JPH1090848A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a color photographic sensitive material for a novel easy and rapid image forming method less liable to affect the environment, ensuring high sensitivity and little fog and imparting satisfactory discrimination. SOLUTION: This color photographic sensitive material has a photographic constituent layer consisting of photosensitive silver halide, a developing agent, a compd. forming a dye by coupling reaction with the oxidized body of the developing agent and a binder on the substrate. This sensitive material is exposed and stuck to a processing material with a processing layer contg. a base and/or its precursor on the substrate while allowing water to exist between the materials by an amt. corresponding to 1/10 to 1 time the amt. of water required to maximumly swell all the coating films of the materials and then they are heated to form an image in the sensitive material. A mercaptoazole compd. is contained in at least one constituent layer of the sensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

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

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

[0005] In view of these viewpoints, many improved techniques have been proposed. For example, IS &T's 48th
Annual Conference Proceed
ings page 180, the dye generated in the development reaction is transferred to the mordant layer, and then separated to remove developed silver and unreacted silver halide. There is disclosed a system that eliminates the need. However, the technology proposed here still requires development processing in a processing bath containing a color developing agent, and it cannot be said that the environmental problem has been solved.

As a system that does not require a processing solution containing a color developing agent, Fuji Photo Film Co., Ltd. has provided a pictography system. In this system, a small amount of water is supplied to a photosensitive member containing a base precursor, and the photosensitive member is bonded to an image receiving member and heated to cause a development reaction. This method is environmentally advantageous in that the above-mentioned treatment bath is not used.

However, when an attempt was made to quickly form an image by heat development using the above-described base generation method using a high-sensitivity photographic photosensitive material, a serious problem was found to occur. That is, when an emulsion provided with high sensitivity for photography is developed at a high temperature, fogging is likely to occur, and it has been difficult to obtain practical discrimination. It is an essential design requirement for photographic materials to achieve both high sensitivity and low fog, and these problems are a serious obstacle to processing photographic materials in a quick and environmentally friendly manner. Was.

On the other hand, as a technique of applying a high silver chloride emulsion to a photographic material for the purpose of speeding up and simplifying a developing process,
US5264337, US5292632, US5
Patent specifications such as 310630 or WO94 / 22054 disclose a technique in which a tabular high silver chloride emulsion having a (100) plane is used for a photographic light-sensitive material for photography. High development speed can be obtained by using a high silver chloride emulsion. By applying the technology disclosed in the above specification to constitute a photosensitive material and attempting to form an image by heat development using the above-described base generation method, the above-mentioned problem of fogging is further exacerbated. There was a tendency. In order to realize a quick and simple image forming method, there has been a demand for development of a technique for suppressing fogging without impairing the developing speed and sensitivity.

[0009]

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 which can provide high sensitivity even with rapid processing and can provide good discrimination with less fogging.

[0010]

The above objects of the present invention have been effectively achieved by the following 1) to 4). 1) A photographic component layer comprising at least one photographic photosensitive layer comprising a photosensitive silver halide emulsion, a developing agent, a compound forming a dye by a coupling reaction with an oxidized form of the developing agent, and a binder on a support. A coated silver halide color photographic light-sensitive material, comprising: a light-sensitive material; and a processing material provided with a constituent layer including a processing layer containing a base and / or a base precursor on a support. After the exposure, the light-sensitive material is bonded and heated in a state where water equivalent to 1/10 to 1 time of the water required for the maximum swelling of all the coating films of these materials is present between the light-sensitive material and the processing material. A silver halide color photographic light-sensitive material which forms a color image therein, characterized in that at least one photographic constituent layer contains a compound represented by the following general formula (A). The silver halide color photographic light-sensitive material that.

[0011]

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In the formula, _Ra represents an alkyl group having 4 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, an aryl group having 6 or more carbon atoms, or a heterocyclic group having 4 or more carbon atoms.
R _b represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. M represents a hydrogen atom, a silver atom or an alkali metal atom.

2) The silver halide emulsion contains at least two types of silver halide emulsions having sensitivity to the same wavelength region and different average grain projected areas. The ratio of the number of silver halide grains per unit area is larger for an emulsion having a larger average grain projected area.
The silver halide color photographic light-sensitive material as described in 1) above, wherein the ratio is larger than the ratio of the value obtained by dividing the coated silver amount of the emulsion by the 3/2 power of the average grain projected area.

3) The developing agent has the following general formula I, II, III
Alternatively, the silver halide color photographic light-sensitive material according to 1) or 2), which is a compound represented by IV.

[0015]

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

4) As the silver halide emulsion, silver halide grains comprising 50 mol% or more of silver chloride in at least one photosensitive layer, and the main outer surface of the grains are composed of (100) planes. And the aspect ratio of the projection surface is 1:
The silver halide color photographic light-sensitive material according to the above 1), 2) or 3), comprising an emulsion comprising tabular grains having an average aspect ratio of 2 or more such as a rectangle of 1 to 1: 2. material.

5) Using the silver halide color photographic light-sensitive material of the above 1), 2), 3) or 4) as a light-sensitive material, and after imagewise exposing the total amount of water required for maximum swelling of the light-sensitive material and the processing material. After supplying water equivalent to 1/10 to 1 times to the photosensitive material or the processing material, they are bonded to each other at 60 ° C. or higher and 100
A color image forming method for forming a color image by heating at a temperature of not more than 5 ° C. and not more than 60 seconds.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The photographic material of the present invention may contain at least one 3-mercapto-1,2,4-triazole represented by the general formula (A) in its photographic constituent layer. is necessary. Conventionally, photographic light-sensitive materials have been incorporated with various mercapto compounds for the purpose of preventing fogging or stabilizing performance during storage. However, in a system in which an image is formed by developing a photosensitive material containing a developing agent at high temperature and in a short time as in the present invention, it is difficult to obtain sufficient discrimination with a generally known anti-fogging agent. Met. In other words, a fogging inhibitor having a weak development suppressing effect and a small desensitizing effect does not sufficiently prevent fogging during high-temperature development, while a compound exhibiting a sufficient anti-fogging effect even at high temperature development tends to impair the sensitivity. there were. As a result of intensive studies made by the present inventors, the compound represented by the formula (A) is specific for improving discrimination when developing a photosensitive material containing a developing agent at high temperature and in a short time. Have been found to exhibit excellent action. Hereinafter, the compound of the general formula (A) will be described in detail. In the formula (A), _Ra is an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Alkyl, aralkyl or aryl groups are preferred. The alkyl group, aralkyl group, aryl group or heterocyclic group has 4 or more carbon atoms in the alkyl group, 7 or more in the aralkyl group, 6 or more in the aryl group, and 4 or more in the heterocyclic group. It is necessary to. In the present invention,
A compound having a relatively large group introduced into R _a (substituent at the 5-position) is used. Although there is no particular upper limit on the number of carbon atoms, it is preferably 40 or less, more preferably 30 or less in any group,
Most preferably, it is 20 or less.

The above alkyl group may have any of a straight-chain, branched or cyclic structure. Examples of the alkyl group include normal hexyl, normal heptyl, normal octyl, normal nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, neopentyl, 1-pentyl,
Ethylpentyl, tert-butyl and cyclohexyl can be mentioned. Examples of the aralkyl group include:
Benzyl and phenethyl can be mentioned. Examples of the aryl group include phenyl, naphthyl, biphenylyl and anthryl. An aromatic ring, an aliphatic ring, or another heterocyclic ring may be condensed with the heterocyclic ring of the above heterocyclic group. As the hetero atom of the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable.
Examples of the heterocycle include a pyridine ring, a thiophene ring, an oxazole ring, a thiazole ring, a quinoline ring, a benzoxazole ring and a benzothiazole ring.

Each of the above groups may have a substituent.
The number of carbon atoms in each of the above groups means the total number of carbon atoms including a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, an alkoxycarbonyl group, an amino, a substituted amino group, an amide group, carbamoyl,
N-substituted carbamoyl group, ureido, N-substituted ureido group, alkylsulfonyl group, arylsulfonyl group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl, cyano, nitro, trifluoromethyl, halogen atom, hydroxyl, mercapto, carboxyl And sulfo. Each group may be further substituted. Carboxyl and sulfo may form salts. There are no particular restrictions on the substitution positions and the number of substitutions of the above substituents.

In the formula (A), R _b is an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. An alkyl group, an aralkyl group or an aryl group is preferred, and an aralkyl group or an aryl group is more preferred. The alkyl group, aralkyl group, aryl group or heterocyclic group has 2 or more carbon atoms in the alkyl group, 7 or more in the aralkyl group, 6 or more in the aryl group, and 4 or more in the heterocyclic group. preferable. Although there is no particular upper limit on the number of carbon atoms in these groups, the number of carbon atoms in each group is preferably 40 or less, more preferably 30 or less, and most preferably 20 or less.

The above alkyl group may have any of a straight-chain, branched or cyclic structure. Examples of alkyl groups include ethyl, propyl, isopropyl, normal heptyl, isobutyl, tert-butyl and cyclohexyl. Examples of the aralkyl group include benzyl and phenethyl. Examples of the aryl group include phenyl, naphthyl, biphenylyl and anthryl. An aromatic ring, an aliphatic ring, or another heterocyclic ring may be condensed with the heterocyclic ring of the above heterocyclic group. As the hetero atom of the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. Examples of the heterocycle include a pyridine ring, a thiophene ring, an oxazole ring, a thiazole ring, a quinoline ring, a benzoxazole ring and a benzothiazole ring. Examples of the substituent of R _b are the same as the examples of the substituent of R _a described above.

In the formula (A), M is a hydrogen atom, a silver atom or an alkali metal atom. A hydrogen atom or a silver atom is preferred, and a hydrogen atom is particularly preferred.

The heterocyclic compound usually has tautomerism. 3-mercapto-1, represented by the formula (A),
2,4-Triazoles (when M is a hydrogen atom) include an enol type and a keto type as described below. In this specification,
Definitions and examples are given for the enol type. of course,
Keto forms are also included in the scope of the present invention.

[0026]

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Examples of the compound represented by the formula (A) are shown below.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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The compound represented by the formula (A) can be synthesized by the following route.

[0037]

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That is, the compound (3) is synthesized by reacting the isothiocyanate (1) with the hydrazide (2). Compound (3) can also be synthesized by reacting thiosemicarbazide (4) with a halogenated (eg, acyl chloride) acyl (5) in the presence of a base. The compound (3) is closed by a dehydration reaction to synthesize the compound (6) represented by the formula (A). The following shows a synthesis example.
In Synthesis Example 1, isothiocyanate (1) and hydrazide (2) are used as starting materials. In Synthesis Example 2, thiosemicarbazide (4) and acyl halide (5) are used as starting materials. Other compounds represented by the formula (A) can be synthesized in the same manner as in Synthesis Example 1 or 2.

Synthesis Example 1 Synthesis of Compound (A-17) 6.8 g (0.05 mol) of benzoylhydrazine was dispersed in 100 ml of acetonitrile. 7.45 g (0.05 mol) of isothiocyanic acid benzyl ester was added to this solution.
Was added dropwise at room temperature. After completion of the dropwise addition, benzoylhydrazine was completely dissolved, and after a while, white crystals were precipitated.
After stirring at room temperature for 6 hours, the crystals were collected by filtration, washed with a small amount of acetonitrile, and dried. Next, the obtained crystal was
It was dissolved in 35 ml of a 0% aqueous sodium hydroxide solution, and heated and stirred at 100 ° C. for 1 hour. Then, after cooling to room temperature, the reaction product was poured into 0.6 liter of ice water and neutralized with dilute hydrochloric acid. The precipitated white crystals were collected by filtration,
After washing with water and drying, crude crystals were obtained. The crude crystals were recrystallized from ethanol to obtain white needles. The yield is 8.8 g,
The yield was 66% and the melting point was 192 to 194 ° C. The mass spectrum of this compound showed a molecular ion peak at +267.

Elemental analysis (C ₁₅ H ₁₃ N ₃ S) Calculated: C 67.39% Found: C 67.53% H 4.90% H 5.02% N 15.72% N 15.69 % S 11.99% S 11.76%

Synthesis Example 2 Synthesis of Compound (A-34) 8.36 g of 4-phenyl-3-thiosemicarbazide
(0.05 mol) was dissolved in 100 ml of tetrahydrofuran, and 8.83 g of pelargonic acid chloride was added to this solution.
(0.05 mol) was added dropwise under ice cooling. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. Thereafter, the reaction mixture was poured into 1 liter of ice water, and the precipitated crystals were collected by filtration, washed with water, and dried. Next, the obtained crystals were dissolved in 30 ml of a 10% aqueous sodium hydroxide solution, and heated and stirred at 100 ° C. for 1 hour. Then, after cooling to room temperature, the reaction product was poured into 0.6 liter of ice water and neutralized with dilute hydrochloric acid. The precipitated white crystals were collected by filtration, washed with water, and then dried,
Crude crystals were obtained. The crude crystals were recrystallized from a mixed solution of ethanol and water to obtain white needles. The yield is 8.9 g and the yield is 62.
%, Melting point 101-103 ° C. The mass spectrometry spectrum of this compound showed a molecular ion peak at +289.

Elemental analysis value (C ₁₆ H ₂₃ N ₃ S) Calculated value: C 66.39% Actual value: C 66.52% H 8.01% H 7.83% N 14.52% N 14.45 % S 11.08% S 11.20%

The compound represented by the formula (A) may be added to any layer of the light-sensitive material. It is preferably added to a layer containing silver halide. Two or more compounds represented by the formula (A) may be used in combination. The amount of the compound represented by the formula (A) is 10 ^{-6 with} respect to 1 mol of silver contained in the light-sensitive material.
It is preferably in the range of 10 to 10 ^-1 mol. It is more preferably in the range of 10 ^{-5 to} 10 ^-1 mol, most preferably in the range of 10 ^{-4 to} 10 ^-2 mol.

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

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

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

At this time, it is preferable that the difference between the average grain projected areas of the emulsions is at least 1.25 times the difference. 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 sensitivity to these same wavelength regions and different average grain projected areas, a separate photosensitive layer may be provided for each emulsion, or one photosensitive layer may be provided. And a plurality of the above emulsions may be mixed and contained. When these emulsions are contained in separate layers, it is preferable to arrange the emulsion having a large average grain projected area in the upper layer (a position close to the light incident direction).

When these emulsions are contained in separate light-sensitive layers, it is preferable to use color couplers having the same hue, but it is preferable to combine color couplers having different hues and mix them. 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 in coating the emulsions having photosensitivity in the same wavelength region is such that the average grain projected area is larger. The amount of silver coated on the emulsion was 3/3 of the average grain projected area of the silver halide grains contained in the emulsion.
It is preferable that the ratio be larger than the ratio of the values divided by the square. Having photosensitivity in these same wavelength regions,
The above-described ratio of the number of coated grains of emulsions having different average grain projected areas can be realized by designing the emulsion having a larger average grain projected area to have a smaller grain volume per projected area. Specifically, for example, an emulsion composed of tabular silver halide grains having a hexagonal or rectangular projection surface is used, and the diameter of a circle equivalent to the projected area is divided by the grain thickness as the emulsion has a larger average grain projected area. This can be achieved by increasing the value, that is, the aspect ratio. Further, this can be achieved by using an emulsion composed of rectangular parallelepiped or rod-shaped silver halide grains and increasing the ratio of the long side to the short side as the emulsion has a larger average grain projected area. By adopting such a configuration, an image having good granularity can be obtained even under development conditions heated to a high temperature. In addition, high developability and a wide exposure latitude can be satisfied at the same time.

In a color negative film which has been conventionally used for photographic photography, the development of silver halide emulsion is suppressed in addition to the improvement of silver halide emulsion in order to achieve the desired granularity. A technique such as the use of a so-called DIR coupler that releases a compound having a property has been incorporated. In the photosensitive material of the present invention, D
Excellent granularity can be obtained even when no IR coupler is used. In addition, the combination of the DIR compounds results in increasingly better granularity.

The emulsion used in the present invention preferably has an arbitrary composition such as silver iodobromide, silver bromide, silver chlorobromide, silver chloroiodobromide, silver chloroiodide or silver chloride. it can. For example, an emulsion mainly composed of silver iodobromide can be used as in the case of the currently used color negative film. In such a case, silver chloride may be contained, but the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less.
Mol% or less. Silver iodobromide having a laminated structure composed of a plurality of layers having different halogen compositions inside silver halide grains, and has a higher iodine degree than any of the layer adjacent to the inside of the grain and the layer adjacent to the surface of the grain. It is further preferable to use a silver halide emulsion composed of grains having at least one layer having a high content.

As the shape of these silver halide grains, so-called tabular grains having a diameter larger than the thickness of the grains are preferably used. The shape of the tabular grains is preferably a grain having a so-called average aspect ratio of 2 or more, and more preferably 5 or more, obtained by dividing the average of the diameter of a circle equivalent to the projected area by the average of the grain thickness.

In the present invention, a photosensitive emulsion mainly composed of silver halide grains composed of silver chlorobromide, silver chloride or the like can be used. In such a case, silver iodide may be contained, 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. These silver halide grains are tabular with an average aspect ratio of 2 or more such that the main outer surface of the grains is constituted by a (100) plane and the projection plane is a rectangle having an aspect ratio of 1: 1 to 1: 2. Emulsions consisting of grains are preferably used. Various methods can be used to produce these emulsions, 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. The key point in the preparation of these emulsions is a method of generating nuclei for tabular growth. As described in the production method of the above-mentioned literature, iodide ions or bromide ions are added at the beginning of grain formation, or specific It is useful to add a compound exhibiting selective adsorptivity to the surface. These silver halide grains have a main outer surface of (10%).
0), the projection plane has a rectangular shape. At this time, it is preferable that the ratio of the vertical and horizontal sides of the rectangle that is the projection plane is in the range of 1: 1 to 1: 2. That is, tabular grains having a projection surface close to a square are more preferable than emulsions consisting of rod-like or cuboid grains close to a cube in order to obtain high sensitivity.

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 shadowed with a heavy metal or the like. Can be measured. The diameter of the silver halide grains used in the present invention (here, the diameter of the silver halide grains means a diameter of a circle equal to the projected area of the grains) is preferably 0.1 to 0.1.
It is 10 μm, more preferably 0.3 to 5 μm, particularly preferably 0.5 to 4 μm.

The light-sensitive material of the present invention comprises at least one layer of a photosensitive silver halide, a developing agent, a compound capable of forming a dye by a coupling reaction with an oxidized form of the developing agent, and a binder. It is constituted by coating a photographic constituent layer including a layer. To form an image after exposing the photosensitive material imagewise, the exposed photosensitive material and a processing material containing a base and / or a base precursor on a support are coated with a maximum of the total coating film of these members. After a water equivalent to 1/10 to 1 time of the water required for swelling is supplied to the photosensitive material or the processing material, they are bonded and heated to perform color development. As the developing agent to be contained in the light-sensitive material of the present invention, it is preferable to use a compound represented by the above general formula I, II, III or IV.

The present invention has been made for the purpose of achieving good granularity and exposure latitude in the above-described thermal development, and aims at reducing the environmental load caused by liquid development. It is also possible to form an image by developing the light-sensitive material of the present invention with an activator method using an alkali processing solution or a processing solution containing a developing agent / base. In the present invention, image information can be captured without removing developed silver and undeveloped silver halide generated by development, but images can also be captured 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 photosensitive 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 member containing an oxidizing agent for silver, a rehalogenating agent or a silver halide solvent is attached to the photosensitive material to remove the developed silver or to complex the silver halide. Solubilization can also occur.

In the present invention, it is preferable that these processes be performed so as not to hinder image information reading 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.

The photosensitive silver halide grains used in the present invention are silver halide grains composed of 50 mol% or more of silver chloride, and the main outer surface of the grains has a (100) plane, and further defines the outer shape of the grains. The use of an emulsion composed of tabular grains in which the length of the shortest side of the three types of sides perpendicular to each other is 0.5 or less with respect to the average value of the lengths of the remaining two sides is as described above. Haze can be significantly reduced.

The silver halide emulsion which can be used in combination with the silver halide emulsion of the present invention includes, specifically,
U.S. Pat. No. 4,500,626, column 50, 4,62.
No. 8,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17, 029 (1978),
No. 17, 643 (December 1978), pp. 22-23,
No. 18,716 (November 1979), p.648,
No. 307, 105 (November 1989) 863-86
5, JP-A-62-253,159, 64-13,
546, JP-A-2-236,546 and 3-11
No. 0,555 and Grafkid "Physics and Chemistry of Photography", published by Paul Monte (P. Glafkides, Chemie et Phi)
sque Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDuff
in, Photographic Emulsion Chemistry, Focal Press, 1
966), "Production and Coating of Photographic Emulsion", by Zelikman et al., Focal Press (VLZelikman et al., Making an
d Coating Photographic Emulusion, Focal
Press, 1964) and the like.

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

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

In the step of forming the grains of the photosensitive silver halide emulsion of the present invention, as a silver halide solvent, a rhodan salt, 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.

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

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

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, gold, platinum, and the like, which are known for an emulsion for a normal type light-sensitive material, are used. A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-11055).
No. 5, Japanese Patent Application No. 4-75,798). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-253,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833 and JP-A-62-4
0,446 can be used. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and the pAg is preferably 6.0.
１10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver. Preferably it is between 10 mg and 8 g / m ² , most preferably between 100 mg and 6 g / m ² .

In order to impart color sensitivity such as green sensitivity and red sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, US Patent No. 4,617,257
No., JP-A-59-180,550 and 64-13,5
No. 46, JP-A-5-45,828 and JP-A-5-45,83
No. 4 and the like. These sensitizing dyes may be used alone, or a combination thereof may be used, and a combination of sensitizing dyes is often used particularly 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 of gelatin or the like, or a 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 20 g or less per 1 m ² , and particularly preferably 10 g or less.

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

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

US Pat. No. 4,366,237, GB 2, 12
5,570, EP 96,570, DE 3,234
No. 533 is preferred.

In the present invention, the coupler is preferably used in an amount of 1/1000 to 1 mol per mol of silver halide, more preferably 1/500 to 1/5 mol. Further, the light-sensitive material of the present invention may contain the following functional coupler. Couplers for correcting unnecessary absorption of coloring dyes include yellow colored cyan couplers described in EP 456, 257 A1, yellow colored magenta couplers described in the EP, magenta colored cyan couplers described in US Pat. No. 4,833,069, US4,83
No. 7,136, (2), a colorless masking coupler represented by the formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45). In the present invention, it is preferable to use a coupler or another compound which releases a photographically useful compound by reacting with an oxidized form of the developing agent. Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound: EP37
Compounds represented by formulas (I) to (IV) described on page 11 of JP-A-8,236A1, compounds represented by formula (I) described on page 7 of EP 436,938A2, JP-A-5-307
No. 248, a compound represented by the formula (1), EP440,1
Formulas (I), (II) and (III) described on pages 5 and 6 of 95A2.
A compound represented by formula (I) of claim 1 of JP-A-6-59411, a compound capable of releasing a ligand, and L described in claim 1 of US Pat. No. 4,555,478.
A compound represented by IG-X.

In the light-sensitive material of the present invention, it is necessary to incorporate a developing agent capable of forming a dye by coupling an oxidant formed by silver development with the above-mentioned coupler. In this case, U.S. Pat. No. 3,531,256,
p-phenylenediamines developing agents and phenol or active methylene couplers;
A combination of a p-aminophenol developing agent and an active methylene coupler can be used. US Patent 4,0
A combination of a sulfonamide phenol and a 4-equivalent coupler as described in JP-A Nos. 21 and 240 and JP-A-60-128438 is excellent in raw preservation when incorporated in a light-sensitive material, and is a preferable combination. When a developing agent is incorporated, a precursor of the developing agent may be used. For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599, Research Disclosure Nos. 14,850 and 15,15.
9, Schiff base type compounds, aldol compounds described in JP-A-13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane-based compounds described in JP-A-53-135628.

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

In the present invention, it is preferable to use a compound represented by the general formula I, II, III or IV as a developing agent. Among them, compounds of the general formula I or II are particularly preferably used. Hereinafter, these developing agents will be described in detail.

The compound represented by the general formula I is a compound generally referred to as sulfonamidophenol, and is a compound known in the art. When used in the present invention, the substituent R
Those having a ballast group having 8 or more carbon atoms in at least one of _{1 to} R ₅ are preferable.

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

The compound represented by the general formula II is a compound 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 a group of atoms 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 heteroaromatic ring, particularly a nitrogen-containing aromatic ring, or an electron-withdrawing group introduced into a benzene ring is preferably used. Examples of such an aromatic ring include a pyridine ring, a pyrazine ring, a pyrimidine ring,
A quinoline ring and a quinoxaline ring are preferred. In the case of a benzene ring, examples of the substituent include an alkylsulfonyl group (for example, a methanesulfonyl group and an ethanesulfonyl group),
Halogen atom (for example, chloro group, bromo group), alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidinecarbamoyl group, morpholinocarbamoyl group), arylcarbamoyl group (for example, Phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), carbamoyl, alkylsulfamoyl (eg, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl) Famoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholinylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group) Amamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), and arylsulfonyl group (for example, Phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group ( For example, an acetyl group, a propionyl group, a butyroyl group) or an arylcarbonyl group (for example, a benzoyl group or an alkylbenzoyl group) can be mentioned. Is preferably 1 or more.

The compound represented by the general formula III is carbamoy
It is a compound generically called luhydrazone. 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~ R₈At 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 enumerated above as the substituent of the benzene ring of Z.
Hereinafter, specific examples of the compounds represented by Formulas I to IV are shown, but the compounds of the present invention are not limited thereto.

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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

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

It is also possible to use a developing agent precursor which does not itself have a reducing property but develops a reducing property by the action of a nucleophilic reagent or heat during the development 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 0.0.
The amount is from 1 to 20 mol, particularly preferably from 0.1 to 10 mol.

In the present invention, as a coupler, a 4-equivalent coupler and a 2-equivalent coupler can be selectively used depending on the type of the base agent, and by using the couplers properly, it is possible to prevent color shift due to interlayer movement of the oxidized developing agent. A specific example of a coupler is the theory of the photographic process (4t
h Ed. THJames Editing, Macmillan, 1977) 291-3
Page 34, and pages 354 to 361, JP-A-58-12
No. 353, No. 58-149046, No. 58-1490
No. 47, No. 59-11114, No. 59-124399
Nos. 59-174835 and 59-231439
No. 59-231540, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-
No. 66249 and the references and patents cited above.

Hydrophobic additives such as couplers, developing agents, and nondiffusible reducing agents can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat.
No. 5,470, No. 4,536,466, No. 4,53
6,467, 4,587,206, 4,55
5,476, 4,599,296, 3-6
A high-boiling organic solvent as described in JP-A-2,256 or the like can be used, if necessary, in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C. Two or more of these dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, and the like can be used in combination. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g, per 1 g of the hydrophobic additive used.
g or less, more preferably 1 g to 0.1 g. Also,
1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less, is suitable for 1 g of the binder. Tokiko Sho 51-3
9,853, JP-A-51-59,943, and a dispersion method using a polymer described in JP-A-62-30,242.
And the method of adding as a fine particle dispersion described in No. For compounds that are substantially insoluble in water,
In addition to the above-mentioned method, fine particles can be dispersed and contained in a binder. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157,636, Nos. (37) to (3)
On page 8), those mentioned as the surfactants described in Research Disclosure described above can be used. Further, phosphate ester type surfactants described in Japanese Patent Application Nos. 5-204325 and 6-19247 and West German Patent Application No. 1,932,299A can also be used.

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

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

Dyes which can be used in the yellow filter layer and the antihalation layer are preferably those which are decolored or eluted during development and do not contribute to the density after processing. The fact that the dye in the yellow filter layer and the antihalation layer is erased or removed at the time of development means that the amount of the dye remaining after the processing is 1/3 or less, preferably 1 /
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 Application EP 549,489A and JP-A-7-15
No. 2129, ExF2-6 dyes. Dyes dispersed in a solid as described in Japanese Patent Application No. 6-259805 can also be used. This dye can be used when the photosensitive material is developed with a processing solution, but is particularly preferable when the photosensitive material is thermally developed using a processing sheet described later. In addition, a mordant and a binder can be dyed with a dye. In this case, as the mordant and the dye, those known in the photographic field can be used.
No. 58-59, No. 500,626, and JP-A-61-88.
256, page 32 to 41, JP-A-62-244043,
Examples include mordants described in JP-A-62-244036. Further, by using a compound that reacts with a reducing agent to release a diffusible dye and a reducing agent, the mobile dye can be released with an alkali at the time of development and eluted in a processing solution or transferred and removed to a processing sheet. Specifically, U.S. Patent Nos. 4,559,290 and 4,783,369, European Patent No. 220,746A2, and Published Technical Report 87-611.
No. 9 and in paragraph Nos. 0080-0081 of Japanese Patent Application No. 6-259805.

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 used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the hydrophilic binder.

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

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 are obtained. It is developed by laminating and heating in a state where water equivalent to about 1 time is present between the two. The present invention has been made for the purpose of achieving good discrimination in the thermal development as described above, and aims to reduce the environmental load caused by performing liquid development. It is also possible to form an image by developing the material with an activator method using an alkaline processing liquid or a processing liquid containing a developing agent / base.

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

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

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

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

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

The heating temperature in the heat development step is about 50 ° C. to 2 ° C.
The temperature is 50 ° C., preferably from 60 ° C. to 150 ° C., particularly preferably from 60 ° C. to 100 ° C.

In order to supply a base required in the heat development step, a processing material having a processing layer containing a base or a base precursor is preferably 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. 4,50,626, columns 58 to 59, and JP-A-61-8
No. 8256, pp. 32-41, JP-A-62-244043.
And mordants described in JP-A-62-244036. 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.

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

In heat development using the processing material, a small amount of water is used for the purpose of accelerating the 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.

As the water, any water can be used as long as it is generally used. Specifically, distilled water, tap water, well water,
Mineral water or 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. Also, JP-A-63-144,
No. 354, No. 63-144, 355, No. 62-38,
460 and JP-A-3-210,555 and 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. The amount of water in the present invention defines an amount required at the time of performing heat development. Therefore, for example, a method of once supplying a larger amount of water than specified in the present invention to a photosensitive material or a processing material and then removing excess water by means of squeezing or the like until bonding, and performing heat development is also described in the present invention. It can be included in the scope of the invention. Various methods can be used for the method of applying moisture. That is, the photosensitive material or processing material is passed through a container holding water to absorb and impart water to the hydrophilic colloid layer, or water is applied to the photosensitive material or processing material using a sponge or felt. A method of applying by applying, or a method of applying water to a photosensitive material or a processing material by jetting water in the form of fine droplets from a head similar to an ink jet recording head can be used.

As a method of applying the water, for example, Japanese Patent Application Laid-Open No. 62-253,159, p.
The method described in 5,544 or the like 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 from 30 ° C to 30 ° C as described in JP-A-63-85,544 and the like.
What is necessary is just 60 degreeC.

When heat development is carried out in the presence of a small amount of water, EP 210,660, US Pat. No. 4,740,
As described in Japanese Patent No. 445, a basic metal compound which is hardly soluble in water as a base precursor and a compound capable of forming a complex with metal ions constituting the basic metal compound using water as a medium (referred to as a complex-forming compound) It is effective to employ a method of generating a base by using a combination of the above. In this case, the basic metal compound which is hardly soluble in water is added to the photosensitive material, and the complex forming compound is added to the processing material.
Desirable in terms of raw preservability.

As a heating method in the developing step, a heating block, a plate, a heating plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far-infrared lamp heater, or the like is contacted. Or through a high-temperature atmosphere.
The method described in JP-A-62-253,159 and JP-A-61-147,244, page 27, can be applied to a method of superposing a photosensitive material and a processing material in such a manner that the photosensitive layer and the processing layer face each other. The heating temperature is preferably from 60C 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 images 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. Further, after the development of the image formation is completed, a second processing material containing an oxidizing agent for silver, a rehalogenating agent or a silver halide solvent is bonded to the photosensitive material to remove developed silver or complex 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 or tabular grains having a high silver chloride content in order to reduce 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, vol2, chapter30, Foundation Press, Londo
n, England. These bleaches effectively oxidize and solubilize photographic silver images. Examples of useful silver bleaches include alkali metal dichromates, alkali metal ferricyanides. Preferred bleaches are those that are soluble in water and include ninhydrin, indandione, hexaketocyclohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzenesulfonic acid, 2,5-dinitrobenzoic acid. Further, there are metal organic complexes, for example, ferric salt of cyclohexyldialkylaminotetraacetic acid, ferric salt of ethylenediaminetetraacetic acid, and ferric salt of citric acid. As the fixing agent, a silver halide solvent which can be contained in a processing material (first processing material) for developing the above-mentioned photosensitive material can be used. Regarding binders, supports, and other additives that can be used for the second processing material,
The same material as the first processing material can be used. The amount of the bleaching agent to be applied should be changed according to the silver content of the light-sensitive material to be laminated, but 0.01 mol to 10 mol of the silver coating amount per unit area of the light-sensitive material / silver coating amount of the light-sensitive material. Used in the range. Preferably 0.1 to 3
Mol / mol of coated silver of photosensitive material, more preferably 0.1 to 2 mol / mol of coated silver of photosensitive material.

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

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

The total content of the silver halide solvent in the processing layer is from 0.01 to 100 mmol / m ² , preferably from 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 so that the silver halide of the light-sensitive material is solubilized and fixed 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 physical developed silver transferred to the processing material is used as an image, palladium sulfide, silver sulfide, or the like is preferably used because Dmin is cut off and Dmax is high.

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

In the present invention, as a method for 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 added to the photosensitive material or the second processing material in an amount equivalent to 0.1 to 1 times the amount required for the above, and the photosensitive material and the second processing material are overlapped with the photosensitive layer and the processing layer facing 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, improvement of peeling property, improvement of sliding property, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are known in the art No. 5 (March 22, 1991, published by Aztec Co., Ltd.), pp. 136-138, JP-A-62-17.
3,463 and 62-183,457. The photosensitive material may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, improving peelability, and the like. As a representative example of the organic fluoro compound,
No. 9053, columns 8 to 17, JP-A-61-20944
No. 62-135826 and hydrophobic fluorine compounds such as oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin. Can be

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

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

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

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

In the present invention, as the support for 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.

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

In order to adhere 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 using a support having a magnetic recording layer described in Japanese Patent Application No. 5-58221 and Japanese Patent Application No. 5-106979.

The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder. Magnetic particles include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited 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 _3, 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 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, magnetic particles are disclosed in JP-A-6-16103.
The surface may be treated with a silane coupling agent or a titanium coupling agent as described in No. 2. 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 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-5-08828
The dispersant described in No. 3 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to
3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ³ g / m ² .
To ² g / m ² , more preferably 0.02 to 0.5 g / m ²
It is. The transmission yellow density of the magnetic recording layer is 0.01 to
0.50 is preferable, 0.03 to 0.20 is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. As a method for applying the magnetic recording layer, air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar, extrusion, etc. can be used. The coating solution described in 341436 is preferred.

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

The polyester support preferably used for the light-sensitive material having the above-described magnetic recording layer will be further described. For details including the light-sensitive material, treatment, cartridge and examples, see the published technical report, official technical report 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 piping, the purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.

Next, a film cartridge in which a photosensitive material can be loaded will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, patrone may contain various antistatic agents, such as carbon black, metal oxide particles, nonions,
Anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are 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.

[0154]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 930 ml of distilled water containing 0.74 g of gelatin having an average molecular weight of 15,000 and 0.7 g of potassium bromide was placed in a reaction vessel, and the temperature was raised to 40 ° C. While stirring this solution vigorously, 30 ml of an aqueous solution containing 1.2 g of silver nitrate and 0.1 ml of potassium bromide were added.
30 ml of an aqueous solution containing 82 g were added over 30 seconds. After maintaining the temperature at 40 ° C. for 1 minute after completion of the addition, the temperature of the reaction solution was reduced to 7
Increased to 5 ° C. 27.0 g of gelatin was added to 200 parts of distilled water.
After adding with water, an aqueous solution containing 22.5 g of silver nitrate 10
0 ml and 80 ml of an aqueous solution containing 15.43 g of potassium bromide were added over 11 minutes while increasing the addition flow rate. Then, 250 ml of an aqueous solution containing 75.1 g of silver nitrate and an aqueous solution containing potassium iodide at a molar ratio of 3:97 to potassium bromide (potassium bromide concentration: 26%) were added at an accelerated flow rate, and the silver in the reaction solution was increased. It was added for 20 minutes so that the potential became -20 mV with respect to the saturated calomel electrode. Further, 75 ml of an aqueous solution containing 18.7 g of silver nitrate and a 21.9% aqueous solution of potassium bromide were added over 3 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 55 ° C. Then, silver nitrate 8.1
g of an aqueous solution containing 120 g and 320 ml of an aqueous solution containing 7.26 g of potassium iodide were added over 5 minutes. After the addition was completed, 5.5 g of potassium bromide and 0.04 mg of potassium hexachloroiridate were added, and the mixture was kept at 55 ° C. for 1 minute.
Further, 180 ml of an aqueous solution containing 44.3 g of silver nitrate and 160 ml of an aqueous solution containing 34.0 g of potassium bromide were added over 8 minutes. The temperature was lowered and desalting was performed according to a standard method.

The obtained emulsion was an emulsion composed of hexagonal tabular grains having an average grain size of 0.66 μm expressed in sphere-equivalent diameter and a ratio of the average grain diameter divided by the average grain thickness of 5.4. This emulsion was designated as emulsion A-1. The following spectral sensitizing dyes, Compound I, potassium thiocyanate,
Spectral sensitization and chemical sensitization were performed by adding chloroauric acid and sodium thiosulfate. The amounts of pAg and chemical sensitizer during chemical sensitization were adjusted so that the degree of chemical sensitization of the emulsion was optimized. The thus prepared green-sensitive emulsion was
1 g.

[0157]

Embedded image

Next, a dispersion of zinc hydroxide used as a base precursor was prepared. The particle size of the primary particles is 0.
31 g of 2 μm zinc hydroxide powder, 1.6 g of carboxymethylcellulose as a dispersant, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed, and the mixture was mixed with glass beads. Dispersed in the mill for 1 hour. After the dispersion, the glass beads were separated by filtration to obtain 188 g of a dispersion of zinc hydroxide. Further, an emulsified dispersion of a magenta coupler was prepared. 7.80 g of magenta coupler (a), 5.45 g of developing agent (b), 2 mg of antifoggant (c), 8.21 g of high boiling organic solvent (d)
And 24.0 ml of ethyl acetate were dissolved at 60 ° C. 12.0 g of lime-processed gelatin and 0.6 of surfactant (e)
The resulting solution was mixed with 150 g of an aqueous solution in which g was dissolved, and emulsified and dispersed at 10,000 rpm for 20 minutes using a dissolver stirrer. After the dispersion, distilled water was added so that the total amount became 300 g, and the mixture was mixed at 2,000 rpm for 10 minutes.

[0159]

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These dispersions and the previously prepared silver halide emulsion were combined and coated on a support with the composition shown in Table 1 to prepare a heat-developable color photographic light-sensitive material of Sample 101.

[0161]

[Table 1]

[0162]

Embedded image

Five types of photographic materials differing from the sample 101 in the type of antifoggant contained therein were prepared, and were set as samples 102 to 106 (Table 1). The comparative antifoggants used for Samples 102 and 103 are shown below.

[0164]

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Further, a processing material P-1 as shown in Tables 2 and 3 was prepared.

[0166]

[Table 2]

[0167]

[Table 3]

[0168]

Embedded image

[0169]

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These photosensitive materials were exposed to light at 1000 lux for 1/100 second through an optical wedge and a green filter. 15 ml / water of 40 ° C. hot water is applied to the surface of the photosensitive material after exposure.
After applying m ² , the processing material and the respective film surfaces were overlapped with each other, heat development was performed using a heat drum at 83 ° C. for 25 seconds. When the photosensitive material was peeled off after the processing, a wedge-shaped image of magenta color was obtained. This sample was subjected to the second step treatment using the second treatment sheet shown in Table 4 below. In the processing of the second step, 10 cc / m ² of water is applied to the second processing sheet, and the sheet is bonded to the photosensitive material after the first processing.
Heated at 0 ° C. for 30 seconds.

[0171]

[Table 4]

[0172]

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The transmission density of the obtained color sample was measured to obtain a so-called characteristic curve. The reciprocal of the exposure corresponding to the density 0.15 higher than the fog density was defined as the relative sensitivity.
It was expressed as a relative value with the value of 1 being 100. The maximum color density was used as a measure of the developing property.

Table 5 summarizes the results.

[0175]

[Table 5]

The following can be understood from the results. First, in the sample 101 containing no mercaptotriazoles, the fogging is high and the maximum color density is slightly low. On the other hand, in the samples 102 and 103 containing the comparative compound, the fog is reduced but the sensitivity is remarkably reduced. On the other hand, in the samples 104 to 106 containing the compound of the present invention, the maximum color density was increased simultaneously with the phenomenon of fogging, the sensitivity was less reduced, and excellent in high-temperature and short-time development with a built-in developing agent. Discrimination can be obtained.

Example 2 A reaction vessel was charged with 21.2 g of gelatin having an average molecular weight of 15,000, 1,000 ml of distilled water containing 0.85 g of sodium chloride and 3.8 ml of sulfuric acid (1N), and the temperature was raised to 40 ° C. 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 to this solution over 45 seconds. Next, an aqueous solution 4 containing 0.55 g of potassium bromide
0 ml was added. Further, 100 ml of an aqueous solution containing 18.3 g of silver nitrate and 10 aqueous solutions containing 6.30 g of sodium chloride
0 ml was added over 3 minutes. Sodium hydroxide (1N)
6.0 ml was added and the temperature of the reaction solution was raised to 75 ° C. After adding 10.0 g of gelatin together with 100 ml of distilled water, 750 ml of an aqueous solution containing 145.4 g of silver nitrate and a 7.0% aqueous solution of sodium chloride were added while accelerating the flow rate, and the silver potential of the reaction solution was applied to a saturated calomel electrode. 1 for
It was added over a period of 45 minutes to 20 mV. Add 0.04 mg of potassium hexachloroiridate, and add
, And the temperature was lowered, and desalting was performed according to a standard method. The resulting emulsion was composed of silver chlorobromide having a silver bromide content of 0.64%, and had an average grain size of 0.1 as a sphere-equivalent diameter.
Emulsion consisting of rectangular tabular grains having a ratio of 7.1 μm obtained by dividing the diameter of a circle equivalent to the average grain projected area by the average grain thickness, and having a projection surface of an average aspect ratio of 1: 1.25. Was. This emulsion was designated as emulsion B-1.

The emulsion was subjected to chemical sensitization and spectral sensitization in the same manner as in Example 1. The resulting emulsion was designated as emulsion B-1g. Emulsion B-1g was used in combination with an anti-fogging agent in the same manner as in Example 1 to prepare six types of photosensitive materials and samples 201 to 206 shown in Table 6.

[0179]

[Table 6]

The same test as in Example 1 was performed on these photosensitive materials, and the photographic characteristics were examined. However, the heat development time was 15 seconds. The results are summarized in Table 7.

[0181]

[Table 7]

From the results, it can be seen that the effect of the present invention of suppressing fogging, increasing the color density, and suppressing the sensitivity is more remarkable in the high silver chloride emulsion.

Example 3 In the preparation of the silver halide emulsion prepared in Example 1,
The following emulsions having different grain sizes and different aspect ratios were prepared by changing the temperature during grain formation, the rate of addition of the reaction solution, and the silver potential of the reaction vessel.

Average grain size Average aspect ratio Emulsion name (equivalent volume sphere conversion) (diameter of circle equivalent to projected area divided by grain thickness) A-1 0.66 μ 5.4 A-2 0.87 μ 7.1 A- 3 0.37μ 3.2

A green-sensitive emulsion which had been subjected to spectral sensitization and chemical sensitization using the same green-sensitive spectral sensitizing dye and chemical sensitizer as in Example 1 was prepared. However,
The amounts of the sensitizing dye and sensitizer were adjusted so that each emulsion was optimally sensitized. Furthermore, blue-sensitive and red-sensitive emulsions were prepared in the same manner by changing the spectral sensitizing dyes used for spectral sensitization to those shown below, and the results were indicated with subscripts b and r. Further, according to the method of preparing a coupler dispersion of Example 1, cyan and yellow coupler dispersions were also prepared. Further, a colorant dispersion was prepared by combining the following yellow, magenta, and cyan leuco dyes and a color developer in order to form a colored layer that can be decolorized during heat development. Using the thus obtained silver halide emulsion, coupler dispersion and colorant dispersion, Tables 8 and 9
A heat-developable color light-sensitive material having a multilayer structure shown in No. 10 was prepared. The compounds used are shown below. For the silver halide emulsions contained in these samples, the ratio between the number of coated grains and the value obtained by dividing the amount of coated silver by the 3/2 power of the average projected area was determined and is shown in Table 11.

[0186]

[Table 8]

[0187]

[Table 9]

[0188]

[Table 10]

[0189]

[Table 11]

[0190]

Embedded image

[0191]

Embedded image

[0192]

Embedded image

[0193]

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The photographic characteristics of these light-sensitive materials were tested in the same manner as in Example 1. First, 1/100 at 1000lux through each optical material through an optical wedge and blue, green and red filters.
A second exposure was given.

After applying 15 ml / m ² of warm water at 40 ° C. to the surface of the photosensitive material after the exposure, the processing material used in Example 1 and each film surface were overlapped with each other.
Heat development was performed at 3 ° C. for 15 seconds. When the photosensitive material is peeled off after processing, the sample exposed with the blue filter has a wedge-shaped image with yellow color, the sample exposed with the green filter has a wedge-shaped image with magenta color, and the sample exposed with the red filter has cyan. A colored wedge-shaped image was obtained. The transmission densities of these color samples were measured, and the characteristic values were determined as in Example 1. The sensitivity was expressed as a relative value where the sensitivity of the blue sensitivity, green sensitivity and red sensitivity of the sample 301 was 100.

[0196]

[Table 12]

From the results, the remarkable effect of the present invention is clear. That is, in the sample 302 containing the comparative antifogging agent with respect to the sample 301, the fogging is reduced, but the maximum color density and the sensitivity are remarkably reduced. For these,
Samples 303 and 30 containing antifoggant of the present invention
Sample No. 4 has low fog, high color development and sensitivity even in high-temperature short-time development, and is excellent in discrimination.

Example 4 The multilayer color photosensitive material prepared in Example 3 was prepared by changing the support on a support prepared by the following method, and a similar test was conducted. . 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
After drying 0 parts by weight and 2 parts by weight of Tinuvin P. 326 (manufactured by Ciba-Geigy) as an ultraviolet absorber, the mixture was melted at 300 ° C. and extruded from a T-die.
The film was stretched 3.3 times at 0 ° C., then stretched 3.3 times at 130 ° C., and heat-set at 250 ° C. for 6 seconds to obtain a 90 μm thick PEN film. The PEN film has a blue dye, a magenta dye and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in Japanese Patent Publication No. 94-6023). 2
7, II-5) was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support with which a winding habit was not easily formed.

2) Coating of Undercoat Layer The support was subjected to a corona discharge treatment, a UV irradiation treatment, and a glow discharge treatment on both surfaces thereof, and then each surface was coated with 0.1 g / m ² of gelatin and sodium α-. Suruhoji-2-ethylhexyl succinate 0.01 g / m ^2, salicylic acid 0.04g / m ^2, p- chlorophenol 0.2 g / m ^2,
_{(CH 2 = CHSO 2 CH 2} CH 2 NHCO) 2 CH 2 0.012g / m 2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, using a bar coater ), An undercoat layer was provided on the high-temperature side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 1
15 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer Tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm has a specific resistance of 5 Ω · cm, which is a dispersion of fine particle powder (secondary aggregated particle diameter of about 0.08 μm). ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02
g / m ^2, it was coated with poly (polymerization degree 10) oxyethylene -p- nonylphenol 0.005 g / m ^2, and resorcin. 3-2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g; Long axis 0.
14 μm, single axis 0.03 μm, saturation magnetization 89 emu / g,
Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface of which is treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (of iron oxide Dispersion was carried out with an open kneader and sand mill), as a curing agent
0.3 g / m ² of C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ was applied with a bar coater using acetone, methyl ethyl ketone and cyclohexanone as a solvent, and the film thickness was 1.2 μm. Was obtained. Silica particles (0.3μ
m) and 3-poly (degree of polymerization: 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) coated and coated with an aluminum oxide (0.15 μm) as an abrasive so as to be 10 mg / m ^2. did. Drying is 115 ° C, 6
(All rollers and conveying devices in the drying zone are at 115 ° C.). X- write saturation magnetization moment 4.2 emu / g to about 0.1, and the magnetic recording layer color density increment of D ^B of the magnetic recording layer in the (blue filter), the coercive force 7.
3 × 10 ⁴ A / m 2 and the squareness ratio were 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀
H ₂₁ OCOOC ₄₀ H ₈₁ (compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (C
H ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied.
This mixture was melted at 105 ° C. in xylene / propylene glycol monomethyl ether (1/1),
Propylene glycol monomethyl ether at room temperature (10
And then dispersed in acetone (average particle size: 0.01 μm) and then added. Silica particles (0.3 μm) as a matting agent and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide (0.15 μm) coated with 15% by weight) as an abrasive are each 15 mg / m 2. ² become so added. drying 115 ° C., was performed for 6 minutes (115 ° C. rollers and conveyors in the drying zone). sliding layer, the dynamic friction coefficient 0.06 (5 mm.phi of stainless steel balls, the load 10
0g, a speed of 6 cm / min), a coefficient of static friction of 0.07 (clip method), and a coefficient of kinetic friction between an emulsion surface and a sliding surface to be described later were excellent at 0.12. A test was conducted using the photosensitive material contained in the cartridge thus prepared, and similarly good results were obtained, confirming the effects of the present invention.

[0202]

The light-sensitive material of the present invention has low fogging, high color-forming properties and high sensitivity even in simple and rapid processing, and is excellent in discrimination.

Claims (5)

[Claims] 1. A photograph comprising at least one photographic photosensitive layer comprising a photosensitive silver halide emulsion, a developing agent, a compound capable of forming a dye by a coupling reaction with an oxidized form of the developing agent, and a binder on a support. A silver halide color photographic light-sensitive material provided with a constituent layer, wherein the light-sensitive material and a processing material provided with a constituent layer including a processing layer containing a base and / or a base precursor on a support, After exposure of the photosensitive material, bonding and heating are performed in a state where water equivalent to 1/10 to 1 time of water required for the maximum swelling of all coating films of these materials is present between the photosensitive material and the processing material. A silver halide color photographic light-sensitive material for forming a color image in the light-sensitive material by using a compound represented by the following general formula (A) in at least one photographic constituent layer A silver halide color photographic light-sensitive material comprising: Embedded image In the formula, _Ra represents an alkyl group having 4 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, an aryl group having 6 or more carbon atoms, or a heterocyclic group having 4 or more carbon atoms. R _b represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. M represents a hydrogen atom, a silver atom or an alkali metal atom. 2. The silver halide emulsion contains at least two types of silver halide emulsions having sensitivity to the same wavelength region and different average grain projected areas. The ratio of the number of silver halide grains per unit area of an emulsion having a larger average grain projected area is larger than the ratio of the value obtained by dividing the coated silver amount of the emulsion by the 3/2 power of the average grain projected area. Claim 1 characterized by the following:
The silver halide color photographic light-sensitive material described in the above. 3. The silver halide color photographic material according to claim 1, wherein said developing agent is a compound represented by the following formula I, II, III or IV. Embedded image In the formula, R _{1 to} R ₄ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group, an aryloxy group, an alkylthio group. An arylthio group, an alkylcarbamoyl group, an arylcarbamoyl group, a 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;
₅ represents an alkyl group, an aryl group or a heterocyclic group. Z
Represents an atomic group forming an aromatic ring, and when Z is a benzene ring, the total value of Hammett constant (σ) of the substituent is 1
That is all. R ₆ represents an alkyl group. X is an oxygen atom,
Represents a sulfur atom, a selenium atom, or an alkyl- or aryl-substituted tertiary nitrogen atom. R ₇ and R ₈ represent a hydrogen atom or a substituent, and R ₇ and R ₈ may combine with each other to form a double bond or a ring. Further, general formulas I to IV
Each include at least one ballast group having 8 or more carbon atoms in order to impart oil solubility to the molecule. 4. The silver halide emulsion according to claim 1, wherein at least one photosensitive layer comprises silver halide grains comprising 50 mol% or more of silver chloride, and the main outer surface of the grains has a (100) plane. And the aspect ratio of the projection surface is 1:
4. A silver halide color photographic light-sensitive material according to claim 1, comprising an emulsion comprising tabular grains having an average aspect ratio of 2 or more, such as a rectangle of 1 to 1: 2. 5. A method according to claim 1, wherein said silver halide color photographic material is 1/10 of the total amount of water required for maximum swelling of said photographic material and said processing material after imagewise exposure. A method of forming a color image by supplying water equivalent to 1 to 1 times to a photosensitive material or a processing material, bonding them together, and heating them at a temperature of 60 ° C. to 100 ° C. for 5 seconds to 60 seconds.