JPH02132439A - Image forming method - Google Patents

Abstract

PURPOSE:To form images which are heightened in the max. density and are lowered in the min. density and are free from unequal densities by subjecting a photosensitive material which is specific in dry film thickness and saturated swelling film thickness to a heat development at a prescribed temp. CONSTITUTION:The heat developable color photosensitive material is the photosensitive material made into the multilayered constitution contg. photosensitive silver halides, reducing agents, and reducible color donative compds. (A), etc. Total dry film thickness of photosensitive layer side is <=10mu and saturated swelling film thickness by water is <=20mu. After water is imparted to this photosensitive material, the material is superposed on a dye fixing material and is then subjected to the heat development at 65 to 85 deg.C, by which the positive image is formed. The compds. expressed by the formula, etc., are usable as the compds. A. In the formula, PWR denotes a group which releases (Time)t-Dye by reduction; Time denotes a group which releases Dye after released from PWR; t denotes 0, 1; Dye denotes a dye (precursor).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to an image forming method using a heat-developable color photosensitive material, and in particular to a method for forming a positive color image having a high maximum density and a low minimum density. The present invention relates to a method of forming an image that can be stably and uniformly obtained with little irradiation.

(Prior Art and Problems) Heat-developable photosensitive materials are well known in this technical field, and for information about heat-developable photosensitive materials and their processes, see, for example, 242 of ``Fundamentals of Photographic Optics'' Non-Silver Salt Photography 1 (published by Corona Publishing, 1982). Pages 255 to 255, US Pat. No. 4,500,626, etc.

Many methods have also been proposed for obtaining positive color images by heat development.

For example, US Pat. No. 4,559,290 describes the so-called DRR.
A reducing agent or its precursor is made to coexist with an oxidized compound that does not have dye-releasing ability, and the reducing agent is oxidized according to the exposure amount of silver halide by heat development, and the reducing agent that remains unoxidized is A method of releasing a diffusible dye by reduction has also been proposed.
No. 87-6199 (Vol. 12, No. 22) describes N as a compound that releases a diffusible dye by a similar mechanism.
A heat-developable color light-sensitive material is described that uses a compound that releases a diffusible dye upon reductive cleavage of a -X bond (X represents an oxygen atom, nitrogen atom, or sulfur atom).

By the way, in order to obtain a multicolor image, it is necessary to combine dye-providing compounds exhibiting different hues with silver halide emulsions having different color sensitivities, and to stack the respective layers on a support. For example, in order to obtain a wide range of colors in the chromaticity diagram using the three primary colors yellow, magenta, and cyan, it is necessary to use a photosensitive layer containing at least three sets of silver halide emulsions each having a different color sensitivity.

Furthermore, in order to suppress staining of color images as much as possible, it is necessary to consume the reducing agent by silver development in the exposed area as quickly as possible. For this reason, it is preferable to use a diffusible electron transfer agent in addition to a diffusion-resistant electron donor as a reducing agent.

However, when water is added to a light-sensitive material in which the above-mentioned reducible dye-donating compound is laminated with an electron transfer agent and an electron donor together with a silver halide emulsion, and the dye-fixing material is superimposed and developed, density unevenness occurs. It was found that it was difficult to obtain a uniform positive image.

In other words, the dye released from the reducible dye-providing compound is diffusely transferred from the light-sensitive material to the dye-fixing material to form the desired image, but in order to obtain a high-density, clear image, it must be developed at a high temperature. There was a need.

However, when developing at a high temperature, density unevenness occurs, which is thought to be caused by uneven temperature distribution or water vapor generation. When the developing temperature is lowered to solve this problem, there is a problem that the image density decreases, and it is difficult to achieve both unevenness and image density.

On the other hand, if the saturated swelling film thickness of the photosensitive material against water is lowered,
Although this is advantageous in that the above-mentioned unevenness and unevenness due to image shift are reduced, a new problem arises in that the minimum density (fogging) is deteriorated.

(Object of the Invention) The object of the present invention is to provide a sharp, uniform, positive image with a high maximum density and a low minimum density using a heat-developable color photosensitive material using a reducible dye-donating compound. It's in the method.

(Structure of the Invention) An object of the present invention is to provide a heat-developable color photosensitive material having a multilayer structure having at least a photosensitive silver halide, a binder, a reducing agent, and a reducible dye-providing compound on a support. The pre-dried thickness of the material on the side where the photosensitive layer is present is 1
This was achieved by an image forming method characterized by thermally developing a photosensitive material having a film thickness of 0μ or less and a saturated swelling film thickness of 20μ or less with water at 65 to 85°C.

In the present invention, the dry film thickness of a photosensitive material refers to the film thickness after all constituent layers of the photosensitive material coated on the side of the support where the photosensitive layer exists, such as the photosensitive layer, intermediate layer, and protective layer, are coated and dried. Refers to thickness. The dry film thickness of the above photosensitive material is preferably 3 μm.
~9μ. More preferably, it is 5μ to 8μ.

In addition, in the present invention, the saturated swelling film thickness of a photosensitive material due to water refers to the thickness of the photosensitive material after coating and drying, adding distilled water to the surface of the coating layer on the side where the photosensitive layer exists, and measuring the swelling at 35°C. This refers to the film thickness when the film thickness increases due to swelling reaches a constant level.

The above-mentioned swollen film thickness is preferably 5μ to 18μ. More preferably, it is 10μ to 17μ.

In the present invention, water is added to the photosensitive material having the above-mentioned structure, and then the material is superimposed on a dye-fixing material and then heated and processed. The treatment temperature at that time is 65-85°C. Particularly preferably, the temperature is 70 to 83°C, and the heating temperature may be within the range of the present invention except for the temperature rise at the initial stage of heating.Heating may be performed at a constant temperature, or the initial temperature may be high and the latter stage low. ,
Conversely, a combination such as a low initial temperature and a high late temperature may be used, as long as the average temperature from 1 second after the start of heating to the end of heating is within the range of the present invention.

Examples of the method for applying water to the photosensitive material include a roller coating method or a wire bar coating method as described in JP-A-59-181353, and JP-A-59-18.
A method of applying water to a photographic material using a water-absorbing member as described in No. 1354, JP-A-59-18134
A method of applying water by forming a bead between a water-repellent roller and a photographic material as described in No. 8;
Various methods can be used, such as a dip method, an extrusion method, a method in which the material is applied by ejecting it as a jet from pores, a method in which the material is applied by crushing a bod. Among these methods, the dipping method is preferred from the viewpoint of rapid water absorption.

The above-mentioned water is not limited to so-called "'pure water", but includes water in the widely customary sense. Further, it may be an aqueous solution containing a base and/or a base breaker described below, or a mixed solvent with a low boiling point solvent such as methanol, DMF, acetone, or diisobutyl ketone. Furthermore, an aqueous solution containing an image formation accelerator and a hydrophilic heat solvent described in JP-A-61147244 may also be used. Furthermore, the inclusion of a surfactant is advantageous in uniformly supplying water to the heat-developable color photosensitive material.

The amount of water used is at least 0.1 times the weight of the pre-coated film of the photosensitive material and dye fixing material, preferably 0.
．． A small amount of at least 1 times the weight of water corresponding to the maximum swelling volume of the entire coating film (particularly less than the weight of water corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film) may be sufficient. . The state of the film when it swells is unstable, and depending on the conditions, it may cause local bleeding.To avoid this, use water equivalent to the volume at maximum swelling of the total coating film thickness of the photosensitive material and dye fixing material. It is preferable that the amount is less than or equal to .

Specifically, the amount is preferably in the range of 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 dye fixing material.

The pressure conditions and method of applying pressure when overlapping the photosensitive material and the dye-fixing material and bringing them into close contact are described in Japanese Patent Application Laid-Open No. 1472-1983.
The method described in No. 44 can be applied.

As a heating means in the development and/or transfer process,
JP-A-61-147 for hot plates, irons, hot rollers, etc.
There is a method described in No. 244.

Further, there are a multistage heated roller described in Japanese Patent Application No. 62-327979, and a method of heating on the outer periphery of a heated drum described in Japanese Patent Application No. 61-139902.

Alternatively, a layer of a conductive material such as graphite, carbon black, or metal may be applied to the photosensitive material and/or the dye fixing material, and the conductive layer may be heated directly by passing an electric current through it. .

When forming a color image using the heat-developable color photosensitive material of the present invention, various steps can be combined. For example, when using a so-called two-sheet type photographic material in which a photosensitive layer and a dye fixing layer are formed on separate supports, the typical steps include (i) exposure step, heat development step, photosensitive material and dye Superimposition process of fixing materials - Transfer process - Peeling process (ii) Exposure process - Superposition process of photosensitive material and dye fixing material - Heat development/transfer process - Peeling process (iii) Exposure process - Heat development process - Solvent application process - Superposition process of photosensitive material and dye fixing material - Transfer process - Peeling process (iv) Exposure process - Solvent application process - Superposition process of photosensitive material and dye fixing material - Heat development/transfer process - The following steps can be mentioned. The peeling step may be omitted depending on the structure of the dye fixing material. The above process is a convenient classification, and when multiple steps are performed in succession, for example, when exposure and heat development are performed continuously, or when one process is performed in multiple stages, for example, 62-8
As described in No. 6123, there are cases where development at a low temperature is followed by normal heat development, and cases where the steps are not clearly separated are also included. The combination of processes to be selected depends on the base generation method, such as incorporating a thermally decomposable base precursor or generating a base by reacting compounds contained in two photographic materials in the presence of a solvent. The choice can also be made by the use of accelerators to control the speed of development transfer.

The heat-developable color light-sensitive material of the present invention has at least silver halide, a binder, a reducing agent, and a reducible dye-providing compound on a support.

The silver halide, reducing agent and reducible dye-providing compound are preferably added in the same layer, but may be added in separate layers.

In order to reproduce a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta, and cyan, compounds that release diffusible dyes of each hue of yellow, magenta, and cyan are required as reducible dye-providing compounds. These are combined with 10 silver halides having different color sensitivities to coat three types of photosensitive layers on a support to obtain a heat-developable color photosensitive material with a multilayer structure. For example, the blue-sensing layer,
A combination of three layers: a green-sensitive layer, a red-sensitive layer, a green-sensitive layer, a red-sensitive layer,
There are combinations of infrared-sensitive layers, etc. Each photosensitive layer can be arranged in various orders commonly known for color photosensitive materials. Further, each of these photosensitive layers may be divided into two or more layers as necessary.

Heat-developable color photosensitive materials consist of a protective layer, an undercoat layer, an intermediate layer,
Various auxiliary layers such as yellow filters, antihalation layers, etc. can be provided.

The reducible dye-providing compound used in the present invention is a non-diffusible compound that releases a diffusible dye when reduced, and a preferable example thereof is a compound represented by the following general formula (1). can be mentioned.

General formula (1) PWR -C-Time )t Dye formula, PWR
represents a group that releases t-Dye upon reduction.

Time represents a group that is released as (Time)t-Dye from PWR and then releases Dye through a subsequent reaction.

t represents an integer of O or 1.

Dye represents a dye or its precursor.

Examples of PWH include U.S. Patent No. 4,139,389;
After reduction as disclosed in JP-A No. 4,139,379, JP-A No. 4,564,577, JP-A-59-185333, and JP-A-57-84453, photographs are taken by an intramolecular nucleophilic substitution reaction. It may correspond to a portion containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound that releases a reagent, or may correspond to a portion containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center, or may correspond to a portion containing an electron-accepting center and an intramolecular nucleophilic substitution reaction center, 1 No. 649, Research Disclosure (1984) IV No. No. 24025 or JP-A No. 61-88257, an electron-accepting quinonoid center in a compound that eliminates a photographic reagent by an intramolecular electron transfer reaction after being reduced, and a linking of the photographic reagent with the electron-accepting quinonoid center. It may correspond to a moiety containing a carbon atom. Also, West German Patent Application Publication (OLS) No. 3,008,588, Japanese Unexamined Patent Publication No. 5
No. 6-142,530, U.S. Pat. No. 4,343,893, U.S. Pat. It may correspond to a moiety containing an aryl group and an atom (sulfur atom, carbon atom, or nitrogen atom) connecting it to a photographic reagent. It also corresponds to a moiety containing a nitro group in a nitro compound that releases a photographic reagent after electron acceptance and a carbon atom connecting it to a photographic reagent, as disclosed in U.S. Pat. No. 4,450,223. or the dieminal dinitride moiety in a dinitro compound that undergoes β-elimination as a photographic reagent after electron acceptance and the carbon linking it with the photographic reagent as described in U.S. Pat. No. 4,609,610. It may correspond to a part containing an atom.

Among the compounds included in general formula (I), European Patent 2
No. 20,746A2, Technical Report No. 87-6199, Japanese Patent Application Publication No. 62-244048, Japanese Patent Application No. 62-34953,
62-34954 etc. N-X bond (
Here, X represents either an oxygen atom, a nitrogen atom, or a sulfur atom) and an electron-withdrawing group in one molecule, SO.
-X bond (X is the same as above) and an electron-withdrawing group in one molecule, c-x' bond (X' is synonymous with X, or One S
A compound having an electron-withdrawing group (representing O2-) and an electron-withdrawing group in one molecule, P described in Japanese Patent Application No. 62-106895
-X (X is the same as above) and a compound having an electron-withdrawing group in one molecule, etc. are preferred. Especially the first N-
An X-bonded type is preferred.

Also available are those described in Japanese Patent Applications No. 62-319989 and No. 62-320771, in which the single bond is cleaved after reduction by a π bond conjugated with an electron-accepting group to release a diffusible dye.

Specific examples and usage methods of such dye-providing compounds are explained in detail in the above-mentioned patent documents, and various compounds can be used in the present invention based on this explanation.

The surface latent image type silver halide used in a preferred embodiment of the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide. .

The silver halide emulsion may be monodisperse or polydisperse, and a mixture of monodisperse emulsions may be used.

Particle size is 0.1-2 μm1 especially 0.2-1.5 μm
is preferred. The crystal habit of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular with a high aspect ratio, or any other crystal habit.

Specifically, U.S. Patent No. 4,500,626, column 50, Research Disclosure, June 1978 issue 9.
pp.-10 (RD17029), U.S. Patent No. 4,628
, No. 021, JP-A-60-196748, JP-A No. 60-1
Any of the silver halide emulsions described in No. 92937, No. 60-2585357, etc. can be used.

Although the silver halide emulsion may be used unripe, it is usually used after being chemically sensitized. For emulsions for conventional light-sensitive materials, known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, etc. can be used alone or in combination. These chemical sensitizations can also be carried out in the presence of nitrogen-containing multi-ring compounds (JP-A-58-126526, JP-A-58-21564).
No. 4).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to tog/rrr in terms of silver.

In the present invention, an organic metal salt can also be used as an oxidizing agent together with photosensitive silver halide. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the organic silver salt oxidizing agent described above include U.S. Pat.
There are penzotriazoles, fatty acids and other compounds described in columns 53 and the like. Furthermore, silver salts of carboxylic acids having an alkynyl group such as silver phenylbrobiol described in JP-A No. 60-113235, and JP-A No. 61-249044
Also useful is acetylene silver, described in No. Two or more types of organic silver salts may be used in combination.

The above organic silver salts are 0 per mole of photosensitive silver halide.
．． 0.01 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg to 10 mg in terms of silver.
g/d is appropriate.

Various antifoggants or photographic stabilizers may also be used in the present invention. An example is RD17
643 (1978) pages 24-25, nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442, or mercabut compounds and their Metal salts, acetylene compounds described in JP-A No. 62-87957, and the like are used.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and others.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holobolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, U.S. Pat.
17029 (1978), pages 12-1'3, and the like.

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 compound that does not substantially absorb visible light,
Compounds exhibiting supersensitization may be included in the emulsion (for example, U.S. Pat. No. 3,615,641, Japanese Patent Application No. 61-226)
294 etc.).

These sensitizing dyes may be added to the emulsion during or before or after chemical ripening.
It may be carried out before or after nucleation of silver halide grains according to No. 756 and No. 4,225,666. The amount added is generally about 10-8 to 10-2 mol per mol of silver halide.

A hydrophilic binder is preferably used for the constituent layers of the photosensitive material or dye fixing material.

An example of this is JP-A-62-253-159 (2
Examples include those described on pages 6) to (28).
Specifically, transparent or translucent hydrophilic binders are preferred, and include natural compounds such as proteins or cellulose derivatives such as gelatin and gelatin derivatives, and polysaccharides such as starch, gum arabic, dextran, bullulan, etc.
Examples include polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Also, the highly absorbent polymer described in JP-A No. 62-245260, i.e. -COOM or -S O
Homopolymers of vinyl monomers having s M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers with each other or with other monomers (e.g. sodium methacrylate, ammonium methacrylate, Sumitomo Chemical Co., Ltd.) Power Gel L-5H) is also used. Two or more of these binders can also be used in combination.

When using a system that performs thermal development by supplying a small amount of water, the use of the above-mentioned highly water-absorbing polymer allows rapid absorption of water. Furthermore, when a highly water-absorbing polymer is used in the dye fixing layer or its protective layer, it is possible to prevent the dye from being retransferred from the dye fixing material to another material after transfer.

In the present invention, the amount of binder applied is 20 per 1M.
The weight is preferably 10 g or less, more preferably 7 g or less.

For constituent layers (including back layers) of photosensitive materials or dye-fixing materials, various polymer latexes are used to improve film properties such as dimensional stabilization, prevention of curling, prevention of adhesion, prevention of film cracking, and prevention of pressure sensitivity. can be contained. Specifically, Japanese Patent Publication Nos. 62-245258 and 62-13664
Any of the polymer latexes described in No. 8, No. 62-110066, etc. can be used.

In particular, using a polymer latex with a low glass transition point (below 40°C) for the mordant layer can prevent cracking of the mordant layer, and using a polymer latex with a high glass transition temperature for the back layer can prevent curling. Effects can be obtained.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a reducing agent precursor which does not itself have reducing properties but exhibits reducing properties by the action of a nucleophile or heat during the development process can also be used.

Examples of reducing agents used in the present invention include U.S. Pat.
, 500', columns 49-50 of No. 626, Nos. 4 and 48 of the same.
Columns 30-31 of No. 3,914, No. 4,330,61 of the same
No. 7, No. 4,590.152, JP-A-60-140
No. 335, pages (17) to (18), 57-4024
No. 5, No. 56-138736, No. 59-178458
No. 59-5383 No. 1, No. 59182449,
No. 59-182450, No. 60-119555, No. 60-128436 to No. 60-128439, No. 60-1198540, No. 60-181742,
There are reducing agents and reducing agent precursors described in European Patent No. 220,746A2, pages 78 to 96, etc. .

Combinations of various reducing agents can also be used, such as those disclosed in US Pat. No. 3,039,869.

If a diffusion-resistant reducing agent is used, an electron transfer agent and/or an electron transfer agent may be added as necessary to facilitate electron transfer between the diffusion-resistant reducing agent and the developable silver halide. Combinations of transfer agent precursors can be used and are a preferred embodiment of the present invention.

In this way, by using an electron transfer agent and/or an electron transfer agent precursor, the pH of the photosensitive layer can be adjusted such that reaction with silver halide will hardly occur with a reducing agent alone.
The reaction with silver halide will proceed sufficiently even at high temperatures.

The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors.
It is desirable that the mobility of the electron transfer agent or its precursor is greater than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-virazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one among the above-mentioned reducing agents as long as it does not substantially migrate in the layer of the photosensitive material. Examples include hydroquinones, sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A-53-110827, and dye-donating compounds with diffusion resistance and reducing properties described below.

In the present invention, the amount of reducing agent added is 0 per mole of silver.
．． 0.001 to 20 mol, particularly preferably 0.01 to 10 mol.

Hydrophobic additives such as dye-donating compounds and diffusion-resistant reducing agents can be introduced into the layers of the light-sensitive material by known methods such as those described in US Pat. No. 2,322,027. In this case, Japanese Patent Application Laid-open No. 59-83154,
-178451, 59-178452, 59-
No. 178453, No. 59-178454, No. 59-1
No. 78455, No. 59-178457, etc., a high boiling point organic solvent may be used as necessary at a boiling point of 50°C to 16°C.
It can be used in combination with a low boiling point organic solvent of 0°C.

The amount of high-boiling organic solvent is 1 g of the dye-donating compound used.
is less than Log, preferably less than 5 g. In addition, less than 1 uncle per 1g of binder, and even 0,5
m5! Below, 0.3- or less is particularly suitable.

Dispersion methods using polymers described in Japanese Patent Publication No. 51-39853 and Japanese Patent Application Laid-Open No. 51-59943 can also be used.

In the case of a compound that is substantially insoluble in water, it can be dispersed and contained in the form of fine particles in the binder in addition to the method described above.

Various surfactants can be used when dispersing hydrophobic compounds in hydrophilic colloids. For example, JP-A-5
Those listed as surfactants on pages (37) to (38) of No. 9-15763'6 can be used.

In the present invention, a compound that activates development and stabilizes images can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. Patent No. 4,
No. 500,626, columns 51-52.

In a system that forms images by diffusion transfer of dyes, as in the present invention, a dye fixing material is used together with a light-sensitive material. The dye-fixing material is in a form that is coated separately on a support separate from the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationships described in column 57 of US Pat. No. 4,500,626 can also be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include U.S. Pat. No. 4,500,626 No. 58-59
column and JP-A-61. -88256 No. (32) to (41)
Mordant described on page 62-244043, 6
Examples include those described in No. 2-244036. Also, dye-receiving polymeric compounds such as those described in US Pat. No. 4,463,079 may be used.

The dye fixing material may be provided with auxiliary layers such as a protective layer, a release layer, and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

A hardening agent can be used in the constituent layers of the light-sensitive material and the dye-fixing material. The hardening agent used is U.S. Patent No. 4,
No. 678,739, column 41, JP-A-59-116655
No. 62-245261, No. 61-18942, and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (
N,N'-ethyle', t-bis(vinylsulfonylacetamido)ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A No. 62-234157, etc.) (compounds described in ).

A high boiling point organic solvent can be used in the constituent layers of the light-sensitive material and the dye-fixing material as a plasticizer, a slippery agent, or a peelability improver between the light-sensitive material and the dye-fixing material. Specifically, JP-A No. 62-253159, page (25) and 6
There is one described in No. 2-245253.

Furthermore, various silicone oils (all silicone oils ranging from dimethyl silicone oil to modified silicone oil in which various organic groups are introduced into dimethylsiloxane) can be used for the above purpose. Examples include various modified silicone oils, especially carboxy-modified silicone oil (product name:
-22-3710) etc. are effective.

Also, Japanese Patent Application Laid-Open No. 62-215953, Japanese Patent Application No. 62-236
The silicone oil described in No. 87 is also effective.

Antifading agents may be used in the photosensitive materials and dye fixing materials. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and subiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

As ultraviolet absorbers, penzotriazole compounds (
U.S. Patent No. 3,533,794, etc.), 4-thiazolidone compounds (U.S. Patent No. 3,352,681, etc.)
, benzophenone compounds (JP-A-46-2784, etc.), and other JP-A-54-48535, JP-A-62-13
There are compounds described in No. 6641, No. 61-88256, and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

As metal complexes, US Pat. No. 4,241,155,
No. 4,245,018, columns 3 to 36, No. 4,25
No. 4,195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages (27)-(29), Japanese Patent Application No. 1983-234103, JP-A No. 62-31096, Japanese Patent Application No. 1983 There are compounds described in No.-230596 and the like.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137).

The anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be included in the dye-fixing material in advance, or may be supplied to the dye-fixing material from outside the photosensitive material. .

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

A fluorescent whitening agent may be used in the photosensitive material or dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside the photosensitive material. An example is K. Veenkataraman g r
The Chemistry of Syntheti
c Dyes J Volume V Chapter 8, JP-A-61-1437
Examples include compounds described in No. 52 and the like. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, penzoxazolyl compounds, naphthalimide compounds, birazoline compounds, carbostyryl compounds, etc. may be mentioned.

Optical brighteners can be used in combination with antifade agents.

Various surfactants can be used in constituent layers of photosensitive materials and dye fixing materials for purposes such as coating aids, improving peelability, improving slipperiness, preventing static electricity, and promoting development. Specific examples of sea surfactants are given in JP-A-62-173463 and JP-A-62-18.
It is described in No. 3457, etc.

The constituent layers of photosensitive materials and dye-fixing materials include improved slipperiness,
An organic fluoro compound may be included for the purpose of preventing static electricity and improving peelability. Representative examples of organic fluorol compounds include Japanese Patent Publication No. 57-9053, columns 8 to 17, Japanese Patent Publication No. 6
1-20944, 62-135826, etc., or hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin. Examples include compounds.

A matting agent can be used in the photosensitive material and the dye fixing material. As a matting agent, silicon dioxide, polyolefin or polymethacrylate may be used.
In addition to the compounds described on page 29 of No. 56, patent applications No. 62-110064 and No. 62-1 include penzoguanamine resin beads, polycarbonate resin beads, and AS resin beads.
There is a compound described in No. 10065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, an antifoaming agent, an antibacterial agent, a colloidal silica, and the like. Specific examples of these additives are given in JP-A-63
-88256, pages (26) to (32).

In the present invention, an image formation accelerator can be used in the light-sensitive material and/or the dye-fixing material. Image formation promoters include promoting redox reactions between silver salt oxidizing agents and reducing agents;
It has functions such as promoting reactions such as generation of dye from dye-donating substance, decomposition of dye, and release of diffusible dye, and promotion of movement of dye from the light-sensitive material layer to the dye fixing layer. The functions include bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents,
It is classified as a surfactant, a compound that interacts with silver or silver ions, etc. However, these substance groups generally have multiple functions and usually have some of the above-mentioned promoting effects. Details of these can be found in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of the base precursor' include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement, or Beckmann rearrangement. A specific example is U.S. Patent No. 4,511,493.
No. 62-65038, etc.

In a system in which thermal development and dye transfer are performed simultaneously in the presence of a small amount of water, it is preferable to include a base and/or a base precursor in the dye fixing material in order to improve the storage stability of the photosensitive material.

In addition to the above, combinations of poorly soluble metal compounds and compounds that undergo complex-forming reactions with metal ions constituting the poorly soluble metal compounds (referred to as complex-forming compounds), as described in European Patent Publication 210,660, and special Kaisho 61-232451
Compounds that generate bases by electrolysis, such as those described in this issue, can also be used as base precursors. In particular, the former method is particularly effective in the present invention. It is advantageous to add the poorly soluble metal compound and the complex-forming compound to the light-sensitive material and the dye-fixing material separately.

That is, those in which a base is produced by superposition are particularly useful in the present invention.

Various image stoppers can be used in the light-sensitive material and/or dye-fixing material in the present invention in order to always obtain a constant image despite fluctuations in processing temperature and processing time during development.

The development stopper referred to here is a compound that neutralizes the base immediately after proper development or reacts with the base to lower the base concentration in the film and stop development, or a compound that inhibits development by interacting with silver and silver salts. It is a compound that Specific examples include acid precursors that release acids when heated, electrophilic compounds that undergo a substitution reaction with a coexisting base when heated, nitrogen-containing heterocyclic compounds, mercapto compounds, and their precursors. For more details, see Japanese Patent Application Laid-Open No. 62-253159 (
It is described on pages 31) to (32).

As the support for the light-sensitive material and dye-fixing material in the present invention, those that can withstand processing temperatures are used.

Common examples include paper and synthetic polymers (films). Specifically, films made from polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polybropylene, polyimide, celluloses (for example, triacetyl cellulose), or films containing pigments such as titanium oxide, as well as polypropylene, etc. Film-processed synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast coated paper), metal, cloth, glass, etc. are used. .

These can be used alone, or can be used as a support laminated on one or both sides with a synthetic polymer such as polyethylene.

In addition, JP-A-62-2531'59
The supports described in No. (29) to (31) pages can be used.

A hydrophilic binder, alumina sol, a semiconductive metal oxide such as tin oxide, carbon black or other antistatic agent may be applied to the surface of these supports.

As shown in FIG. 1, methods for exposing and recording an image on a photosensitive material include a method in which an original image is scanned and exposed through a slit using an exposure device of an image forming apparatus such as a copying machine; Other methods include methods of directly photographing landscapes and people using a camera, methods of exposing through reversal film or negative film using a printer or enlarger, methods of transmitting image information via electrical signals to light-emitting diodes, various lasers, etc. There are methods of exposing the image by emitting light, and outputting image information to an image display device such as a CRT, liquid crystal display, electroluminescent display, or plasma display, and exposing the image directly or through an optical system.

Light sources for recording images on photosensitive materials include natural light, ``tungsten lamps, light emitting diodes, laser light sources, CRT light sources, etc. as mentioned above, such as U.S. Patent No. 4.5.00,
The light source described in column 56 of No. 626 can be used.

Further, image exposure can also be performed using a wavelength conversion element that combines a nonlinear optical material and a coherent light source such as a laser beam. Here, nonlinear optical materials are materials that can exhibit nonlinearity between the polarization and electric field that appear when a strong optical electric field such as a laser beam is applied, and include lithium niobate, potassium dihydrogen phosphate (KDP) ), lithium iodate, inorganic compounds such as BaBa04,
Urea derivatives, nitroaniline derivatives, e.g. nitroviridine-N-oxide derivatives such as 3-methyl-4-nitroviridine-N-oxide (POM), JP-A-61-
Compounds described in No. 53462 and No. 62-210432 are preferably used. As the form of the wavelength conversion element, single crystal guided waveguide type, fiber type, etc. are known, and either of them is useful.

The above-mentioned image information includes image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Nippon Television Signal Standard (NTSC), and images obtained by dividing an original image into a large number of pixels using a scanner. signal, CG, C
Image signals created using a computer such as AD can be used.

Example 1 The method for preparing silver halide emulsions will be described.

1 Halogen ■) A well-stirred gelatin aqueous solution (20 g of gelatin, 1 g of potassium bromide, and OH (Clh) ts (C
The following solution (I) and solution (I [[) were simultaneously added at the same flow rate over 30 minutes to a solution prepared by adding 0.5 g of go) and keeping the temperature at 50°C. In this way, a monodisperse silver bromide emulsion having an average grain size of 0.42 μm and adsorbing a dye was prepared.

After washing with water and desalting, add 20g of lime-treated ossein gelatin, adjust the pH to 6.4 and PAg to 8.2, and then 60°C.
Sodium thiosulfate 9■, chlorauric acid 0.01
% aqueous solution 6d, 4-hydroxy-6-methyl-1.3,
3a,7=190 μl of tetrazaindene was added and chemical sensitization was performed for 45 minutes. The yield of emulsion was 635 g.

3 Halogen ■) A well-stirred aqueous solution (2 gelatin in 730 d of water)
0 ■, potassium bromide 0.30 g, sodium chloride 6 g and the following chemical A 0.015 g were added and kept at 60.0°C), the following (1) solution and (I[) solution were added at the same time for 60 minutes. Added at equal flow rates. (1) After the addition of the solution, a methanol solution (I [[) solution] of the following sensitizing dye was added. In this way, a monodisperse cubic emulsion adsorbed with a dye having an average grain size of 0.45 μm was prepared.

After washing with water and desalting, add 20g of gelatin and adjust the pH to 6.4.
After adjusting PAg to 7.8, chemical sensitization was performed at 60.0°C. The chemical used at this time was triethylthiourea 1
．． 6■ and 4-hydroxy6-methyl-1.3.3a,7
- The aging time was 55 minutes using 100 ml of tetrazaindene. The yield of this emulsion was 635 g.

(Drug A) CH3 CI{3 dye solution 0. 14g is dissolved in 70cc of methanol.

Next, a method for preparing a dispersion of zinc hydroxide will be described.

12.5 g of zinc hydroxide with an average particle size of 0.2 μ, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 d of a 2% gelatin aqueous solution and milled using glass beads with an average particle size of 0.75 mm. The mixture was ground for 30 minutes.

Separate the glass beads to obtain a dispersion of zinc hydroxide 5
Halogen ■ A well-stirred gelatin aqueous solution (water 80 g (1 part gelatin 20 g 1 potassium bromide 3 g and [0(Clh)i
s(CHz)zS(CIlz)golf 0. 3
The following solutions (1) and (II) were added simultaneously over 30 minutes. Thereafter, the following solutions (I[[) and (IV)] were added simultaneously over a period of 20 minutes. After addition, 1% potassium iodide aqueous solution 30c
c was added, and then the following dye solution was added.

After washing with water and desalting, add 20g of lime-treated ossein gelatin.
After adjusting H to 6.2 and pAg to 8.5, sodium thiosulfate and 4-hydroxy-6-methyl-1.3.3a,
Optimal chemical sensitization was carried out by adding 7-tetrazaindene and chloroauric acid. In this way, 600 g of a monodisperse octahedral silver iodobromide emulsion with an average grain size of 0.45 μm was obtained.

Next, a method for preparing a dispersion of an electron transfer agent will be described.

10g of electron transfer agent powder with the following structure, surfactant 2 below
g was added to 100 m of a 2% gelatin aqueous solution and dispersed in a mill in the same manner as a zinc hydroxide dispersion to obtain an electron transfer agent dispersion.

Electron transfer agent surfactant CHzCOOCHtCH (CzHs) CJqNaOsS
CHCOOCHzCH(CJs)C4■q Next, a method for preparing a gelatin dispersion of a dye-providing compound will be described.

Magenta co Dye-donating substance (1) Yellow electron donor ■ Electron donor ■ Electron transfer agent precursor High boiling point solvent ■ 0.6 g of sodium sylbenzenesulfonate and 50 d of water
After stirring and mixing, use a homogenizer for 10 minutes at 100%
Dispersion was carried out at 00 rpm. This dispersion is called a gelatin dispersion of a dye-providing compound.

(Preparation method of color mixing inhibitor dispersion for intermediate layer) Electron donor ■2
3.5g, high boiling point solvent 8.5g ethyl acetate 30#t
l! In addition, the mixture was heated and melted at about 50°C to form a homogeneous solution. 100g of a 10% aqueous solution of this solution and lime-treated gelatin
After stirring and mixing 0.5 g of sodium dodecylhenzenesulfonate and 50 parts of water, the mixture was dispersed using a homogenizer at 10,000 rpm for 10 minutes. This dispersion is called a gelatin dispersion of a color mixing inhibitor for an intermediate layer.

Using the above, a photosensitive material 101 as described below was made.

Each of yellow, magenta, and cyan was added to 40 all of ethyl acetate according to the above recipe, and dissolved by heating at about 60° C. to form a uniform solution. This solution, 100 g of a 3% aqueous solution of lime-treated gelatin and Dode water-soluble polymer (1)'' Antifoggant (1) SO3K Antifoggant (2) Surfactant (1) 1 Aerosol OT Surfactant (2) 1 (2) Photosensitive materials 102 to 110 were prepared in exactly the same manner as photosensitive material 101, except that the amounts of gelatin and hardener in the first to sixth layers were changed as described below.

Surfactant (4) 9 Hardener (1) 9 1, Screw (vinyl sulfo nylacetamido)ethane Next, we will discuss how to make the dye fixing material.

A dye fixing material R-1 was prepared by coating on a paper support laminated with polyethylene according to the composition shown in the following table.

Silicone oil 1 Mordant 6 Surfactant 2 Aerosol OT CsF+7SOJCHzCOOKCsH, High boiling point organic solvent 6 Rheophos 95 (manufactured by Ajinomoto) Polymer 95 Fluorescent brightener CH, Vinyl alcohol sodium acrylate copolymer (7 5/ 2 5 mol) Matting agent 111
0 Penzoguanamine resin average particle size 10μ Tungsten light bulbs are used for the above multilayer structure color photosensitive materials 101 to 105, and the concentration is continuously changed B, G
, R, and Gray color separation filters at 4000 lux for 1/10 second.

This exposed photosensitive material was immersed in water at 35°C for 5 seconds,
Immediately thereafter, the film was superimposed on the image receiving material R-1 so that the film surfaces were in contact with each other.

The water-absorbed film was heated for 15 seconds using a heat roller whose temperature was adjusted as shown in Table 3.

Next, when it is peeled off from the image-receiving material, B, G,
Blue corresponding to R and gray color dispersion filters,
Uneven images of green, red, and gray were obtained.

Table 3 shows the results of measuring the maximum density (Dmax) and minimum density (DIIlin) of each color of cyan, magenta, and yellow in the gray part and the maximum density of cyan, magenta, and yellow in the B, G, and R parts. Shown below.

60 From the above results, the sample of the photosensitive material of the present invention, which has a dry film thickness of 10μ or less and a saturated swelling film thickness of 20μ or less, is developed at 65 to 85°C, has a high maximum density and a low minimum density. , it can be seen that an image with less density unevenness can be obtained.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Heisei drinking year l Year Chang = t'. 3B

Claims (1)

[Claims] A heat-developable color photosensitive material having a multilayer structure, which has at least a photosensitive silver halide, a binder, a reducing agent, and a reducible dye-providing compound on a support, and the entire dry film on the side of the photosensitive material where the photosensitive layer is present. A photosensitive material having a thickness of 10μ or less and a saturated swelling film thickness of 20μ or less with water is 65
An image forming method characterized by thermal development at ~85°C.