JPH1062936A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sensitive material imparting satisfactory graininess by easy rapid development and used in an unfixed state. SOLUTION: The silver halide color photographic sensitive material contg. photosensitive silver halide, a coupler and a binder on the substrate is exposed, a processing material is stuck to the sensitive material and they are heated to form an image on the sensitive material. The unreacted silver halide is not fixed and the sensitive material is used as a negative original while practically leaving the unreacted silver halide. The total amt. of applied silver in the sensitive material is >=0.1g/m<2> and the sensitive material contains an emulsion in which flat platy particles each having an aspect ratio of >=2 as (100) high silver chloride particles account for >=50% of the total projection area of all particles.

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

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

[0005] 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.

The present inventors have proposed a recording material for photographing,
In order to simply and quickly use no processing solution, or to reduce the use of the processing solution as much as possible, a method of using a photosensitive material photographed without fixing was studied. As a result, there is a problem that the image quality is deteriorated due to the optical scattering of the remaining silver halide.

A silver halide light-sensitive material for photography requires high sensitivity. In order to increase the sensitivity, it is effective to increase the sensitivity of silver halide grains and increase the amount of silver halide applied. Utilizing the rapid development advantage of high silver chloride emulsions in photographic materials,
S52643337, US5292632, US53
Patent specifications such as 10635 or WO94 / 22054 disclose a technique in which a tabular high silver chloride emulsion having a (100) plane is used as a photographic light-sensitive material for photography. The use of a high silver chloride emulsion provides advantages such as a high developing speed and the ability to process the photographic material and the photographic material using the same processing solution. However, these documents do not disclose any operation or effect when the photosensitive material is used without being fixed. In addition, silver halide grains composed of (100) planes whose length of one side is twice or more or 0.5 times or less the arithmetic average of the lengths of the other two sides are highly sensitive to fog in photothermographic materials. That low performance can be obtained
0014. However, there is no description about the operation and effect when an unfixed photosensitive material is used.

Many other reports have been made on silver chloride tabular grains having a (100) plane. For example, US-5
314798, EP-534395A, EP-6173
21A, EP-617317A, EP-617318
A, EP-617325A, WO94 / 22051, E
P-616255A, US-5356664, US-5
320938, US-5275930 and the like.

Further, various reports have been made on tabular grains mainly composed of (111) planes, and they are described in detail in, for example, US Pat. No. 4,439,520 and the like. Further, US Pat. No. 5,250,403 describes so-called ultrathin tabular grains having an equivalent circle equivalent diameter of 0.7 μm or more and a thickness of 0.07 μm or less. US4,
435 and 501 disclose a technique for epitaxially growing a silver salt on the surface of a tabular grain. Also, recently, for improving the performance of tabular grains, EP0699947A, E
P0699951A, EP0699945A, EP07
01164A, EP06999944A, EP07011
65A, EP06999948A, EP06999946
A, EP06999949A, EP0699950A, and many other inventions are disclosed. However, these documents do not disclose any operation or effect when the photosensitive material is used without fixing.

Regarding increasing the coating amount of silver halide, for example, IMGING PROCESS AND MATERIALS NEBLE
As described in TTES EIGHTH EDITION (1989), page 287, FIG. 9-8, etc., it can be easily understood in consideration of the active area for development. However, when the amount of coated silver is increased, the amount of unfixed silver halide is inevitably increased when an unfixed photosensitive material is used, so that the image quality is significantly deteriorated. Therefore, improvement in image quality when an unfixed photosensitive material is used has a new problem to be solved different from the case where a conventional fixed photosensitive material is used.

[0013]

As apparent from the above description, a first object of the present invention is to provide a photographic light-sensitive material capable of forming an image easily, quickly and with less environmental load. To provide. Furthermore, simple,
An object of the present invention is to provide an excellent color photographic light-sensitive material capable of giving good granularity and exposure latitude even in a rapid processing. In particular, the greatest object is to improve the image quality when the photosensitive material is used without fixing.

[0014]

The objects of the present invention are: 1) a compound which forms a dye on a support by a coupling reaction with a photosensitive silver halide and an oxidized form of a developing agent;
A silver halide color photographic light-sensitive material comprising at least one light-sensitive layer comprising a base and / or a base precursor, after exposure of the light-sensitive material, comprising a processing layer containing a base and / or a base precursor. The coated processing material is bonded on the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material and heated to form a color image on the photosensitive material side, and unreacted silver halide is not fixed during processing. In a silver halide color photographic light-sensitive material used as a negative original while substantially leaving unreacted silver halide remaining, the total coated silver amount of the light-sensitive material is 0.1 g / m ² or more; Silver halide grains comprising at least 50 mol% of silver chloride in the non-conductive layer, and the main outer surface of the grains is constituted by a (100) plane, and the aspect ratio of the projection plane is 1: 1. A silver halide color photographic light-sensitive material containing an emulsion in which tabular grains having an aspect ratio of 2 or more, such as rectangles of 1 to 1: 2, occupying 50% or more of the total projected area. .

2) A silver halide color photographic material comprising at least one photosensitive layer comprising a photosensitive silver halide, a compound forming a dye by a coupling reaction with an oxidized form of a developing agent, and a binder on a support. After exposure of the light-sensitive material, a processing material comprising a support and a constituent layer including a processing layer containing a base and / or a base precursor coated on a support, is coated on the surface of the light-sensitive material and the surface of the processing material of the processing material. A color image is formed on the photosensitive material side by heating and bonding, and the unreacted silver halide is not fixed during processing, and is used as a negative original with substantially unreacted silver halide remaining. Silver halide color photographic light-sensitive material, the total coated silver amount of the light-sensitive material is 0.1 g
/ M ² or more, and in at least one photosensitive layer,
Silver halide grains comprising at least 70 mol% of silver bromide, wherein the main outer surface of the grains is composed of (111) planes, the average equivalent circular diameter is at least 0.7 μm, and the average thickness is A silver halide color photographic light-sensitive material comprising an emulsion comprising ultrathin tabular grains having a particle size of less than 0.07 μm.

3) The silver halide color photographic light-sensitive material as described in 1) or 2) above, wherein the total coated silver amount is 1.0 g / m ² or more.

4) Without bleaching the developed silver during processing,
The silver halide color photographic light-sensitive material according to any one of 1) to 3), wherein the light-sensitive material is used while developing silver remains.

[0018]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the first embodiment of the present invention described in 1), that is, silver chloride of (%) having 50% or more having a (100) plane will be described.

In the first embodiment of the present invention, at least one photosensitive layer contains silver halide grains comprising at least 50 mol% of silver chloride, and the main outer surface of the grains is (100) An emulsion is used in which tabular grains having an aspect ratio of 2 or more and occupying 50% or more of the total projected area are rectangular such that the projection plane is a rectangle having an aspect ratio of 1: 1 to 1: 2. It suffices that 50% or more of the projected area of the silver halide grains contained in the emulsion satisfy the above definition. Further, it is preferable that 70% or more of the projected area satisfies the above-mentioned rule.

The aspect ratio in the present invention is a value obtained by dividing the diameter of a circle equivalent to the projected area by the grain thickness. In the first embodiment of the present invention, the silver halide grains have a rectangular projection surface because the main outer surface of the grains is constituted by a (100) plane. At this time, it is necessary that the ratio of the vertical and horizontal sides of the rectangle as the projection plane is in the range of 1: 1 to 1: 2.
That is, the effects of the present invention cannot be obtained by using an emulsion composed of rod-shaped or rectangular parallelepiped grains. In the present invention, tabular grains whose projection surface is close to a square and whose ratio of the vertical and horizontal sides of the projection surface is in the range of 1: 1 to 1: 1.5 are preferred.

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

The halogen composition of the emulsion used in the first embodiment of the present invention is silver chlorobromide, silver chloroiodide, silver chloroiodobromide or silver chloride containing 50 mol% or more of silver chloride. Although the emulsion of the first embodiment of the present invention may contain silver iodide, the silver iodide content is preferably 6 mol% or less, more preferably 2 mol% or less.
Mol% or less. It is also preferable to use a silver halide emulsion composed of grains having a laminated structure composed of a plurality of layers having different halogen compositions inside the silver halide grains. The size of the silver halide grains used in the first embodiment of the present invention is preferably from 0.1 to 10 μm, more preferably from 0.3 to 5 when represented by the diameter of a circle equal to the projected area.
μm, particularly preferably 0.5 to 4 μm.

50 mol% used in the first embodiment of the present invention
Aspect ratio such that the silver halide grains are composed of silver chloride as described above, and the main outer surface of the grains is composed of (100) planes, and the aspect ratio of the projection plane is 1: 1 to 1: 2. In order to produce an emulsion composed of two or more tabular grains, various methods including a known production method can be used. For example, JP-A-5-204073 and JP-A-51
-88017, JP-A-63-24238, and Japanese Patent Application No. 5-264059 can be used arbitrarily.

The key to preparing the tabular grains of the first embodiment of the present invention is a method of generating nuclei for tabular growth. As described in the production method of the above-mentioned literature, iodine is formed at the beginning of grain formation. It is useful to add a chloride ion or a bromide ion or to add a compound exhibiting selective adsorption to a specific surface.

Next, the ultrathin tabular grains according to the second aspect of the present invention described in 2) will be described.

Ultrathin tabular grains (hereinafter referred to as "tabular grains") used in the second embodiment of the present invention are silver halide grains having two opposing parallel main planes.

The tabular grains of the second embodiment of the present invention have one twin plane or two or more parallel twin planes.

The twin plane is defined as (111) when ions at all lattice points on both sides of the (111) plane are in a mirror image relation.
Surface. In a second aspect of the present invention, the twin plane spacing is as described in US Pat. No. 5,219,720.
0.012 μm or less, or as described in JP-A-5-249585, the (111) distance between the main planes / the twin plane spacing is 1
It may be 5 or more.

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

In the emulsion of the second embodiment of the present invention, tabular grains preferably occupy 50 to 100% of the total projected area, more preferably 80 to 100%, particularly preferably 90 to 100%.

If it is less than 50%, the advantages of tabular grains (improvement of sensitivity / granularity ratio and sharpness) cannot be fully utilized, which is not preferable.

The average grain thickness of the tabular grains according to the second embodiment of the present invention is preferably 0.01 to 0.07 μm, more preferably 0.01 to 0.06 μm.
m, particularly preferably 0.01 to 0.05 μm.

The average grain thickness is an arithmetic mean 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 the thickness exceeds 0.07 μm, the effects of the present invention are hardly obtained, which is not preferable.

The average equivalent circle diameter of the tabular grains according to the second embodiment of the present invention is preferably from 0.7 to 5 μm, more preferably from 1 to 4.5 μm, particularly preferably from 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.

If the average equivalent circle diameter is less than 0.7 μm, the effects of the present invention cannot be easily obtained, 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 is called the aspect ratio. That is, it is a value obtained by dividing the equivalent circle diameter of the projected area of each silver halide grain by the grain thickness.

As an example of the method of measuring the aspect ratio, a method of obtaining a diameter (equivalent circle equivalent diameter) and a thickness of a circle having an area equal to the projected area of each particle by taking a transmission electron microscope photograph by a replica method is known. is there. In this case, the thickness is calculated from the length of the shadow of the replica. The emulsion of the second embodiment of the present invention has an average aspect ratio to all tabular grains of 10 to 100, more preferably 12 to 8.
0, 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, the effect of the present invention is hardly obtained, which is not preferable. If it exceeds 100, the pressure property deteriorates, which is not preferable.

Various methods can be used to form tabular grains having a small grain thickness and a high aspect ratio used in the second embodiment of the present invention. For example, US Pat.
No. 494,789 can be used. In order to form tabular grains having a high aspect ratio, it is important to generate twin nuclei having a small size. Therefore, at low temperature, high pBr and low pH, gelatin is used in a small amount and a small amount of methionine,
It is preferable to use a phthalated gelatin derivative or to shorten the nucleation time to perform nucleation. After nucleation, only tabular grains (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 the parallel multiple twins are selectively removed. Form crystal 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 according to the second embodiment of the present invention comprises a hexagonal tabular grain having a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 2 to 1. Preferably, it occupies 100 to 50%, more preferably 100 to 70%, particularly preferably 100 to 90% of the projected area of all grains therein. Mixing of tabular grains other than the above hexagons is not preferred in terms of homogeneity between grains.

The emulsion of the second embodiment of the present invention is preferably monodisperse. The variation coefficient of the equivalent circle diameter of the projected area of all the silver halide grains of the second embodiment of the present invention is preferably 30 to 3%, more preferably 25 to 3%, particularly preferably 20 to 3%. is there. If it exceeds 20%, it is not preferable in terms of homogeneity between particles. The variation coefficient of the equivalent circle diameter is a value obtained by dividing the standard deviation of the equivalent circle diameter of each silver halide grain by the average equivalent circle diameter.

The composition of the tabular grains according to the second embodiment of the present invention includes silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide containing silver bromide in an amount of 70 mol% or more. However, it is preferable to use silver bromide, silver iodobromide, silver chloroiodobromide,
Silver iodobromide and silver bromide are particularly preferably used. The silver bromide content is preferably at least 80 mol%, more preferably at least 90 mol%. The emulsion of the second embodiment of the present invention may contain silver chloride, but the silver chloride content is preferably at most 8 mol%, more preferably at most 3 mol%. Silver iodobromide having a laminated structure composed of a plurality of layers having different halogen compositions inside silver halide grains, containing iodine more than any of the layer adjacent to the grain inner side and the grain surface adjacent to the grain itself It is more preferable to use a silver halide composed of grains having at least one layer having a high ratio.

When there is a phase containing iodide or chloride, these phases may be uniformly distributed or localized in the grains. The preferred range of the silver iodide content of the tabular grains of the second embodiment of the present invention is from 0.1 to 20 mol%, more preferably from 0.1 to 15 mol%, particularly preferably from 0.2 to 10 mol%. %. If it is less than 0.1 mol%, it is not preferable because effects such as enhancement of dye adsorption and increase in intrinsic sensitivity are hardly obtained. If it exceeds 10 mol%, the developing speed is generally slow, which is not preferable.

The preferred variation coefficient of the intergranular silver iodide content distribution of the emulsion grains of the second embodiment of the present invention is 30 to 3%, more preferably 25 to 3%, particularly preferably 20 to 3%. is there. 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.

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

The tabular grains of the second embodiment of 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. , 27, 636 (1956), 2) C.I. R.
Berry, D.M. C. Skilman, J .; Appl.
Phys. , 35, 2165 (1964), 3) J.
F. Hamilton, Photo. Sci. Eng. ,
11, 57 (1967), 4) T.I. Shiozawa,
J. Soc. Photo. Sci. Jap. , 34,16
(1971), 5) T.I. Shiozawa, J .; So
c. Photo. Sci. Jap. , 35, 213 (19
72), etc., which can be analyzed by an X-ray diffraction method or a direct observation method using a low-temperature transmission electron microscope.

When dislocation lines are directly observed using a transmission electron microscope, the silver halide grains taken out of the emulsion are carefully screened so as not to apply enough pressure to generate the dislocation lines. Then, observation is performed by a transmission method in a state where the sample is cooled so as to prevent damage (for example, printout) by an electron beam. In this case, the thicker the particle, the more difficult it is for 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-63-220238 discloses 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 tabular grains without dislocation lines in photographic properties such as sensitivity and reciprocity. In the case of tabular grains, the position and the number of dislocation lines for each grain as viewed from the direction perpendicular to the main plane can be determined from the photograph of the grain taken using an electron microscope as described above.

In the case where the tabular grains of the second embodiment of the present invention have dislocation lines, their positions are selected, for example, from the apexes and fringe portions of the grains, or from the entire main plane portion. Although it is optional, it is particularly preferable to limit it to the fringe portion. The fringe portion referred to in the second embodiment of the present invention refers to the outer periphery of the tabular grain. Specifically, in the distribution of silver iodide from the side to the center of the tabular grain, the iodide is the first point when viewed from the side. Outside the point where the silver content exceeds or falls below the average silver iodide content of the whole grain.

In the case where the tabular grains of the second embodiment of the present invention have dislocation lines, the density of the dislocation lines is arbitrary, and 1
0 or more, 30 or more, 50 or more may be selected according to the case.

The emulsions of the first and second embodiments of the present invention and photographic emulsions other than the present invention used together therewith will be described below.

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), No. 17, 643 (1978)
No. 18,716 (197)
Nov. 1997) p. 648, No. 307, 105 (198)
Nov. 9, pp. 863-865, JP-A-62-253,
No. 159, No. 64-13,546, JP-A-2-23
No. 6,546, No. 3-110, 555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glaf)
kides, Chemie etPhisque Photographique, Paul Monte
l, 1967), Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chem)
istry, Focal Press, 1966), "Manufacture and Coating of Photographic Emulsions", by Zerikman et al., Published by Focal Press (VLZelikm)
an et al., Making and Coating Photographic Emulusi
on, Focal Press, 1964) and the like.

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

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

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

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

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

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

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

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

The light-sensitive materials of the first and second embodiments of the present invention include a compound (hereinafter referred to as a coupler) which forms a dye on a support by a coupling reaction with a photosensitive silver halide and an oxidized developing agent; And a photographic constituent layer including at least one photographic photosensitive layer comprising a binder and a binder.

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 ranges 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 having sensitivity to the same wavelength region and 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 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 that the emulsion having a large average grain projected area is disposed in the upper layer (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 when coating the emulsions having photosensitivity in the same wavelength region. 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.

In a color negative film which has been conventionally used for photography, the development of a silver halide emulsion is not only improved to achieve the desired granularity, but also the development is suppressed during a coupling reaction with an oxidized 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.

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

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

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

It is preferable to use the following couplers. Yellow coupler: couplers represented by formulas (I) and (II) of EP502,424A: EP513,4
No. 96A, couplers represented by formulas (1) and (2); and Japanese Patent Application No. 4-134523, a coupler represented by formula (I) of claim 1; Coupler represented by general formula D on line 55, coupler represented by general formula D in paragraph 0008 of JP-A-4-274425: coupler described in claim 1 on page 40 of EP498, 38A1, and EP447,969A4 Coupler represented by formula (Y) on page 4, US 4,47
Formulas (I) to (I) on lines 36 and 58 in column 7 of 6,219
A coupler represented by V). Magenta coupler: JP-A-3-39737, 6-4
No. 3611, 5-204106, JP-A-4-362
The coupler described in No. 6. Cyan coupler: JP-A-4-204843, JP-A-4
No. 43345, Japanese Patent Application No. 4-23633. Polymer coupler: JP-A-2-44345.

US Pat. No. 4,366,237, GB2,12, and US Pat.
5,570, EP 96,570, DE 3,234
No. 533 is preferred.

Further, 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 1 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 coupler described above. 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 Nos. 21 and 240 and JP-A-60-128438 is excellent in raw preservation when incorporated in a light-sensitive material, and is a preferable combination. 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 Nos. 14,850 and 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-53-135628.

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

In the present invention, it is preferable to use a compound represented by the general formula I, II, III or IV as a developing agent contained in the light-sensitive material. Among them, compounds of the general formula I or II 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 represent 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, and 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 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 I to IV 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 I is a compound generically called sulfonamidophenol, and is a compound known in the art. When used in the present invention, the substituent R
Those having a ballast group having 8 or more carbon atoms in at least one of _{1 to} R ₅ are preferable.

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

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

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

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

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

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

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

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

The hydrophobic additives such as a coupler, a developing agent and a diffusion-resistant reducing agent can be introduced into the layer of the 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 Japanese Patent Application Nos. 5-204325 and 6-19247 and West German Patent Application No. 1,932,299A can also be used.

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

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

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

As the dye that can be used in the light-sensitive material of the present invention, known dyes can be used. For example, a dye that dissolves in the alkali of the developing solution, or a type of dye that decolorizes by reacting with components in the developing solution, sulfite ions, the base agent, and the alkali can be used. Specifically, dyes described in European Patent Application EP 549,489A and JP-A-7-15
No. 2129, ExF2-6 dyes. Dyes dispersed in a solid as described in Japanese Patent Application No. 6-259805 can also be used. This dye can be used when the photosensitive material is developed with a processing solution, but is particularly preferable when the photosensitive material is thermally developed using a processing sheet described later. In addition, a mordant and a binder can be dyed with a dye. In this case, as the mordant and the dye, those known in the photographic field can be used.
Nos. 50,626, columns 58-59 and JP-A-61-882.
No. 56, pages 32 to 41, JP-A-62-244043, JP-A-62-244036 and the like. Further, by using a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, the mobile dye can be released with an alkali at the time of development and eluted in a processing solution or transferred and removed to a processing sheet. Specifically, U.S. Patent Nos. 4,559,290 and 4,783,369, European Patent No. 220,746A2, and Published Technical Report 87-6119.
And Japanese Patent Application No. 6-259805, paragraphs 0080-0081.

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

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

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

The light-sensitive materials of the first and second embodiments of the present invention can be used to form an image after imagewise exposure, by forming a base and / or a base precursor on a support and a base material on a support. The processing material to be contained is adhered on the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material and thermally developed to form an image. 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 light-sensitive materials of the first and second embodiments of the present invention do not fix unreacted silver halide during processing. Therefore, a color image is formed on the photosensitive material side, but silver halide remains. When the photosensitive material is used without fixing as defined in the present invention, that is, when the remaining silver halide is left, a tabular high silver chloride having a (100) plane according to the first embodiment of the present invention is used. A light-sensitive material containing an emulsion and a light-sensitive material containing a second form of an ultrathin tabular emulsion can provide an image having excellent sharpness.

The present invention has been made for the purpose of achieving good granularity and exposure latitude in the above-described thermal development, and aims to reduce the environmental load caused by liquid development. It is also possible to form an image by developing the light-sensitive material of the present invention with an activator method using an alkali processing solution or a processing solution containing a developing agent / base.

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

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

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

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

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

The heating temperature in the heat development step is about 50 ° C. to 2
The temperature is 50 ° C., but especially 60 ° C. to 150 ° C. is useful.

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

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

In the heat development using the processing material, a small amount of water is used for the purpose of accelerating the development, facilitating the transfer of the processing material, and accelerating the diffusion of unnecessary substances. Specifically, it is described in U.S. Pat. Nos. 4,704,245 and 4,470,445, JP-A-61-238056, and the like. In water, inorganic alkali metal salts and organic bases, low-boiling solvents, surfactants, antifoggants, complex-forming compounds with poorly soluble metal salts,
A fungicide and a fungicide may be included. Any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the 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-63-144,35.
Nos. 5, 62-38,460 and JP-A-3-210,5.
The device described in No. 55 or the like or water may be used. Water can be applied to the photosensitive material, the processing material, or both. The amount used is 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 for applying the water, for example, Japanese Patent Application Laid-Open No. 62-253,159
No. (5), the method described in JP-A-63-85544 is 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-63-85,544.
The temperature may be 30 ° C. to 60 ° C. as described in the item.

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

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

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

In the light-sensitive material of the present invention, silver developed in the light-sensitive material is removed at the same time as the development, or an oxidizing agent for silver, which acts as a bleaching agent, is contained in the processing material to cause these reactions 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 processing material of the present invention, any commonly used silver bleaching agent can be used. Such bleaches are disclosed in U.S. Pat. No. 1,315,464.
And 1,946,640, and Photographic
Chemistry ol2, chapter30, Foundation Press London
England. These bleaches effectively oxidize and solubilize photographic silver images. Examples of useful silver bleaches include alkali metal dichromates, alkali metal ferricyanides. Preferred bleaches are those that are soluble in water and include ninhydrin, indandione, hexaketocyclohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzenesulfonic acid, 2,5-dinitrobenzoic acid. Further, there are metal organic complexes, for example, ferric salt of cyclohexyldialkylaminotetraacetic acid, ferric salt of ethylenediaminetetraacetic acid, and ferric salt of citric acid. Binder, support, which can be used for the second processing material,
As for other additives, the same processing material (first processing material) as described above for developing the photosensitive material can be used. The amount of the bleaching agent to be applied should be changed according to the silver content of the light-sensitive material to be laminated, but is preferably 0.01 mol to 10 mol / mol of the coated silver per unit area of the light-sensitive material.
It is used in the range of the coated silver mole of the light-sensitive material. 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-59-136733
No. 4,124,398, JP-A-55-2.
Bleached sheets described in No. 8098 can be used. The photosensitive material of the present invention does not fix unreacted silver halide after thermal development, and uses the unreacted silver halide as a negative original while substantially remaining on the photosensitive material side,
Used to form an image on paper or the like. In the present invention, "not fixing unreacted silver halide" means that there is no fixing step as an additional step after thermal development. In the present invention, the phrase "with substantially unreacted silver halide remaining" means that 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more of unreacted silver halide remains. It is called as it is.

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

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

In the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds. The most preferred antistatic agent is Zn
_{O, TiO 2, SnO 2,} Al 2 O 3, In 2 O 3, SiO 2, MgO, BaO,
A particle size of at least one selected from MoO ₃ and V ₂ O ₅ having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less; Metal oxides or their composite oxides (Sb P, B InS, Si,
C) and fine particles of a sol, a metal oxide, or a composite oxide thereof. Preferably 5 to 500 mg / m ² as the content of the sensitive material, particularly preferably from 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is from 1/300 to 1
00/1 is preferred, more preferably 1/100 to 10
0/5.

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

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

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

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

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

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

The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. The magnetic particles include a ferromagnetic iron oxide such as γFe ₂ O ₂ , Co-coated γFe ₂ O ₃ , Co-coated magnetite,
Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite can be used. Co
Co-coated ferromagnetic iron oxide, such as γ-Fe ₂ O _2, is preferred. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g. The saturation magnetization (σs) of the ferromagnetic material is preferably from 3.0 × 10 ^{4 to} 3.0.
× 10 ⁵ A / m, particularly preferably 4.0 × 10 ⁴ to
2.5 × 100 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in JP-A-6-1610.
As described in No. 32, the surface thereof may be treated with a silane coupling agent or a titanium coupling agent. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.

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

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

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

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

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

Next, a film cartridge in which a photosensitive material can be loaded will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, patrone may contain various antistatic agents, such as carbon black, metal oxide particles, nonions,
Anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A-1-312537,
No. 3,12,538. Especially 25 ° C, 25
The resistance at% RH is preferably 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, and it is also effective to reduce the diameter of the 25 mm cartridge of the current 135 size to 22 mm or less in order to reduce the size of the camera. The volume of the patrone case is 30cm
^It is preferably 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 also be used. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are U
S4,834,306 and 5,226,613.

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-5-241251, JP-A-5-19364, and JP-A-5-19364
-19363 can be used.

[0163]

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 A method of adjusting cubic silver chloride emulsions (comparative) R-1, R-2 and R-3 will be described. 1000 ml of distilled water containing 30.0 g of gelatin, 3.4 g of sodium chloride and 20.0 ml of sulfuric acid (1N) was placed in a reaction vessel, and the temperature was raised to 55 ° C. To this solution, 1.7 ml of an aqueous solution of N, N'-dimethylimidazolidin-2-thione (1%) was added, and while stirring vigorously, 2000 ml of an aqueous solution containing 7.1 g of silver nitrate and 200 ml of an aqueous solution containing 2.41 g of sodium chloride were added. Added in 24 minutes. Next, 500 ml of an aqueous solution containing 162.8 g of silver nitrate and 500 ml of an aqueous solution containing 59.88 g of sodium chloride were added over 80 minutes while increasing the addition flow rate. Sixty minutes after the start of the addition of these reaction solutions, potassium hexachloride iridate was added at 0.
04 mg was added. 55 ° C for 5 minutes after completion of addition of the reaction solution
, And the temperature was lowered, and desalting was performed according to a standard method.

The obtained emulsion was an emulsion composed of cubic grains having an average grain size of 0.69 μm expressed by a diameter equivalent to a circle. This emulsion was designated as emulsion R-1. Emulsion R-1 except that the temperature of the reaction vessel was 45 ° C. and 40 ° C., respectively.
Emulsions R-2 and R-3 were prepared in exactly the same manner as in Example 2 and used in Example 2. The average grain size of the obtained emulsion was 0.51 μm and 0.33 μm, respectively.

A method for preparing a high silver chloride tabular emulsion (invention) H-1, H-2, H-3 comprising (100) planes will be described. 21.2 g of gelatin having an average molecular weight of 15,000,
0.85 g of sodium chloride and 3.8 m of sulfuric acid (1N)
1 ml of distilled water containing 1.
The temperature was raised to ° C. Silver nitrate 6.
30 ml of an aqueous solution containing 1 g and 2.00 g of sodium chloride
And 30 ml of an aqueous solution containing 0.21 g of potassium bromide were added over 45 seconds. Then 0.55 g of potassium bromide
40 ml of an aqueous solution containing Furthermore, silver nitrate 18.
100 ml of an aqueous solution containing 3 g and 6.30 of sodium chloride
g of an aqueous solution containing 100 g were added over 3 minutes. 6.0 ml of sodium hydroxide (1N) was added and the temperature of the reaction solution was raised to 75 ° C. After adding 10.0 g of gelatin together with 100 ml of distilled water, 750 ml of an aqueous solution containing 145.4 g of silver nitrate and a 7.0% aqueous solution of sodium chloride 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 45 minutes to 120 mV. After adding 0.04 mg of potassium hexachloroiridate and keeping the mixture at 75 ° C. for 30 minutes, the temperature was lowered and desalting was performed according to a conventional method.

The obtained emulsion had a silver bromide content of 0.64 mol%.
The average grain size expressed as a circle equivalent diameter is 0.69 μm, the ratio of the circle diameter equivalent to the average grain projected area divided by the average grain thickness is 7.1, and the projected surface is average. It was a (100) silver chlorobromide emulsion consisting of rectangular tabular grains having an aspect ratio of 1: 1.25. Emulsion H-
It was set to 1. The molecular weight of gelatin used at the beginning of the reaction and the amount of gelatin were adjusted to adjust the molecular weight of gelatin to 0.51 μm and 0.33 μm, respectively.
2 and H-3 were made and used in Example 2. Table 1 shows a comparison of grain characteristics between these emulsions R-1 to R-3 and H-1 to H-3.

[0168]

[Table 1]

Next, a method for preparing silver iodobromide tabular grains (comparative) will be described. Distilled water 93 containing 0.74 g of gelatin having an average molecular weight of 15,000 and 0.7 g of potassium bromide
0 ml was placed in the reaction vessel and the temperature was raised to 42 ° C. 30 ml of an aqueous solution containing 1.2 g of silver nitrate with vigorous stirring
30 ml of an aqueous solution containing 0.82 g of potassium bromide.
In seconds. After maintaining at 40 ° C. for 1 minute after completion of the addition,
The temperature of the reaction solution was raised to 75 ° C. Gelatin 27.
After adding 5 g together with 200 ml of distilled water, 22.5 g of silver nitrate were added.
g and an aqueous solution containing 15.43 g of potassium bromide were added over 11 minutes while accelerating the addition flow rate.

Next, an aqueous solution 25 containing 75.1 g of silver nitrate
0 ml and a molar ratio of potassium iodide to potassium nitrate of 3:97
Was added over 20 minutes so that the silver potential of the reaction solution became 2 mV with respect to the saturated calomel electrode while accelerating the addition flow rate. 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 4 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 73 ° C. for 1 minute after the addition was completed, the temperature of the reaction solution was lowered to 55 ° C. Then, silver nitrate 8.1
g of an aqueous solution containing 120 g and 320 ml of an aqueous solution containing 7.26 g of potassium iodide were added over 5 minutes. After the addition was completed, 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.
Further, 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 over 10 minutes. The temperature was lowered and desalting was performed according to a standard method.

The obtained emulsion was a silver iodobromide emulsion (silver iodide content: 5.7 mol%) composed of hexagonal tabular grains having an average equivalent circular diameter of 1.81 μm expressed by a circle equivalent diameter. This emulsion was designated as emulsion A-1. Emulsion A-1 was prepared by changing the initial amount of gelatin and the amount of potassium bromide to prepare grains having grain equivalent circular diameters of 1.21 μm and 0.76 μm.
-2 and A-3. Emulsions A-2 and A-3 are used in Example 2.

Tabular silver iodobromide emulsion B-1 H ₂ SO ₄ was added to 1000 cc of an aqueous solution containing 0.5 g of oxidized gelatin and 0.41 g of KBr, and the mixture was adjusted to pH = 2 and stirred while maintaining at 40 ° C. 3M AgNO ₃
55 cc of the aqueous solution and 55 cc of the 0.3 M KBr aqueous solution were simultaneously added by a double jet for 110 seconds. Then Na
OH was added to adjust the pH to 5.0 and 75 ° C for 35 minutes.
Temperature, and after adding 33 g of oxidized gelatin,
512 cc of 1.2 M AgNO ₃ aqueous solution and 1.4 M of K
While accelerating the flow rate of the 440 cc Br aqueous solution while maintaining the pAg at 8.58 (the flow rate at the end is 5.2 times that at the start) 3.
Added for 3 minutes.

Thereafter, the temperature was lowered to 54 ° C. and 0.4M AgN
104 cc of an O ₃ aqueous solution and 279 of a 0.12 M KI aqueous solution
cc 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 M AgNO was added.
₃ 110cc aqueous solution and 125c 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 adjusted to pH = 5.5 and pAg = 8.2 by adding 75 g of gelatin.

In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains, and the iodine odor of tabular grains having an average equivalent circular diameter of 1.92 μm and an average grain thickness of 0.05 μm. Silver iodide emulsion (silver iodide content: 3.9 mol%)
Met. This emulsion was designated as emulsion B-1. Also, pAg
Etc. are appropriately changed so that the average equivalent circular diameter is 1.27 μ,
Emulsions B-2 and B-3 having 81 µm and average grain thicknesses of 0.06 µ and 0.05 µ were prepared. Table 2 shows a comparison of emulsion properties.
Shown in

[0175]

[Table 2]

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

[0177]

Embedded image

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 emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. After the dispersion, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes. These dispersions were combined with the previously prepared silver halide emulsion to prepare four types of heat-developable color photographic light-sensitive materials of Samples 101 to 104 shown in Table 3.

[0180]

[Table 3]

[0181]

Embedded image

[0182]

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[0183]

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Furthermore, the processing materials P- as shown in Tables 4 and 5
1. P-2 was prepared.

[0185]

[Table 4]

[0186]

[Table 5]

[0187]

[Table 6]

[0188]

Embedded image

[0189]

Embedded image

These photosensitive materials were exposed to light at 1000 lux for 1/100 second through an optical wedge and a green filter. 15 ml of 40 ° C warm water is applied to the surface of the photosensitive material after exposure.
/ M ^2, and the processing material and the respective film surfaces were overlapped with each other, and then heat-developed at 83 ° C. for 15 seconds using a heat drum. When the photosensitive material was peeled off after the processing, a wedge-shaped image of magenta color was obtained.

This sample was subjected to the second step processing using the following processing material P-2 in order to evaluate the difference from the fixed photosensitive material. In the processing of the second step, water of 10 cc / m ² was applied to the processing material P-2, and the processing material P-2 was adhered to the photosensitive material after the first processing, and heated at 60 ° C. for 30 seconds. The transmission density of the obtained color sample was measured, and the sensitivity of each photosensitive material was measured using a so-called characteristic curve. When the reciprocal of the exposure corresponding to the density 0.15 higher than the fog density was used as the relative sensitivity, , Photosensitive material 101, 10
2, 103 and 104 all matched within ± 0.1 in the above-mentioned processing without fixing. Therefore, these photosensitive materials have almost the same sensitivity, and the difference in RMS granularity can be regarded as an effect of the silver halide used therein.

In order to examine the granularity of these samples, exposure was performed so that the magenta color density became plus 1.0 in each of the processes (with and without fixing), and the same heat development was performed to form the color pieces. The RMS granularity was measured using a diffuse light source with an aperture having a diameter of 48 μm. The comparison between the difference between the non-fixed state and the fixed state is based on the RMS of the sample that was treated with the treatment material P-2 (with fixation), followed by treatment with the treatment material P-1 (unfixed) and treatment with the treatment material P-1. It was performed by measuring the granularity. No bleaching of the silver halide was performed in any case. Table 7 summarizes these results.

[0193]

[Table 7]

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.

[0195]

Embedded image

[0196]

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In addition, cyan and yellow coupler dispersions were prepared according to the method for preparing the coupler dispersion of Example 1. Further, 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 colored layer capable of being decolorized during heat development. Using the thus obtained silver halide emulsion, coupler dispersion and colorant dispersion, Tables 8 to 1
The heat-developable color light-sensitive material having a multilayer structure shown in FIG.
14) was created.

[0198]

[Table 8]

[0199]

[Table 9]

[0200]

[Table 10]

[0201]

[Table 11]

[0202]

Embedded image

[0203]

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[0204]

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[0205]

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Table 12 summarizes the emulsions used for each layer.

[0207]

[Table 12]

The photographic characteristics of these light-sensitive materials were tested in the same manner as in Example 1. First, each photosensitive material was exposed to light at 1000 lux for 1/100 second through an optical wedge and blue, green and red filters. 15 ml / m ² of 40 ° C. warm water is applied to the surface of the photosensitive material after the exposure, and the processing material used in Example 1 and each other film surface are overlapped with each other, and then heated at 83 ° C. for 30 seconds using a heat drum. Heat development was performed. When the photosensitive material is peeled off after processing, the sample exposed with the blue filter has a wedge-shaped image with yellow color, the sample exposed with the green filter has a wedge-shaped image with magenta color, and the sample exposed with the red filter has cyan. A colored wedge-shaped image was obtained. To determine the granularity of these samples,
Exposure is performed so that the magenta and cyan coloring densities become 1.0, and the same heat development is performed to form a colored piece, and the RM is formed using a diffuse light source with an aperture of 48 μm in diameter.
The S granularity was measured. The results are summarized in Table 13.

[0209]

[Table 13]

The results show that the effect of the present invention is remarkable. That is, even when the light-sensitive material for color photography of the present invention has a three-layer structure of O, M, and U layers respectively corresponding to B, G, and R light components of yellow, magenta, and cyan, respectively, The goodness of the observed granularity was similarly effective.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 20, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0170

[Correction method] Change

[Correction contents]

Next, an aqueous solution 25 containing 75.1 g of silver nitrate
0 ml and a molar ratio of potassium iodide to potassium bromide of 3:97
Was added over 20 minutes so that the silver potential of the reaction solution became 2 mV with respect to the saturated calomel electrode while accelerating the addition flow rate. 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 4 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 73 ° C. for 1 minute after the addition was completed, the temperature of the reaction solution was lowered to 55 ° C. Then, silver nitrate 8.1
g of an aqueous solution containing 120 g and 320 ml of an aqueous solution containing 7.26 g of potassium iodide were added over 5 minutes. After the addition was completed, 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.
Further, 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 over 10 minutes. The temperature was lowered and desalting was performed according to a standard method.

Claims (4)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one photosensitive layer comprising a photosensitive silver halide, a compound capable of forming a dye by a coupling reaction with an oxidized form of a developing agent, and a binder on a support. After exposure of the light-sensitive material, a processing material comprising a support and a constituent layer including a processing layer containing a base and / or a base precursor coated on a support, is coated on the surface of the photosensitive layer of the light-sensitive material and the surface of the processing layer of the processing material. A color image is formed on the photosensitive material side by heating and bonding, and the unreacted silver halide is not fixed during processing, and is used as a negative original with substantially unreacted silver halide remaining. Silver halide color photographic light-sensitive material, the total coated silver amount of the light-sensitive material is 0.1 g
/ M ² or more, and in at least one photosensitive layer, 50
Silver halide grains comprising at least mol% of silver chloride, the main outer surface of which is constituted by a (100) plane, and the aspect ratio of a projection plane is a rectangle of 1: 1 to 1: 2. A silver halide color photographic light-sensitive material comprising an emulsion in which tabular grains having an aspect ratio of 2 or more account for 50% or more of the total projected area. 2. A silver halide color photographic material comprising at least one photosensitive layer comprising a photosensitive silver halide, a compound capable of forming a dye by a coupling reaction with an oxidized form of a developing agent, and a binder on a support. After exposure of the light-sensitive material, a processing material comprising a support and a constituent layer including a processing layer containing a base and / or a base precursor coated on a support, is coated on the surface of the light-sensitive material and the surface of the processing material of the processing material. A color image is formed on the photosensitive material side by heating and bonding, and the unreacted silver halide is not fixed during processing, and is used as a negative original with substantially unreacted silver halide remaining. Silver halide color photographic light-sensitive material, the total coated silver amount of the light-sensitive material is 0.1 g
/ M ² or more, and in at least one photosensitive layer,
Silver halide grains comprising 70 mol% or more of silver bromide, wherein the main outer surfaces of the grains are composed of (111) planes, the average equivalent circular diameter is at least 0.7 μm, and the average thickness is A silver halide color photographic light-sensitive material comprising an emulsion comprising ultrathin tabular grains having a particle size of less than 0.07 μm. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein the total amount of applied silver is 1.0 g / m ² or more. 4. The silver halide color photographic material according to claim 1, wherein the developed silver is not bleached during processing.