JPH10171090A - Sliver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a superior silver halide color photographic sensitive material capable of easy and rapid image formation, small in environmental load, especially, high in sensitivity and maximum density and image quality. SOLUTION: The silver halide color photographic sensitive material is provided, on a support, with a photosensitive layer comprising photosensitive silver halide grains and a compound to be allowed to release a dye by reaction with the oxidation product of a developing agent and a binder and after exposure it is allowed to form a color image by sticking the face of the photosensitive layer to the face of a processing layer containing a processing agent including a color eraser and heat developing it. At least one of the photosensitive layers contains an emulsion containing flat silver halide grains having an average equivalent circle diameter of >=0.7μm and an average thickness of <0.07μm and a dye to be erased by reaction with the color eraser at the time of development processing, and this dye is resistant to diffusion and at least a part of the dey is resistant to diffusion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel silver halide color photographic material for recording an image.

[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 having photosensitivity in blue, green, and red regions, on a transmission support (hereinafter, may be simply referred to as a "photosensitive layer"). Are contained in the photosensitive layers in combination with so-called color couplers which form dyes of yellow, magenta and cyan, each of which is a complementary color. 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 Color development and bleaching,
The original scene was reproduced by applying the fixing process.
A color print consisting of a dye image can be obtained.

[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] In view of these viewpoints, many improved techniques have been proposed. In particular, various techniques using so-called high silver chloride milk having a high silver chloride content have been proposed for the purpose of simple and rapid development processing. The use of a high silver chloride emulsion provides advantages such as an increase in the development speed and an increase in the reusability of the processing solution. For this reason, in recent years, the type of photosensitive material for printing such as color photographic paper, which uses a high silver chloride emulsion, has become the mainstream.

As another attempt, an environmental load is reduced and a simplicity is improved by constructing a system that does not use a color developing agent or a bleaching agent used in an existing color image forming system. Technology has also been reported. For example, IS &T's 48th Annual C
onference Proceedings 180
On the page, after the dye generated by the development reaction is transferred to the mordant layer, it is peeled off to remove the developed silver and unreacted silver halide, eliminating the need for a bleach-fix bath, which was essential for conventional color photographic processing. Is disclosed. However,
The technology proposed here still requires development in a processing bath containing a color developing agent, and it is hard to say that the environmental problem has been solved.

As a system that does not require a processing solution containing a color developing agent, Fuji Photo Film Co., Ltd. has provided a pictography system and a pictrostat system. In this system, a small amount of water is supplied to a photosensitive material containing a base precursor, and the photosensitive material is bonded to an image receiving material.
The development reaction is caused by heating. This method is environmentally advantageous in that the above-mentioned treatment bath is not used. However, since this method is used for fixing a formed dye to a dye fixing layer and appreciating the dye image as a dye image, development of a system which can be used as a recording material for photographing has been desired.

Further, various silver halides which are preferable in a so-called thermal development system in which development is performed at a high temperature with respect to a conventional liquid development system have been proposed. For example, Japanese Patent Publication No. 2-48,101 discloses a technique for improving the progress of heat development by using a tabular silver halide having a grain size of 5 times or more the grain thickness for a heat-developable color photosensitive material. . Japanese Patent Application Laid-Open No. 62-78,555 discloses that a tabular photosensitive silver halide grain having a silver iodide content of 4 to 40 mol% and a particle diameter to grain thickness ratio of 5 or more is treated with an organic compound. There is disclosed a technique for improving the long-term storage stability of a photothermographic material by adding 0.05 to 1 mol to 1 mol of a silver salt. Japanese Patent Application Laid-Open No. 62-79,447 discloses a tabular photosensitive silver halide grain having a grain size ratio to grain thickness of 5 or more, and a silver iodide content of 4 to 40 mol%. There is disclosed a technique for improving the sensitivity and the maximum density during thermal development by incorporating photosensitive silver halide grains having an average grain size of 0.4 μm or less.

[0009] However, since these techniques are also aimed at photographic light-sensitive materials for printing, development of a system which can be used as a recording material having sensitivity for photography has been desired.

[0010] In view of the above, various studies have been made on the development of a photographic material having a low environmental load and capable of simple image recording by applying the above system. Silver halide materials for photography require high sensitivity in all of the green-sensitive emulsion layer, the red-sensitive emulsion layer, and the blue-sensitive emulsion layer. To increase the sensitivity,
It is effective to increase the sensitivity of silver halide grains and increase the amount of silver halide applied.

Techniques for silver halide tabular grains having a small grain thickness and a high aspect ratio are disclosed in US Pat.
No. 0,403. Such silver halide grains have many advantages such as efficient use of silver and improvement in the relationship between sensitivity and granularity. More recently, techniques relating to tabular grains having a small grain thickness and a high aspect ratio have been disclosed in EP0699944A and EP0701.
165A, EP06999949A, EP06999947
A, US Pat. No. 5,494,789. However, simply increasing the sensitivity of the emulsion is not sufficient as a photographic light-sensitive material having a multilayer structure. In particular, in order to form a multilayer structure, it is necessary to improve color separation. Generally, such a problem is improved by including a coloring dye.

However, in a photographic material in which a developing agent is incorporated in a photographic material, it is observed that the development time is slowed down by containing a coloring dye. This is thought to be because the dye consumes alkali for its dissociation. Therefore, it was sometimes difficult to incorporate a sufficient amount of dye therein.

[0013]

As is apparent from the above description, it is an object of the present invention to provide a high-quality silver halide for photographing capable of forming an image easily, quickly and with less environmental load. An object of the present invention is to provide a color photographic light-sensitive material. In particular, it is an object of the present invention to provide a high-quality color photographic material having high sensitivity, high maximum density, and excellent color separation.

[0014]

The above object is achieved by the present invention described below. That is, the present invention provides: (1) a support comprising at least one photosensitive layer comprising a photosensitive silver halide particle, a compound forming a dye by a coupling reaction with an oxidized form of a developing agent, and a binder; In a silver halide color photographic light-sensitive material that forms a color image by laminating a photosensitive layer surface of a photosensitive material with a processing layer surface of a processing material containing a decoloring agent and performing heat development, at least one photosensitive layer has Average equivalent circle equivalent diameter is 0.7μm or more and average thickness is 0.07
containing an emulsion composed of tabular grains having a particle diameter of less than μm, and wherein the photosensitive material contains a dye that is decolorized by a reaction with a decoloring agent during development processing, and the dye is diffusion-resistant. A silver halide color photographic light-sensitive material characterized in that at least a part of the dye which has been decolorized after processing has diffusion resistance. (2) The following general formulas (I) to (I) in which the dye loses color during processing
The silver halide color photographic light-sensitive material according to (1), which is any of the dyes represented by V). General formula (I) A51 = L51-(L52 = L53) _m51-
Q51 General formula (II) A51 = L51-(L52 = L53) _n51-
A52 General formula (III) A51 (= L51-L52) _p51 = B51 General formula (IV) (NC) ₂ C = C (CN) -Q51 (wherein, = represents a double bond, and-represents a single bond. A51,
A52 represents an acidic nucleus, and B51 represents a basic nucleus. Q51 represents an aryl group or a heterocyclic group. L5
1, L52 and L53 each represent a methine group. m51
Represents 0, 1 or 2. n51 and p51 represent 0, 1, 2 or 3, respectively. However, the general formulas (I) to (I)
The compound represented by V) does not have a carboxyl group or a sulfo group, and the compounds represented by general formulas (I) to (IV) have a diffusion-resistant group and are treated (decolored). )
The later product is also resistant to diffusion and does not substantially elute from the photosensitive material. (3) The silver halide according to (1) or (2), wherein at least two types of silver halide emulsions having photosensitivity in the same wavelength region and having different average projected areas are used in combination. It is a color photographic light-sensitive material.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the emulsion constituting the present invention will be described. In the present invention, tabular grains (hereinafter, referred to as "tabular grains") are silver halide grains having two opposing parallel main planes.

The tabular grains used in the present invention have 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 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 emulsion constituting the present invention, the tabular grains preferably occupy 50 to 100%, more preferably 80 to 100%, particularly preferably 90 to 100% of the total projected area of all grains. 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 the tabular grains used in the present invention is less than 0.07 μm, preferably 0.01 μm or more and less than 0.07 μm, more preferably 0.01 to 0.06 μm, and particularly preferably 0.1 to 0.06 μm.
01 to 0.05 μm. The average grain thickness is the arithmetic average of the grain thickness of all tabular grains in the emulsion. If the average particle thickness is less than 0.01 μm, the pressure property is undesirably deteriorated. If it exceeds 0.07 μm, it is difficult to obtain the effects of the present invention, which is not preferable.

The average equivalent circle equivalent diameter of the tabular grains used in the present invention is 0.7 μm or more, preferably 0.7 μm or more.
μm to 5 μm, more preferably 1 to 4.5 μm
m, particularly preferably 1 to 4 μm. The average equivalent circle diameter is the arithmetic mean of the equivalent circle equivalent diameters of all tabular grains in the emulsion. Note that the equivalent circle equivalent diameter refers to the diameter of a circle having an area equal to the projected area of the particle. 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 ratio of the equivalent circle equivalent diameter to the thickness of silver halide grains, that is, the value obtained by dividing the equivalent circle diameter of the projected area of each silver halide grain by the grain thickness is called the aspect ratio. As an example of a method for measuring the aspect ratio, a transmission electron micrograph is taken by a replica method and the diameter of a circle having an area equal to the projected area of each particle (equivalent circle equivalent diameter)
There is a method of obtaining the thickness. In this case, the thickness is calculated from the length of the shadow of the replica.

The emulsion constituting the present invention has an average aspect ratio to all tabular grains of 10 to 100, more preferably 12 to 80, particularly preferably 15 to 50. The average aspect ratio is the arithmetic average of the aspect ratios of all tabular grains in the emulsion. If the average aspect ratio is less than 10, it is difficult to obtain the effects of the present invention, which is not preferable. If it exceeds 100, the pressure property deteriorates, which is not preferable. Various methods can be used to form tabular grains having a small grain thickness and a high aspect ratio used in the present invention. For example, the grain forming method described in US Pat. No. 5,494,789 can be used. Can be.

In the emulsion constituting the present invention, hexagonal tabular grains 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 are all contained in the emulsion. It preferably occupies 100 to 50% of the projected area of the grains,
More preferably 100 to 70%, particularly preferably 10 to 70%
It accounts for 0 to 90%. It is not preferable that a large amount of tabular grains other than the above-mentioned hexagons are mixed in terms of homogeneity between grains.

In order to form tabular grains having a high aspect ratio, it is important to generate twin nuclei of a small size.
Therefore, at low temperature, high pBr and low pH, the amount of gelatin is reduced, and the amount of methionine is low, low molecular weight, phthalated gelatin derivative is used, and the nucleation time is shortened. Preferably, nucleation is performed. After nucleation, only the tabular grain nuclei (parallel multiple twin nuclei) are grown by physical ripening, and other normal crystal nuclei, single twin nuclei, and non-parallel multiple twin nuclei are eliminated, and selectively parallel multiple nuclei. Form twin nuclei. Thereafter, a soluble silver salt and a soluble halogen salt are added, and the grains are grown to prepare an emulsion composed of tabular grains.

The emulsion constituting the present invention is preferably monodisperse. The coefficient of variation of the particle size distribution of the tabular grains used in the present invention is preferably 30 to 3%, more preferably 25 to 3%, and particularly preferably 20 to 3%. If it exceeds 30%, it is less preferable in terms of homogeneity between particles, but the present invention is not limited thereto. The variation coefficient of the grain size distribution is a value obtained by dividing the standard deviation of the equivalent circle equivalent diameter of each silver halide grain by the average equivalent circle equivalent diameter.

As the composition of the tabular grains used in the present invention, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and the like can be used. It is preferable to use silver iodobromide. When there is a phase containing iodide or chloride, these phases may be uniformly distributed in the grains or may be localized. Other silver salts such as silver rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains.

The preferred silver iodide content of the tabular grains used in the present invention is 0.1 to 20 mol%, more preferably 0.1 to 15 mol%, and 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 20 mol%, the developing speed is generally slow, which is not preferable.

The variation coefficient of the intergranular silver iodide content distribution of the emulsion constituting the present invention is preferably 30 to 3%, more preferably 25 to 3%, and particularly preferably 20 to 3%.
It is. If it exceeds 30%, it is not preferable in terms of homogeneity between particles. 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 used in the present invention may have dislocation lines. A dislocation line is a linear lattice defect on the slip plane of a crystal at the boundary between an already slipped region and a region that has not yet slipped. Regarding dislocation lines of silver halide crystals, 1) C.I. R. Berry, J.M. Appl. Phys
s. , 27, 636 (1956), 2) C.I. R. Ber
ry, D.S. C. Skilman, J .; Appl. Phys
s. , 35, 2165 (1964), 3) J. F. Ha
Milton, Photo. Sci. Eng. , 11,5
7 (1967), 4) T.I. Shiozawa, J .; So
c. Photo. Sci. Jap. , 34, 16 (197
1), 5) T.I. Shiozawa, J .; Soc. Pho
t. Sci. 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 directly observing dislocation lines 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 an electron beam to pass through. Therefore, it is possible to more clearly observe using an electron microscope of a high-pressure type (200 kV or more for a thickness of 0.25 μm).

JP-A-63-220,238 describes a technique for introducing dislocation lines into silver halide grains while controlling the dislocation lines. It is shown that tabular grains into which dislocation lines are introduced are superior to photographic properties such as sensitivity and reciprocity law as compared with tabular grains without dislocation lines. In the case of tabular grains,
As described above, the position and the number of dislocation lines of each particle when viewed from the direction perpendicular to the main plane can be obtained from the photograph of the particle taken using the electron microscope.

When the tabular grains used in the present invention have dislocation lines, their positions can be selected from, for example, those which are limited to the apexes and / or fringe portions of the grains or which are introduced over the entire main plane portion. It is possible and optional, but it is particularly preferable to limit the fringe. The fringe part in the present invention refers to the outer periphery of tabular grains,
Specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the point where the silver iodide content at a certain point exceeds or falls below the average silver iodide content of the whole grain for the first time viewed from the side. Point outside. When the tabular grains used in the present invention have dislocation lines, the density of the dislocation lines is arbitrary,
The selection may be made according to the case of 10 or more, 30 or more, 50 or more per particle.

In the light-sensitive material of the present invention, a silver halide emulsion (hereinafter, referred to as "another silver halide emulsion") other than the silver halide tabular grain emulsion constituting the present invention as one photosensitive layer. Can be used together. Other silver halides (other than the above tabular grains) usable in the present invention include any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver iodochloride and silver chloroiodobromide. , But preferably 30
Silver iodobromide, silver chloride, silver bromide and silver chlorobromide containing not more than mol% of silver iodide.

Other silver halide emulsions usable in the present invention may be of the surface latent image type or of the internal latent image type.
The emulsion of the internal latent image type is used as a direct reversal emulsion by combining a nucleating agent and light fogging. Further, so-called multi-structure particles having different halogen compositions between the inside and the surface of the particles may be used. Of the multi-structure grains, those having a double structure are particularly called a core-shell type, and an emulsion using such grains is sometimes called a core-shell emulsion. Other silver halide grains that can be used in the present invention are preferably composed of multi-structure grains, and more preferably a core-shell type grain. However, the present invention is not limited to this.

The other silver halide emulsion which can be used in the present invention is preferably monodisperse.
The coefficient of variation described in US Pat. No. 0,555 is preferably 20% or less. It is more preferably at most 16%, further preferably at most 10%. However, the present invention is not limited to this monodispersed emulsion.

The average grain size of other silver halide grains (other than the above-mentioned silver halide tabular grains; the same applies hereinafter) which can be used in the present invention is from 0.1 μm to 2.2 μm.
And preferably 0.1 μm to 1.2 μm. The crystal habit of the silver halide grains may be cubic, octahedral, high aspect ratio tabular, potato-shaped, or any other.
More preferably, it is a cube.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,
029 (1978) and JP-A-62-253159 can be used. The other silver halide emulsions that can be used in the present invention can be used together with the above-mentioned tabular silver halide emulsion used in the present invention in one photosensitive layer.
The silver halide tabular grain emulsion constituting the present invention preferably accounts for 40% or more, more preferably 50% or more, of the projected area of all silver halide grains in the emulsion layer.

In the process of preparing the photosensitive silver halide emulsion used in the present invention (including both the silver halide tabular grain emulsion and other silver halide emulsions constituting the present invention; the same applies hereinafter), an excess It is preferable to perform so-called desalting for removing 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 sedimentation method (flocculation) using a gelatin derivative (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. Preferably, a sedimentation method using a compound represented by the following sedimentation agent a or sedimentation agent b is used, but the present invention is not limited thereto. An ultrafiltration method may be used without using any of the above settling agents. The removal of the excess salt may be omitted.

[0037]

Embedded image

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 chromium, and compounds thereof for various purposes. These may be used alone or in combination of two or more. The addition amount depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide.
Also, when containing, the particles may be put uniformly,
Further, it may be localized inside or on the surface of the particle.

The preferable addition amount of iridium used in the present invention is 10 ^-9 to 10 ^-4 mol, more preferably 10 ^-8 to 10 ^-6 mol, per mol of silver halide. In the case of a core-shell emulsion, iridium may be added to the core and / or the shell. As the iridium compound that can be added, K ₂ IrCl ₆ or K ₃ IrCl ₆ is preferably used.

The preferred addition amount of rhodium used in the present invention is 10 ^-9 to 10 ^-6 mol per mol of silver halide. Further, preferable amount of iron used in the present invention, 10 ^-7 to 10 ^-3 mol per mol of silver halide, and more preferably 10 ^-6 to 10 ^-3 mol. A part or all of these heavy metals are pre-doped into a fine grain emulsion such as silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and then the fine grain emulsion is added to obtain a silver halide emulsion. A method of locally doping the surface is also preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion used in the present invention, as a solvent for the silver halide, a rhodan salt, ammonia, a thiourea compound or a JP-B-47-1 is used.
An organic thioether derivative described in 1,386 or a sulfur-containing compound described in JP-A-53-144319 can be used. In the stage of forming silver halide grains, JP-B-46-7,781 and
No. 222,842, JP-A-60-122,935 and the like can be added.

Gelatin is advantageously used as a protective colloid used in the preparation of the photosensitive silver halide emulsion used in the present invention and as a binder for other hydrophilic colloids. Colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other high polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose and cellulose sulfates; sodium alginate, starch derivatives; polyvinyl alcohol;
Use of various kinds of synthetic hydrophilic polymer materials such as homo- or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin, Britain, Society of
The Scientific, Photography of Japan (Bull. Soc. Sci. Phot., Japan), No. 16: Page
30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin may also be used.

For other conditions, refer to "Chemie et Phisque Photographique" by P. Glafkides.
Published by Paul Montel (1967), Photographic Emulsio by GFDuffin
n Chemistry), published by The Focal Press
cal Press 1966), Viel Zelikuman et al. (V.
L. Zelikman et al) "Making and Coating Photographic Emulsions (Making and C)
oating Photographic Emulsion ”, published by The Focal Press, 1964, and the like. 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.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a so-called controlled double jet method in which the 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). During or after grain formation, the surface of the silver halide grain may be replaced with a halogen that forms a sparingly soluble silver halide grain.

The reaction solution may be stirred by 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 2.2-6.0, more preferably 3.5-5.5. JP-A-5-119,429
Described above, a silver halide emulsion comprising silver halide grains having a phase with a high silver iodide content on the grain surface and chemically sensitized before desalting and adding iodide ions is also used. be able to.

The sensitizing dyes used in the photosensitive silver halide used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Dyes are included. Specifically, U.S. Pat. No. 4,617,257;
80,550, 60-140,335, RD17
029 (1978), pp. 12-13, and the like. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. A dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light, together with a sensitizing dye,
A compound exhibiting supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641;
145 etc.).

In the present invention, in any of the above-mentioned addition methods, the total amount of the sensitizing dye may be added at one time.
Moreover, you may divide into several times. Further, the sensitizing dye may be added in the form of a mixture with a soluble silver salt and / or a halide. These sensitizing dyes can be added to the emulsion at any time. That is, at the beginning of the formation of silver halide emulsion grains (may be added before nucleation),
On the way, after formation, or at the beginning, during, or after the desalting process,
It can be added at the time of redispersion of gelatin, before, during or after chemical sensitization, or at any time during preparation of a coating solution.
Preferably, it is added during or after the formation of silver halide grains, or before, during or after chemical sensitization. Addition after chemical sensitization means adding a sensitizing dye after all chemicals necessary for chemical sensitization are added at the same temperature as chemical sensitization.

More specifically, the sensitizing dye is disclosed in US Pat.
As described in U.S. Pat. No. 83,756, it may be present in a reaction system between a soluble silver salt (for example, silver nitrate) and a halide (for example, potassium bromide) before silver halide grains are formed. As described in US Pat. No. 4,225,666, it may be present in the above reaction system after the nucleation of silver halide grains and before the end of the step of forming silver halide grains. A sensitizing dye may be present in the reaction solution simultaneously with the formation of the silver halide grains, that is, simultaneously with the mixing of the silver salt and the halide. Is storage stability under high temperature conditions,
And better in gradation.

The concentration after the addition, the solvent, the time for addition (the addition may be performed at once or over time), the temperature and the pH
Etc. may be any condition. Either addition at the liquid surface or addition in the liquid may be used. These conditions are described in JP-A-3-11.
No. 0,555, and the like.

The sensitizing dye is added after being dissolved in a water-compatible organic solvent such as methanol, ethanol, propanol, fluorinated alcohol, methyl cellosolve, dimethylformamide, acetone or water (which may be alkaline or acidic). Or two or more of the above may be used in combination. It may also be added in the form of a dispersion in a water / gelatin degradation system or in the form of a lyophilized powder. Further, it may be added in the form of a powder or a solution dispersed using a surfactant.

The sensitizing dye used in the photosensitive silver halide emulsion used in the present invention is described, for example, in JP-A-3-296,74.
5, No. 4-31,854 and the like. The use amount of these sensitizing dyes is suitably about 10 ^-8 to 10 ^-1 mol per mol of silver halide used for emulsion production.

Further, in the present invention, Japanese Patent Application Laid-Open
No. 3,145, page 3 to page 5, compounds represented by formula (A) (shown below) and specific examples thereof can be used together with sensitizing dyes. This compound is often used for supersensitization, improvement of storage stability, and suppression of sensitivity change of a coating solution over time. In a photosensitive material spectrally sensitized to an infrared region of 750 nm or more, more effective effects may be obtained. However, in some cases, it may have the effect of lowering the sensitivity.

[0055]

Embedded image

In the above formula, A represents a divalent aromatic residue. R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄ each represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an alkylthio group, an arylthio group, an amino group, Or an unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, a heterocyclylamino group, an aryl group, a heterocyclyloxy group, and a mercapto group. However,
At least one of A, R ₁₁ , R ₁₂ , R ₁₃ , and R ₁₄
One has a sulfo group. W ₁ and W ₂ are each -C
Represents H = or -N =. However, either one of at least W ₁ and W ₂ represent -N =.

The compound of the formula (A) is a compound known as a supersensitizer of a sensitizing dye in a general photosensitive material for wet development processing (US Pat. No. 2,875,05).
No. 8, U.S. Pat. No. 3,695,888,
192,242 and JP-A-59-191,032), and also a compound known as a supersensitizer in heat-developable color photographic materials (JP-A-59,180,5).
No. 50). Details and specific examples of the above compounds are described in
No. 3-23,145.

The light-sensitive silver halide emulsion used in the present invention can be used as it is without chemical sensitization, but it is more preferable to use the one whose chemical sensitization has increased the sensitivity. As chemical sensitization,
Any of sulfur sensitization, gold sensitization, reduction sensitization, and a combination thereof may be used. In addition, chemical sensitization with a compound containing a chalcogen element other than sulfur such as selenium or tellurium, or chemical sensitization with a noble metal such as palladium or iridium can be performed alone or in combination with the above-described chemical sensitization.

Also, 4-hydroxy-6-methyl-
A method of adding an inhibitor such as a nitrogen-containing heterocyclic compound represented by (1,3,3a, 7) -tetraazaindene is also preferably used. The preferred range of the addition amount is 10 ^-1 to 10 ^-5 mol per mol of silver halide. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, and more preferably 5.5 to 9.5.

The sulfur sensitizer is a compound containing sulfur which can react with active gelatin or silver, for example, thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonic acid ,
Rhodan, mercapto compounds and the like are used. In addition, U.S. Patent Nos. 1,574,944 and 2,41
No. 0,689, No. 2,278,947, No. 2,7
Nos. 28,668 and 3,656,955 can also be used. The coating amount of the photosensitive silver halide used in the present invention is 1 mg / m 2 in terms of silver.
^{2 to} 10 g / m ² , preferably 0.1 g
/ M ^{2 to} 9 g / m ²

The light-sensitive silver halide emulsion used in the present invention may be used as it is after unripe, but is usually used after chemically sensitizing it. Known sulfur sensitization method for emulsions for general photosensitive materials,
Reduction sensitization, noble metal sensitization, selenium sensitization, and the like can be used alone or in combination. 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).

In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described in RD 17643 (1978), pp. 24-25, and JP-A-59-16883.
No. 442, nitrogen-containing carboxylic acids and phosphates, or mercapto compounds and metal salts thereof described in JP-A-59-111,636;
Acetylene compounds described in No. 7 are 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.
Benzotriazoles, fatty acids, and other compounds described in No. 0,626, columns 52 to 53, and the like. Also,
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 0.0
1 to 10 mol, preferably 0.01 to 1 mol can be used in combination. Total coating amount of the photosensitive silver halide and organic silver salts 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

The light-sensitive material of the present invention comprises a photosensitive silver halide, a compound capable of forming a dye by a coupling reaction with an oxidized developing agent (hereinafter referred to as "coupler") on a support, and a binder. It is constituted by coating a photographic constituent layer including at least one photosensitive layer.

In the present invention, in order to construct a photosensitive material used for recording an original scene and reproducing it as a color image, color reproduction by a subtractive color method can be basically used. That is, at least three types of photosensitive layers having photosensitivity are provided in the blue, green, and red regions, and yellow, magenta, and cyan dyes are formed in each photosensitive layer, which are complementary colors to the photosensitive wavelength region. The color information of the original scene can be recorded by including a color coupler which can be used. The original scene can be reproduced by exposing the color image having the same relationship between the photosensitive wavelength and the color hue through the dye image thus obtained. Further, information of a dye image obtained by photographing an original scene can be read by a scanner or the like, and an ornamental image can be reproduced based on this information.

As the light-sensitive material of the present invention, a light-sensitive layer having photosensitivity in three or more wavelength regions can be provided. It is also possible to provide a relationship other than the above-described complementary colors between the photosensitive wavelength region and the color hue. In such a case, after capturing the image information as described above,
The original color information can be reproduced by performing image processing such as hue conversion.

In the present invention, it is preferable to contain at least two types of silver halide emulsions which are photosensitive in the same wavelength region and have different average grain projected areas. The phrase “having photosensitivity in the same wavelength region” as used in the present invention refers to having photosensitivity in the same wavelength region. Therefore, even if the emulsions have slightly different spectral sensitivity distributions and the main photosensitive areas overlap, the emulsions are regarded as having sensitivity in the same wavelength region.

At this time, it is preferable to use the emulsion such that the difference in the average grain projected area between the emulsions has a difference of at least 1.25 times. More preferably, it is at least 1.4 times.
Most preferably, it is 1.6 times or more. When three or more emulsions are used, it is preferable that the above-mentioned relationship be satisfied between the emulsion having the smallest average grain projected area and the largest emulsion.

In the present invention, in order to contain a plurality of emulsions having photosensitivity in these same wavelength regions and having different average grain projected areas, a separate photosensitive layer may be provided for each emulsion. A plurality of emulsions may be mixed and contained in one photosensitive layer.

When these emulsions are contained in separate layers, it is preferable to arrange the emulsion having a large average grain projected area in the upper layer (a position close to the light incident direction).

When these emulsions are contained in separate light-sensitive layers, it is preferable to use color couplers having the same hue, but it is preferable to use couplers having different hues. It is also possible to use different coloring hues, or to use couplers having different absorption profiles of the coloring hues in the respective photosensitive layers.

In the present invention, the ratio of the number of silver halide grains per unit area of the light-sensitive material of these emulsions is determined by the ratio of the average grain projected area to the emulsions having the same wavelength range. It is preferable that the larger the emulsion, the larger the ratio of the silver coating amount of the emulsion divided by the 3/2 power of the average grain projected area of the silver halide grains contained in the emulsion. By adopting such a configuration, an image having good granularity can be obtained even under development conditions heated to a high temperature. In addition, high developability and a wide exposure latitude can be satisfied at the same time.

The dye constituting the present invention, which is decolorized by a reaction with a decoloring agent during development processing, will be described. The dye constituting the present invention is one that is decolorized by a reaction with a decoloring agent during development processing and has diffusion resistance. Further, at least a part of the dye constituting the present invention has diffusion resistance even when the color is erased after the development processing. By using such a dye, it is possible to provide a photosensitive material which is excellent in storability, sharpness and granularity, and which can be processed easily and quickly. Also, it is preferable from an environmental point of view because unnecessary materials are not taken out of the photosensitive material. Specific examples of such dyes include cyanines, merocyanines, oxonols, arylidenes (including heteroarylidenes), anthraquinones, triphenylmethanes, azo dyes, and azomethine dyes. Can be.

The preferred dyes constituting the present invention are those represented by the following formulas (I) to (IV). General formula (I) A51 = L51-(L52 = L53) _m51-
Q51 General formula (II) A51 = L51-(L52 = L53) _n51-
A52 General formula (III) A51 (= L51-L52) _p51 = B51 General formula (IV) (NC) ₂ C = C (CN) -Q51 (wherein, = represents a double bond, and-represents a single bond. A51,
A52 represents an acidic nucleus, and B51 represents a basic nucleus. Q51 represents an aryl group or a heterocyclic group. L5
1, L52 and L53 each represent a methine group. m51
Represents 0, 1, and 2. n51 and p51 are each 0,
1, 2, and 3 are represented. However, the compounds represented by the general formulas (I) to (IV) do not have a carboxyl group or a sulfo group, and the compounds represented by the general formulas (I) to (IV) have a diffusion-resistant group. The product after the treatment (decoloration) is also diffusion-resistant and does not substantially elute from the photosensitive material. )

The acidic nucleus represented by A51 or A52 is preferably a cyclic ketomethylene compound or a compound having a methylene group sandwiched between electron-withdrawing groups. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5
-One, rhodanine, hydantoin, thiohydantoin,
2,4-oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione,
Dioxopyrazolopyridine, hydroxypyridine, pyrazolidinedione, 2,5-dihydrofuran-2-one,
Pyrrolin-2-one can be mentioned. These may have a substituent. Among these, preferred compounds are 2-pyrazolin-5-one, isoxazolone, dioxopyrazolopyridine, hydroxypyridine and pyrazolidinedione, and particularly preferred is 2-pyrazolin-5.
-One, isoxazolone and hydroxypyridine.

The compounds having a methylene group sandwiched between electron attractive groups can be represented as Z51-CH ₂ -Z52, wherein Z51, Z52 are each -CN, -SO
₂ R51, -COR51, -COOR51, -CON
_{(R52) 2, -SO 2 N} (R52) 2, -C [= C
(CN) ₂ ] R51, -C [= C (CN) ₂ ] N (R5
1) represents ₂ , R51 represents an alkyl group, an aryl group, or a heterocyclic group, and R52 represents a hydrogen atom or a group described for R51. R51 and R52 may each have a substituent, and when there are a plurality of R51 or R52 in the molecule, they may be the same or different. Z5
1 and Z52 may be the same.

Examples of the basic nucleus represented by B51 include:
Examples thereof include pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole, and pyrrole. Each of these may have a substituent. Preferred compounds among these are indolenine, benzoxazole,
Benzimidazole, benzothiazole and pyrrole are particularly preferred, and indolenine and benzoxazole are particularly preferred. Examples of the aryl group represented by Q51 include a phenyl group and a naphthyl group, each of which may have a substituent (preferably an electron donating group).
Of these, a phenyl group substituted with a dialkylamino group, a hydroxyl group, an alkoxy group, or an alkyl group is preferred, and a phenyl group substituted with a dialkylamino group is particularly preferred. Examples of the heterocyclic group represented by Q51 include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran Oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and chroman, each of which may have a substituent. Of these, pyrrole and indole are preferred.

The methine groups represented by L51, L52 and L53 may have a substituent, and the substituents may be linked to each other to form a 5- or 6-membered ring (for example, cyclopentene, cyclohexene). . Examples of the substituent which the above group may have include a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, octanesulfonamide) and a sulfamoyl group (eg, sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl) Moyl), a sulfonylcarbamoyl group (eg, methanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), an acylsulfamoyl group (eg, acetylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), a linear or cyclic alkyl group (eg, Methyl, isopropyl, cyclopropyl, cyclohexyl, 2-ethylhexyl, dodecyl, octadecyl, 2-phenethyl, benzyl), alkenyl group (eg, vinyl, allyl), alkoxy group (eg, Alkoxy, octyloxy, dodecyloxy, 2-methoxyethoxy), an aryloxy group (e.g., phenoxy), halogen atom (e.g. F, Cl, Br), amino group (e.g., diethylamino, ethyl dodecyl amino),
Ester groups (eg, ethoxycarbonyl, octyloxycarbonyl, 2-hexyldecyloxycarbonyl), acylamino groups (eg, acetylamino, pivaloylamino, benzoylamino), carbamoyl groups (eg, unsubstituted carbamoyl, ethylcarbamoyl, diethylcarbamoyl, phenylethylcarbamoyl) ), Aryl groups (eg, phenyl, naphthyl), alkylthio groups (eg, methylthio, octylthio), arylthio groups (eg, phenylthio, naphthylthio), acyl groups (eg, acetyl, benzoyl, pivaloyl), sulfonyl groups (eg, methanesulfonyl, benzenesulfonyl) A ureido group (e.g., 3-propylureido, 3,
3-dimethylureido), urethane group (eg, methoxycarbonyl, butoxycarbonyl), cyano group, hydroxyl group, nitro group, heterocyclic group (eg, benzoxazole ring, pyridine ring, sulfolane ring, furan ring, pyrrole ring, pyrrolidine ring, morpholine Ring, piperazine ring, pyrimidine ring) and the like.

The dyes used in the present invention are preferably those represented by formula (I), (II) or (III), and more preferably represented by formula (I) or (II)
It is a compound represented by I), and particularly preferably a compound represented by the general formula (I). Specific examples of the dye used in the present invention are shown below, but the present invention is not limited to these.

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The dye constituting the present invention is described in International Patent WO8.
8/04794, European Patent EP 274723, 2
Nos. 76,556 and 299,435, U.S. Pat.
27,583, 3,486,897, 3,74
Nos. 6,539, 3,933,798 and 4,13
0,429 and 4,040,841;
No. 68,623, No. 52-92,716, No. 55-1
55,350, 55-155,351, 61-
205,934, JP-A-2-173,630, and JP-A-2-173630
-230,135, 2-277,044, 2-
Nos. 282,244, 3-7,931, 3-16
7,546, 3-13,937, 3-206,
No. 443, No. 3-208, 047, No. 3-192, 1
No. 57, 3-216, 645, 3-274, 04
No. 3, 4-37, 841, 4-45, 436,
Nos. 4-138,449, 5-197,077, Japanese Patent Application Nos. 5-273,811, 6-7,761, 6
No. 155,727, or the like, or can be synthesized according to the method.

The dye constituting the present invention can be used in a yellow filter layer, a magenta filter layer, and an antihalation layer. Accordingly, for example, when the photosensitive layer is provided in the order of a red photosensitive layer, a green photosensitive layer, and a blue photosensitive layer from the side closest to the support, a yellow filter layer and a green photosensitive layer are provided between the blue photosensitive layer and the green photosensitive layer. A magenta filter layer can be provided between the red photosensitive layer and the red photosensitive layer, and a cyan filter layer (antihalation layer) can be provided between the red photosensitive layer and the support. The amount of dye used is
The transmission density of each layer is blue, green, red light respectively,
It is used so as to be 0.03 to 3.0, more preferably 0.1 to 2.0. Specifically, although it depends on the ε and the molecular weight of the dye, the amount may be 0.005 to ² mmol / m ² , preferably 0.05 to 1 mmol / m ² .

The light-sensitive material of the present invention may be used by mixing two or more dyes in one layer. For example, three kinds of dyes of yellow, magenta and cyan can be mixed and used in the above-mentioned antihalation layer. The photosensitive material of the present invention is
An oil droplet obtained by dissolving a decolorizable dye in oil and / or an oil-soluble polymer is used in a state of being dispersed in a hydrophilic binder. An emulsification dispersion method is preferable as the preparation method, and for example, a method described in US Pat. No. 2,322,027 can be used. In this case, US Pat. No. 4,555,470
Nos. 4,536,466 and 4,587,206
Nos. 4,555,476 and 4,599,296
High boiling oils such as those described in JP-B No. 3-62,256 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. Further, two or more high boiling oils can be used in combination. Further, an oil-soluble polymer can be used in place of or in combination with oil, and an example thereof is PCT International Publication No. WO88.
/ 00723. The amount of the high-boiling oil and / or the polymer is 0.01 g to 10 g, preferably 0.1 g to 5 g, per 1 g of the dye used. Further, as a method of dissolving the dye in the polymer, a latex dispersion method can be used. The process and specific examples of the latex for impregnation are described in US Pat.
9,363, West German Patent Publication (OLS) 2,541,2
No. 74, No. 2,541, 230, JP-B-53-4
1,091 and European Patent Publication No. 029,104.

In dispersing the oil droplets in the hydrophilic binder, various surfactants can be used. For example, surfactants described in JP-A-59-157,636, pp. 37-38, and publicly known technique No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, can be used. Also, Japanese Patent Application No. 5-204,325
No. 6-19,247, West German Published Patent No. 93
A phosphate ester type surfactant described in 2,299A can also be used. As the hydrophilic binder, a water-soluble polymer is preferable. Examples include gelatin, proteins of gelatin derivatives, or cellulose derivatives, starch, gum arabic,
Natural compounds such as polysaccharides such as dextrin and pullulan and synthetic high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer are exemplified.
These water-soluble polymers can be used in combination of two or more. Particularly preferred is a combination with gelatin.
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 may be used in combination.

In the present invention, the coloring matter is decolorized during the treatment by the reaction with the decoloring agent. The decolorizer, alcohols or phenols (R51OH), an amine or aniline ((R52) ₃ N), hydroxylamines ((R52) ₂ NOR52), sulfinic acids (R51
SO ₂ H or its salt), sulfurous acid or its salt, thiosulfuric acid or its salt, carboxylic acids (R51CO ₂ H
Or its salt), hydrazines ((R52) ₂ NN
(R52) ₂ ), guanidines ([(R52) ₂ N] ₂
C = NH), aminoguanidines ((R52) ₂ NR5
2N (R52N) C = NH) , amidines, thiols (R51SH), cyclic or chain-like active methylene compounds (Z53-CH ₂ -Z54, wherein Z53, Z54 and Z
51 and Z52, and Z53 and Z54 may combine to form a ring), a cyclic or chain active methine compound (Z53-CH (R51) -Z54 or Z53).
53-CH (Z54) -Z55, wherein Z55 is Z53
Is synonymous with Z53, Z54, Z55 (or R5
1) may be combined with each other to form a ring), and anionic species generated from these compounds. Of these, preferred are hydroxylamines, sulfinic acids, sulfurous acid, guanidines, aminoguanidines, heterocyclic thiols, cyclic or linear active methylene, active methine compounds, and particularly preferred are guanidines, aminoguanidine Kind. These decolorizing agents may be added to the light-sensitive material from the beginning, or may be added to the light-sensitive material by any method during processing. As a form of the decoloring agent at the time of addition, a precursor that has been turned into a precursor may be added.

The above-described decoloring agent comes into contact with the dye during the treatment, and decolorizes the dye by nucleophilic addition to the dye molecule.
The silver halide light-sensitive material preferably containing a dye is heated in the presence of water and a processing member containing a decolorant or a decolorant precursor after imagewise exposure or simultaneously with imagewise exposure,
Thereafter, by peeling both off, a color-developed image is obtained on the silver halide light-sensitive material and the dye is decolorized. In this case, the density of the dye after decoloring is 1/3 or less, preferably 1/5 or less of the original density. The amount of decolorant used is
It is 0.1 to 200 moles, preferably 0.5 to 100 moles, of the dye.

In a color negative film conventionally used for photography, not only the silver halide emulsion is improved to achieve the desired granularity, but also the development is suppressed during the coupling reaction with the oxidized form of the developing agent. A technique such as the use of a so-called DIR coupler that releases a compound having a property has been incorporated. In the photosensitive material of the present invention, D
Excellent granularity can be obtained even when no IR coupler is used. In addition, the combination of the DIR compounds results in increasingly better granularity.

As the binder for the constituent layers of the light-sensitive material of the present invention, hydrophilic binders are preferably used. Examples are the above-mentioned Research Disclosure and
No. 13, 546, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, for example, gelatin, protein or cellulose derivative such as gelatin derivative, starch, gum arabic,
Examples include natural compounds such as polysaccharides such as dextran and pullulan, and synthetic high molecular compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer. Also, U.S. Pat. No. 4,960,681,
No. 2-245260, etc., ie, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or these vinyl monomers or other vinyl monomers (For example, sodium methacrylate, ammonium methacrylate, Sumitagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) are 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 1 m
^It is preferably 1 g or more and 20 g or less per 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.
Page, JP-A-58-123,533, and JP-A-58-149,
No. 046, No. 58-149, 047, No. 59-11
No. 1,148, No. 59-124, 399, No. 59-1
Nos. 74,835, 59-231,539, 59-
No. 231,540, No. 60-2,950, No. 60-
No. 2,951, No. 60-14, No. 242, No. 60-2
No. 3,474, No. 60-66,249, No. 8-11
Nos. 0,608, 8-146,552 and 8-14
No. 6,578 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-4-274,425: coupler described in claim 1 on page 40 of EP498,381A1, EP447,969A1
No. 4, couplers represented by formula (Y) on page 4
Formulas (I) to 76, 219, column 7, lines 36 and 58
A coupler represented by (IV). Magenta coupler: JP-A-3-39,737;
43,611 and 5-204,106,
The coupler described in 3,626. Cyan coupler: JP-A-4-204,843, JP-A-4-43,345, JP-A-4-23,633. Polymer coupler: JP-A-2-44,345.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB2,12
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 compound: EP 378,236 A1, No. 11
Compounds of formulas (I) to (IV) described on page
A compound represented by formula (I) described on page 7 of 436,938A2, a compound represented by formula (1) of JP-A-5-307248, and a compound represented by formula (I) described on pages 5 and 6 of EP440,195A2. , (II) and (III), the compound represented by formula (I) of claim 1 of JP-A-6-59411, and a compound capable of releasing a ligand;
A compound represented by LIG-X according to claim 1 of Claim 8.

In the present invention, the amount of the coupler to be used is preferably 1/1000 mol to 1 mol, more preferably 1/500 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 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,
p-phenylenediamines developing agents and phenol or active methylene couplers;
A combination of a p-aminophenol developing agent and an active methylene coupler can be used. US Patent 4,0
A combination of a sulfonamide phenol and a 4-equivalent coupler as described in JP-A-21,240, JP-A-60-128,438 and the like is excellent in raw preservation when incorporated in a light-sensitive material, and is a preferable combination. is there. When a developing agent is incorporated, a precursor of a 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 No. 1
Schiff base type compounds described in 5,159, and 13,92.
4, aldol compounds, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135,628.

Further, the sulfonamide phenol-based active compounds described in Japanese Patent Application No. 7-180,568,
The combination of a hydrazine-based drug and a coupler described in JP-A Nos. 287 and 7-63,572 are also preferable for use in the light-sensitive material of the present invention.

In the present invention, as a developing agent to be contained in the light-sensitive material, a compound represented by the general formula ID, IID, IIID or IVD
It is preferable to use a compound represented by the formula: Among them, the compounds of the general formula ID or IID are particularly preferably used. Hereinafter, these developing agents will be described in detail.

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In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group. , Alkylthio, arylthio, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano, alkylsulfonyl, arylsulfonyl, alkoxycarbonyl, aryloxy Represents a carbonyl group, an alkylcarbonyl group, an arylcarbonyl group or an acyloxy group, and R ₅ represents an alkyl group, an aryl group or a heterocyclic group. Z represents a group of atoms forming a (hetero) aromatic ring;
Is a benzene ring, the total value of Hammett constant (σ) of the substituent is preferably 1 or more. R ₆ represents an alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring. Further, each of the general formulas ID to IVD contains at least one ballast group having 8 or more carbon atoms in order to impart oil solubility to the molecule.

The compound represented by the general formula ID is a compound generically referred to as sulfonamidophenol, and is a compound known in the art. When used in the present invention, it is preferable that at least one of the substituents R _{1 to} R ₅ has a ballast group having 8 or more carbon atoms.

In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom (for example, chloro or bromo), an alkyl group (for example, methyl, ethyl, isopropyl, n-butyl,
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 IID 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.

In the formula, Z represents an atomic group forming a (hetero) aromatic ring. The (hetero) 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), an alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethyl Carbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidinecarbamoyl group, morpholinocarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfur Famoyl groups (eg, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl) Group, piperidylsulfamoyl group, morpholinylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group) , A sulfamoyl group, a cyano group, an alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), an arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), an alkoxycarbonyl group (eg, methoxycarbonyl) Group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, propionyl group,
Examples thereof include a butyroyl group) and an arylcarbonyl group (for example, a benzoyl group and an alkylbenzoyl group). The sum of the Hammett constant σ values of the above substituents is preferably 1 or more.

The compound represented by the general formula IIID is a compound generally called carbamoylhydrazone. General formula IVD
Are compounds generally referred to as sulfonylhydrazine. Both are compounds known in the art. When used in the present invention, it is preferable that at least one of R _{5 to} R ₈ has a ballast group having 8 or more carbon atoms.

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. In addition, among the compounds of the general formulas ID to IVD, in the present invention, the compounds of ID and IID are particularly preferable from the viewpoint of raw storage stability.

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

[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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

[0135]

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[0136]

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[0137]

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When a diffusion-resistant developing agent is used in the present invention, an electron transfer agent may be used, if necessary, to promote electron transfer between the diffusion-resistant developing agent and developable silver halide. And / or an electron transfer agent precursor can be used in combination. Particularly preferably, the above-mentioned US Patent No. 5,139,919 and European Patent Publication No. 418,
No. 743 is used. Also, Japanese Patent Application Laid-Open No. 2-23
As described in JP-A Nos. 0,143 and 2-235,044, a method of stably introducing a compound into a 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, Japanese Patent Application Laid-Open No.
An electron donor precursor as described in Japanese Patent No. 0,443 is also preferably used. Further, in the present invention, 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, and JP-A-4-24-2
Nos. 49,245 and 2-46,450,
186,240 are preferably used.
Japanese Patent Publication No. 3-63,733 and Japanese Patent Application Laid-Open No. 1-150,1.
No. 35, No. 2-46, 450, No. 2-64,634
No. 3-43,735, European Patent Publication No. 451,8.
A development inhibitor releasing reducing compound as described in No. 33 may also be used.

Further, in the present invention, a developing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat in the developing process can be used. In addition, the following reducing agents may be incorporated in the photosensitive material. Examples of reducing agents that can be used in the present invention include U.S. Pat. No. 4,500,626, 49-50.
Column, No. 4,839,272, No. 4,330,617
Nos. 4,590,152 and 5,017,454
No. 5,139,919, JP-A-60-140,3
No. 35, pages (17) to (18), Nos. 57-40, 245, 56-138, 736, 59-178, 458;
Nos. 59-53,831, 59-182,449,
Nos. 59-182,450 and 60-119,555
No. 60-128, 436, No. 60-128, 43
No. 9, No. 60-198, 540, No. 60-181, 7
No. 42, No. 61-259, 253, No. 62-244,
Nos. 044, 62-131, 253, 62-13
Nos. 1,256 and 64-13,546, (40) to (57)
Page, JP-A-1-120,553, EP 220,
746A2, pages 78 to 96, and the like. No. 3,039, U.S. Pat.
Combinations of various reducing agents, such as those disclosed in US Pat. No. 869, may also be used. The developing agent or the reducing agent may be incorporated in a processing sheet described later, or may be incorporated in a photosensitive material. In the present invention, a developing agent and
The total amount of the reducing agent is 0.01 to 20 mol, particularly preferably 0.01 to 10 mol, per mol of silver.

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 ID. In the developing agent of the general formula ID, the coupling site is substituted by a sulfonyl group, and at the time of coupling, the sulfonyl group is released as sulfinic acid. Therefore, 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, a 2-equivalent coupler is used for the developing agents of the general formulas IID and IIID. General formula
In the developing agents of IID and IIID, the coupling site is substituted by a carbamoyl group, and the hydrogen atom on the nitrogen atom is released as a proton during coupling, so 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 both of the theory.
Of the Photographic Process (4th Ed. T.
H. James editing, Macmillan, 1977) pp. 291-334,
And pages 354 to 361, JP-A-58-12,353.
Nos. 58-149,046 and 58-149,04
Nos. 7, 59-11, 114, 59-124, 39
No. 9, 59-174, 835, 59-231, 5
No. 39, No. 59-231, 540, No. 60-2, 95
No. 1, 60-14, 242, 60-23, 474
No. 60-66,249, and the above-mentioned documents and gazettes.

A hydrophobic additive such as a coupler, a developing agent, and a diffusion-resistant reducing agent 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 organic solvent is 10 g or less, preferably 5 g, per 1 g of the hydrophobic additive used.
g or less, more preferably 1 g to 0.1 g. Also,
1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less, is suitable for 1 g of the binder. Tokiko Sho 51-3
9,853, JP-A-51-59,943, and a dispersion method using a polymer described in JP-A-62-30,242.
And the method of adding as a fine particle dispersion described in No. For compounds that are substantially insoluble in water,
In addition to the above-mentioned method, fine particles can be dispersed and contained in a binder. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157,636, Nos. (37) to (3)
On page 8), those mentioned as the surfactants described in Research Disclosure described above can be used. Further, phosphate ester type surfactants described in JP-A-7-56,267, JP-A-7-228,589 and West German Patent Application No. 1,932,299A can also be used. In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,626, 51st.
-52 column.

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 and above the silver halide emulsion layers 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.

Dyes which can be used in the yellow filter layer and the antihalation layer are preferably those which are decolored or eluted during development and do not contribute to the density after processing. 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 /
10 or less, and the components of the dye may be eluted from the photosensitive material or transferred to the processing material during development,
It may be converted to a colorless compound by reacting during development.

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 of the present invention, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include the aforementioned Research Disclosure, US Pat. No. 5,089,378.
Nos. 4,500,627 and 4,614,702
No., JP-A-64-13564, pages (7) to (9), (57) to
(71) and (81)-(97), U.S. Pat.
No. 10, 4,626,500, 4,983,49
No. 4, JP-A-62-174,747 and 62-23
9,148, JP-A-1-150,135, 2-1
10,557, 2-178,650, RD17,
No. 643 (1978), pp. 24 to 25. These compounds are 5 × 1 per mole of silver.
It is preferably from 0 ^-6 to 1 × 10 ^-1 mol, more preferably from 1 × 10 ^-5 to 1 × 10 ^-5 mol.
1 × 10 ^-2 mol is preferably used.

After the photosensitive material of the present invention has been exposed imagewise,
To form an image, the exposed photosensitive material and a processing material containing a base and / or a base precursor on a support are laminated on the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material, and then heat-developed. Then, an image is formed. At the time of development, water equivalent to 1/10 to 1 time of the water required for the maximum swelling of all the coating films constituting the photosensitive material and the processing material is supplied to the photosensitive material or the processing material, and then the color development is performed by bonding and heating. The method used is preferably used, but the present invention is not limited by this. Further, a method in which a developing agent is incorporated in a photosensitive material or a processing material as necessary is preferably used, but the present invention is not limited thereto.

The heat treatment of the light-sensitive material of the present invention is known in the art. For the heat-developable light-sensitive material and the process thereof, see, for example, pages 553 to 555 of Basics of Photographic Engineering (1970, published by Corona Co., Ltd.). , April 1978, 40 pages of video information, Nabletts Handbook of Photography and
Reprography 7th Ed. (Vna Nostrand and Reinhold Comp
any), pages 32-33, U.S. Patent No. 3,152,904.
No. 3,301,678 and No. 3,392,02
No. 3,457,075, British Patent No. 1,13
Nos. 1,108, 1,167,777 and Research Disclosure, June 1978, pages 9 to 15 (RD-17029).

Next, processing materials and processing methods used in the case of the heat development processing in the present invention 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 formation reaction. Examples of the base precursor include a salt of an organic acid and a base that are decarboxylated by heat, a compound that releases an amine by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. A specific example is described in U.S. Pat.
Nos. 4,493 and 4,657,848 and Known Technique No. 5 (March 22, 1991, Aztec Co., Ltd.), pp. 55-86. Further, European Patent Publication No. 210,660 described later and US Pat.
No. 740,445 describes 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 using water as a medium (referred to as a complex forming compound). A method of generating a base in combination may be used. The amount of the base or the base precursor used is 0.
It is 1 to ²⁰ g / m ² , preferably 1 to 10 g / m ² .

A thermal 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 (methylurea, ethylene urea, etc.), sulfonamide derivatives (compounds described in JP-B-1-40,974 and JP-B-4-13,701, 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 from 10% by weight to 500% by weight, preferably from 20% by weight to 3% by weight of the binder of the layer to be added.
00% by weight. The heating temperature in the thermal development process is about 50 ° C
To 250 ° C, but particularly useful is 60 ° C to 150 ° C.

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. In addition to the processing material, the air is shut off during the heat development, the material is prevented from volatilizing from the photosensitive material, the processing material other than the base is supplied to the photosensitive material, and the photosensitive material becomes unnecessary after the development. The material may have a function of removing materials (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 and other purposes. As the mordant, those known in the field of photography can be used, and US Pat. No. 4,500,626, columns 58-59, JP-A-61-88,256, pages 32-41, and JP-A-62-2.
And mordants described in JP-A-44,043 and JP-A-62-244,036. US4,46
A dye-receiving polymer compound described in JP-A-3,079 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.

When performing thermal development using the above processing materials,
A small amount of water is used for the purpose of promoting development, facilitating transfer of processing materials, and promoting diffusion of unnecessary substances. Specifically, U.S. Patent Nos. 4,704,245 and 4,470,445,
It is described in JP-A-61-238,056. Water contains inorganic alkali metal salts, organic bases, low-boiling solvents,
A surfactant, an antifoggant, a complex forming compound with a poorly soluble metal salt, a fungicide, and a bactericide may be contained. 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 thermal developing apparatus using the photosensitive material and the processing material of the present invention, water may be used up or circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. JP-A-63-144,354 and JP-A-63-14.
4,355, 62-38,460, JP-A-3-2
The apparatus described in No. 10,555 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 1/10 to 1 times the amount required for maximally swelling the entire coating film (excluding the back layer) of the photosensitive material and the processing material. As a method of applying the water, for example, Japanese Patent Application Laid-Open No. 62-253,
159 (5), JP-A-63-85,544 and the like are preferably used. Further, 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 material or both in advance. The temperature of the water to be applied is determined by the method described in JP-A-63-855.5.
The temperature may be 30 ° C to 60 ° C as described in No. 44 or the like.

When heat development is performed 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, or a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater, an infrared or 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 material in such a manner that the photosensitive layer and the processing layer face each other. The heating temperature is preferably from 70C to 100C.

For processing a photographic element comprising the light-sensitive material of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-75247 and JP-A-59-1777.5.
No. 47, 59-181, 353, 60-18, 9
No. 51, Japanese Utility Model Application Publication No. 62-25,944, Japanese Patent Application No. 4-27
7,517, 4-243,072, 4-24
Nos. 4,693, 6-164,421, 6-16
An apparatus described in US Pat. No. 4,422 or the like is 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 the 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 light-sensitive material of the present invention, silver developed in the light-sensitive material is removed at the same time as the development, or a silver oxidizing agent acting as a bleaching agent is contained in the processing material, and these reactions occur during thermal development. be able to. Further, after the development of the image formation is completed, the second material containing the oxidizing agent for silver can be bonded to the photosensitive material to remove the developed silver. However, it is preferable that the developed silver is not bleached during processing because the processing is simple.

As the bleaching agent that can be used in the above-mentioned processing materials, any commonly used silver bleaching agent can be used.
Such bleaching agents are disclosed in U.S. Patent Nos. 1,315,464 and 1,946,640 and Photographic Che.
mistry ol2, chapter30, Foundation Press London En
gland. 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. With respect to the binder, the support, and other additives that can be used for the second processing material, the same materials as the processing material (first processing material) for developing the photosensitive material can be used. The amount of the bleaching agent to be applied should be changed according to the amount of silver contained in the light-sensitive material to be bonded, but 0.01 mol to 10 mol of the amount of silver applied per unit area of the light-sensitive material / silver coated light-sensitive material Used in the molar range. The ratio is preferably from 0.1 to 3 mol / mol of the coated silver of the photosensitive material, and more preferably from 0.1 to 2 mol / mol of the coated silver of the photosensitive material.

Both the first processing material and the second processing material
It can have at least one polymerizable timing layer.
The polymerizable timing layer can temporarily delay the bleaching 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. Pat.
A barrier timing layer as described in US Pat. Nos. 1,496 and 4,229,516 may be used. When applying this timing layer, it is applied in a thickness of 5 to 50 microns, preferably 10 to 30 microns.

In the present invention, as a method of bleaching the developed photosensitive material using the second processing material, it is necessary to maximize the swelling of all coating films except for the back layer of both the photosensitive material and the second processing material. After supplying water equivalent to 0.1 to 1 times the amount to the photosensitive material or the second processing material, the photosensitive material and the second processing material are overlapped with the photosensitive layer and the processing layer facing each other. Heat at a temperature of 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-59-13673
No. 3, U.S. Pat. No. 4,124,398;
A bleaching sheet described in JP-A-28,098 can be used. The light-sensitive material of the present invention does not fix unreacted silver halide after thermal development, and is used as a negative original while leaving unreacted silver halide substantially on the light-sensitive material side. Used to form an image.
In the present invention, "without fixing unreacted silver halide"
"It means that there is no fixing step as an additional step after the heat development. In the present invention, the phrase "with substantially unreacted silver halide remaining" means that 50 mol% or more, preferably 70 mol% or more of unreacted silver halide is used.
More preferably, it means that 80 mol% or more is left.

In the present invention, it is preferable that the processing time from the time when the film surfaces of the processing sheet and the photosensitive material are overlapped in the presence of water to the time when they are peeled off is within 30 seconds.

In the light-sensitive material of the present invention, various surfactants can be used for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, accelerating 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, and JP-A No. Sho 62.
-173,463 and 62-183,457. The light-sensitive material of the present invention has slip prevention,
An organic fluoro compound may be included for the purpose of preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9,053, columns 8-17,
Nos. 1-20,944, 62-135,826, etc .; fluorinated surfactants; oily fluorinated compounds such as fluorinated oil; solid fluorinated compounds such as tetrafluoroethylene resin; Hydrophobic fluorine compound.

The light-sensitive material of the present invention preferably has a slip property. It is preferable to use a slip agent on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.1.
25 or less and 0.01 or more. The measurement at this time is 5mm in diameter
(25 ° C., 60% RH) when conveyed at 60 cm / min with respect to the stainless steel balls. 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 Z
nO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ ,
Particle size of at least one selected from SiO ₂ , MgO, BaO, 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. 0.001 to 1.0 μm crystalline metal oxides or fine particles of these composite oxides (Sb, P, B, InS, Si, C, etc.), and sol-like or metal oxides or these composite oxides Fine particles. Preferably 5 to 500 mg / m ² as a content of the photosensitive 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. 62-245,258 and 6
Any of the polymer latexes described in 2-136,648 and 62-110,066 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. 0.8 to 10 as particle size
μm is preferred, and the particle size distribution is preferably narrow, and it is preferred 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 simultaneously add fine particles having a particle size of 0.8 μm or less 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 (0.25 µm), colloidal silica (0.03 µm)
Is mentioned. Specifically, JP-A-61-88,256
It is described on page (29). Other examples include benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, and the like, as described in JP-A-63-274944 and JP-A-63-27.
No. 4,952. In addition, the compounds described in the aforementioned Research Disclosure can be used.

In the present invention, as the support for 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.

In particular, when the requirements for heat resistance and curl characteristics are strict, a support for a photosensitive material is disclosed in JP-A-6-41,281.
Nos. 6-43,581, 6-51,426, 6-51,437, 6-51,442, 6-8
No. 2,961, No. 6-82,960, No. 6-123,
937, 6-82,959, 6-67,346
No. 6-118,561, 6-266,050
Nos. 6-202,277 and 6-175,282
No. 6-118, 561, 7-219, 129
And the supports described in JP-A Nos. 7-219, 144 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, gelatin hardeners such as chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine) And the like, epichlorohydrin resin, active vinyl sulfone compound and the like. 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
Nos. 24,645, 5-40,321, 6-35,
No. 092, Japanese Patent Application Nos. 5-58,221 and 6-317,
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in No. 875.

[0172] The magnetic recording layer is composed of a magnetic particle and a binder.
An aqueous or organic solvent-based coating solution dispersed in a support
It is what was applied to. The magnetic particles are γFe_TwoO_ThreeWhat
Which ferromagnetic iron oxide, Co-coated γFe_TwoO_Three, Co adherent
Magnetite, Co-containing magnetite, ferromagnetic dioxide
Ferromagnetic metals, ferromagnetic alloys, hexagonal Ba ferrite
G, Sr ferrite, Pb ferrite, Ca ferrite
Etc. can be used. Co deposited γFe_TwoO_ThreeCo coating
Ferromagnetic iron oxide is preferred. Needle shape, rice grain
Shape, spherical shape, cubic shape, plate shape, etc. Specific surface area
Then it is 20m in SBET^Two/ G or more, preferably 30 m^Two/
g or more is particularly preferred. Saturation magnetization (σs) of ferromagnetic material
Is preferably 3.0 × 10^Four~ 3.0 × 10^FiveAt A / m
Yes, particularly preferably 4.0 × 10^Four~ 2.5 × 10 ^Five
A / m. The ferromagnetic particles are converted to silica and / or
Surface treatment with lumina or an organic material may be performed. Further
The magnetic particles are described in JP-A-6-161,032.
Silane coupling agent or titanium on the surface as
It may be treated with a coupling agent. JP-A-4-25
No surface is described in JP-A Nos. 9,911 and 5-81,652.
Magnetic particles coated with organic materials can also 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 described in JP-A-4-219,569. Natural polymers (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The above resin has a Tg of -40C to 300C.
° C, weight average molecular weight is 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, the reaction products of these isocyanates with polyalcohols (for example, the reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and the condensation products of these isocyanates And polyisocyanates. For example, JP-A-6-59,3
No. 57.

As a method for dispersing the magnetic particles in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. JP-A-5-088
No. 283 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.
m 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 particle dispersion coating solution is 0.005 to ³ g / m ² , preferably 0.01 to ² g / m ² as the weight of the magnetic particles.
m ² , more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is 0.01 to 0.5.
50 is preferable, and 0.03 to 0.20 is more preferable.
0.04 to 0.15 is particularly preferred. 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. 341 and 436 are preferable.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, anti-adhesion, 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. It is preferable that the abrasive is a non-spherical inorganic particle abrasive. 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. Regarding a photosensitive material having a magnetic recording layer, US Pat.
No. 589, No. 5,250,404, No. 5,229,2
No. 59, No. 5,215,874, EP 466,130
No.

The polyester support preferably used for the above-mentioned photosensitive material having a magnetic recording layer will be further described. The details including the photosensitive material, processing, cartridges and examples are disclosed in Japanese Unexamined Patent Application, Publication No. 94-6023.
(Invention Association; 1994. 3.15).
Polyester is formed using diol and aromatic dicarboxylic acid as essential components, and 2,6 as aromatic dicarboxylic acid.
-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,0
00. The Tg of the polyester is 50 ° C. or higher,
Further, the temperature is preferably 90 ° C. or higher.

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. Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ ) may be applied to improve the surface state. 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 carried out 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, but the application of the antistatic agent is preferred. Later. An ultraviolet absorber may be incorporated into this polyester. In addition, to prevent light pumping, Mitsubishi Kasei
The purpose can be achieved by applying a dye or pigment commercially available for polyesters such as Diaresin and 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 described in JP-A Nos. 1-312,537 and 1-312,538. Especially 25 ° C,
The resistance at 25% RH is preferably 10 ¹² Ω 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 25 mm cartridge of five sizes to 22 mm or less. The volume of the patrone case is 3
It is preferably 0 cm ³ or less, more 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 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.

In the present invention, the main purpose is to take in image information as digital data with a scanner or the like without removing developed silver and undeveloped silver halide generated by development. The photographed information can be used after being optically exposed to a printing material such as color paper in an analog manner.

In the present invention, it is possible to combine other methods for reducing the trouble of reading image information after photographing and subsequent image formation and development. In particular, undeveloped silver halide causes a high haze in the gelatin film and increases the background density of the image, and thus the silver halide of the present invention is considered to have a remarkable effect of reducing the effect. The detailed mechanism of its action will become clear in future studies.

As a method for producing a print on a color paper or a photothermographic material using this color photographing material,
JP-A-5-241,251, JP-A-5-19,364,
The method described in JP-A-5-19,363 can be used.

[0183]

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 <Preparation of Emulsion A-1 (Comparative Example)> Average molecular weight 15,000
950 ml of distilled water containing 12.5 g of Gelatin 0, 4.35 g of potassium bromide and 0.32 g of potassium iodide was placed in a reaction vessel, and the temperature was raised to 45 ° C. To this solution, 50 ml of an aqueous solution containing 8.3 g of silver nitrate and 50 ml of an aqueous solution containing 2.67 g of potassium bromide were added over 45 seconds with vigorous stirring. After completion of the addition, potassium hexachloride iridate is added.
38 mg were added. After maintaining at 45 ° C. for 4 minutes, the temperature of the reaction solution was raised to 63 ° C. After adding 17.0 g of gelatin together with 130 ml of distilled water, 150 ml of an aqueous solution containing 51.2 g of silver nitrate and a 24.8% aqueous solution of potassium bromide were added while accelerating the flow rate, and the silver potential of the reaction solution was changed to a saturated calomel electrode. It was added over a period of 13 minutes to 0 mV. After maintaining at 63 ° C. for 2 minutes after completion of the addition, the temperature of the reaction solution was lowered to 45 ° C. Then, 5.9 g of silver nitrate
50 ml of an aqueous solution containing 5.82 g of potassium iodide and 320 ml of an aqueous solution containing 5.82 g of potassium iodide were added over 5 minutes. Further, 350 ml of an aqueous solution containing 104.3 g of silver nitrate and a 25% aqueous solution of potassium bromide were added over 45 minutes so that the silver potential of the reaction solution became 90 mV with respect to the saturated calomel electrode. After completion of the addition, 1.4 g of potassium bromide and 4 mg of sodium ethylthiosulfonate were added, and the mixture was kept at 45 ° C. for 5 minutes. The resulting photosensitive silver halide emulsion had an average equivalent circular diameter of 0.
The emulsion was composed of hexagonal tabular grains having a diameter of 42 µm and an average grain thickness of 0.19 µm. This photosensitive silver halide emulsion was designated as Emulsion A-1.

<Preparation of Emulsion B-1 (Comparative Example)> 930 ml of distilled water containing 0.74 g of gelatin having an average molecular weight of 15,000 and 0.7 g of potassium bromide was placed in a reaction vessel, and then placed in a reaction vessel.
The temperature was raised to 0 ° C. While vigorously stirring this solution, 30 ml of an aqueous solution containing 1.2 g of silver nitrate and 0.82 g of potassium bromide
Was 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. After adding 27.0 g of gelatin together with 200 ml of distilled water, 100 ml of an aqueous solution containing 22.5 g of silver nitrate and 80 ml of an aqueous solution containing 15.43 g of potassium bromide were added over 11 minutes while increasing the addition flow rate.

Next, an aqueous solution 25 containing 75.1 g of silver nitrate
0 ml and the molar ratio of potassium iodide to potassium bromide is 3: 9
An aqueous solution (potassium bromide concentration: 26%) of No. 7 was added for 20 minutes while accelerating the addition flow rate and adjusting the silver potential of the reaction solution to 2 mV with respect to the saturated calomel electrode.
Further, 75 ml of an aqueous solution containing 18.7 g of silver nitrate and a 21.9% aqueous solution of potassium bromide were added over 3 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 55 ° C. Then, silver nitrate8.
120 ml of an aqueous solution containing 1 g 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 mg of potassium hexachloroiridate were added, and the mixture was kept at 55 ° C. for 1 minute. Then, 180 ml of an aqueous solution containing 44.3 g of silver nitrate and 160 ml of an aqueous solution containing 34.0 g of potassium bromide were added. Was added over 8 minutes. The temperature was lowered and desalting was performed according to a standard method. The resulting photosensitive silver halide emulsion was an emulsion comprising hexagonal tabular grains having an average equivalent circular diameter of 0.90 μm and an average grain thickness of 0.24 μm. This photosensitive silver halide emulsion was designated as emulsion B-1.

<Preparation of Emulsion C-1 (Invention)> H ₂ SO ₄ was added to 1,000 cc of an aqueous solution containing 0.5 g of oxidized gelatin and 0.37 g of KBr, and the pH was adjusted to 2 while maintaining the temperature at 40 ° C. After stirring, 55 cc of a 0.3 mol aqueous AgNO ₃ solution and 55 cc of a 0.3 mol aqueous KBr solution were simultaneously added by a double jet for 110 seconds. Then Na
The pH was adjusted to 5.0 by adding OH and pAg =
After adjusting the temperature to 9.9, the temperature was raised to 75 ° C. in 35 minutes, and 35 g of oxidized gelatin was added.
512 cc of NO ₃ aqueous solution and 1.4 mol of KBr aqueous solution 4
40 cc was added for 33 minutes while accelerating the flow rate while maintaining the pAg at 7.72 (the flow rate at the end was 5.2 times that at the start). Thereafter, the temperature was lowered to 55 ° C., 104 cc of a 0.4 mol AgNO ₃ aqueous solution and 279 cc of a 0.12 mol KI aqueous solution.
Was added in a fixed amount for 5 minutes, and subsequently, an aqueous KBr solution was added to adjust the pAg to 8.8, and then 1.8 mol of AgNO ₃ was added.
Aqueous solution 110cc and 1.8M KBr aqueous solution 125c
c was added. Thereafter, the emulsion was cooled to 35 ° C., washed with water by a conventional flocculation method, and 75 g of gelatin was added to adjust the pH to 5.5 and the pAg to 8.2. The resulting grains were tabular grains comprising more than 99% of the total projected area of all grains, having an average equivalent circular diameter of 0.99 μm and an average grain thickness of 0.06 μm. This photosensitive silver halide emulsion was designated as Emulsion C-1.

Chemical sensitization Spectral sensitization and chemical sensitization of emulsions A-1 to C-1 will be described. For these emulsions, 60 ° C., pH =
6.2, under the condition of PAg = 8.4, the following spectral sensitizing dyes I, II and III, compound I, potassium thiocyanate,
Spectral sensitization and chemical sensitization were performed by adding 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 amount of the chemical sensitizer was adjusted so that the sensitivity of each emulsion at the time of 1/100 second exposure was maximized. The green-sensitive emulsion thus prepared was represented by a suffix of g, such as A-1g.

[0189]

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[0190]

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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.

Further, 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 ml 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 the temperature was adjusted to 50 ° C.
, And emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. After dispersion, the total amount is 30
Add distilled water so that the amount becomes 0 g, and add 10 g at 2,000 rpm.
Mix for minutes.

Dye dispersion for magenta layer (this invention)
Was emulsified and dispersed as follows. That is, 2.0 g of the magenta dye A10, 2.0 g of tricresyl phosphate, 3.5 g of an oil layer component in which 22 cc of cyclohexane was dissolved, 3.5 g of lime-treated gelatin, and a surfactant (e)
An aqueous layer component containing 0.26 g and 37 cc of water was mixed, and 10,000 RP at 40 ° C. using a homogenizer.
M for 3 minutes, add 44 cc of water and add
Mix at 0 RPM for 10 minutes to make a uniform dispersion. The obtained dispersion had an average particle size of 0.18 μm. For comparison with the above dyes, a magenta leuco dye and zinc were used in combination to form a layer capable of forming a decolorable color layer during heat development. A dispersion of the colorant was prepared.

Sample 101 having the composition shown in Table 1 was obtained by combining these dispersions with the previously prepared silver halide emulsion.
To 103 were prepared.

[0195]

[Table 1]

[0196]

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[0197]

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[0198]

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Further, the processing materials P-
1, P-2 was produced.

[0200]

[Table 2]

[0201]

[Table 3]

[0202]

[Table 4]

[0203]

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[0204]

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These photosensitive materials were exposed to light at 1,000 lux for 1/100 second through an optical wedge and a green filter. 18 ml of warm water at 40 ° C on the surface of the photosensitive material after exposure
/ M ^2, and the processing material P-1 and the respective film surfaces were overlapped with each other, and then heat-developed at 83 ° C. for 30 seconds using a heat drum. When the photosensitive material was peeled off after the processing, a wedge-shaped image of magenta color was obtained.

Further, for fixing, the processing material P-2
Was used to perform the treatment in the second step. The process of the second step is
The processing material P-2 was coated with 12 cc / m ² of water, bonded to the photosensitive material after the first processing, and heated at 70 ° C. for 20 seconds.

Observation of the unexposed portion of the obtained sample revealed that all the colored layers were decolorized. Further, the transmission density of the obtained color sample was measured, and the transmission density was 0.1% lower than the fog density.
The reciprocal of the exposure amount corresponding to 5 higher densities was defined as relative sensitivity, and the value for the photosensitive material 101 was set to 100, and the results are shown in Table 5.

[0208]

[Table 5]

[0209] The maximum concentrations of these samples were measured. No bleaching of the silver halide was performed in any case. The tendency of the results did not change with and without fixing. Table 5 summarizes the results without fixing.

From the results shown in Table 5, it is understood that the light-sensitive material of the present invention is an excellent light-sensitive material having high sensitivity and high maximum density. When the processed photographic material and the processed material were respectively extracted by liquid chromatography, it was found that all of the decolored dye remained in the photographic material and was not transferred to the processed material.

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. A blue-sensitive emulsion is suffixed with b, for example, as in A-1b,
Red-sensitive emulsions are given a suffix r, for example, A-1r
It was expressed as follows.

[0212]

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[0213]

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Further, according to the method of preparing a coupler dispersion of Example 1, cyan and yellow coupler dispersions were prepared. Cyan and yellow dye dispersions were prepared according to the method of preparing a dye dispersion of Example 1. Further, for comparison, a colorant dispersion was prepared by combining the following yellow, magenta, and cyan leuco dyes with a zinc complex for the purpose of forming a decolorable colored layer during heat development. Using the thus obtained silver halide emulsion, coupler dispersion and colorant dispersion, heat-developable color light-sensitive materials (201 to 203) having a multilayer structure shown in Table 6 were prepared.

[0215]

[Table 6]

[0216]

[Table 7]

[0219]

[Table 8]

[0218]

[Table 9]

[0219]

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[0220]

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[0221]

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[0222]

Embedded image

The photographic characteristics of these light-sensitive materials were tested in the same manner as in Example 1. When the photosensitive material is peeled off after the heat development processing, the sample exposed with the blue filter has a wedge-shaped image of yellow color, the sample exposed with the green filter has a wedge-shaped image of magenta color, and the sample exposed with the red filter. In the example, a wedge-shaped image of cyan color was obtained. Further, from these samples, the color separation properties of the green-sensitive layer and the red-sensitive layer against blue light were evaluated. As a result, it was found that the light-sensitive material of the present invention was excellent. Further, the sensitivity and the maximum concentration of these samples were measured in the same manner as in Example 1. No fixing was performed. The results are summarized in Table 7.

[0224]

[Table 10]

From the above results, it can be seen that the photosensitive material of the present invention has high sensitivity and high maximum density.

[0226]

As described above, according to the present invention, it is possible to provide a high-quality silver halide color photographic light-sensitive material for photography capable of forming an image easily, quickly and with less environmental load. In particular, an excellent high-quality color photographic light-sensitive material having high sensitivity and high maximum density can be provided.

Claims (3)

[Claims] 1. A photosensitive material comprising at least one photosensitive layer comprising a photosensitive silver halide particle, a compound forming a dye by a coupling reaction with an oxidized form of a developing agent, and a binder on a support. Of the photosensitive layer surface
In a silver halide color photographic light-sensitive material which forms a color image by laminating with a processing layer surface of a processing material containing a decoloring agent and performing heat development, at least one of the photosensitive layers has an average equivalent circle equivalent diameter of 0.7 μm. As described above, the emulsion contains tabular grains having an average thickness of less than 0.07 μm, and the light-sensitive material contains a dye that is decolorized by a reaction with a decolorant during development processing. A silver halide color photographic light-sensitive material characterized in that it is diffusion-resistant, and at least a part of the dye which has been decolorized after development processing is diffusion-resistant. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the dye is any of the dyes represented by the following general formulas (I) to (IV) which decolor during processing. . General formula (I) A51 = L51-(L52 = L53) _m51-
Q51 General formula (II) A51 = L51-(L52 = L53) _n51-
A52 General formula (III) A51 (= L51-L52) _p51 = B51 General formula (IV) (NC) ₂ C = C (CN) -Q51 (wherein, = represents a double bond, and-represents a single bond. A51,
A52 represents an acidic nucleus, and B51 represents a basic nucleus. Q51 represents an aryl group or a heterocyclic group. L5
1, L52 and L53 each represent a methine group. m51
Represents 0, 1 or 2. n51 and p51 represent 0, 1, 2 or 3, respectively. However, the general formulas (I) to (I)
The compound represented by V) does not have a carboxyl group or a sulfo group, and the compounds represented by general formulas (I) to (IV) have a diffusion-resistant group and are treated (decolored). )
The later product is also resistant to diffusion and does not substantially elute from the photosensitive material. ) 3. The silver halide color according to claim 1, wherein at least two types of silver halide emulsions having a sensitivity in the same wavelength region and having different average projected areas are used in combination. Photosensitive material.