JPH1062933A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve uneven image density due to simple and rapid processing. SOLUTION: This photosensitive material has three photosensitive layers different from each other in color sensitivity and consisting of photosensitive silver halide, a developing agent, couplers and a binder on a substrate. A color image is formed by overlaying the photosensitive material on a processing material and heating them. The photosensitive material has a dry film thickness of all the coating layers in the range of 6-21μm, and a water-swollen film thickness of 5-40μm, and the photosensitive emulsion layer contains flat silver halide grains each having (100) principal face and a high silver chloride content, and a rectangular form with a length to breadth ratio of (1:1)-(1:2) and an aspect ratio of >=2 and occupying >=50% of the projection areas of the total silver halide grains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel heat-developable silver halide color photographic material for recording a color 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.

US Pat. No. 5,526,433 discloses a technique for applying the advantage of rapid developability of a high silver chloride emulsion to a photographic material.
No. 7, US Pat. No. 5,292,632, US Pat. No. 5,310,635 or WO 94/22054 include (1)
A technique of using a tabular high silver chloride emulsion having a (00) plane as a photographic light-sensitive material for photography has been disclosed. 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.

[0007] However, as described in the above specification, various problems arise from the developing characteristics of the high silver chloride emulsion. First, in order to obtain a good granularity, it is necessary to suppress the development of the grains which have begun to be developed.However, a high silver chloride emulsion has a high development speed of individual grains, and thus, the exposed grains are high. Is likely to vary in the development start time, and it is difficult to obtain a highly sensitive photographic response in the early stage of development. Second, the graininess is likely to deteriorate if the high developability of the high silver chloride emulsion grains is to be used. Therefore, it is technically difficult to achieve characteristics such as a wide exposure latitude and excellent granularity required for a photographic material for photography using a high silver chloride emulsion. This situation cannot be said, and many fundamental problems remain in realizing a photographic material using such a high silver chloride emulsion.

As another attempt, the environmental load is reduced and the simplicity is improved by constructing a system which does not use a color developing agent or a bleaching agent used in the 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. provides a pictography system. In this system, a small amount of water is supplied to a light-sensitive material containing a base precursor, the light-sensitive material is bonded to an image-receiving material, and heated to cause a development reaction. This method is environmentally advantageous in that the above-mentioned treatment bath is not used. However, in this method, the formed dye is fixed to the dye fixing layer on the image receiving material side, and is used for appreciating the dye image as a dye image. Therefore, it is desired to develop a system that can be used as a recording material for photographing. I was

The present inventors have tried to construct a photographic material using the high silver chloride emulsion by applying this system. However, it has been found that there is a new problem that the dry film thickness of the photographic material and the saturated swelling due to water affect the developability, causing image density unevenness. The photographic material is used in such a manner that it is used after being enlarged and exposed to a final print photographic material, and is often read at a high resolution by a scanner. .

[0011]

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 in which density unevenness does not occur in an image even when processing is performed quickly.

[0012]

The object of the present invention is to provide: (1) a compound and a binder which form a dye on a support by coupling reaction with a photosensitive silver halide, a developing agent, and an oxidized form of the developing agent; A silver halide color photographic light-sensitive material having at least three light-sensitive layers having different color sensitivity, comprising a processing layer containing a base and / or a base precursor on a support after exposure of the light-sensitive material. In a silver halide color photographic light-sensitive material in which a color image is formed by bonding a processing layer surface of a processing material provided with a constituent layer and a photosensitive layer surface of a light-sensitive material and performing heat development, the photosensitive layer surface of the light-sensitive material is The dry film thickness of the entire coating film is 6 to 21 μm, the saturated swelling film thickness of water is 5 to 40 μm, and the photosensitive layer contains 50 mol% or more of silver halide. A tabular shape which is a silver halide grain and whose main outer surface is composed of a (100) plane and whose projection plane is a rectangle having an aspect ratio of 1: 1 to 1: 2 and an aspect ratio of 2 or more; A silver halide color photographic light-sensitive material containing an emulsion in which grains account for 50 mol% or more of the total projected area.

(2) The silver halide color photographic light-sensitive material has the following general formula (I), (II), (III) or (IV)
(1) The silver halide color photographic material as described in (1), which contains at least one developing agent represented by the formula:

[0014]

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[0015]

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[0016]

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[0017]

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Where R₁~ R_FourIs a hydrogen atom, a halogen atom
, Alkyl group, aryl group, alkylcarbonamide
Group, arylcarbonamide group, alkylsulfonamido
Group, arylsulfonamide group, alkoxy group, ant
Oxy, alkylthio, arylthio, alk
Kill carbamoyl group, aryl carbamoyl group, carb
Moyl group, alkyl sulfamoyl group, aryl sulf
Amamoyl group, sulfamoyl group, cyano group, alkyls
Ruphonyl group, arylsulfonyl group, alkoxycarbo
Nyl group, aryloxycarbonyl group, alkylcarbo
Group, an arylcarbonyl group or an acyloxy group
Represents, R_FiveRepresents an alkyl group, an aryl group or a heterocyclic group
Represent. Z represents a group of atoms forming a (hetero) aromatic ring;
Is a benzene ring, the Hammett constant of the substituent
The total value of (σ) is 1 or more. R ₆Represents an alkyl group
You. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl
Represents a tertiary nitrogen atom substituted by aryl or aryl. R
₇, R₈Represents a hydrogen atom or a substituent;₇, R₈But
It may combine with each other to form a double bond or a ring. Sa
Furthermore, each of the general formulas I to IV imparts oil solubility to the molecule.
Therefore, it contains at least one ballast group having 8 or more carbon atoms.
No.

(3) The heat development is 1/10 of the total amount of water required for maximum swelling of the entire coating film of the photosensitive material and the processing material.
Water is supplied to the photosensitive layer surface of the photosensitive material or the processing layer surface of the processing material, and then the photosensitive layer surface of the photosensitive material is bonded to the processing layer surface of the processing material.
The silver halide color photographic light-sensitive material according to (1) or (2), wherein the heat treatment is performed by heating at a temperature below for not less than 5 seconds and not more than 60 seconds. Is more effectively achieved.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in at least one photosensitive layer, silver halide grains comprising at least 50 mol% of silver chloride, and the main outer surface of the grains are (100) planes And the aspect ratio of the projection plane is 1:
An emulsion in which 50% or more of the total projected area is occupied by tabular grains having an aspect ratio of 2 or more such as a rectangle of 1 to 1: 2 is used, but the projected area of the silver halide grains contained in the emulsion is reduced. It is sufficient that 50% or more satisfies the above rule.
Further, it is preferable that 70% or more of the projected area satisfies the above-mentioned rule. The aspect ratio in the present invention refers to a value obtained by dividing the diameter of a circle equivalent to the projected area by the grain thickness. In the silver halide grains of the present invention, the main outer surface of the grains is (10%).
0), the projection plane has a rectangular shape. 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. In other words, when using an emulsion composed of rectangular particles close to a rod or a cube,
The effect of the present invention cannot be obtained. The ratio of the vertical and horizontal sides of the rectangle, which is the projection plane, is approximately 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 present invention is silver chlorobromide, silver chloroiodide, silver chloroiodobromide or silver chloride containing 50 mol% or more of silver chloride. The emulsion of the present invention may contain silver iodide, but the silver iodide content is preferably at most 6 mol%, more preferably at most 2 mol%. It is also preferable to use a silver halide emulsion composed of grains having a laminated structure composed of a plurality of layers having different halogen compositions inside the silver halide grains. The size of the silver halide grains used in the present invention is preferably from 0.1 to 10 μm, more preferably from 0.3 to 5 μm, particularly preferably from 0.5 to 5 μm, when expressed by the diameter of a circle equal to the projected area. 4 μm.

Various methods can be used to produce the emulsion of the present invention, including known methods. For example,
JP-A-5-204073, JP-A-51-88017
JP-A-63-24238 and Japanese Patent Application No. 5-26.
The method described in No. 4059 or the like can be arbitrarily used.

In preparing the tabular grains of the present invention,
The point is the method of generating nuclei that grow on a plate, and as described in the production method of the above-mentioned literature, a compound that adds iodide ions or bromide ions at the initial stage of grain formation or exhibits selective adsorption on a specific surface. Is useful.

The light-sensitive material of the present invention comprises a photosensitive silver halide, a developing agent, a compound which forms a dye by a coupling reaction with an oxidized form of the developing agent (hereinafter referred to as a coupler), and a binder. And a photographic constituent layer including at least one photographic photosensitive layer. In a more preferred embodiment, the above general formula (I)
It contains at least one developing agent represented by (II), (III) or (IV). In order to form an image after exposing the photosensitive material of the present invention imagewise, the exposed photosensitive material and a processing material containing a base and / or a base precursor on a support are coated by coating all of these materials. After supplying water equivalent to 1/10 to 1 time of the water required for the maximum swelling of the film to the photosensitive material or the processing material, they are attached and heated to perform color development. US52 mentioned above
No. 64337, US5292632, US53106
No. 35 or WO 94/22054 also disclose tabular high silver chloride emulsions composed of (100) planes, which contain a conventional aromatic primary amine developing agent. This is a liquid development type technology using a color developing bath, and in such a case, density unevenness does not pose a problem.
In the method of the present invention, uneven density is a problem.

A photosensitive material containing silver halide grains having (100) planes whose length of one side is twice or more or 0.5 times or less the arithmetic average of the lengths of the other two sides is thermally developed. Japanese Patent Publication No. 7-120014 discloses a technique for reducing the fogging of a photosensitive material for printing using a silver bromide or silver chlorobromide emulsion during thermal development.
And, as is clear from the grain photograph attached to the patent specification, the shape of the silver halide grains is a rectangular parallelepiped and has a different shape from the tabular grains defined in the present invention. Technology.

The rapid development of a high silver chloride emulsion can be achieved only by subjecting a photosensitive material containing a tabular high silver chloride emulsion composed of (100) planes and a developing agent to color development by the development method defined in the present invention. Excellent graininess required for photographic materials for photography can be achieved while maintaining developability.

The developing agent to be contained in the light-sensitive material of the present invention is represented by the above general formula (I), (II), (III) or (I)
It is preferable to use the compound represented by V). Among these, the compounds of the general formula (I) or (II) are particularly preferably used.

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

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

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 carbamoy
It is a compound generically called luhydrazine. Table in general formula IV
Is a compound commonly referred to as sulfonylhydrazine
Things. Both are compounds known in the art.
You. When used in the present invention, R _Five ~ R₈ At least one of
One having a ballast group having at least 8 carbon atoms is preferred.
No.

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 the groups 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.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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

[0048]

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[0049]

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[0050]

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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 color between the photosensitive wavelength region and the color hue. In such a case, the original color information can be reproduced by performing image processing such as hue conversion after capturing the image information as described above.

In the present invention, it is preferable to contain at least two types of silver halide emulsions having photosensitivity in 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 so that the difference in the average grain projected area between the emulsions is 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 the same wavelength region and different average grain projected areas, a separate photosensitive layer may be provided for each emulsion, or one emulsion may be provided. 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 arranged 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. However, it is preferable to mix couplers having different hues to form a color coupler. It is also possible to use different coloring hues, and to use couplers having different coloring hue absorption profiles for each photosensitive layer.

In the present invention, the ratio of the number of silver halide grains per unit area of the light-sensitive material of these emulsions is determined by the ratio of the average grain projected area to the emulsions having the same wavelength region. It is preferred that the larger the emulsion, the larger the ratio of the amount of silver coated 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 conventionally used for photography, not only the silver halide emulsion is improved to achieve the desired granularity, but also the development is suppressed during the coupling reaction with the oxidized form of the developing agent. A technique such as using 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.

After the photosensitive material of the present invention has been exposed, a processing material containing a base and / or a base precursor and 1/10 of the water required for maximum swelling of the entire coating film constituting the photosensitive material and the processing material are obtained. After supplying water equivalent to 1 time from the above, the layers are bonded and heated to develop.

The present invention has been made for the purpose of obtaining an image without density unevenness in the above-described thermal development, and aims to reduce the environmental load caused by performing liquid development. An image can also be formed 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.

In the present invention, image information can be taken in without removing developed silver and undeveloped silver halide generated by development, or an image can be taken after removal. In the latter case, a means for removing them at the same time as or after the development can be applied.

In order to remove the developed silver in the light-sensitive material at the same time as the development and to complex or solubilize the silver halide,
The processing material may contain an oxidizing agent or a rehalogenating agent for silver that acts as a bleaching agent, or a silver halide solvent that acts as a fixing agent, to cause these reactions during thermal development.

After the development of the image is completed, a second material containing a silver oxidizing agent, a rehalogenating agent or a silver halide solvent is bonded to the light-sensitive material to remove developed silver or to form a silver halide complex. Or solubilization.

In the present invention, it is preferable to perform these processes to the extent that image information is not obstructed after photographing and subsequent image formation and development. In particular, undeveloped silver halide causes a high haze in the gelatin film and raises the background density of the image. It is preferable to remove the whole amount or a part of the total amount.

In the present invention, the dry film thickness of the photosensitive material is
This is the film thickness after all the constituent layers of the photosensitive material, such as the photosensitive layer, the intermediate layer, the protective layer, and the antihalation layer, applied to the side of the support on which the photosensitive layer is present are coated and dried. The thickness of the photosensitive material is 6 to 21 .mu.m. Preferably 8 to
18 μm. More preferably, it is 9 to 16 μm Z. Most preferably, it is 10 to 15 μm.

In the present invention, the saturated swelling film thickness of the photosensitive material with water is defined as the swelling measured by applying distilled water at 40 ° C. to the surface of the coating layer of the photosensitive material after coating and drying where the photosensitive layer is present. , The film thickness increased by swelling when the film thickness reaches a certain value. The swelled film thickness is 5 to 40 μm or less.
Preferably it is 6 to 35 μm or less. More preferably, it is 7 to 30 μm or less. Most preferably, 8 to 25
μm or less. Examples of a method for applying water to the photosensitive material include a roller coating method or a wiper coating method described in JP-A-59-181353, and a water absorption method described in JP-A-59-181354. A method of applying water to a photographic material using a member,
No. 81348, a method of forming a bead between a water-repellent roller and a photographic material to apply water as described in JP-A No. 81348, a dip method, an extrusion method, a method of jetting a jet from a fine hole as a jet, and applying the water. Various methods such as a method of crushing a pod can be used. Among them, the dip method is preferable from the viewpoint of water absorption speed. The above-mentioned water is not limited to so-called "pure water", but includes water in a sense widely used. An aqueous solution containing a base and / or a base precursor described below may be used, or a mixed solvent with a low boiling point solvent such as methanol, DMF, acetone, and isobutyl ketone may be used. Further, an aqueous solution containing an image formation accelerator and a hydrophilic heat solvent as described in JP-A-61-147244 may be used. The addition of a surfactant is advantageous for uniformly supplying water to the heat-developable color light-sensitive material.

Specific examples of the silver halide emulsion used in the present invention include US Pat. No. 4,500,626, column 50, US Pat. No) 17,029
No. 17, 643 (December 1978)
Mon.) p. 22-23, No. 18,716 (Jan. 1979)
(January) p. 648, No. 307, 105 (1989, January)
January) pages 863 to 865, JP-A-62-253,159.
No. 64-13,546, JP-A-2-236,54
No. 6, No. 3-110, 555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkides, C.
hemie etPhisque Photographique, Paul Montel 1967)
Duffin, Photographic Emulsion Chemistry, GFDuffin Photographic Emulsion Chemistry, F
ocal Press 1966), "Manufacture and Coating of Photographic Emulsions" by Zerikuman et al., Published by Focal Press (VLZelikman et a
l., Making and Coating Photographic EmulusionFocal
Press, 1964) and the like.

In the process of preparing the photosensitive silver halide emulsion of the present invention, it is preferable to carry out 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 Nos. 2-236542, 1-116,637 and 5-181,246 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, an ammonia, a 4-substituted thiourea compound or a JP-B-47-11,
No. 386, or an organic thioether derivative described in
For example, a sulfur-containing compound described in 3-144,319 can be used.

For other conditions, see the above-mentioned “Physics and Chemistry of Photography” by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisque Photographique, Paul Mont
el1967), Duffin's "Photoemulsion Chemistry", Published by Focal Press (GFDuffin Photographic Emulsion Chemis)
try, Focal Press 1966), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (VLZelikman
et al., Making and Coating Photographic Emulusion
Focal Press, 1964). That is, any of the acidic method, the neutral method, and the ammonia method may be used,
As a method of reacting the soluble silver salt and the soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. 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).
5, No. 5-241, 267, etc.). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
0,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0.
１10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide used in the present invention is preferably in the range of 1 mg / m ² to 10 g / m ² in terms of silver, more preferably in the range of 0.1 g / m ² to 10 g / m ² , A range from 0.1 g / m ² to 5 g / m ² is particularly preferred.

In order to give the photosensitive silver halide used in the present invention color sensitivity such as green sensitivity and red sensitivity, 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

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

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

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

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

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

The light-sensitive material of the present invention may contain the following functional coupler. Couplers for correcting unnecessary absorption of coloring dyes are disclosed in EP 456,257.
The yellow colored cyan coupler described in A1;
Yellow colored magenta coupler described in P, US
Magenta colored cyan couplers described in US Pat. No. 4,833,069, US Pat. No. 4,837,136 (2), WO92
/ 11575. Colorless masking couplers of formula (A) of claim 1 of claim 1 (especially the exemplified compounds on pages 36-45). In the present invention, it is preferable to use a coupler or another compound which releases a photographically useful compound by reacting with an oxidized form of the developing agent. Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compounds: compounds represented by formulas (I) to (IV) described on page 11 of EP 378,236A1, EP43
A compound represented by the formula (I) described on page 7 of US Pat. No. 6,938A2, a compound represented by the formula (1) described in JP-A-5-307248, and a compound represented by the formula (I) described on pages 5 and 6 of EP440,195A2. , (II) and (III), a compound represented by formula (I) of claim 1 of JP-A-6-59411, a ligand-releasing compound, and a LIG described in claim 1 of US Pat. No. 4,555,478. A compound represented by -X.
In the present invention, the amount of the coupler used is 1 silver halide.
It is preferably from 1/1000 mol to 1 mol per mol,
500 mol to 1/5 mol are more preferred.

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

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

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 kind 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.

Hydrophobic additives such as couplers, developing agents, and diffusion-resistant reducing agents can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat.
No. 5,470, No. 4,536,466, No. 4,53
6,467, 4,587,206, 4,55
5,476, 4,599,296, 3-6
A high-boiling organic solvent as described in JP-A-2,256 or the like can be used, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g, per 1 g of the hydrophobic additive used.
g or less, more preferably 1 g to 0.1 g. Also,
1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less, is suitable for 1 g of the binder. Tokiko Sho 51-3
9,853, JP-A-51-59,943, and a dispersion method using a polymer described in JP-A-62-30,242.
And the method of adding as a fine particle dispersion described in No. For compounds that are substantially insoluble in water,
In addition to the above-mentioned method, fine particles can be dispersed and contained in a binder. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157,636, Nos. (37) to (3)
On page 8), those mentioned as the surfactants described in Research Disclosure described above can be used. Further, phosphate ester type surfactants described in JP-A-7-56267 and JP-A-7-228589 and West German Patent Publication No. 1,932,299A can also be used.

In the present invention, a compound for stabilizing an image simultaneously with activation of development can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

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

Dyes which can be used in the yellow filter layer and the antihalation layer are preferably those which are decolored or eluted during development and do not contribute to the density after processing. The fact that the dye in the yellow filter layer and the antihalation layer is erased or removed at the time of development means that the amount of the dye remaining after the processing is 1/3 or less, preferably 1 /
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.

Known dyes can be used in the light-sensitive material of the present invention. 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 Publication EP549,489A and JP-A-7-15
No. 2129, ExF2-6 dyes. Solid-dispersed dyes as described in JP-A-8-101487 can also be used. This dye can be used when the photosensitive material is developed with a processing solution, but is particularly preferable when the photosensitive material is thermally developed using a processing sheet described later. In addition, a mordant and a binder can be dyed with a dye. In this case, as the mordant and the dye, those known in the photographic field can be used.
No. 58-59, No. 500,626, and JP-A-61-88.
256, page 32 to 41, JP-A-62-244043,
Examples include mordants described in JP-A-62-244036. Further, by using a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, the mobile dye can be released with an alkali at the time of development and eluted in a processing solution or transferred and removed to a processing sheet. Specifically, U.S. Patent Nos. 4,559,290 and 4,783,369, European Patent No. 220,746A2, and Published Technical Report 87-611.
No. 9 as well as those described in paragraphs 0080-0081 of JP-A-8-101487.

Decolorizable leuco dyes and 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 added so that the saturated swelling film thickness falls within the range of the present invention. Depending on the amount and kind of binder used in the light-sensitive material, the hardener is 40 mg / m ² of the light-sensitive material.
A suitable dose is between 500 and 500 mg, preferably between 70 and 200 mg.

Various antifoggants or photographic stabilizers and precursors thereof can be used in the light-sensitive material. 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.

After the light-sensitive material of the present invention has been exposed, a processing material containing a base and / or a base precursor, and 1/10 of water required for maximum swelling of the entire coating film constituting the light-sensitive material and the processing material After supplying water equivalent to 1 time from the above, the layers are bonded and heated to develop. The present invention has been made for the purpose of achieving good granularity and exposure latitude in thermal development as described above,
The aim is to reduce the environmental burden of performing liquid development, but to form an image by developing the photosensitive material of the present invention with an activator method using an alkaline processing solution or a processing solution containing a developing agent / base. It is also possible.

Heat treatment of photosensitive materials is well 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 .

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

In thermal development using the processing material, a small amount of water is used for the purpose of promoting development, promoting the transfer of the processing material, and promoting the diffusion of unnecessary substances. Specifically, it is described in U.S. Pat. Nos. 4,704,245 and 4,470,445, JP-A-61-238056, and the like. In water, inorganic alkali metal salts and organic bases, low-boiling solvents, surfactants, antifoggants, complex-forming compounds with poorly soluble metal salts,
A fungicide and a fungicide may be included. Any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the 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 with a heated plate, a hot presser, a heated roller, a heated drum, a halogen lamp heater, an infrared and far infrared lamp heater, or the like. 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 material of the present invention may have a form having a conductive heating element layer as a heating means for heat development. The exothermic elements of this fever include:
Those described in JP-A-61-145544 can be used.

In the present invention, image information can be taken in without removing developed silver and undeveloped silver halide generated by development, but an image can also be taken after removal. In the latter case, a means for removing them at the same time as or after the development can be applied.
In order to remove developed silver in the photosensitive material and to complex or solubilize silver halide at the same time as development, it acts as a silver oxidizing or rehalogenating agent that acts as a bleaching agent or a fixing agent in the processing material. The reaction can be caused during thermal development by containing a silver halide solvent. After the development of the image is completed, a second material containing a silver oxidizing agent, a rehalogenating agent or a silver halide solvent is bonded to the light-sensitive material to remove the developed silver or to complex the silver halide. Solubilization can also occur. In the present invention, it is preferable to carry out these processes to the extent that image information is not obstructed after photographing and subsequent image formation and development. In particular, undeveloped silver halide causes a high haze in the gelatin film and raises the background density of the image. It is preferable to remove the whole amount or a part of the total amount.
It is also preferable to use tabular grains having a high aspect ratio and a high silver chloride content for the purpose of reducing the haze of the silver halide itself.

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. As the fixing agent, a silver halide solvent which can be contained in a processing material (first processing material) for developing the above-mentioned photosensitive material can be used. The same binder, support, and other additives that can be used in the second processing material can be used as in the first processing material. The amount of the bleaching agent to be applied should be changed according to the silver content of the light-sensitive material to be laminated, but 0.01 mol to 10 mol of the silver coating amount per unit area of the light-sensitive material / silver coating amount of the light-sensitive material. Used in the range. 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.

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

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

The total silver halide solvent content in the processing layer is 0.01 to 100 mmol / m ² , preferably 0.1 to 50 mmol / m ² . More preferably 10
５０50 mmol / m ² . The molar ratio is 1/20 to 20 times, preferably 1/10, relative to the amount of silver applied to the light-sensitive material.
It is 10 times, more preferably 1/3 to 3 times. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropylglycol, or an alkali or acidic aqueous solution, or may be added to a coating solution after dispersing solid fine particles.

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

Both the first processing material and the second processing material
It can have at least one polymerizable timing layer.
The polymerizable timing layer can temporarily delay the bleaching / fixing reaction until the desired reaction between the 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. Nos. 4,056,394;
No. 061,496 and 4,229,516. When applying this timing layer, it is applied in a thickness of 5 to 50 microns, preferably 10 to 30 microns.

In the present invention, as a method of bleaching / fixing the developed photosensitive material using the second processing material, all the coating films except for the back layer of both the photosensitive material and the second processing material are maximally swollen. Water is provided to the photosensitive material or the second processing material in an amount equivalent to 0.1 to 1 times the amount required for the photosensitive material and the second processing material, and the photosensitive material and the second processing material are overlapped so that the photosensitive layer and the processing layer face each other. 5 to 6 seconds at a temperature of 100 to 100 ° C
Heat for 0 seconds. With respect to the amount of water, the type of water, the method of applying water, and the method of superposing the photosensitive material and the processing material, the same materials as in the first processing material can be used.

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

In the light-sensitive material, various surfactants can be used for the purpose of coating aid, improving peelability, improving slipperiness, preventing static charge, accelerating development and the like. Specific examples of the surfactant are known in the art No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, 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. The content in the light-sensitive material is preferably from 5 to 500 mg / m ² , particularly preferably 1 to 500 mg / m ^2.
It is a 0~350mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is from 1/300 to 10
0/1 is preferable, and 1/100 to 100 is more preferable.
/ 5.

The constitution of the photosensitive material or the processing sheet (including the back layer) 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. 0.8 to 10 as particle size
μm is preferred, and the particle size distribution is preferably narrow, and it is preferred that 90% or more of the total number of particles be contained between 0.9 and 1.1 times the average particle size. It is also preferable to simultaneously add fine particles having a particle size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm
), Poly (methyl methacrylate / methacrylic acid = 9)
/ 1 (molar ratio) 0.3 µm)), polystyrene particles (0.25 µm), colloidal silica (0.03 µm)
Is mentioned. Specifically, JP-A-61-88256
No. (29). Other examples include benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, and the like, as disclosed in JP-A-63-274944 and JP-A-63-274.
No. 4952. Other research
The compounds described in the disclosure can be used.

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

In particular, when the requirements for heat resistance and curl characteristics are severe, a support for a photosensitive material disclosed in JP-A-6-41281 is used.
No. 6-43581, No. 6-51426, No. 6-
No. 51437, No. 6-51442, No. 6-82961
Nos. 6-82960, 6-123937, 6
-82959, 6-67346, 61-1185
The supports described in JP-A Nos. 61, 7-219129 and 7-219144 can be preferably used.
Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

[0127] 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.

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 by using a support having a magnetic recording layer described in JP-A-6-317875 and JP-A-5-58221.

The magnetic recording layer is obtained by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support. 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, 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 substance in the above-mentioned binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. JP-A-5-88283
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 light-sensitive material having the above-mentioned magnetic recording layer will be further described. For details including the light-sensitive material, treatment, cartridge, and examples, see Japanese Unexamined Patent Application, Publication No. 94-6023 ( 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.

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

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.

[0138]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of silver halide emulsion A-1 of the present invention 1200 ml of an aqueous gelatin solution (gelatin-1) was placed in a reaction vessel.
(Deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 25.0 g, HNO ₃ 1N solution
5 ml, pH 4.3), NaCl-1 solution (100 ml
10 g of NaCl in the mixture).
While maintaining the temperature at 0 ° C., the Ag-1 solution (AgNO
₃ containing 20 g) and X-1 solution (NaCl in 100 ml)
6.67 g, containing 0.71 g of KBr)
At the same time, and 36.0 ml of the mixture was added simultaneously. After stirring for 3 minutes, 43.4 ml of solution X-2 (containing 1.1 g of KBr in 100 ml) was added at 186.0 ml / min. Then, after lowering the temperature to 30 ° C. in 3 minutes, Ag-
1 solution and X-3 solution (containing 7.02 g of NaCl in 100 ml)
108.0 ml of the mixture was added simultaneously at 8.0 ml / min. Then, after stirring for 1 minute, 20 cc of NaCl-1 solution was added.
7.0 cc of NaOH 1N was added. After that, the temperature was set to 7
The temperature was raised to 5 ° C. and ripened for 5 minutes.

Thereafter, the Ag-1 solution and the X-1 solution were mixed with CDJ (co
ntrolled double jet), keeping it at 120mV,
45 until the total amount of the Ag-1 solution reaches 857.1 ml.
The addition rate was increased at a constant rate from 13.8 ml / min to 24.0 ml / min for 1 minute. Finally, a settling agent was added, the temperature was lowered to 35 ° C., and the precipitate was washed by settling. An aqueous gelatin solution was added, and the pH was adjusted to 6.0 at 60 ° C.

A replica TEM image of the particles was observed. The obtained emulsion was composed of silver chlorobromide having a silver bromide content of 5.0 mol%, and had an average grain size expressed by a diameter equivalent to a sphere of 0.8.
9 μm, average particle size 1.60 μm in height, 1.60 in width
The projection plane of μm is a rectangle having an average aspect ratio of about 1: 1.
The ratio of the diameter of a circle having a thickness of 0.145 μm and equivalent to the average grain projected area divided by the average grain thickness, the so-called aspect ratio is 1
It was a (100) major plane emulsion containing 92% or more of tabular grains having a coefficient of variation of 2.4 and a coefficient of variation of 0.15.

Preparation of silver halide emulsion A-2 of the present invention: 1200 ml of an aqueous gelatin solution (gelatin-1) was placed in a reaction vessel.
(Deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 25.0 g, HNO ₃ 1N solution
5 ml, pH 4.3), NaCl-1 solution (100 ml
10 g of NaCl in the mixture).
While maintaining the temperature at 0 ° C., the Ag-1 solution (AgNO
₃ containing 20 g) and X-1 solution (NaCl in 100 ml)
6.67 g, containing 0.71 g of KBr)
At the same time, and 36.0 ml of the mixture was added simultaneously. After stirring for 3 minutes, 43.4 ml of solution X-2 (containing 1.1 g of KBr in 100 ml) was added at 186.0 ml / min. Then, after lowering the temperature to 30 ° C. in 3 minutes, Ag-
1 solution and X-3 solution (containing 7.02 g of NaCl in 100 ml)
108.0 ml of the mixture was added simultaneously at 8.0 ml / min. Then, after stirring for 1 minute, 20 cc of NaCl-1 solution was added.
7.0 cc of NaOH1N was added, and the potential was 80 mV, p
After adjusting H to 6.5, 2 cc of aqueous hydrogen peroxide (35%) was added.
Was added. Thereafter, the temperature was raised to 75 ° C., and the mixture was aged for 5 minutes.

Then, the potential was set to 140 mV, and while keeping the potential, silver chlorobromide fine particles (Br
171 g in terms of total silver was added over 45 minutes. Finally, a settling agent was added, the temperature was lowered to 35 ° C., and the precipitate was washed by settling. Add an aqueous gelatin solution and p
H was adjusted to 6.0.

A replica TEM image of the particles was observed. The obtained emulsion was composed of silver chlorobromide having a silver bromide content of 5.0 mol%, and had an average grain size expressed by a diameter equivalent to a sphere of 0.9.
2 μm, average particle size 1.79 μm in height, 1.79 in width
The projection plane of μm is a rectangle having an average aspect ratio of about 1: 1.
The ratio of the diameter of a circle having a thickness of 0.128 μm equivalent to the average grain projected area divided by the average grain thickness, that is, the so-called aspect ratio is 1
It was a (100) major plane emulsion containing 89% or more of tabular grains having a coefficient of variation of 5.9 and a coefficient of variation of 0.17.

Preparation of Silver Halide Emulsion A-3 of the Present Invention 21.2 g of gelatin having an average molecular weight of 15,000, 0.85 g of sodium chloride, and 1000 ml of distilled water containing 3.8 ml of sulfuric acid (1N) were placed in a reaction vessel. The temperature was raised to ° C. To this solution, 30 ml of an aqueous solution containing 6.1 g of silver nitrate and 30 ml of an aqueous solution containing 2.00 g of sodium chloride and 0.21 g of potassium bromide were added over 45 seconds with vigorous stirring. Next, 40 ml of an aqueous solution containing 0.55 g of potassium bromide was added. Further, 100 ml of an aqueous solution containing 18.3 g of silver nitrate and 100 ml of an aqueous solution containing 6.30 g of sodium chloride were added over 3 minutes. 6.0 ml of sodium hydroxide (1N) was added, and the temperature of the reaction solution was reduced to 7%.
Increased to 5 ° C. 10.0 g of gelatin in 100 parts of distilled water
After the addition, 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 addition flow rate, and adjusting the silver potential of the reaction solution to 120 mV with respect to the saturated calomel electrode. Added over 45 minutes. Potassium hexachloride iridate 0.04m
g, keep at 75 ° C. for 30 minutes, then lower the temperature,
Desalting was performed according to a conventional method.

A replica TEM image of the particles was observed. The resulting emulsion was composed of silver chlorobromide having a silver bromide content of 0.64 mol%, and had an average grain size of 0.1 as a sphere-equivalent diameter.
69 μm, average particle size 0.92 μm in height, 1.1 in width
The projection surface of 5 μm is a rectangle having an average aspect ratio of approximately 1: 1.25, a thickness of 0.163 μm, and a ratio obtained by dividing the diameter of a circle equivalent to the average particle projection area by the average particle thickness, that is, an aspect ratio of 7 .1 and 9 tabular grains having a coefficient of variation of 0.13.
It was a (100) major plane emulsion containing 1% or more.

Preparation of silver halide emulsion A-4 for comparison Next, 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 put into a reaction vessel, and the temperature was raised to 55 ° C. To this solution was added N, N'-dimethylimidazolidin-2-thione (1
%) Aqueous solution (1.7 ml) 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 over 24 minutes. Next, 500 m of an aqueous solution containing 162.8 g of silver nitrate
500 m of an aqueous solution containing 1 and 59.88 g of sodium chloride
was added over 80 minutes while accelerating the addition flow rate. Sixty minutes after the start of addition of these reaction solutions, 0.04 mg of potassium hexachloroiridate was added. After keeping the temperature at 55 ° C. for 5 minutes from the completion of the addition of the reaction solution, the temperature was lowered and desalting was performed according to a standard method. A replica TEM image of the particles was observed. The obtained emulsion was an emulsion composed of cubic grains having an average grain size of 0.69 μm and an average grain size of 0.56 μm expressed by a diameter equivalent to a sphere.

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

[0149]

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By changing the spectral sensitizing dyes used for spectral sensitization of the silver halide emulsions of A-1G to A-4G to those shown below, blue sensitivity (A-1B to A-4B) and red sensitivity were obtained. Emulsions (A-1R to A-4R) were prepared.

[0151]

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Next, a dispersion of zinc hydroxide used as a base precursor was prepared. The particle size of the primary particles is 0.
31 g of 2 μm zinc hydroxide powder, 1.6 g of carboxymethylcellulose and 0.4 g of sodium polyacrylate as a dispersant, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed, and the mixture was mixed with glass beads. Dispersed in the mill for 1 hour. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide. further,
An emulsified dispersion of the magenta coupler was prepared. 7.80 g of a magenta coupler (a), 5.45 g of a developing agent (b),
Antifoggant (c) 2 mg, high boiling organic solvent (d) 8.2
1 g and 24.0 ml of ethyl acetate were dissolved at 60 ° C. Aqueous solution 15 containing 12.0 g of lime-processed gelatin and 0.6 g of sodium dodecylbenzenesulfonate
The above solution was mixed in 0 g, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. After dispersion, distilled water was added so that the total amount was 300 g, and 200 g was added.
Mix at 0 rpm for 10 minutes.

[0153]

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Further, a coupler dispersion of cyan and yellow was prepared according to the same preparation method. 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. The silver halide emulsions A-1B, A-1G, A-
1R, a heat-developable color light-sensitive material 101 having a multilayer structure shown in Tables 1 and 2 using a coupler dispersion and a colorant dispersion.
It was created.

[0155]

[Table 1]

[0156]

[Table 2]

[0157]

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[0158]

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[0159]

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[0160]

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[0161]

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Further, the processing materials P- as shown in Tables 3 to 5
1. P-2 was prepared.

[0163]

[Table 3]

[0164]

[Table 4]

[0165]

[Table 5]

[0166]

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[0167]

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Light-sensitive materials 102 to 116 were prepared in the same manner as in light-sensitive material 101, except that the amounts of the silver halide emulsion and the hardener were changed as shown in Tables 6 to 9. Furthermore, the photosensitive materials 117 to 132 were prepared by changing the dry film thickness by uniformly reducing the amount of gelatin in all layers. Tables 6 to 9 show the dry film thicknesses of these photographic materials and the saturated swelling film thickness at a water temperature of 40 ° C.

These photosensitive materials were exposed to 4000 lux for 1/100 second in combination with a CC optical filter manufactured by FUJIFILM Corporation so that the color density became gray of 1.0. 15 ml / m ² of 40 ° C. hot water was applied to the surface of the photosensitive material after the exposure, 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. After processing, the photosensitive material was peeled off to obtain a gray image. This sample was subjected to the second process using the processing material P-2. In the processing of the second step, 10 cc / m ² of water is applied to the processing material P-2, and the processing material P-2 is bonded to the photosensitive material after the first processing using the processing material P-1.
Heated at 60 ° C. for 30 seconds. Density unevenness of the obtained color sample was determined by visual inspection. The results are shown in Tables 6-9.

[0170]

[Table 6]

[0171]

[Table 7]

[0172]

[Table 8]

[0173]

[Table 9]

As is clear from Tables 6 to 9, it is found that the photosensitive material of the present invention has good density unevenness.

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

Claims (3)

[Claims] 1. A three-layered photosensitive layer comprising a photosensitive silver halide, a developing agent, a compound which forms a dye by a coupling reaction with an oxidized form of the developing agent and a binder on a support and at least different color sensitivity. The surface of a processing material of a silver halide color photographic light-sensitive material, comprising a processing layer containing a base and / or a base precursor-containing processing layer on a support after exposure of the light-sensitive material; In a silver halide color photographic light-sensitive material for forming a color image by laminating and heat-developing the photosensitive layer surface of the photosensitive layer surface of the photosensitive material, the dry thickness of the entire coating film of the photosensitive layer surface of the photosensitive material is 6 to 21μ, The film has a saturated swelling film thickness of 5 to 40 μm with water, and 50 mol% in the photosensitive layer.
A silver halide grain comprising silver chloride as described above, wherein the main outer surface of the grain is constituted by a (100) plane, and the aspect ratio of a projection plane is a rectangle having an aspect ratio of 1: 1 to 1: 2. Tabular grains with an aspect ratio of 2 or more and a total projected area of 5
A silver halide color photographic light-sensitive material containing an emulsion in which 0 mol% or more is occupied. 2. The silver halide color photographic light-sensitive material according to claim 1,
The following general formula (I), (II), (III) or (IV)
Contain at least one developing agent
2. The silver halide color printing according to claim 1, wherein
True photosensitive material. Embedded imageEmbedded imageEmbedded imageEmbedded imageWhere R₁~ R_FourIs hydrogen atom, halogen atom, alkyl
Group, aryl group, alkylcarbonamide group, aryl
Carbonamide group, alkyl sulfonamide group, aryl
Sulfonamide group, alkoxy group, aryloxy
Group, alkylthio group, arylthio group, alkylcarba
Moyl group, arylcarbamoyl group, carbamoyl group,
Alkylsulfamoyl group, arylsulfamoyl
Group, sulfamoyl group, cyano group, alkylsulfonyl
Group, arylsulfonyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, alkylcarbonyl group,
Represents an arylcarbonyl group or an acyloxy group;
_FiveRepresents an alkyl group, an aryl group or a heterocyclic group. Z
Represents an atomic group forming a (hetero) aromatic ring, and Z represents
Ring, the sum of the Hammett constants (σ) of the substituents
The total value is 1 or more. R ₆Represents an alkyl group. X is an acid
Elementary, sulfur, selenium or alkyl substitution
Represents an aryl-substituted tertiary nitrogen atom. R₇, R₈Is
R represents a hydrogen atom or a substituent;₇, R₈Are joined to each other
To form a double bond or a ring. In addition, general
Each of Formulas I-IV has a carbon atom to impart oil solubility to the molecule.
It contains at least one ballast group of several or more. 3. The method according to claim 1, wherein the heating and developing comprises adding water corresponding to 1/10 to 1 times the total amount of water required for the maximum swelling of the entire coating film of the photosensitive material and the processing material. The method according to claim 1, wherein after the supply to the processing layer surface, the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material are bonded to each other and heated at a temperature of 60 ° C to 100 ° C for 5 seconds to 60 seconds. 3. The silver halide color photographic light-sensitive material according to 1 or 2.