydroxyl group.

Silver salts of aromatic carboxylic acids and other carboxyl group-containing compounds include silver salts of benzoic acid, silver salts of 3,5-dihydroxybenzoic acid, silver salts of 0-methylbenzoic acid, m-
Silver salt of methylbenzoic acid, silver salt of p-methylbenzoic acid, 2
．． Silver salts of substituted benzoic acids such as silver salts of 4-dichlorobenzoic acid, silver salts of acetamidobenzoic acid, silver salts of p-phenylbenzoic acid, silver salts of gallic acid, silver salts of tannic acid, silver salts of phthalic acid. , silver salt of terephthalic acid, silver salt of salicylic acid, silver salt of phenylacetic acid, silver salt of pyromellitic acid, 3-carboxymethyl-4-methyl-4- as described in U.S. Pat. No. 3,785,830. Examples include silver salts of thiazoline-2-thione, and silver salts of aliphatic carboxylic acids containing thioether groups as described in U.S. Pat. No. 3,330,663.

In addition, there are compounds having a mercapto group or a thione group, and normal salts of derivatives thereof.

For example, silver salt of 3-mercapto-4-phenyl-1,2,4-triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2-mercaptobenzthiazole, 2-(
s-ethyl glycolamide) benzthiazole silver,
salts of dithiocarboxylic acids such as silver salts of thioglycolic acid and silver salts of dithioacetic acid described in JP-A-48-28221, such as S-alkyl (alkyl group having 12 to 22 carbon atoms) silver thioglycolate. silver salt, thioamide silver salt, 5-carboxy-1-methyl-2-phenyl-4-thiopyridine silver salt, mercaptotriazine silver salt, 2-mercaptobenzoxazole silver salt, mercaptooxadiazole SH salt, Silver salts described in U.S. Pat. No. 4,123,274, such as the 1,2,4-mercaptotriazole derivative 3-amino-5-pendylthio 1.2
．． Silver salt of 4-1-lyazole, U.S. Pat. No. 3.301,
3-(2carboxyethyl)-4 described in specification No. 678
-A silver salt of a thione compound such as a silver salt of -methyl-4-thiazoline-2thione.

In addition, there are SF4 salts of compounds having imino groups.

For example, Special Publication No. 44-30270, No. 45-1841
Silver salts of benzotriazole and its derivatives described in Publication No. 6, such as silver salts of benzotriazole, silver salts of alkyl-substituted benzotriazoles such as silver salts of methylbenzotriazole, and silver salts of 5-chlorobenzotriazole, which are halogen-substituted. Silver salts of benzotriazole, iH salts such as 4-hydroxyhencytriazole and 5-nitrohencytriazole, silver salts of carboimidohencytriazole such as butylcarboimidobenzotriazole, as described in U.S. Pat. No. 4,220,709 1.2. Silver salt of 4-triazole or 1-H-tetrazole, silver salt of carbazole, jl of saccharin? There are silver salts of imidazole and imidazole m4.

Also useful are the thermally decomposable silver salts described in JP-A-60-113235 and the acetylene silver compounds described in Japanese Patent Application No. 60-90089.

In the present invention, the total coating amount of photosensitive silver halide and organic silver oxidizing agent is 50 mg to 10 g in terms of silver.
/m' is appropriate.

As the reducing agent used in the present invention, US Pat.
No. 1.286 describes a p-phenylene type color developer represented by N,N-diethyl-3-methyl-p-phenyl diamine. Additional useful reducing agents include aminophenols, which are described in US Pat. No. 3,761,270. Particularly useful aminophenol reducing agents include 4-amino-2,6-dichlorophenol, 4-amino-2,6-dibromophenol, and 4-amino-2,6-dichlorophenol.
Amino-2-methylphenol sulfate, 4-amino-3-methylphenol sulfate, 4-amino-
Examples include 2,6-dichlorophenol hydrochloride. Furthermore, Research Disclosure Magazine No. 151 No.
l 5 1 0"8", 'U.S. Patent No. 4,021,24
No. 0 describes 2,6-dichloro-4-substituted sulfonamidophenol, 2,6-dipromo-4-substituted sulfonamidophenol, and the like, which are useful. In addition to the phenolic reducing agents described above, naphtholic reducing agents such as 4-amino-naphthol derivatives and 4-substituted sulfonamide naphthol derivatives are also useful. Furthermore, as a commonly used color developer, U.S. Patent No. 2
．． Aminohydroxypyrazoline derivatives described in US Pat. No. 895,825, aminopyrazoline visiting conductors of U.S. Pat.
On the page (RD-19412, RD-19415),
Hydrazone derivatives have been described.

Other available reducing agents include hydroquinone, t-
Butylhydroquinone, methylhydroquinone and 2.5
- Alkyl-substituted hydroquinones such as dimethylhydroquinone, catechols, pyrogallols, halogen-substituted hydroquinones such as chlorohydroquinone and dichlorohydroquinone, alkoxy-substituted hydroquinones such as methoxyhydroquinone, and polyhydroxybenzene derivatives such as methylhydroxynaphthalene.
Furthermore, methyl gallate, ascorbic acid, ascorbine # derivatives, hydroxylamines such as N,N'-di(2-ethoxyethyl)hydroxylamine, 1-phenyl-3-pyrazolidinone, 4,4-dimethyl-1-
Phenyl-3-pyrazolidinone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidinone, 4
, 4-dimethyl-1-ρ-tolyl-3-pyrazolidinone, 4-hydroxymethyl-4-methyl-1-p-tolyl-3-pyrazolidinone, 1-P-tolyl-3-pyrazolidinone, 5.5-dimethyl-1-phenyl -3-pyrazolidinone, 4-methyl-1.5-diphenyl-3-pyrazolidinone, 5-methyl-1.5-diphenyl-3-pyrazolidinone, 4-methyl-1-phenyl-3-pyrazolidone, 5-methyl-1 -Phenyl-3-pyrazolidone, 4.4-dihydroxymethyl-1-phenyl-3-pyrazolidone, 4.4-dihydroxymethyl-1-p-tolyl-3-pyrazolidone, 1.4-diphenyl-3-pyrazolidone, 1 .5-difninyl-3-pyrazolidone,
4-methyl-4-hydroxymethyl-1-phenyl-3
-pyrazolidone, 4-hydroxymethyl-1-phenyl-3-pyrazolidone, 1-o-tolyl-3-pyrazolidone, 1-m-tolyl-3-virazolidone, 1-p-tolyl-3-pyrazolidone, 4.5- 3-pyrazolidinones such as dimethyl-1-phenyl-3-pyrazolidone, 1-p-hydroxyethylphenyl-3-biracisotone, 1,4-dimethyl-3-pyrazolidone, reductones,
Hydroxytetronic acids are useful.

Regarding the useful concentration of the reducing agent used in the present invention, it is generally about 0.01 mol to about 20 mol, preferably 0.1 mol, of the reducing agent per 1 mol of the total of organic silver salt and silver halide. ~10 moles.

In the present invention, hydroquinones and 3-pyrazolidinones are particularly preferred. Although one kind of compound selected from each of these can be used, it is preferable to use a combination of hydroquinones and 3-pyrazolidinones, for example, hydroquinone and 4-hydroxymethyl-4-methyl-1-p-). A combination of true 3-pyrazolidinone, a combination of hydroquinone and 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolinone, a combination of hydroquinone and 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidinone, or A combination of hydroquinone and 4,4-dihydroxymethyl-1-P-1-true 3-pyrazolidinone is used.

When hydroquinones and 3-pyrazolidinones are used together, the content of hydroquinones in the photographic material is about 0.06 mol to about 6.3 mol per mol of silver, preferably about 0.
The amount is 1 mol to 1.5 mol. Similarly, the content of pyrazolidinones ranges from about 0.006 mole to about 0.00 mole per mole of silver. 6
mol, preferably from about 0.02 to about 0.16 mol.

Silver halide solvents used in the present invention include sodium thiosulfate, sodium thiocyanate, ammonium thiosulfate and others described in the above-mentioned US Pat. No. 2,543,181; and cyclic imides and '? Combinations of elementary bases such as valhyrate or waracil in combination with ammonia or amines and U.S. Pat. No. 2,857,274
Combinations as described in the subsections are also included.

1,1-bissulfonyl alkanes and their derivatives are also known and can be used as halogenated kFifa agents in the present invention.

The following silver halide solvents other than those mentioned above can be used. That is, the organic thioether derivatives described in Japanese Patent Publication No. 47-11386 include 1,8-di-hydroxy-3,6-dithiaoctane, 1,10-dithia-4,
7,13,16-titraoxacyclooctadecane, 2
．． 2°-thiogentanol, 1,17-di(N-ethylcarbamyl)-6,12-dithia-9-oxaheptadecane, 3,15-dioxa-6,9,12-trithioheptanedecane, and 6,9-dioxa-3,12-dithiatetradecane-1,14-diol, etc.) and compounds of the following general formula described in JP-A-53-144319 can be used.

In the formula, X represents a sulfur atom or an oxygen atom. RO and R1 may be the same or different and each represents an aliphatic group, an aryl group, a heterocyclic residue, or an amino group.

RO and R1 may be bonded to each other to form a 5- or 6-membered heterocycle.

R2 represents an aliphatic group or an aryl group.

R1 and R2 may be combined with each other to form a 5- or 6-membered heterocycle.

The silver halide solvent only needs to be involved in the photographic system during or after development, but it may coexist with silver halide etc. from the beginning. Preferably, the solvent of item L is supplied to the photographic system by being incorporated into a separate material containing the image-receiving layer and combined with the light-sensitive material. Further, the timing of supply is preferably at the same time as or after development.

The amount of silver halide solvent used is 1/20 to 20 of the coating weight.
times (molar ratio), preferably 1/10 to 10 times (molar ratio)
It is.

Generally, the photosensitive layer (I) and the image-receiving layer (n) may be formed on the same support, or may be formed on separate supports to form a photosensitive material and an image-receiving material. Image receiving layer (n
) and the photosensitive layer (1) can also be peeled off. For example, after imagewise exposure, the photosensitive material can be developed by uniform heat development or by using a processing solution, and then the image-receiving layer (II) or the photosensitive layer can be peeled off. In addition, when a photosensitive material in which the photosensitive layer (1) is coated on a support and an image-receiving material in which the image-receiving layer (II) is coated on the support are formed separately, the photosensitive material is imagewise exposed. After uniform heating or development with a processing solution, the image-receiving material can be stacked to transfer the mobile silver salt to the image-receiving layer (11). There is also a method in which only the photosensitive material (I) is imagewise exposed, and then the received image F' (II) is superimposed and developed.

The image receiving layer (If) may include a white reflective layer.
For example, a layer of titanium dioxide dispersed in gelatin can be provided on a layer containing physical development nuclei on a transparent support.
The titanium dioxide layer forms a white opaque layer, and a reflective silver image can be obtained by viewing the transferred silver image from the transparent support side.

A conventional method such as using a pressure roller can be used to bring the photosensitive material and the image-receiving material into close contact with each other, but heating can also be used at the time of the close contact to ensure sufficient contact.

Physical development nuclei are used in the mobile silver salt image-receiving layer and are contained in a water-soluble binder.

Hydrophilic binders are typically transparent or translucent hydrophilic colloids, such as gelatin, gelatin conductors, cellulose conductors, proteins: lees! Minutes, gum arabic, dextrin, pullulan, etc. ff1
Included are natural substances such as lI, synthetic polymeric substances such as polyvinyl alcohol, polyvinylpyrrolidone, water-soluble polyvinyl compounds such as acrylamide polymers, and the like. Other synthetic polymeric compounds include dispersed vinyl compounds which increase the soot stability of photographic materials, especially in latex form.

Particularly effective is regenerated cellulose.

To create such an image-receiving layer, cellulose ester,
For example, cellulose diacetate is impregnated with physical development nuclei by vapor deposition, then coated on a support and then hydrolyzed with alkaline, or in situ by reacting silver nitrate with sodium sulfide in a cellulose ester solution. A method in which physical development nuclei are prepared, coated on a support, and then alkali hydrolyzed; a cellulose ester layer coated on a tempered support is hydrolyzed with alkali, and at the same time physical development nuclei are placed in the hydrolyzed layer. embedding method, and method of creating regenerated cellulose by alkaline hydrolysis of the cellulose ester layer and then reacting, for example, chlorofL acid with a reducing agent in the hydrolyzed layer to create physical development nuclei. can be used.

In the present invention, the image-receiving layer contains physical development nuclei, and the physical development nuclei reduce the diffused mobile silver salt to silver, which is then fixed to the fixed layer.

Although the image-receiving layer used in the present invention necessarily contains physical development nuclei,
It usually also contains hydrophilic colloid substances, as well as whitening agents such as optical brighteners, stain inhibitors such as boric acid,
Contains coating surfactant, hardening agent, etc.

Physical development nuclei include heavy metals such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, and copper;
All conventionally known physical development nuclei can be used, such as noble metals such as palladium, platinum, silver, and gold, or sulfides, selenides, and tellurides of these heavy metals. These physically developable nuclear materials can be prepared by reducing the corresponding metal ions to form metal colloidal dispersions or by mixing full-pressure ionic solutions with soluble sulfide, selenide or deluride solutions to form water-insoluble ions. metal sulfides,
It is obtained by making a colloidal dispersion of metal selenide or metal telluride.

Regarding the function of physical development nuclei in the silver transfer method, for example, Etwin, H., and Rand et al., 1956 1
No. 2,774,667, published February 18th. To create a receiver element that gives a high contrast image, these physical development nuclei are deposited on the receiver layer.
Usually 10-6 to 10-1 g/m', preferably 10
Contain 1 to 10-2 g/go.

The amount of the above-mentioned compound used as a color toning agent varies depending on the type of compound, but if it is too small, the color tone of the silver transferred image will be reddish-black, and if it is too large, it will become a candy color or the overall optical density will decrease. Usually about 10-9 to 10-
3 mol/♂, preferably 10-7 to 10-4 mol/♂.

The image receiving material also contains a silver halide solvent such as sodium thiosulfate.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, and urethane. It may also include derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidone terms, and the like.

The photographic material produced according to the present invention may contain a water-soluble dye in the photographic emulsion layer or other hydrophilic colloid layer as a filter dye, to prevent irradiation, or for various other purposes. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.

Among them, merocyanine dyes such as oxonol dyes and hemioxonol dyes are useful. The dye may be mordanted after specification with a cationic polymer such as dialkylaminoalkyl acrylate.

In the photosensitive material produced using the present invention, if the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc.
They may be mordanted with cationic polymers and the like.

The photographic light-sensitive material and image-receiving material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other binder layers. For example, chromium salts (chromium alum,
chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1, 3,5-
triacryloyl-hexahydro-s-triazine, 1
．． 3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-
5-triazine), mucohalogen acids (mucochloric acid, mucophenoquine chloride), etc. can be used alone or in combination.

Preferred embodiments used in the present invention will be explained in detail below.

A light-sensitive material for silver salt diffusion transfer is composed of at least one silver halide emulsion layer provided on a support, and generally contains 0.5 to 3.5 g/r of silver halide in terms of silver nitrate.
It is applied in the range n'. In addition to this silver halide emulsion layer, auxiliary layers such as an undercoat layer, an intermediate layer, a protective layer, and a peeling layer are provided as necessary. For example, the photosensitive materials used in the present invention include Japanese Patent Publication Nos. 3'8-18134 and 3B-18
135, etc., such as methyl cellulose, sodium salt of carboxymethyl cellulose, sodium alginate, etc., can be used as a coating layer for the silver halide emulsion layer to ensure uniform transfer. The 'tr layer is such that it does not substantially prevent or suppress diffusion. Silver halide emulsion layers in light-sensitive materials and image-receiving layers in image-receiving materials often contain hydrophilic colloid substances such as gelatin, gelatin m4 such as phthalated gelatin, carboxymethyl cellulose, and hydroxymethyl cellulose. It contains one or more types of hydrophilic polymer colloidal substances such as cellulose TA 4, dextrin, soluble starch, polyvinyl alcohol, and polystyrene sulfonic acid.

In general, the photosensitive material of the present invention contains at least one basic metal compound that is sparingly soluble in water.

The treatment composition for silver salt diffusion transfer treatment of the present invention is p
Complex-forming compounds, such as those mentioned above, when used in the wrong form to raise H: Preservatives, such as sodium sulfite: Thickening agents, such as carboxymethylcellulose, and droxyethylcellulose dicapric acid. Agents, such as potassium bromide: Silver halide solvents, such as sodium thioate, Toning agents, such as 1-phenyl-5-mercaptotetrazole: Surfactants, such as polyoxene alkylene compounds, alkylhenzenesulfonic acids, onium compounds, developing agents. Nuclear 1 e.g. British Patent No. 1.001゜5
58 and, if necessary, a developing agent such as those described above. These compounds can be contained in the image-receiving material and/or the processing solution.

In addition, sodium carbonate, sodium bicarbonate,
It may be used in combination with an alkaline agent or pH buffer such as sodium borate, borax, potassium phosphate, or sodium hydroxide.

pH in the image forming reaction system for diffusion transfer processing of the present invention
As mentioned above, is mainly prepared using a basic metal compound that is sparingly soluble in water and a complex-forming compound, but the pH of the image forming reaction system before the present invention is applied is about 5 to 14, preferably about 7. ~13. The optimum pH of a particular diffusion transfer processing composition depends on the photographic material used, the desired image, the types of various compounds used in the processing liquid composition, etc.

In addition to the silver halide emulsion layer, the photosensitive stone used in the present invention may optionally include a coating layer, an intermediate layer, a protective layer, and a peeling layer. A Mi sublayer, such as one layer, may be provided. For example, Tokko Kokko 38-181
34, No. 38-18135, etc., such as methyl cellulose, sodium carboxymethyl cellulose sodium salt, sodium alginate, etc., are used as a coating layer of the silver halide emulsion layer to make the transfer uniform. You can also measure it.

■Specific effects of the invention According to the present invention, p
Since H is increased, a high-density, high-sensitivity silver image can be easily obtained in a short time, and an image forming method can be obtained in which processing machines and processing liquids can be easily managed.

(1) Specific Embodiments of the Invention Ten specific embodiments of the present invention will be shown and the present invention will be roughly explained in detail.

Example 1 An image-receiving layer consisting of carboxymethyl cellulose (4:1) with gelatin containing metallic palladium cores on a 110 g/rn' paper support coated on both sides with polyethylene was coated with a hydrophilic colloid on a dry weight basis. 3g/d, and Na2S 2032. Og/nf and 1-pheny)Li-5-mercaptotetrazole 5 X 10-5
An image-receiving material (A) was prepared by adding mol/rn''.An image-receiving material (B) was prepared in the same manner by adding 3.6 g of guanidine picolinate to the image-receiving layer of the image-receiving material (A).

111 and 0.25 g/m' of carbon black for antihalation on the same paper support as the image-receiving material.

1.2 g/m'' of zinc hydroxide and 0.8 g/m'' of hydroquinone with an average particle size of 0.2 μ and 4-hydroxymethyl-
4-Methyl-1-phenyl-3-byraduricinone 0.2
Seratin layer containing g/lTl' (gelatin 2.0g/m
”), and silver chlorobromide (2M bromide 2 mol %) with an average particle size of 0.3μ was placed on it at 2.0 g/m in terms of nitric acid SH.
A light-sensitive material was prepared by providing an ortho-sensitized Zawata gelatin silver chlorobromide emulsion layer.

This photosensitive material is imagewise exposed, 20 cc/m'' of water is supplied to the film surface, the image receiving surface and the coated surface of each of the above image receiving materials are superimposed and brought into close contact with each other, and after 1 minute, both materials are peeled off. With material (A), almost no image was obtained, but with image-receiving material (B), the maximum density was 2.10.
, a positive image with a minimum density of 0.35 was formed.

Example 2 A method for preparing a silver iodobromide emulsion will be described.

40 g of gelatin and 26 g of KBr were dissolved in 3000 mj2 of water, and the solution was stirred while being maintained at 50°C. Next, a solution of 34 g of silver nitrate dissolved in 200 mQ of water was added to the above solution over a period of 10 minutes, and a solution of 3.3 g of potassium iodide dissolved in 100 mQ of water was added over a period of 2 minutes. The pH of the silver iodobromide emulsion thus prepared was adjusted, and the pH was adjusted to 6.0 after precipitation and excess salt was removed.
A silver iodobromide emulsion weighing 1400 g was obtained.

Next, a method for preparing an acetylene silver emulsion will be described.

20 g of gelatin and 4.6 g of 4-acetylaminophenyl acetylene were dissolved in 10,100 O of water and 200 mL of ethanol.

This solution was kept at 40°C and stirred.

A solution prepared by dissolving 4.5 g of silver nitrate in 200 mJl of water was added to this solution over 5 minutes.

The pH of the dispersion was adjusted and excess salt was removed by settling. Thereafter, the pH was adjusted to 63, yielding 300 g of acetylene silver emulsion.

A method for preparing a dispersion of a 1-phenyl-3-pyrazolidone derivative will be described.

The 1-phenyl-3-pyrazolidone derivative with the following structure is 2
．． 5g, W blood vitality seven questions
Hexyl ester sulfonic acid so' 10.5 g, )-ricresyl phosphate 2.5 g! 30 mfi of ethyl acetate was added thereto, and the mixture was heated and dissolved at about 60° C. to form a homogeneous solution. After stirring and mixing this solution and 100 g of a 10% aqueous solution of lime-treated gelatin,
minutes 10. OOORPMk: Dispersed. This minute it
is called a dispersion of 1-phenyl-3-pyrazolidone derivative.

A 1-phenyl-3-pyrazolidone conductor photosensitive material was prepared as follows.

(a) Silver iodobromide emulsion 20g (b) Acetylene silver emulsion 40g (c) Succinic acid-2-
1% aqueous solution of sodium dithylhexyl ester sulfonate 2cc (d) 1-phenyl-3-pyrazolidone 3-conductor dispersion 40g (e) Along hydroxide surface (0.2μ; aqueous dispersion) 1. (a) of sg or more
(e) was mixed and the solution heated and dissolved was placed on a polyethylene terephthalate film with a thickness of 180 μm to a wet film thickness of BO.
It was applied so that it was μ.

Furthermore, as a protective layer, a mixture of (a) 30 g of a 10% aqueous gelatin solution, (b) 10 cc of a 1% aqueous solution of sodium succinate-2-ethyl-hexyl ester sulfonate, and (c) 60 cc of water was added on top of the photosensitive emulsion. A photosensitive material N-1 was prepared by applying the photosensitive material to a wet film thickness of 40 μm.

Photosensitive material N-1 was imagewise exposed using the image-receiving material of Example 1) 4 (8), and the film surface was exposed to 20 cc/r.
Supply n' water and overlap the coated ITi surfaces and join them.9
It was heated for 25 seconds in a heat block L at 0°C.

When peeled off immediately after heating, a dark brown positive image was ``formed'' on the image-receiving material. As a result of measuring this positive image with a reflective self-recording densitometer, the minimum density was 0.34. The highest concentration was 1.52.

Similarly, in Photosensitive material N-1, the acetylene silver emulsion was removed and 10 g of silver iodobromide emulsion was roughly added in an amount corresponding to the amount of silver.
I made -2.

When this was processed in the same manner as photosensitive material N-1, the minimum density was 0.30. A maximum concentration of 0.98 was obtained.

Photosensitive material N-3 was prepared in exactly the same manner as photosensitive material N-1 except that zinc hydroxide was roughly removed from photosensitive material N-1. Using the image receiving material (A) of Example 1, I'f
When processed in the same manner as 1, the maximum i”x c4ffl 0,
21, fjt istone concentration of 0.45 was obtained.

From the above results, 1. the image forming method of the present invention is simple and
It can be seen that four images can be obtained in a short period of time.

Claims (1)

[Claims] In an image forming method in which a photographic material having a photosensitive silver halide photosensitive material and an image receiving material containing physical development nuclei is subjected to silver salt diffusion transfer treatment in the presence of a reducing agent and a silver halide solvent, water is not used during this treatment. Image formation characterized by raising the pH by a reaction between a basic metal compound that is sparingly soluble in water and a compound that can undergo a complex formation reaction with water as a medium and the metal ions constituting the basic metal compound that is sparingly soluble in water. Method.