JPH1062935A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive material for photographing which enables formation of an image with good discrimination in fast and simple processes and shows excellent storage property of an image. SOLUTION: This photosensitive material contains photosensitive silver halide, color developing agent, coupler and binder on a supporting body. After the photosensitive material is exposed for an image by using a treating material, the material as laminated with the treating material is heated while water is present between these by the amt. as 0.1 to 1 time of the amt. required to swell the whole coating films of the photosensitive material and the treating material to the max. Thus, an image is formed on the photosensitive material and subjected to heat developing processes and/or additional processes after heat development to produce a complex of the part or whole silver halide and/or developed silver remaining on the photosensitive material and/or to remove these. In this method, the photosensitive material contains planer particles having the average thickness aμm and bmol% silver chloride content in the silver halide satisfying the relation of a- log(b+1)}/9<=0.07.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silver halide color photographic material for recording an image and a color image forming method using the same.

[0002]

2. Description of the Related Art Photosensitive materials utilizing silver halide have been increasingly developed in recent years, and it is now possible to easily obtain high-quality color images. For example, in a method generally called a color photograph, a photograph is taken using a color negative film, and image information recorded on the developed color negative film is optically printed on color photographic paper to obtain a color print. In recent years, this process has been highly developed, and anyone can use the color lab, which is a large-scale centralized base that produces large quantities of color prints with high efficiency, or the so-called minilab, which is a small, simple printer processor installed in stores. But you can easily enjoy color photos.

[0003] The principle of color photography that is currently widespread employs color reproduction by a subtractive color method. In a general color negative, a light-sensitive layer using a silver halide emulsion, which is a light-sensitive element provided with photosensitivity in the blue, green, and red regions, is provided on a transmission support. So-called color couplers for forming complementary colors of yellow, magenta and cyan dyes are contained in combination.
The color negative film that has been imagewise exposed by photography is developed in a color developer containing an aromatic primary amine developing agent. At this time, the exposed silver halide grains are developed or reduced by a developing agent, and respective dyes are formed by a coupling reaction between the oxidized product of the developing agent and the color coupler described above. Metallic silver (developed silver) generated by development and unreacted silver halide are removed by bleaching and fixing, respectively, to obtain a dye image. A color photographic paper, which is a color photographic material in which a photosensitive layer having a similar combination of a photosensitive wavelength region and a color hue is coated on a reflective support, is subjected to optical exposure through a color negative film after development processing, and By performing the color development, bleaching, and fixing processes described above, it is possible to obtain a color print composed of a dye image reproducing the original scene.

[0004] Although these systems are now widespread, demands for their simplicity are increasing. First, the processing bath for performing the color development, bleaching and fixing described above requires precise control of the composition and temperature, and requires specialized knowledge and skilled operations. Second, these processing solutions contain substances that must be environmentally controlled, such as color developing agents and iron chelates, which are bleaching agents. Is often required. Third, although the development process has been shortened in recent years, these development processes require a long time, and it cannot be said that it is still insufficient for a demand for quickly reproducing a recorded image.

[0005] As a system for performing simpler and faster processing, a system that does not use a color developing agent or a bleaching agent used in existing color image forming systems is constructed to reduce the environmental burden and to simplify the processing. There are also reports of techniques for improving. For example, IS &T's 48th
Annual Conference Processe
The dings page 180 shows that the dye generated in the development reaction is transferred to the mordant layer and then removed to remove developed silver and unreacted silver halide. There is disclosed a system that eliminates the need. However, the technology proposed here still requires development processing in a processing bath containing a color developing agent, and it cannot be said that the environmental problem has been solved. Fuji Photo Film Co., Ltd. has provided a pictography system as a system that does not require a processing solution containing a color developing agent. In this system, a small amount of water is supplied to a photosensitive member containing a base precursor, and the photosensitive member is bonded to an image receiving member and heated to cause a development reaction. This method is environmentally advantageous in that the above-mentioned treatment bath is not used.

The above-mentioned system is used for fixing a formed dye to a dye fixing layer on an image receiving material and viewing the dye as a dye image. When this system is used for a recording material for photography in which an image is formed on a photosensitive material,
Because undeveloped silver halide remains in the processed light-sensitive material, the developed image may be discolored or faded under normal light, or the density of the undeveloped portion may increase. Image quality is degraded. In order to prevent this, the processed photosensitive material
A method of performing stabilization treatment with a film or a solution containing a fixing agent is disclosed in JP-A-50-543429 and JP-A-1-1613.
No. 43, etc. It is also disclosed in US Pat. No. 4,012,2 that a fixing agent is used as an image stabilizer on the same support of a heat developable and heat stabilizable photographic material.
No. 60, JP-A-57-1500842 and 57-15-15
No. 4,173, and the like.

These techniques make it possible to use these compounds effectively in silver halide photographic materials to provide light-insensitive silver complexes after exposure and processing. The complex can impart photostability to a developed image contained in the processed silver halide light-sensitive material. However, these reports are still insufficient in simplicity and speed in developing and fixing processes.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a photographic material which can form an image easily, quickly and with good discrimination and has excellent image storability.

[0009]

The object of the present invention has been attained by the following (1) to (4). (1) A silver halide color photographic light-sensitive material having at least one light-sensitive layer comprising at least a light-sensitive silver halide, a color developing agent, a dye-providing coupler and a binder on a support, After imagewise exposure,
Using a processing material having a processing layer containing at least a base and / or a base precursor on a support, it is equivalent to 0.1 to 1 times the amount required for maximally swelling all coating films of both the photosensitive material and the processing material. In a state where water is present between the photosensitive material and the processing material, the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material are superimposed and heated to form an image on the photosensitive material side. And / or a silver halide color photographic light-sensitive material that forms a color image by complexing part or all of the silver halide and / or developed silver remaining in the light-sensitive material by an additional processing step after the heat development. Wherein the photosensitive layer contains an emulsion comprising tabular silver halide grains satisfying the following relational expression: Relational expression a− {log (b + 1)} / 9 ≦ 0.07 (a represents an average thickness (μm) of photosensitive silver halide grains in the photosensitive layer. B represents silver chloride content of silver halide. Rate (mol%).)

(2) When the tabular silver halide grains are 5
The silver halide color photographic light-sensitive material according to (1), wherein the silver halide grains comprise 0 mol% or more of silver chloride, and the main outer surface of the grains is constituted by a (100) plane.

(3) The tabular silver halide grains have an average equivalent circular diameter of at least 0.7 μm and an average thickness of 0.1 μm.
(1) The silver halide color photographic light-sensitive material as described in (1), wherein the thickness is from 0.01 to less than 0.07 μm.

(4) A silver halide color photographic light-sensitive material having at least one photosensitive layer comprising at least a photosensitive silver halide, a color developing agent, a dye-providing coupler and a binder on a support; Using a processing material having thereon a processing layer containing at least a base and / or a base precursor, after exposing the photosensitive material imagewise, 0.1% of the amount required to swell all coating films of both the photosensitive material and the processing material to the maximum. In a state where water equivalent to 1 to 2 times is present between the photosensitive material and the processing material, the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material are overlapped and heated to form an image on the photosensitive material side. A color for partially or entirely complexing the silver halide and / or developed silver remaining on the light-sensitive material by the heat development step and / or an additional processing step after the heat development. In the image forming method, color image forming method characterized in that it contains an emulsion photosensitive layer is composed of tabular silver halide grains the following relational expression is established.

Relational expression a− {log (b + 1)} / 9 ≦ 0.07 (a represents the average thickness (μm) of the photosensitive silver halide grains in the photosensitive layer. Represents the silver chloride content (mol%).)

[0014]

DETAILED DESCRIPTION OF THE INVENTION According to the study of the present inventors, when color image information is photoelectrically read while the information of the residual silver halide and the developed silver is left, the residual silver halide and the developed silver are used. Light scattering and printout of residual silver halide and the resulting formation of dyes cause degradation of image information. Therefore, when the obtained image information is reproduced on another recording material, reading cannot be performed unless a sufficiently strong light source is used, and there is a problem in that noise is mixed during reading and the image quality such as sharpness and granularity is deteriorated. According to the study of the present inventors, by complexing some or all of the silver halide and the developed silver remaining on the photosensitive material, the bleach-fixing method using the processing solution of the prior art, in which the processing step is complicated, is described. As described above, high image quality and improved image storability can be achieved by simple processing without removing the photosensitive material from the processing bath.

As a method of complexing a part or all of the remaining silver halide and the developed silver, a conventionally known bleach-fixing agent is used during thermal development or in an additional step after thermal development. It is possible to do. When a bleaching agent and / or a fixing agent are acted upon simultaneously with the thermal development, a small amount of water used for the thermal development rapidly forms a complex of silver halide and part or all of the developed silver. The bleaching agent and the fixing agent will be described later. When a part or all of the silver halide and the developed silver are complexed in an additional step after the thermal development, a conventionally known bleach-fixing agent is contained in the second processing material. In this case, a solvent may be added in order to rapidly form a complex of silver halide and part or all of the developed silver, and the solvent may be a small amount of water as in the heat development of the present invention. Further, a thermal solvent or an auxiliary solvent which promotes complexing of the bleach-fixing agent may be used. These will also be described later.

The silver complex formed in the heat development step or the additional step is preferably diffused toward the processing material and removed from the light-sensitive material, but a part or all of the formed silver complex is preferably light-sensitive material. Even if it remains above, it does not affect the effect of the present invention.

Further, the present inventors have studied that, in the above-mentioned complexation of residual silver halide, it is advantageous to use an emulsion composed of tabular grains having a high silver chloride content or tabular grains having a high aspect ratio. Was revealed. The following relationship was found as conditions for the grain thickness and the silver chloride content suitable for the residual silver halide complexation. a− {log (b + 1)} / 9 ≦ 0.07 The above expression is preferably a− {log (b + 1)} / 9 ≦ 0.05, and particularly preferably a− {log (b + 1)} / 9. ≦ 0.03.

In the present invention, tabular grains (hereinafter referred to as "tabular grains") are silver halide grains having two opposing parallel main planes. In the present invention, a silver halide grain composed of 50 mol% or more of silver chloride is a tabular grain whose main outer surface is a (100) plane (tabular grain A) or an average equivalent circle. The diameter is at least 0.
Tabular grains having a thickness of 7 μm and an average thickness of 0.01 to less than 0.07 μm (tabular grains B) are preferred.

First, the tabular emulsion A will be described. Tabular grains A are further tabular grains having an aspect ratio of 2 or more such that the projection surface has a rectangular shape with an aspect ratio of 1: 1 to 1: 2,
50 of the total projected area of silver halide grains contained in the emulsion
% Is preferred. Furthermore, the projected area of 7
Preferably, 0% or more satisfies the above rule.

The shape of these silver halide grains can be determined by electron microscopic observation of the silver halide grains and a reference latex sphere used as a size standard at the same time by a carbon replica method in which shadowing is performed with a heavy metal or the like. Can be measured.

The aspect ratio referred to in the present invention is a value obtained by dividing the diameter of a circle equivalent to the projected area by the grain thickness. As an example of a method of measuring the aspect ratio, there is a method of obtaining a diameter (equivalent circle equivalent diameter) and a thickness of a circle having an area equal to the projected area of each particle by photographing a transmission electron microscope photograph by a replica method. In this case, the thickness is calculated from the length of the shadow of the replica.

In the tabular grain A, the main outer surface of the grain is (1).
00) plane, the projection plane has a rectangular shape. At this time, it is preferable that the ratio of the vertical and horizontal sides of the rectangle that is the projection plane is in the range of 1: 1 to 1: 2. That is, tabular grains having a projected surface close to a square are preferable to emulsions composed of rod-like or rectangular parallelepiped grains.

The halogen composition of the tabular grains A is 50
Silver chlorobromide, silver chloroiodide, silver chloroiodobromide or silver chloride containing at least mol% is preferably used. Tabular grains A may contain silver iodide, but the silver iodide content is preferably at most 6 mol%, more preferably at most 2 mol%. It is also preferable to use a silver halide emulsion composed of grains having a laminated structure composed of a plurality of layers having different halogen compositions inside the silver halide grains. The size of the silver halide grains of the tabular grains A is preferably from 0.1 to 10 μm, more preferably from 0.3 to 5 μm, when represented by an equivalent circle equivalent diameter.
m, particularly preferably 0.5 to 4 μm. The average thickness of the silver halide grains of the tabular grains A is 0.07 to 0.3.
μm is preferable, and more preferably 0.07 to 0.25
μm, particularly preferably 0.07 to 0.2 μm.

The average grain thickness is the arithmetic average of the grain thickness of all tabular grains in the film emulsion.

A known method is used to produce tabular grains A, which are silver halide grains composed of 50 mol% or more of silver chloride and whose main outer surface is composed of (100) planes. Various methods can be used initially. For example, JP-A-5-204073, JP-A-51-8
8017, JP-A-63-24238, and Japanese Patent Application No. 5-264059 can be used arbitrarily.

The key point in preparing such tabular grains is a method of generating nuclei for tabular growth.
It is useful to add iodide ions or bromide ions at the initial stage of grain formation, or to add a compound exhibiting selective adsorption to a specific surface, as in the production method of the above-mentioned literature.

A technique for thermally developing a light-sensitive material containing silver halide grains having (100) planes whose length of one side is twice or more or 0.5 times or less the arithmetic average of the lengths of the other two sides. Is disclosed in Japanese Patent Publication No. 7-120014,
It is a technique for reducing fogging of a photosensitive material for printing using a silver bromide or silver chlorobromide emulsion at the time of thermal development, and, as is clear from the grain photograph attached to the patent specification, Since the shape of silver halide grains is a rectangular parallelepiped and has a different shape from the tabular grains defined in the present invention, it is a technique different from the present invention. A photosensitive material containing a tabular high silver chloride emulsion composed of (100) planes and a developing agent,
By performing color development by the development method defined in the present invention, it is possible to achieve excellent granularity required for a photographic material for photography while maintaining rapid developability of a high silver chloride emulsion.

Next, the tabular grains B will be described. Tabular grain B has one twin plane or two or more parallel twin planes. The twin plane refers to the (111) plane when ions at all lattice points on both sides of the (111) plane are in a mirror image relationship.

When the tabular grains are viewed from above, the tabular grains have a triangular shape, a hexagonal shape, or a rounded shape obtained by rounding them, and have outer surfaces parallel to each other.

In the silver halide emulsion of the present invention, the tabular grains B preferably occupy 100 to 50% of the total projected area, more preferably 100 to 80%, and particularly preferably 100 to 90%. If it is less than 50%, the advantages of tabular grains (improvement in sensitivity / granularity ratio and sharpness) cannot be fully utilized, which is not preferable.

The average grain thickness of such tabular grains B is preferably 0.01 to 0.07 μm,
It is more preferably 0.01 to 0.06 μm, and particularly preferably 0.01 to 0.05 μm. If the average particle thickness is less than 0.01 μm, the pressure property is undesirably deteriorated.
If the thickness exceeds 0.07 μm, the effects of the present invention are hardly obtained, which is not preferable.

The average equivalent circle diameter of the tabular grains B is preferably 0.7 to 5 μm, more preferably 1 to 4.5 μm, and particularly preferably 1 to 4 μm. If the average equivalent circle diameter is less than 0.7 μm, it is difficult to obtain the effects of the present invention, which is not preferable. If the thickness exceeds 5 μm, the pressure property deteriorates, which is not preferable.

The average equivalent circle diameter is the arithmetic mean of the equivalent circle diameters of all tabular grains in the emulsion.

Tabular grains B preferably have an average aspect ratio to all tabular grains of 10 to 100, more preferably 12 to 80, and particularly preferably 15 to 50.
It is. If the average aspect ratio is less than 10, the effect of the present invention is hardly obtained, which is not preferable. If it exceeds 100, the pressure property deteriorates, which is not preferable.

The average aspect ratio is the arithmetic average of the aspect ratios of all tabular grains in the emulsion.

Various methods can be used to form tabular grains B, which are tabular grains having a small grain thickness and a high aspect ratio, and various methods can be used. For example, US Pat.
No. 03 can be used.

The preferred emulsion for tabular grain B is a hexagonal tabular grain having a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 2 to 1 in the emulsion. It preferably occupies 100 to 50%, more preferably 100 to 70%, particularly preferably 100 to 90% of the projected area of all grains. Mixing of tabular grains other than the above hexagons is not preferred in terms of homogeneity between grains.

The emulsion of the present invention is preferably monodisperse. The variation coefficient of the circle-equivalent diameter of the projected area of all silver halide grains of the present invention is preferably 30 to 3%,
It is more preferably from 25 to 3%, particularly preferably from 20 to 3%. If it exceeds 30%, it is not preferable in terms of homogeneity between particles.

The variation coefficient of the equivalent circle diameter is a value obtained by dividing the standard deviation of the equivalent circle diameter of each silver halide grain by the average equivalent circle diameter.

As the composition of the tabular grains B, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like can be used.
It is preferable to use silver bromide, silver iodobromide, or silver chloroiodobromide.

When there is a phase containing iodide or chloride, these phases may be uniformly distributed or localized in the grains.

Other silver salts, for example, rhodan silver, silver sulfide,
Silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as part of silver halide grains.

The preferred range of the silver iodide content of the tabular grains B is 0.1 to 20 mol%, more preferably 0.1 to 20 mol%.
To 15 mol%, particularly preferably 0.2 to 10 mol%
It is. If it is less than 0.1 mol%, it is not preferable because effects such as enhancement of dye adsorption and increase in intrinsic sensitivity are hardly obtained. If it exceeds 10 mol%, the developing speed is generally slow, which is not preferable.

The variation coefficient of the intergranular silver iodide content distribution of the tabular grains B is preferably 30 to 3%, more preferably 25 to 3%, and particularly preferably 20 to 3%. The silver iodide content of each emulsion grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer.

The variation coefficient of the silver iodide content distribution is a value obtained by dividing the variation (standard deviation) of the silver iodide content of each grain by the average silver iodide content.

The tabular grains A and B of the present invention may have dislocation lines.

A dislocation line is a linear lattice defect on the slip surface of a crystal at a boundary between a region already slipped and a region not yet slipped.

Regarding the dislocation lines of the silver halide crystal,
1) C.I. R. Berry, J.M. Appl. Phys. ,
27, 636 (1956), 2) C.I. R. Berry,
D. C. Skilman, J .; Appl. Phys. ,
35, 2165 (1964), 3) J.I. F. Hamil
ton, Photo. Sci. Eng. , 11,57 (1
967), 4) T.I. Shiozawa, J .; Soc. P
hot. Sci. Jap. , 34, 16 (1971),
5) T. Shiozawa, J .; Soc. Photo. S
ci. Jap. , 35, 213 (1972), which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope.

When dislocation lines are directly observed using a transmission electron microscope, the silver halide grains taken out of the emulsion are carefully screened so as not to apply enough pressure to generate the dislocation lines. Then, observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) by an electron beam.

In this case, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, it is necessary to use a high-pressure electron microscope (200 kV or more for a thickness of 0.25 μm) to observe more clearly. Can be.

JP-A-63-220238 discloses a technique for introducing dislocation lines into silver halide grains while controlling the dislocation lines.

It has been shown that tabular grains having dislocation lines introduced therein are superior in photographic properties such as sensitivity and reciprocity law to tabular grains having no dislocation lines.

In the case of tabular grains, the position and number of dislocation lines for each grain as viewed from the direction perpendicular to the main plane can be determined from the photograph of the grain taken using an electron microscope as described above. it can.

When the tabular grains of the present invention have dislocation lines,
The position can be arbitrarily selected from, for example, a peak portion and a fringe portion of the particle, or can be selected to be introduced over the entire main plane portion, and is arbitrary, but is particularly preferably limited to the fringe portion.

The fringe portion referred to in the present invention refers to the outer periphery of tabular grains, and more specifically, in the distribution of silver iodide from the sides to the center of the tabular grains, the silver iodide-containing portion at the first point when viewed from the sides. Outside the point where the ratio exceeds or falls below the average silver iodide content of the whole grain.

When the tabular grains of the present invention have dislocation lines,
The density of dislocation lines is arbitrary, and 10 or more
It may be selected according to the case such as 0 or more, 50 or more.

The emulsions of the present invention and the photographic emulsions other than the present invention used together therewith will be described below. Specifically, U.S. Pat. Nos. 4,500,626, column 50, 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,029 (1978)
No. 17, 643 (December 1978) 22-
23 pages, No. 18,716 (November 1979) 64
8 pages, No. 307, 105 (November 1989) 86
3-865 pages, JP-A-62-253159, 64
-13,546, JP-A-2-236546, and 3
-110,555 and Grafkid, "Physics and Chemistry of Photography", published by Paul Monte (P. Glafkides, Chemie etPh)
isque Photographique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, Focal Press (GFDu
ffin, Photographic Emulsion Chemistry, Focal Pres
s, 1966), "Manufacture and coating of photographic emulsions" by Zerikman et al., Focal Press (VLZelikman et al., M.
aking and Coating Photographic Emulusion, Focal Pre
ss, 1964) and the like.

In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting for removing excess salts. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When incorporated, the particles may be uniformly introduced or may be localized inside or on the surface of the particles. Specifically, emulsions described in JP-A-2-236542, JP-A-1-116637 and JP-A-4-126629 are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, a rhodan salt, ammonia, a 4-substituted thiourea compound or a JP-B-47-11, as a silver halide solvent,
No. 386, or an organic thioether derivative described in
For example, a sulfur-containing compound described in 3-144,319 can be used.

For other conditions, see the above-mentioned "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisque Photographique, Paul Mont
el, 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chem)
istry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZelikm)
an et al., Making and Coating Photographic Emulusi
on, Focal Press, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodispersed emulsion, a simultaneous mixing method is preferably used. An inverse mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329 and JP-A-55-158, JP-A-55-142329). No. 124, U.S. Pat. No. 3,650,75
No. 7). Further, the method of stirring the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be selected in any manner according to the purpose. The preferred pH range is 2.2-7.0, more preferably 2.5-6.0.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, gold, platinum, and the like, which are known for an emulsion for a normal type light-sensitive material, are used. A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-11055).
No. 5, Japanese Patent Application No. 4-75,798). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
0,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0.
１10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver, and preferably in the range of 100 mg to 5 g / m ² .

In order to impart color sensitivity such as green sensitivity and red sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, US Patent No. 4,617,257
No., JP-A-59-180,550 and 64-13,5
No. 46, JP-A-5-45,828 and JP-A-5-45,83
No. 4 and the like. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. . Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,641, JP-A-63-23,145.
No. etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after chemical ripening, or as described in U.S. Pat. Nos. 4,183,756 and 4,225,666.
And before and after the nucleation of silver halide grains. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or one solution of a surfactant. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The additives used in such a process and the known photographic additives that can be used in the present invention are described in the above-mentioned RD.
No. 17, 643, No. 18, 716 and No. 3
07, 105, and the corresponding portions are summarized in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right column 866-868 Super color Sensitizer-page 649, right column 4. Brightener 24, page 648, right column, page 868 5. Antifoggant 24, page 25, page 649, right column, 868-870 Stabilizer 6. Light absorber, pages 25-26 Page 649, right column, page 873 Filter-page 650, left column Dye, ultraviolet ray absorber 7. Dye image stabilizer page 25, page 650, left column, page 872 8. Hardening agent page 26, page 651, left column 874-875 9. Binder Page 26 651 Left column 873-874 10. Plasticizers and lubricants Page 27 650 Right column 876 11. Coating aids, 26-27 Page 650 Right column 875-876 Surfactants 12. Statistic Click inhibitor 27 page 650, right column, 876-877, pp. 13. mat agent, pp. 878-879

As a method for developing the light-sensitive material of the present invention after exposure, there are thermal development and an activator method for developing the light-sensitive material of the present invention with an alkaline processing solution. It is also possible to form an image by developing the light-sensitive material of the present invention with a processing solution containing a developing agent / base.

Heat treatment of a photosensitive material is known in the art. For a photothermographic material and its process,
For example, the basics of photo engineering (Corona, 1970)
Pages 553-555, published April 1978, video information 4
Page 0, Nabletts Handbook of Photography and Reprogra
phy 7th Ed. (Vna Nostrand and Reinhold Company)
Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075, British Patent 1,131,10
8, No. 1,167,777, and Research Disclosure Magazine, June 1978, pp. 9-15 (RD-
17029).

Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material and development is performed using a processing solution containing no color developing agent. The processing solution in this case is characterized in that it does not contain a color developing agent contained in a normal developing solution component, and may contain other components (for example, an alkali, an auxiliary developing agent, etc.). Regarding the activator treatment, European Patent No. 545,
No. 491A1, No. 565, 165A1, and the like.

The method of developing with a processing solution containing a developing agent / base is described in RD. No. 17643, pp. 28-29, No. 1
No. 30710, left column to right column, and No. 30710
5 pages 880-881. Next, in the present invention, a processing material and a processing method used in the case of heat development processing will be described in detail.

In the light-sensitive material of the present invention, it is preferable to use a base or a base precursor for the purpose of accelerating the silver development and the dye-forming reaction. As base precursors, salts of organic acids and bases that decarboxylate by heat, intramolecular nucleophilic substitution,
There are compounds that release amines by Rossen rearrangement or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat. Nos. 4,514,493 and 4,657,848 and Known Technology No. 5 (March 22, 1991, Aztec Co., Ltd.), pp. 55-86. Have been.
Further, as described in European Patent Publication No. 210,660 and U.S. Pat. No. 4,740,445 described below, a basic metal compound which is hardly soluble in water and a metal ion constituting the basic metal compound are used. A method in which a base is generated by a combination of compounds capable of forming a complex with water (hereinafter referred to as a complex forming compound) may be used. The amount of the base or base precursor used is 0.1 to 20 g / m ² , preferably 1 to 10 g / m ² .

A heat solvent may be added to the light-sensitive material of the present invention for the purpose of promoting thermal development. Examples include U.S. Pat. Nos. 3,347,675 and 3,667,9.
Organic compounds having a polarity as described in JP-A No. 59-59 are exemplified. Specifically, amide derivatives (benzamide etc.), urea derivatives (methyl urea, ethylene urea etc.), sulfonamide derivatives (compounds described in JP-B-1-40974 and JP-B-4-13701, etc.), polyol compounds Sorbitols), and polyethylene glycols. When the thermal solvent is insoluble in water, it is preferably used as a solid dispersion. The layer to be added may be either a photosensitive layer or a non-photosensitive layer depending on the purpose. The amount of the hot solvent added is 10% of the binder of the layer to be added.
% To 500% by weight, preferably 20% to 300% by weight.
% By weight.

The heating temperature in the heat development step is about 50 ° C. to 2
A temperature of 50 ° C is suitable, but a temperature of 60 ° C to 150 ° C is preferred, and a temperature of 60 ° C to 100 ° C is more preferred.

In order to supply a base required in the heat development step, a processing material having a processing layer containing a base or a base precursor is used. Other processing materials include blocking air during heat development, preventing material from volatilizing from the photosensitive material, supplying processing materials other than base to the photosensitive material, and making photosensitive material unnecessary after development. It may have a function of removing the material inside (YF dye, AH dye, etc.) or unnecessary components generated during development. As the support and the binder for the processing material, the same materials as those for the photosensitive material can be used. A mordant may be added to the processing material for the purpose of removing the above-mentioned dye or other purposes. As the mordant, those known in the field of photography can be used.
No. 0,626, columns 58 to 59 and JP-A-61-8825.
6, pages 32 to 41, JP-A-62-244043, JP-A-62-244036, and the like. Alternatively, a dye-receiving polymer compound described in US Pat. No. 4,463,079 may be used. Further, the above-mentioned thermal solvent may be contained.

The treatment layer of the treatment material contains a base or a base precursor. The base may be either an organic base or an inorganic base, and the base precursors described above may be used. The amount of the base or base precursor used is 0.1 to 20 g / m ² , preferably 1 to 10 g / m ² .

In thermal development using the processing material, a small amount of water is used for the purpose of promoting development, promoting the transfer of the processing material, and promoting the diffusion of unnecessary substances. Specifically, it is described in U.S. Pat. Nos. 4,704,245 and 4,470,445, JP-A-61-238056, and the like. In water, inorganic alkali metal salts and organic bases, low-boiling solvents, surfactants, antifoggants, complex-forming compounds with poorly soluble metal salts,
A fungicide and a fungicide may be included. Any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photosensitive material and the processing member of the present invention, water may be used up or may be used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144,354 and JP-A-63-144,35.
Nos. 5, 62-38,460 and JP-A-3-210,5.
The device described in No. 55 or the like or water may be used. Water can be applied to the photosensitive material, the processing material, or both. The amount used is 0.1 to 1 times the amount required for maximally swelling the entire coating film (excluding the back layer) of the photosensitive material and the processing member. Preferably 0.
This is an amount corresponding to 1 to 0.5 times the amount. As a method for applying water, for example, the methods described in JP-A-62-253,159, page (5) and JP-A-63-85,544 are preferably used. In addition, the solvent can be enclosed in microcapsules, or can be used in the form of a hydrate incorporated in the photosensitive material or the processing member or both in advance.
The temperature of the water to be applied may be 30 ° C. to 60 ° C. as described in JP-A-63-85,544.

When heat development is carried out in the presence of a small amount of water, EP 210,660, US Pat. No. 4,740,
No. 445, a combination of a basic metal compound which is hardly soluble in water and a compound capable of forming a complex with a metal ion constituting the basic metal compound and water as a medium (referred to as a complex forming compound). It is effective to adopt a method of generating a base. In this case, it is desirable to add a basic metal compound that is hardly soluble in water to the light-sensitive material and to add the complex-forming compound to the processing material from the viewpoint of raw storage stability.

As a heating method in the developing step, a heating block, a plate, a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared and far infrared lamp heater, or the like is contacted. Or through a high-temperature atmosphere.
The method described in JP-A-62-253,159 and JP-A-61-147,244, page 27, can be applied to a method of superposing a photosensitive material and a processing member in such a manner that the photosensitive layer and the processing layer face each other.

For processing the photographic element of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-7
Nos. 5,247, 59-177,547, 59-1
81,353, 60-18,951, Shokai 62
-25,944, Japanese Patent Application No. 4-277,517, 4
-243,072, 4-244,693, 6-
Devices described in JP-A-164,421 and JP-A-6-164,422 are preferably used. As a commercially available device, there can be used Pictrostat 100, Pictrostat 200, Pictrostat 300, Pictrostat 330, Pictrostat 50, Pictrograph 3000, Pictograph 2000, etc., manufactured by Fuji Photo Film Co., Ltd. .

The light-sensitive material and / or processing sheet of the present invention may have a form having a conductive heating element layer as a heating means for heat development. The elements described in JP-A-61-145544 can be used as the heat-generating elements.

In the present invention, the processing material may contain a development stopper, and the development stopper may act simultaneously with the development.

The term "development terminator" as used herein means that after proper development,
It is a compound that quickly neutralizes a base or reacts with a base to reduce the base concentration in a film and stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-253,15
No. 9, pages (31) to (32).

As the bleaching agent that can be used in the processing material of the present invention, any commonly used silver bleaching agent can be used. Such bleaches are disclosed in U.S. Pat. No. 1,315,464.
And 1,946,640, and Photographic
Chemistry, vol2, chapter30, Foundation Press, Londo
n, England. These bleaches effectively oxidize and solubilize photographic silver images. Examples of useful silver bleaches include alkali metal dichromates, alkali metal ferricyanides. Preferred bleaches are those that are soluble in water and include ninhydrin, indandione, hexaketocyclohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzenesulfonic acid, 2,5-dinitrobenzoic acid. Further, there are metal organic complexes, for example, ferric salt of cyclohexyldialkylaminotetraacetic acid, ferric salt of ethylenediaminetetraacetic acid, and ferric salt of citric acid. As the fixing agent, a silver halide solvent which can be contained in a processing material (first processing material) for developing the above-mentioned photosensitive material can be used. Regarding binders, supports, and other additives that can be used for the second processing material,
The same material as the first processing material can be used. The amount of the bleaching agent to be applied should be changed according to the silver content of the light-sensitive material to be laminated, but 0.01 mol to 10 mol of the silver coating amount per unit area of the light-sensitive material / silver coating amount of the light-sensitive material. Used in the range. Preferably 0.1 to 3
Mol / mol of coated silver of photosensitive material, more preferably 0.1 to 2 mol / mol of coated silver of photosensitive material.

As the silver halide solvent, known solvents can be used. For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sulfites such as sodium sulfite and sodium hydrogen sulfite; thiocyanates such as potassium thiocyanate and ammonium thiocyanate; 8-di-3,
6-dithiaoctane, 2,2′-thiodiethanol,
6,9-dioxa-3,12-dithiatetradecane-
Thioether compounds such as 1,14-diol, uracils described in Japanese Patent Application No. 6-325350, compounds having a 5- or 6-membered imide ring such as hydantoin, and the following general formulas described in JP-A-53-144319. The compounds of I) can be used. Analytica Chemica Acta, 248, 604-614 (1991
) Are also preferred. Japanese Patent Application No. 6-206
No. 331, compounds capable of fixing and stabilizing silver halide can also be used as a silver halide solvent.

General Formula (I) N (R ¹ ) (R ² ) —C (＝ S) —X—R ^{3 In the} formula, X represents a sulfur atom or an oxygen atom. R ¹ and R ² may be the same or different and each represents an aliphatic group, an aryl group, a heterocyclic residue or an amino group.
R ³ represents an aliphatic or aryl group. R ¹ and R ² or R ² and R ³ may combine with each other to form a 5- or 6-membered heterocycle. The above-mentioned silver halide solvents may be used in combination. Among the above compounds, compounds having a 5- or 6-membered imide ring, such as sulfites, uracil and hydantoin, are particularly preferred. In particular, uracil or hydantoin is preferably added as a potassium salt since the reduction in gloss during storage of the treated member can be improved.

The total silver halide solvent content in the processing layer is from 0.01 to 100 mmol / m ² , preferably from 0.1 to 50 mmol / m ² . More preferably, it is 10 to 50 mmol / m ² . In a molar ratio of 1/20 to 20 times the amount of silver applied to the light-sensitive material, preferably 1 to 20 times.
It is / 10 to 10 times, and more preferably 1/3 to 3 times. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropylglycol, or an alkali or acidic aqueous solution, or may be added to a coating solution after dispersing solid fine particles.

The processing material may contain a physical development nucleus and a silver halide solvent, solubilize the silver halide of the photosensitive material and fix it to the processing layer simultaneously with the development. The physical development nucleus and the soluble silver salt diffused from the light-sensitive material are reduced and converted into physically developed silver, and fixed to the processing layer.
Physical development nuclei include zinc, mercury, lead, cadmium,
As a physical development nucleus such as heavy metals such as iron, chromium, nickel, tin, cobalt, copper, and ruthenium; or precious metals such as palladium, platinum, silver, and gold; or colloidal particles of chalcogen compounds such as sulfuric acid, selenium, and tellurium. All known ones can be used. These physical development nucleus substances reduce the corresponding metal ion with a reducing agent such as ascorbic acid, sodium borohydride, hydroquinone,
It is obtained by making a metal colloidal dispersion or by mixing a soluble sulfide, selenide or telluride solution to form a colloidal dispersion of a water-insoluble metal sulfide, metal selenide or metal telluride. These dispersions are preferably formed in a hydrophilic binder such as gelatin. The method of preparing colloidal silver particles is
It is described in U.S. Pat. No. 2,688,601.
If necessary, a desalting method for removing an excessive salt known in the method for preparing a silver halide emulsion may be performed. The physical development nuclei preferably have a particle size of 2 to 200 nm. These physical development nuclei are usually added to the processing layer in an amount of 10 ^{−3 to} 100 mg / m ² , preferably 10 ^−2.
To 10 mg / m ² is contained. Physical development nuclei can be separately prepared and added to a coating solution, but in a coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or gold chloride and a reducing agent are reacted. May be created. Silver, silver sulfide, palladium sulfide and the like are preferably used as physical development nuclei. When using physically developed silver transferred to the complexing agent sheet as an image, palladium sulfide,
Silver sulfide and the like are preferably used because Dmin is short and Dmax is high.

Both the first processing material and the second processing material
It can have at least one timing layer. This timing layer can temporarily delay the bleaching / fixing reaction until the reaction between the desired silver halide and the dye-providing compound or the developing agent is substantially completed. The timing layer can be made of gelatin, polyvinyl alcohol, or polyvinyl alcohol-polyvinyl acetate. This layer may also be used, for example, in U.S. Patent Nos. 4,056,394, 4,061,49.
6 and 4,229,516. When applying this timing layer, it is applied in a thickness of 5 to 50 microns, preferably 10 to 30 microns.

The additional processing steps will be described. In the present invention, as a method of bleaching / fixing the developed photosensitive material using the second processing material, an amount required for maximally swelling the entire coating film excluding the back layer of both the photosensitive material and the second processing material. Is applied to the photosensitive material or the second processing material, and then the photosensitive material and the second processing material are overlapped so that the photosensitive layer and the processing layer face each other.
Heat at a temperature of 0 ° C to 100 ° C for 5 to 60 seconds.
With respect to the amount of water, the type of water, the method of applying water, and the method of superposing the photosensitive material and the processing material, the same materials as in the first processing material can be used.

More specifically, JP-A-59-136733
No. 4,124,398, JP-A-55-2.
No. 8098, a bleaching / fixing sheet can be used.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 to 1 mol per mole of the photosensitive silver halide.
10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 0.05 to 10 g / m ^{2 in} terms of silver, preferably 0.1 to 10 g / m ² .
4 g / m ² is suitable.

As the binder for the constituent layers of the photosensitive material, hydrophilic binders are preferably used. The decree includes the above-mentioned Research Disclosure and JP-A-64-13.
No. 546, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also,
U.S. Pat. No. 4,960,681, JP-A-62-24
No. 5,260, etc., the superabsorbent polymer,
Homopolymer of a vinyl monomer having COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, Sumitomo Chemical Sumitagel L-5 manufactured by Co., Ltd.
H) is also used. These binders may be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like according to various purposes, and it is also preferable to use them in combination. In the present invention, the coating amount of the binder is preferably 1 g or more and 20 g or less per 1 m ^{2, and} more preferably 2 g or more and 10 g or less.

The coupler usable in the present invention may be a 4-equivalent coupler or a 2-equivalent coupler. Further, the diffusion-resistant group may form a polymer chain. An example of a coupler is THJames "The Theory of the Photographic Pro
cess ", 4th edition, pages 291-334, and 354-361.
Pp. JP-A-58-123533 and JP-A-58-14904.
No. 6, No. 58-149047, No. 59-11148
No. 59-124399, No. 59-174835
Nos. 59-231439 and 59-231540
No., No. 60-2950, No. 60-2951, No. 60
-14242, 60-23474, 60-66
No. 249, Japanese Patent Application No. 6-270700, and 6-3070
No. 49, No. 6-321380, and the like.

It is preferable to use the following couplers. Yellow coupler: couplers represented by formulas (I) and (II) of EP502,424A: EP513,4
No. 96A, couplers represented by formulas (1) and (2); and Japanese Patent Application No. 4-134523, a coupler represented by formula (I) of claim 1; Coupler represented by general formula D on line 55, coupler represented by general formula D in paragraph 0008 of JP-A-4-274425: coupler described in claim 1 on page 40 of EP 498,381 A1, and 4 coupler of EP 447,969 A1. Coupler represented by formula (Y) on page 4, US 4,47
Formulas (I) to (I) on lines 36 and 58 in column 7 of 6,219
A coupler represented by V). Magenta coupler: JP-A-3-39737, 6-4
No. 3611, 5-204106, JP-A-4-362
The coupler described in No. 6. Cyan coupler: JP-A-4-204843, JP-A-4
No. 43345, Japanese Patent Application No. 4-23633. Polymer coupler: JP-A-2-44345.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237 and GB 2,12.
5,570, EP 96,570, DE 3,234
No. 533 is preferred.

The light-sensitive material of the present invention may contain the following functional coupler. Couplers for correcting unnecessary absorption of coloring dyes are disclosed in EP 456,257.
The yellow colored cyan coupler described in A1;
Yellow colored magenta coupler described in P, US
Magenta colored cyan couplers described in US Pat. No. 4,833,069, US Pat. No. 4,837,136 (2), WO92
/ 11575. Colorless masking couplers of formula (A) of claim 1 of claim 1 (especially the exemplified compounds on pages 36-45). In the present invention, it is preferable to use a coupler or another compound which releases a photographically useful compound by reacting with an oxidized form of the developing agent. Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compounds: compounds represented by formulas (I) to (IV) described on page 11 of EP 378,236A1, EP43
A compound represented by the formula (I) described on page 7 of US Pat. No. 6,938A2, a compound represented by the formula (1) described in JP-A-5-307248, and a compound represented by the formula (I) described on pages 5 and 6 of EP440,195A2. , (II) and (III), a compound represented by formula (I) of claim 1 of JP-A-6-59411, a ligand-releasing compound, and a LIG described in claim 1 of US Pat. No. 4,555,478. A compound represented by -X.

In the present invention, the amount of the coupler to be used is preferably 1/100 mol to 1 mol, more preferably 1/50 mol to 1/5 mol, per mol of silver halide.

In the light-sensitive material of the present invention, it is necessary to incorporate a color developing agent capable of forming a dye by coupling an oxidant formed by silver development with the above-mentioned coupler. In this case, U.S. Pat. No. 3,531,256 discloses a p-phenylenediamine developing agent and a phenol or active methylene coupler, and U.S. Pat. No. 3,761,270 discloses a p-aminophenol developing agent and an active methylene coupler. Combinations can be used. U.S. Pat. No. 4,021,240, JP-A-60-128438 and the like.
The combination of equivalent couplers is a preferable combination because it is excellent in raw storage when incorporated in a light-sensitive material. When a color developing agent is incorporated, a precursor of the color developing agent may be used. For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599,
Research Disclosure No. 14, 850 and above
Nos. 15 and 159, Schiff base compounds, 1
Aldol compounds described in US Pat.
No. 492, JP-A-53-135628.
The urethane-based compounds described in (1) can be cited.

Further, a sulfonamide phenol-based active compound described in Japanese Patent Application No. 7-180,568, and Japanese Patent Application No. 7-492.
Combinations of a hydrazine-based drug and a coupler described in JP-A Nos. 87 and 7-63572 are also preferable for use in the light-sensitive material of the present invention.

In the present invention, it is preferable to use a compound represented by the following general formula I, II, III or IV as a developing agent. Among them, compounds of the general formula I or II are particularly preferably used.

[0100]

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[0101]

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[0102]

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[0103]

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Where R₁ ~ R_Four Is a hydrogen atom, a halogen atom
, Alkyl group, aryl group, alkylcarbonamide
Group, arylcarbonamide group, alkylsulfonamido
Group, arylsulfonamide group, alkoxy group, ant
Oxy, alkylthio, arylthio, alk
Kill carbamoyl group, aryl carbamoyl group, carb
Moyl group, alkyl sulfamoyl group, aryl sulf
Amamoyl group, sulfamoyl group, cyano group, alkyls
Ruphonyl group, arylsulfonyl group, alkoxycarbo
Nyl group, aryloxycarbonyl group, alkylcarbo
Group, an arylcarbonyl group or an acyloxy group
Represents, R_Five Represents an alkyl group, an aryl group or a heterocyclic group
Represent. Z represents a group of atoms forming a (hetero) aromatic ring;
Is a benzene ring, the Hammett constant of the substituent
The total value of (σ) is 1 or more. R ₆ Represents an alkyl group
You. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl
Represents a tertiary nitrogen atom substituted by aryl or aryl. R
₇ , R₈ Represents a hydrogen atom or a substituent;₇ , R₈ But
It may combine with each other to form a double bond or a ring. Sa
Furthermore, each of the general formulas I to IV imparts oil solubility to the molecule.
Therefore, it contains at least one ballast group having 8 or more carbon atoms.
No.

Hereinafter, these developing agents will be described in detail. The compound represented by the general formula I is a compound generically referred to as sulfonamidophenol, and is a compound known in the art. When used in the present invention, the substituents R ₁ to
It is preferable that at least one of R ₅ has a ballast group having 8 or more carbon atoms.

[0106]

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In the formula, R _{1 to} R ₄ represent a hydrogen atom, a halogen atom (for example, chloro group, bromo group), an alkyl group (for example, methyl group, ethyl group, isopropyl group, n-butyl group,
t-butyl group), aryl group (for example, phenyl group, tolyl group, xylyl group), alkylcarbonamide group (for example, acetylamino group, propionylamino group, butyroylamino group), arylcarbonamide group (for example, benzoylamino group) Alkylsulfonamide group (for example, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (for example, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (for example, methoxy group, ethoxy group, butoxy group), aryl Oxy group (for example, phenoxy group), alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group,
Tolylthio group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenyl) Carbamoyl group,
Ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, dibutylsulfamoyl group) , Piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), Sulfamoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), Xycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, propionyl group, butyroyl group), arylcarbonyl group (for example, benzoyl group) Group, alkylbenzoyl group) or acyloxy group (eg, acetyloxy group, propionyloxy group, butyroyloxy group)
Represents Among R _{1 to} R ₄ , R ₂ and R ₄ are preferably a hydrogen atom. Also, Hammett's constant σ of R _{1 to} R ₄
The sum of the p values is preferably 0 or more. R ₅ represents an alkyl group (for example, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group, stearyl group), an aryl group (for example, phenyl group, tolyl group, xylyl group,
-Methoxyphenyl group, dodecylphenyl group, chlorophenyl group, trichlorophenyl group, nitrochlorophenyl group, triisopropylphenyl group, 4-dodecyloxyphenyl group, 3,5-di- (methoxycarbonyl)
A heterocyclic group (eg, a pyridyl group).

The compound represented by the general formula II is a compound generally called carbamoylhydrazine. Both are compounds known in the art. When used in the present invention,
Those having a ballast group having 8 or more carbon atoms in R ₅ or a substituent of the ring are preferred.

[0109]

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In the formula, Z represents an atomic group forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinoxaline ring and the like are preferable. In the case of a benzene ring, examples of the substituent include an alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), a halogen atom (eg, chloro group, bromo group), and an alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group,
Ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidinecarbamoyl group, morpholinocarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkyl Sulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholinylsulfamoyl group), Arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), Amoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (eg, methoxycarbonyl group) , An ethoxycarbonyl group, a butoxycarbonyl group), an aryloxycarbonyl group (eg, a phenoxycarbonyl group), an alkylcarbonyl group (eg, an acetyl group, a propionyl group, a butyroyl group), or an arylcarbonyl group (eg, a benzoyl group, an alkylbenzoyl group) However, the sum of the Hammett constant σ values of the above substituents is preferably 1 or more.

The compound represented by the general formula III is a compound generally called carbamoylhydrazone. The compound represented by the general formula IV is a compound generically called sulfonylhydrazine. Both are compounds known in the art. When used in the present invention, at least one of R _{5 to} R ₈
One having a ballast group having at least 8 carbon atoms is preferred.

[0112]

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[0113]

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In the formula, R ₆ represents an alkyl group (for example, a methyl group or an ethyl group). X represents an oxygen atom, a sulfur atom, a selenium atom, or an alkyl- or aryl-substituted 3
Represents a tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent (Z
R ₇ and R ₈ may be bonded to each other to form a double bond or a ring. Among the compounds of the general formulas I to IV, the compounds of the formulas I and II are preferred in the present invention, particularly from the viewpoint of raw preservability.

In the above, each of R _{1 to} R ₈ includes those having a possible substituent, and examples of the substituent include those described above as the substituent for the benzene ring of Z.
Hereinafter, specific examples of the compounds represented by Formulas I to IV are shown, but the compounds of the present invention are not limited thereto.

[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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The compounds described above can be synthesized by generally known methods. The simple synthesis routes are listed below.

[0128]

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[0129]

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[0130]

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When a diffusion-resistant developing agent is used,
If necessary, an electron transfer agent and / or an electron transfer agent precursor can be used in combination to promote electron transfer between the diffusion-resistant developing agent and the developable silver halide. Particularly preferably, said US Pat.
No. 9,919 and EP-A-418,743 are used. Also, JP-A-2-230143,
As described in JP-A-2-235,044, a method of stably introducing the compound into the layer is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned developing agents or its precursors. It is desirable that the electron transfer agent or its precursor has a higher mobility than the diffusion-resistant developing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used. Further, various reducing agents can be used in the intermediate layer and the protective layer for various purposes such as preventing color mixing and improving color reproduction. Specifically, European Patent Publication Nos. 524,649 and 357,
040, JP-A-4-249,245, JP-A-2-46,
No. 450 and JP-A-63-186,240 are preferably used. In addition, Japanese Patent Publication 3-63,733
No., JP-A-1-150,135, JP-A-2-46,450
Nos. 2,64,634, 3-43,735 and EP-A-451,833 are also used.

A developing agent precursor which does not itself have a reducing property but develops a reducing property by the action of a nucleophilic reagent or heat during the development process can also be used. In addition, the following reducing agents may be incorporated in the light-sensitive material. Examples of the reducing agent used in the present invention include, for example, U.S. Pat. No. 4,500,626, columns 49 to 50, 4,839,272, and 4,33.
0,617, 4,590,152, 5,01
7,454,5,139,919;
Nos. 140,335, pp. (17)-(18), pp. 57-40, 2;
No. 45, No. 56-138, 736, No. 59-178,
No. 458, No. 59-53, 831, No. 59-182,
No. 449, No. 59-182, No. 450, No. 60-11
9,555, 60-128,436, 60-1
No. 28,439, No. 60-198,540, No. 60-
Nos. 181,742, 61-259,253, 62
-244,044, 62-131,253, 6
Nos. 2-131, 256 and 64-13, 546 (4
0) to (57), JP-A-1-120,553, and EP 220,746A2, pages 78 to 96, and the like. Also, U.S. Pat.
Combinations of various reducing agents, such as those disclosed in 039,869, can also be used. The developing agent or reducing agent may be incorporated in a processing sheet described later,
It may be built in a photosensitive material. In the present invention, the total amount of the developing agent and the reducing agent is 0.01 to 1 mol of silver.
-20 mol, particularly preferably 0.1-10 mol.

In the present invention, as a coupler, a 4-equivalent coupler and a 2-equivalent coupler can be selectively used depending on the type of the base drug. First, a 4-equivalent coupler is used for the developing agent of the general formula I. The developing agent of the general formula I is
Since the coupling site is substituted by a sulfonyl group, and the sulfonyl group is released as sulfinic acid during coupling, the leaving group on the coupler side must be released as a cation. Therefore, it reacts with a 4-equivalent coupler capable of releasing a proton as a leaving group during coupling, but does not react with a 2-equivalent coupler whose leaving group is an anion. Conversely, two equivalent couplers are used for developing agents of general formulas II and III. General formula II, III
In the developing agent (1), the coupling site is substituted by a carbamoyl group, and the hydrogen atom on the nitrogen atom is released as a proton during the coupling, so that the leaving group on the coupler side must be released as an anion. Therefore, it reacts with a 2-equivalent coupler capable of releasing an anion as a leaving group during coupling, but does not react with a 4-equivalent coupler whose leaving group is a proton. By using this combination, it is possible to prevent color smearing due to interlayer movement of the oxidized form of the developing agent. Specific examples of couplers include 4-equivalent and 2-equivalent theories of the photographic process (4th Ed. TH James, edited by Macmillan, 1977), pages 291 to 334, and 35.
Pages 4 to 361, JP-A-58-12353, 58-
No. 149046, No. 58-149047, No. 59-1
Nos. 1114, 59-124399, 59-174
No. 835, No. 59-231539, No. 59-2315
No. 40, No. 60-2951, No. 60-14242,
The details are described in JP-A-60-23474 and JP-A-60-66249, and in the above-mentioned documents and patents.

Hydrophobic additives such as couplers, developing agents, and nondiffusible reducing agents can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat.
No. 5,470, No. 4,536,466, No. 4,53
6,467, 4,587,206, 4,55
5,476, 4,599,296, 3-6
A high-boiling organic solvent as described in JP-A-2,256 or the like can be used, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the hydrophobic additive used. In addition, 1 cc or less, more preferably 0.5 cc or less, especially 0.1 cc, per 1 g of the binder.
3cc or less is appropriate. Japanese Patent Publication No. 51-39,853,
A dispersion method using a polymer described in JP-A-51-59,943 or a method of adding a fine particle dispersion described in JP-A-62-30,242 can also be used.
In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing a hydrophobic compound in a hydrophilic colloid,
Various surfactants can be used. For example, those described as the surfactants described in Research Disclosure described above, pages (37) to (38) of JP-A-59-157,636, can be used. Also, Japanese Patent Application No. 5-2043
No. 25, No. 6-19247, West German Published Patent No. 1,933
A phosphate ester type surfactant described in 2,299A can also be used.

In the present invention, a compound capable of activating development and stabilizing an image at the same time as the photosensitive material can be used in the present invention. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

In the light-sensitive material, various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer and an antihalation layer are provided between the silver halide emulsion layers and the uppermost layer, and the lowermost layer. May be provided, and various auxiliary layers such as a back layer may be provided on the side opposite to the support. Specifically, the layer structure described in the above patent, the undercoat layer described in US Pat. No. 5,051,335,
Intermediate layers having solid pigments as described in JP-A-167,838 and JP-A-61-20,943;
No. 553, No. 5-34,884, No. 2-64,634
Intermediate layer having a reducing agent or a DIR compound as described in
US Patent Nos. 5,017,454 and 5,139,91
9, an intermediate layer having an electron transfer agent as described in JP-A-2-235,044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer obtained by combining them. be able to.

As the dye which can be used in the yellow filter layer and the antihalation layer, those which are decolored or eluted during development and do not contribute to the density after processing are preferred. The fact that the dye in the yellow filter layer and the antihalation layer is erased or removed at the time of development means that the amount of the dye remaining after the processing is 1/3 or less, preferably 1 /
The dye component may be 10 or less, and the components of the dye may be eluted from the light-sensitive material or transferred into the processing material at the time of development, or may be changed to a colorless compound by reacting at the time of development.

As the dye that can be used in the light-sensitive material of the present invention, known dyes can be used. For example, a dye that dissolves in the alkali of the developing solution, or a type of dye that decolorizes by reacting with components in the developing solution, sulfite ions, the base agent, and the alkali can be used. Specifically, dyes described in European Patent Application EP 549,489A and JP-A-7-15
No. 2129, ExF2-6 dyes. Dyes dispersed in a solid as described in Japanese Patent Application No. 6-259805 can also be used. This dye can be used when the photosensitive material is developed with a processing solution, but is particularly preferable when the photosensitive material is thermally developed using a processing sheet described later. In addition, a mordant and a binder can be dyed with a dye. In this case, as the mordant and the dye, those known in the photographic field can be used.
No. 58-59, No. 500,626, and JP-A-61-88.
256, page 32 to 41, JP-A-62-244043,
Examples include mordants described in JP-A-62-244036. Further, by using a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, the mobile dye can be released with an alkali at the time of development and eluted in a processing solution or transferred and removed to a processing sheet. Specifically, U.S. Patent Nos. 4,559,290 and 4,783,369, European Patent No. 220,746A2, and Published Technical Report 87-611.
No. 9 and in paragraph Nos. 0080-0081 of Japanese Patent Application No. 6-259805.

A decolorizable leuco dye or the like can be used. Specifically, a silver halide containing a leuco dye which has been developed in advance with a developer of a metal salt of an organic acid is disclosed in JP-A-1-150132. A light-sensitive material is disclosed. Since the leuco dye and the developer complex react with heat or an alkali agent to decolor, when the light-sensitive material is subjected to thermal development in the present invention, the combination of the leuco dye and the developer is preferable. Known leuco dyes can be used, and Moriga,
Yoshida, "Dyes and Chemicals", 9, 84 pages (Chemical Products Association),
"Handbook of New Dyes", p. 242 (Maruzen, 1970), R. Garn
er “Reports on the Progress of Appl.Chem” 56, 1
P. 99 (1971), "Dyes and Chemicals", p. 19, p. 230 (Chemical Products Industry Association, 1974), "Coloring Materials" 62, 288.
Page (1989), "Dye Industry", 32, 208 and the like. As the developer, a metal salt of an organic acid is preferably used in addition to the acid clay-based developer and phenol formaldehyde resin. As metal salts of organic acids, metal salts of salicylic acids, metal salts of phenol-salicylic acid-formaldehyde resin, rhodan salts, metal salts of xanthogenates, and the like are advantageous, and zinc is particularly preferable as the metal. Among the above color developers, oil-soluble zinc salicylate is disclosed in U.S. Pat. Nos. 3,864,146 and 4,046.
No. 941 and those described in Japanese Patent Publication No. 52-1327 can be used.

The light-sensitive material of the present invention is preferably hardened with a hardener. U.S. Pat.
678,739, column 41, 4,791,042,
JP-A-59-116,655 and JP-A-62-245,26.
No. 1, No. 61-18,942, JP-A-4-218,0
No. 44 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-methylol-based hardeners (such as dimethylol urea), boric acid, metaboric acid and polymer hardeners (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the hydrophilic binder.

In the light-sensitive material, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-64-13,564 (7). Pages (9), (57)-(71) and (81)-(97), U.S. Patent No. 4,775,610,
Nos. 4,626,500 and 4,983,494, JP-A-62-174,747 and JP-A-62-239,148.
No., JP-A-1-150,135 and 2-110,55
No. 7, 2-178,650 and RD 17, 643 (1978) (24) to (25). These compounds are used in an amount of 5 × 10 ^-6 to 1 / mol silver.
× 10 ^-1 mol is preferable, and 1 × 10 ^-5 to 1 × 10
^-2 mol is preferably used.

In the light-sensitive material, various surfactants can be used for the purpose of coating aid, improvement of peelability, improvement of sliding property, prevention of static charge, acceleration of development and the like. Specific examples of the surfactant are known in the art No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, JP-A-62-17.
3,463 and 62-183,457. The photosensitive material may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, improving peelability, and the like. As a representative example of the organic fluoro compound,
No. 9053, columns 8 to 17, JP-A-61-20944
No. 62-135826 and hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin. Can be

The light-sensitive material preferably has a slip property. The content of the slip agent is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level. Usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane. And polymethylphenylsiloxane. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

In the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
_{O, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, MgO, BaO,
A particle size of at least one selected from MoO ₃ and V ₂ O ₅ having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less; Metal oxides or their composite oxides (Sb, P, B, In, S,
Fine particles of Si, C, etc.), and fine particles of a sol, a metal oxide, or a composite oxide thereof. Preferably 5 to 500 mg / m ² as the content of the sensitive material, particularly preferably from 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or the composite oxide to the binder is from 1/300 to
100/1 is preferable, and 1/100 to 1 is more preferable.
00/5.

The constitution (including the back layer) of the photosensitive material or the processing sheet includes dimensional stability, curl prevention, adhesion prevention,
Various polymer latexes can be contained for the purpose of improving film physical properties such as prevention of cracking of the film and prevention of pressure increase / decrease sensation. Specifically, JP-A Nos. 62-245258 and 62
Any of the polymer latexes described in JP-B-136648 and JP-A-62-10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow. It is preferable that 90% or more of the total number of particles be contained between 0.9 and 1.1 times the average particle size. . It is also preferable to add fine particles of 0.8 μm or less at the same time in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm),
Poly (methyl methacrylate / methacrylic acid = 9/1)
(Molar ratio) 0.3 μm)), polystyrene particles (0.2
5 μm) and colloidal silica (0.03 μm). Specifically, it is described in JP-A-61-88256 (page 29). In addition, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, and the like are disclosed in JP-A-63-274944 and JP-A-63-274954.
There is a compound described in No. In addition, the compounds described in the aforementioned Research Disclosure can be used.

In the present invention, as the support of the photosensitive material and the processing sheet, those which can withstand the processing temperature are used. In general, the Photographic Society of Japan, "Basics of Photographic Engineering-Silver Halide Photography-", published by Corona Co., Ltd. (Showa 54)
Years) Papers described on pages (223) to (240) and photographic supports such as synthetic polymers (films). Specifically, polyethylene terephthalate, polyethylene naphthalate,
Examples include polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, and celluloses (eg, triacetyl cellulose). These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, Japanese Patent Laid-Open No. 62-253,15
No. 9, pages 29-31, JP-A-1-161,236 (14)-
(17), JP-A-63-316,848, JP-A-2-2
No. 2,651, No. 3-56,955, U.S. Pat.
The support described in 001,033 or the like can be used.

Particularly when the requirements for heat resistance and curl characteristics are strict, a support for a photosensitive material is disclosed in JP-A-6-41281.
No. 6-43581, No. 6-51426, No. 6-
No. 51437, No. 6-51442, Japanese Patent Application No. 4-251
No. 845, No. 4-231825, No. 4-253545
Nos. 4-258828, 4-240122, 4-221538, 5-21625, 5-15
No. 926, 4-331919, 5-199704
And the support described in JP-A-6-13455 and JP-A-6-14666 can be preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

In order to bond the support and the light-sensitive material constituting layer, it is preferable to perform a surface treatment. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates,
Active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), epichlorohydrin resin,
Active vinyl sulfone compounds and the like can be mentioned.
SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

Further, as a support, for example, JP-A-4-14-1
No. 24645, No. 5-40321, No. 6-35092
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in Japanese Patent Application No. 5-58221 and Japanese Patent Application No. 5-106979.

The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. The magnetic particles include a ferromagnetic iron oxide such as γFe ₂ O ₂ , Co-coated γFe ₂ O ₃ , Co-coated magnetite,
Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite can be used. Co
Co-coated ferromagnetic iron oxide, such as γ-Fe ₂ O _2, is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in SBET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10 ⁴ to 3.0.
0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ⁴
２．５2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in JP-A-6-1610.
As described in No. 32, the surface thereof may be treated with a silane coupling agent or a titanium coupling agent. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, or a natural product described in JP-A-4-219569. Polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. Tg of the above resin is −40 ° C. to 300 ° C.,
The weight average molecular weight is from 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate, reaction products of these isocyanates with polyalcohols (for example, a reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and a product formed by condensation of these isocyanates. And polyisocyanates.
No. 7.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin-type mill, an annular-type mill, etc. are preferably used, as in the method described in JP-A-6-35092. JP-A-5-08828
The dispersant described in No. 3 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to
3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ³ g / m ² .
To ² g / m ² , more preferably 0.02 to 0.5 g / m ²
It is. The transmission yellow density of the magnetic recording layer is 0.01 to
0.50 is preferable, 0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. Abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. Sensitive materials having a magnetic recording layer are described in US Pat. Nos. 5,336,589, 5,250,404, 5,229,259, 5,215,874 and EP 466,130. .

The polyester support preferably used for the above-mentioned light-sensitive material having a magnetic recording layer will be further described. For details including the light-sensitive material, treatment, cartridge, and examples, see Japanese Patent Publication No. Invention Association; 1994. 3.15). Polyester is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5 as aromatic dicarboxylic acid.
-, 1,4-, and 2,7-naphthalenedicarboxylic acid,
Terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is 2,6-naphthalenedicarboxylic acid in an amount of 50 mol% to 10 mol%.
It is a polyester containing 0 mol%. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester is 50 ° C. or higher, and 9
0 ° C. or higher is preferred.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is from 0.1 hour to 1500 hours, more preferably from 0.5 hour to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web. The surface is provided with irregularities (for example,
Conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ) may be applied) to improve the surface condition. It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. In order to prevent light pumping, it is possible to achieve the object by applying a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, a film cartridge in which a photosensitive material can be loaded will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, patrone may contain various antistatic agents, such as carbon black, metal oxide particles, nonions,
Anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A-1-312537,
No. 3,12,538. Especially 25 ° C, 25
The resistance at% RH is preferably 1012Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same as the current 135 size.
It is also effective to set the diameter of a cartridge having a size of 25 mm to 22 mm or less. The volume of the patrone case is 30
cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

A cartridge that rotates the spool to feed the film may also be used. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are U
S4,834,306 and 5,226,613.

As a method for producing a print on a color paper or a photothermographic material using this color photographing material,
JP-A-5-241251, JP-A-5-19364, and JP-A-5-19364
-19363 can be used.

[0161]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Gelatin having an average molecular weight of 15,000 30.0
g, 3.4 g of sodium chloride and sulfuric acid (1N)
Put 1000 ml of distilled water containing 0 ml into the reaction vessel,
The temperature was raised to 55 ° C. To this solution, 1.7 ml of an aqueous solution of N, N'-dimethylimidazolidin-2-thione (1%) was added, and an aqueous solution containing 7.1 g of silver nitrate was added with vigorous stirring.
Aqueous solution 20 containing 00 ml and 2.41 g of sodium chloride
0 ml was added over 24 minutes. Then, silver nitrate 162.
500 ml of an aqueous solution containing 8 g and 59.8 sodium chloride
500 ml of an aqueous solution containing 8 g was added over 80 minutes while accelerating the addition flow rate. Sixty minutes after the start of addition of these reaction solutions, 0.04 mg of potassium hexachloroiridate was added. 5 after completion of addition of reaction solution
After maintaining at 55 ° C. for minutes, the temperature was lowered and desalting was carried out according to a conventional method. The obtained emulsion was an emulsion composed of cubic grains having an average grain size of 0.69 μm expressed by a diameter equivalent to a sphere. This emulsion was designated as emulsion A-1. Emulsions A-2 and A-3 were prepared and used in Example 2 in exactly the same manner as Emulsion A-1, except that the temperature of the reaction vessel was 45 ° C. and 40 ° C., respectively. The average grain size of the obtained emulsion was 0.51 μm and 0.38 μm, respectively.

Next, 1000 ml of distilled water containing 21.2 g of gelatin, 0.85 g of sodium chloride and 3.8 ml of sulfuric acid (1N) was placed in a reaction vessel, and the temperature was raised to 40 ° C.
To this solution, 30 ml of an aqueous solution containing 6.1 g of silver nitrate and 30 ml of an aqueous solution containing 2.00 g of sodium chloride and 0.21 g of potassium bromide were added over 45 seconds with vigorous stirring. Next, an aqueous solution 4 containing 0.55 g of potassium bromide
0 ml was added. Further, 100 ml of an aqueous solution containing 18.3 g of silver nitrate and 100 ml of an aqueous solution containing 6.30 g of sodium chloride were added over 3 minutes. 6.0 ml of sodium hydroxide (1N) was added, and the temperature of the reaction solution was increased to 75 ° C.
Was raised. 10.0 g of gelatin in 100 ml of distilled water
And an aqueous solution 75 containing 145.4 g of silver nitrate.
0 ml and a 7.0% aqueous solution of sodium chloride were added over 45 minutes while accelerating the addition flow rate and adjusting the silver potential of the reaction solution to 120 mV with respect to the saturated calomel electrode. After adding 0.04 mg of potassium hexachloroiridate and keeping the mixture at 75 ° C. for 30 minutes, the temperature was lowered and desalting was performed according to a conventional method. The resulting emulsion had a silver bromide content of 0.1.
The projection surface is composed of 64% silver chlorobromide, has an average grain size of 0.69 μm expressed as a sphere-equivalent diameter, a ratio of a circle diameter equivalent to an average grain projected area divided by an average grain thickness of 7.1, and a projection surface. Was an emulsion consisting of rectangular tabular grains having an average aspect ratio of 1: 1.25. This emulsion was designated as emulsion B-1. The molecular weight of gelatin used at the beginning of the reaction and the amount of gelatin were adjusted so that the sphere-equivalent average particle size was 0.51 each.
Emulsions B-2 and B-3 of μm and 0.33 μm were prepared and used in Example 2.

Next, gelatin having an average molecular weight of 15,000 was added.
930 distilled water containing 74 g and 0.7 g of potassium bromide
ml was placed in a reaction vessel and heated to 40 ° C. 30 m of an aqueous solution containing 1.2 g of silver nitrate while vigorously stirring this solution
1 and 30 ml of an aqueous solution containing 0.82 g of potassium bromide were added over 30 seconds. After maintaining the temperature at 40 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was raised to 75 ° C. Gelatin 2
After adding 7.0 g together with 200 ml of distilled water, silver nitrate 2
14. 100 ml of an aqueous solution containing 2.5 g and potassium bromide
80 ml of an aqueous solution containing 43 g was added over 11 minutes while accelerating the addition flow rate. Then 75.1 silver nitrate
g of an aqueous solution containing potassium iodide at a molar ratio of 3:97 to potassium bromide (concentration of potassium bromide: 26%), and the silver potential of the reaction solution was saturated calomel. It was applied for 20 minutes so as to be 2 mV with respect to the electrode. Further, 75 ml of an aqueous solution containing 18.7 g of silver nitrate and 21.9% aqueous solution of potassium bromide were mixed with 3
It was added over a period of minutes so that the silver potential of the reaction solution was 0 mV with respect to the saturated calomel electrode. After completion of addition 1
After maintaining at 73 ° C. for minutes, the temperature of the reaction solution was lowered to 55 ° C. Next, 120 ml of an aqueous solution containing 8.1 g of silver nitrate
And 320 ml of an aqueous solution containing 7.26 g of potassium iodide were added over 5 minutes. After completion of the addition, 5.5 g of potassium bromide and 0.04 m of potassium hexachloride iridate
g, and kept at 55 ° C. for 1 minute.
180 ml of an aqueous solution containing 4.3 g and potassium bromide
160 ml of an aqueous solution containing 0 g were added over 10 minutes. The temperature was lowered and desalting was performed according to a standard method. The resulting emulsion had an average particle size of 0.6 expressed as a sphere-equivalent diameter.
6 μm, the ratio of the average particle diameter divided by the average particle thickness being 6.
This emulsion was composed of 2 hexagonal tabular grains. This emulsion was designated as emulsion C-1. Emulsion C-1 was prepared by changing the initial amount of gelatin and the amount of potassium bromide to prepare grains having a circle diameter equivalent to the projected area of 0.93 μm and 0.76 μm. -3. Emulsions C-2 and C-3 are used in Example 2.

Next, sulfuric acid was added to 1000 cc of an aqueous solution containing 0.5 g of oxidized gelatin and 0.37 g of potassium bromide, and the mixture was adjusted to pH = 2 and stirred while maintaining the temperature at 40 ° C.
20cc of 0.3M AgNO ₃ aqueous solution and 20cc of 0.3M potassium bromide aqueous solution were
For 2 seconds. Then, the pH was adjusted to 5.0 by adding NaOH, the temperature was raised to 75 ° C. in 35 minutes, 35 g of oxidized gelatin was added, and 512 cc of a 1.2 M aqueous AgNO 3 solution and 440 cc of a 1.4 M aqueous potassium bromide solution were added.
Was added for 33 minutes while maintaining the pAg at 8.58 and accelerating the flow rate (the flow rate at the end was 5.2 times that at the start). Thereafter, the temperature was lowered to 55 ° C., and a 0.4 M AgNO ₃ aqueous solution 10
4 cc and 279 cc of a 0.12 M aqueous potassium iodide solution were added in a fixed amount for 5 minutes, and then an aqueous potassium bromide solution was added to adjust the pAg to 8.8, and then 1.8 M AgNO was added.
₃ 110cc aqueous solution and 1.8M potassium bromide aqueous solution 1
25 cc was added. Thereafter, the emulsion was cooled to 35 ° C., washed with water by a usual flocculation method, and gelatin 75%.
g was added to adjust the pH to 5.5 and the pAg to 8.2. The obtained particles had an average particle size of 0.65 μm, and the value obtained by dividing the diameter of a circle equivalent to the projected area by the particle thickness was 38.4. This emulsion was designated as emulsion D-1. In addition, by appropriately changing the conditions, the diameter of the circle equivalent to the average projected area is 1.27 μm.
The emulsions D-2 and D-3 of m and 0.81 μm were prepared. Table 1 summarizes the grain size, silver chloride content, and average thickness of the prepared emulsions A to D.

[0165]

[Table 1]

These emulsions were subjected to spectral sensitization and chemical sensitization by adding the following spectral sensitizing dye, Compound I, potassium thiocyanate, chloroauric acid and sodium thiosulfate. At this time, the spectral sensitizing dye was changed in proportion to the grain surface area of each emulsion. The amounts of pAg and the chemical sensitizer during chemical sensitization were adjusted so that the degree of chemical sensitization of each emulsion was optimized. The green-sensitive emulsion thus prepared is A
"G" is represented by a subscript such as "-1g".

[0167]

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Next, a dispersion of zinc hydroxide used as a base precursor was prepared. The particle size of the primary particles is 0.
31 g of 2 μm zinc hydroxide powder, 1.6 g of carboxymethylcellulose and 0.4 g of sodium polyacrylate as a dispersant, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed, and the mixture was mixed with glass beads. Dispersed in the mill for 1 hour. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide.

Furthermore, an emulsified dispersion of a magenta coupler was prepared. 7.80 g of magenta coupler (a), 5.45 g of developing agent (b), 2 mg of antifoggant (c), 8.21 g of high boiling organic solvent (d) and 24.0 m of ethyl acetate
were dissolved at 60 ° C. The above solution was mixed with 150 g of an aqueous solution in which 12.0 g of lime-processed gelatin and 0.6 g of sodium dodecylbenzenesulfonate were dissolved, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. After the dispersion, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes. These dispersions and the previously prepared silver halide emulsion were combined and coated on a support with the composition shown in Table 2 to give samples 101 to 10
Four types of heat-developable color photographic light-sensitive materials were prepared.

[0170]

[Table 2]

[0171]

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Further, the processing materials P-1 and P
-2, and a second processing sheet P-3 as shown in Table 4 was prepared.

[0173]

[Table 3]

[0174]

[Table 4]

[0175]

[Table 5]

[0176]

Embedded image

[0177]

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[0178]

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These photosensitive materials were exposed to light at 1000 lux for 1/100 second through an optical wedge and a green filter. 15 ml of 40 ° C warm water is applied to the surface of the photosensitive material after exposure.
/ M ² , and the film surface of the processing material P-1 or P-2 is superimposed on each other, and then, 8
Heat development was performed at 3 ° C. for 15 seconds. (First step) When the photosensitive material was peeled off after the processing, a wedge-shaped image of magenta color was obtained. This sample was subjected to the second step treatment using the treatment material P-3 described above. The processing in the second step is processing material P-3.
Was coated with 10 cc / m ² of water, bonded to the photosensitive material after the treatment in the first step, and heated at 60 ° C. for 30 seconds. Similarly, a sample not subjected to the treatment in the second step was prepared. Regarding the processing result of each photosensitive material, the result of measuring the highest density part and the covering density part of this sample immediately after processing with a densitometer, and the processed sample was exposed to a 200,000 lux white light for 1 second, and then darkened. The fogging density portion after being left in the medium for 5 minutes was measured with a densitometer. These results are summarized in Table 6.

[0180]

[Table 6]

The following can be understood from the results. Processing material P
In the system using -3, the increase in fog density was small even after exposure to 200,000 lux, and post-development was suppressed. In particular, in a system using the photosensitive materials 102 and 104 of the present invention, the rise in the fog density is extremely small.

Example 2 Blue-sensitive and red-sensitive emulsions were prepared by changing the spectral sensitizing dyes used for spectral sensitization of the silver halide emulsion prepared in Example 1 to those shown below. Further, according to the method of preparing a coupler dispersion of Example 1, cyan and yellow coupler dispersions were also prepared. The compounds used are shown below.

[0183]

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[0184]

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Further, for the purpose of forming a colored layer which can be decolorized at the time of heat development, a dispersion of a colorant is also prepared by combining the following yellow, magenta and cyan leuco dyes with a zinc complex (a color developer (y)). Prepared.

[0186]

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Using the thus obtained silver halide emulsion, coupler dispersion and colorant dispersion, Table 7 was used.
Heat developing color light-sensitive materials 201 to
204 was created.

[0188]

[Table 7]

[0189]

[Table 8]

[0190]

[Table 9]

[0191]

[Table 10]

[0192]

[Table 11]

[0193]

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[0194]

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The photographic characteristics of these light-sensitive materials were tested in the same manner as in Example 1. First, 1/100 at 1000lux through each optical material through an optical wedge and blue, green and red filters.
A second exposure was given. After applying 15 ml / m ² of warm water at 40 ° C. to the surface of the photosensitive material after the exposure, and superposing the processing material P-1 or P-2 used in Example 1 on each other film surface, the heat drum was put on. For 15 seconds at 83 ° C. (First step) When the photosensitive material is peeled off after processing, the sample exposed with a blue filter has a wedge-shaped image of yellow color, the sample exposed with a green filter has a wedge-shaped image of magenta color, and has a red filter. A wedge-shaped image of cyan color was obtained from the exposed sample.

The sample was subjected to the second step treatment using the treatment material P-3 used in Example 1. In the processing in the second step, 10 cc / m ² of water was applied to the processing material P-3, and the processing material P-3 was bonded to the photosensitive material after the processing in the first step, and heated at 60 ° C. for 30 seconds. Similarly, a sample not subjected to the treatment in the second step was prepared. With respect to the processing results of these color samples, the density was measured in the same manner as in Example 1. Tables 12 and 13 summarize the results.

[0197]

[Table 12]

[0198]

[Table 13]

As shown in the above table, good results were obtained as in Example 1.

[Example 3] [0200] The multilayer coated sample prepared in Example 2 was prepared in the same manner as described above except that the support was changed to a support prepared by the following method. Similarly, good results were obtained, and the effect of the present invention was confirmed. 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy) as an ultraviolet absorber, 300 ° C.
After being melted at, it was extruded from a T-die, stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-fixed at 250 ° C for 6 seconds to form a 90 μm thick PEN.
I got a film. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in the official gazette number 94-6023). 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV discharge treatment, and a glow discharge treatment on both surfaces, and then gelatin 0.1 g / m ² , sodium α-sulfoside was applied to each surface. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m
² , p-chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂
(CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² undercoat liquid was applied (10 cc / m
² , using a bar coater) and an undercoat layer was provided on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer having the following composition, a transparent magnetic recording layer, and a sliding layer were coated as a back layer on one surface of the support after the undercoating.

3-1) Coating of antistatic layer Tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, a dispersion of fine particle powder (secondary aggregated particle diameter of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05 g / m
² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.005
It was coated with g / m ^2, and resorcin.

3-2) Coating of Transparent Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area: 43 m ² / g, major axis 0.14 μm,
Uniaxial 0.03μm, saturation magnetization 89emu / g, Fe + 2 / Fe + 3 = 6/9
4, the surface was treated with 2 wt% of iron oxide by aluminum oxide silicon) 0.06 g / m ² of diacetyl cellulose 1.2g
/ m ² (dispersion of iron oxide was carried out by open kneader and sand mill), C ₂ H ₅ C (CH ₂ CONH-C ₆ H ₃ (CH ₃ ) NC
O) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone, and dibutyl phthalate as solvents to obtain a 1.2 μm-thick magnetic recording layer. As a lubricant C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ 50 m
g / m ² , an abrasive aluminum oxide (0.20 μm and a matting agent) coated with silica particles (1.0 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight). 1.0 .mu.m) were each added in an amount of 50 mg / m ² and 10 mg / m ^2. Drying at 115 ℃,
The test was carried out for 6 minutes (all rollers and conveyors in the drying zone were at 115 ° C). The X-light (blue filter) increases the DB color density of the magnetic recording layer by about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, and the coercive force is 7.3 × 10 ⁴ A /.
m, and the squareness ratio was 65%.

3-3) Preparation of Sliding Layer Hydroxyethylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (O
H) C ₁₀ H ₂₀ COOC ₄₁ H ₈₁ (6 mg / m ² ), silicone oil BYK-
310 (manufactured by BYK Japan KK) 1.5 mg / m ² was applied. This mixture was melted at 105 ° C in xylene / propylene glycol monomethyl ether (1/1), poured and dispersed in propylene monomethyl ether (10 times the volume) at room temperature, and then dispersed in acetone. (Average particle size: 0.01 μm). Drying was carried out at 115 ° C for 6 minutes.
° C). The sliding layer had excellent characteristics such as a coefficient of dynamic friction of 0.10 (a stainless steel ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a coefficient of static friction of 0.08 (clip method), and a coefficient of dynamic friction between the emulsion surface and the sliding layer of 0.15.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location G03C 1/42 G03C 1/42 7/392 7/392 Z

Claims (4)

[Claims] 1. A silver halide color photographic material having on a support at least one photosensitive layer comprising at least a photosensitive silver halide, a color developing agent, a dye-providing coupler and a binder. After imagewise exposing the material, a processing material having at least a processing layer containing at least a base and / or a base precursor on a support is used. An image is formed on the photosensitive material side by superposing and heating the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material in a state where water equivalent to 1 to 1 time is present between the photosensitive material and the processing material. Further, in the heat development step and / or an additional processing step after the heat development, part or all of the silver halide and / or developed silver remaining in the light-sensitive material is complexed to form a heat-sensitive material. A silver halide color photographic light-sensitive material forming a color image, wherein the light-sensitive layer contains an emulsion comprising tabular silver halide grains satisfying the following relational expression. . Relational expression a− {log (b + 1)} / 9 ≦ 0.07 (a represents an average thickness (μm) of photosensitive silver halide grains in the photosensitive layer. B represents silver chloride content of silver halide. Rate (mol%).) 2. The tabular silver halide grains are silver halide grains comprising 50 mol% or more of silver chloride,
2. The silver halide color photographic light-sensitive material according to claim 1, wherein the main outer surfaces of the grains are tabular grains composed of (100) planes. 3. The tabular silver halide grains have an average equivalent circular diameter of at least 0.7 μm and an average thickness of 0.01.
2. A silver halide color photographic light-sensitive material according to claim 1, further comprising an emulsion composed of tabular grains having a particle size of from 0.03 to less than 0.07 .mu.m. 4. A silver halide color photographic light-sensitive material having at least one photosensitive layer comprising at least a photosensitive silver halide, a color developing agent, a dye-providing coupler and a binder on a support; After image-wise exposing the photosensitive material using a processing material having a processing layer containing at least a base and / or a base precursor, 0.1 times the amount required for maximally swelling all coating films of both the photosensitive material and the processing material. In the state where water equivalent to 1 time is present between the photosensitive material and the processing material, the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material are superimposed and heated to form an image on the photosensitive material side, Further, part or all of the silver halide and / or developed silver remaining on the photosensitive material is complexed by the heat development step and / or an additional processing step after the heat development. A color image forming method,
A color image forming method, wherein the photosensitive layer contains an emulsion comprising tabular silver halide grains satisfying the following relational expression. Relational expression a− {log (b + 1)} / 9 ≦ 0.07 (a represents an average thickness (μm) of photosensitive silver halide grains in the photosensitive layer. B represents silver chloride content of silver halide. Rate (mol%).)