JP2001083669A - Silver halide photosensitive material, processing method for same and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photosensitive material capable of forming an image by a general-purpose current color negative developing system, excellent in processing stability and suitable for rapid processing by forming a specified filter layer and a photosensitive layer containing couplers each forming a dye by reaction with the oxidized body of a developing agent and a silver halide emulsion. SOLUTION: The silver halide photosensitive material has a mosaic or striped filter layer having plural regions different from each other in spectral sensitivity characteristics and a photosensitive layer containing couplers each forming a dye by reaction with the oxidized body of a developing agent and a silver halide emulsion on the substrate. The couplers are at least one yellow coupler, at least one magenta coupler and at least one cyan coupler. The photosensitive layer contains the color developing agent which is at least one of compounds of formulae I, II, etc. In the formulae, R1-R4 are each H, halogen, alkyl or the like, R5 is alkyl, aryl or a heterocyclic group and Z is a group of atoms forming an aromatic ring.

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 light-sensitive material for photographing, a method for processing the light-sensitive material and an image forming method, and more particularly to a color filter silver halide light-sensitive material capable of color development. Silver halide photosensitive material), a processing method of the photosensitive material and an image forming method.

[0002]

2. Description of the Related Art In a method known as conventional color photography, a photographic silver halide light-sensitive material (a so-called photographic color negative film) usually comprises a layer which records blue light to form a yellow dye image, and a green light. It comprises a layer for recording to form a magenta dye image and a layer for recording red light to form a cyan dye image.

The performance elements of this color negative film for photographing are expressed by sensitivity and image quality, and the image quality elements are further classified into granularity, sharpness, and color reproducibility. Contains a compound that adjusts the spectral sensitivity distribution to achieve the desired color reproducibility and releases a development inhibitor during development (so-called DIR compound) while improving the sensitivity, granularity, and sharpness of each photosensitive layer In this way, a design is made to enhance the interlayer development suppressing effect (so-called interimage effect).

On the other hand, the form of such a conventionally used color negative film makes the structure of the photosensitive material very complicated. Not only does it require a coating step of laminating at least three types of photosensitive layers on a support, but also, for example, colloidal silver, a dye, a dye-forming coupler, and a color paper to enhance the color sensitivity of these three types of photosensitive layers. Such materials require many materials such as a masking coupler for improving the fidelity of color when optically exposed, and fine particles of silver and a dye for preventing halation.

[0005] The complicated form sometimes causes unexpected fluctuations in photographic performance, and a simpler and simplified configuration has been desired in order to guarantee the performance stability as much as possible.

In the above-described image forming method other than the yellow / magenta / cyan dye, a color filter array film having an image forming emulsion layer formed on a support provided with a color filter array (a color filter silver halide light-sensitive film). Materials) are known.

[0007] Journal of Imaging
Technology Volume10, Number
r1 (1984) describes an example in which a monochrome emulsion is used as an image recording emulsion layer and is coated with a stripe color filter array pattern of yellow, green, and cyan. A positive film using blue is known.

In the case of a color filter silver halide light-sensitive material, the image recording emulsion layer only needs to have a function of recording density information of a single color discriminated by a color filter as a color separating means, and the constitution is extremely simple. I can do it. However, it is difficult to easily obtain an image because the developing method as an image forming method is a special monochrome process.

A color negative film which 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 an oxidized form of the developing agent and a color coupler generated at the same time. By removing metallic silver (developed silver) generated by development and unreacted silver halide by bleaching and fixing, respectively, a dye image is obtained.

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. By applying the same color development, bleaching and fixing processes, a color print composed of a dye image and reproducing the original scene can be obtained.

[0011] 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 regulated, 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 building systems that do not use color developing agents or bleaching agents used in current color image forming systems. Is growing.

In view of these viewpoints, many improved techniques have been proposed. For example, IS &T's 48th
Annual Conference Processe
The dings page 180 shows that the dye generated by the development reaction is transferred to the mordant layer, and then removed to remove developed silver and unreacted silver halide. A system is disclosed that eliminates the need for a bath.

However, the technology proposed here still requires development 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, a pictography system is provided by Fuji Photo Film Co., Ltd. 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. In this method, the formed dye is diffused and transferred to a dye-fixing layer and fixed, and the dye is used for viewing as a dye image. Therefore, it is desired to develop a system that can be used as a recording material for photographing. Was. However, since the color light-sensitive material used in the above method contains a colored dye-providing substance,
It is difficult to obtain sufficient sensitivity as a color photosensitive material for photography. In addition, although the bleeding of the dye image caused by diffusion transfer is not a problem for appreciation, it satisfies the quality required for color photosensitive materials for photographing used for enlargement and other purposes (hereinafter sometimes simply referred to as photosensitive materials). It does not do.

Further, Japanese Patent Application Laid-Open Nos. 8-234388 and 10-
No. 90848 describes a silver halide photographic material having a photosensitive silver halide emulsion, a hydrophilic binder and a water-insoluble basic compound, after or simultaneously with imagewise exposure, a complex-forming compound, a matting agent, etc. A method is disclosed in which an image is formed by overlapping with a processing sheet having the following formula and performing heat development in the presence of water. These are preferable as a photographic light-sensitive material because they do not contain a colored compound, but it is still difficult to say that they have sufficient performance in view of sensitivity and resolution as a photographic light-sensitive material.

In general, a photographic light-sensitive material is used in which an emulsion layer is coated on a transmission-type support, and an ornamental image is formed by projecting a transmission image generated by development or optically reading the image. Is done. In order to obtain a transmission density sufficient for such a purpose by thermal development, a larger amount of a base precursor is required in the light-sensitive material as compared with reflection-type image formation. However, when the base precursor is contained in the light-sensitive material as a dispersion, an increase in the amount of addition increases optical scattering and lowers the resolution of the light-sensitive material. However, if the amount of base generation is insufficient, the transmission density of the entire image is reduced, or the transmission density of a specific color is insufficient, so that the color balance cannot be maintained, and the sensitivity of a specific layer decreases. This is a very serious problem for producing a photothermographic material which can be thermally developed as described above, and at present it has not been sufficiently solved.

[0017]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a color filter silver halide light-sensitive material which is capable of forming an image with a versatile current color negative developing system, and which is suitable for processing stability and rapid processing. It is an object of the present invention to provide a silver halide photosensitive material for photographing), a method for processing the photosensitive material, and an image forming method.

[0018]

The above object of the present invention is achieved by the following constitution.

1. A coupler having a mosaic or striped filter layer having at least two regions having different spectral sensitivity characteristics on a support, and comprising a coupler and a silver halide emulsion which react with an oxidized form of a developing agent to form a dye. A silver halide light-sensitive material having at least one light-sensitive layer.

2. 2. The silver halide light-sensitive material according to 1, wherein the coupler is at least one of a yellow coupler, a magenta coupler, and a cyan coupler.

3. A method for processing a silver halide light-sensitive material, comprising subjecting the silver halide light-sensitive material described in 1 or 2 to color development processing.

4. A mosaic or striped filter layer having at least two regions having different spectral sensitivity characteristics on a support, and at least one photosensitive layer containing a silver halide emulsion and a developing agent. Silver halide photosensitive material.

5. 5. The silver halide photosensitive material as described in 1, 2, or 4, wherein at least one photosensitive layer contains a color developing agent.

6. The color developing agent is represented by the following general formula (1)
(5) The silver halide photosensitive material as described in (5), which is at least one of the compounds represented by (5).

[0025]

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[Wherein R ^{1 to} R ⁴ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
Alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, sulfamoyl group, cyano group, alkylsulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyl group, Represents an arylcarbonyl group or an acyloxy group. R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group. R ⁶ represents a substituted or unsubstituted 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 , R ⁸ , R ⁹ and R ¹⁰ represent a hydrogen atom or a substituent,
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may combine with each other to form a double bond or a ring. Z represents an atomic group forming an aromatic ring. 7.5) After exposing the silver halide light-sensitive material described in 6 or 7,
An image forming method, wherein an image is formed by performing heat development.

An image forming method comprising forming an image by subjecting the silver halide light-sensitive material described in 8.5 or 6 to an activator process.

9. 8. The image forming method according to 7, wherein the heat development is performed using a processing sheet.

10. 7. The halogen according to 1, 2, 4, 5, or 6, wherein 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion is tabular grains having an aspect ratio of 2 or more. Silver halide photosensitive material.

11. 11. The silver halide light-sensitive material according to 1, 2, 4, 5, 6, or 10, wherein the light-sensitive layer has two or more layers.

12. The silver halide light-sensitive material according to 11, wherein the filter layer is provided between two or more light-sensitive layers.

Hereinafter, the present invention will be described in detail.

As a method for producing the filter layer of the present invention, a method using dyed starch particles, a method for forming a stripe or mosaic pattern by printing,
Various methods used for a color liquid crystal display device, a color CCD image pickup device and the like can be used, such as a method using thermal transfer, a method using ink jet, a method using a photoresist (photocurable resin), a method using a photograph, and the like. Nos. 55-6342 and 63-261361;
-127016, 6-100811, 7-29
No. 4714, No. 8-22108, No. 9-185077
And Nos. 9-145909 and 9-178925.

As the spectral transmission characteristics of the filter layer of the present invention, a combination of Y (yellow), M (magenta), and C (cyan), which are the three primary colors of light of the subtractive color method, is preferable.
B (blue), G (green), and R, which are the three primary colors of light of the additive method
A combination of (red) may be used, and in addition to these, a black matrix portion may be provided.

The pattern of the filter layer of the present invention may be any of a stripe pattern and a mosaic pattern.

The size of the filter layer of the present invention is as follows:
In the case of a stripe shape, the thickness is preferably 1 to 50 μm per color, more preferably 5 to 30 μm. In the case of a mosaic shape, the thickness is preferably 1 μm to 100 μm per unit area, more preferably 5 μm to 50 μm. The thickness of the color filter layer is preferably 1 to 50 μm, more preferably 2 to 20 μm, in any of the stripe and mosaic shapes.

The photosensitive silver halide used in the present invention is:
Any halogen composition such as silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodobromide, or silver iodochloride may be used. Generally, silver iodobromide, silver bromide, and silver chloroiodobromide are preferably used when sensitivity is important, and silver chloride, silver chlorobromide and the like are preferably used when processing speed is important. Silver halide emulsions containing these grains were prepared by Simmy & Physics Photographic by Paul Grafkides (Paul Montel).
Co., Ltd., 1967); Photographic Emulsion Chemistry by G.F.
Focal Press, 1966); Making and Coating Photographic Emulsion (The F.)
ocalPress, 1964), JP-A-51-39027, and JP-A-55-142329.
Nos. 58-113928, 54-48521 and 58-4938, and 60-138538, and pages 88 of the Abstracts of the 58th Annual Meeting of the Photographic Society of Japan. That is, any method such as an acid method, a neutral method, and an ammonia method may be used. The method of reacting the soluble silver salt with the soluble halide is a one-sided mixing method, a double-mixing method, a combination thereof, or a method in which the grains are excessive in silver ion. (Reverse mixing method), a method of supplying a soluble silver salt and a soluble halide salt to a fine seed crystal and growing the same.

The silver halide grains contained in the silver halide emulsion of the present invention may have a regular shape such as a cubic, octahedral or tetradecahedral shape, or an irregular shape such as a tabular twin. The mixture may be a mixture of both, but preferably contains tabular grains. The tabular silver halide grains preferably used in the present invention have an average value (average aspect ratio) of the ratio of grain diameter / thickness (aspect ratio) of 2 or more,
The average aspect ratio is preferably from 3 to 20, and more preferably from 4 to 15.

Preferably, 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion of the present invention are tabular grains having an aspect ratio (ratio of grain diameter / thickness) of 2 or more. , More preferably 3-20, and even more preferably 4-15.

In these tabular silver halide grains, the outer wall of the crystal may be substantially composed of {111} planes, or may be composed of {100} planes. Also,
It may have both the {111} plane and the {100} plane.

The tabular (iodo) bromide grains preferably have dislocations. Dislocations of silver halide grains are described, for example, in J. Am. F. Hamilton, Photogr. Sci.
Eng. , 57 (1967); Shiozaw
a, J. et al. Soc. Photogr. Sci. Japan
n, 35, 213 (1972), which can be observed by a direct method using a transmission electron microscope at a low temperature. The dislocation position of the silver halide grains is 0.58 to 1.0 L from the center of the silver halide grains toward the outer surface.
It is desirable that the occurrence occurs in the region up to, but more preferably, it occurs in the region of 0.80 to 0.98 L. The direction of the dislocation line is approximately from the center to the outer surface, but often meanders. Regarding the number of dislocations in the silver halide grains, it is desirable that grains containing one or more dislocations exist in an amount of 50% (number) or more, and the higher the ratio (number) of the number of tabular grains having dislocation lines, the more preferable.

In the tabular grains, the particle diameter is a diameter when a projected image of the grains is converted into a circular image having the same area. The projected area of a particle can be determined from the sum of the particle areas.
In any case, a silver halide crystal sample distributed on a sample table to such an extent that the grains do not overlap can be obtained by observing with an electron microscope. The average projected area diameter of the tabular silver halide grains is represented by a circle-equivalent diameter of the projected area of the grains, and is preferably 0.30 μm or more, more preferably 0.30 to 5 μm, and still more preferably 0.40 μm. ~
2 μm. The particle size of the particles was determined to be 10,000 to 7 with an electron microscope.
It can be obtained by magnifying and projecting by a factor of 10,000 and actually measuring the projected area on the print. The average particle diameter (φ) can be obtained by the following equation, where n is the number of measured particle diameters and ni is the frequency of particles having the particle diameter φi.

Average particle size (φ) = (Σni · φi) / n (The number of particles to be measured is assumed to be 1,000 or more indiscriminately.) For the particle thickness, the sample is observed obliquely with an electron microscope. Can be obtained by: The preferred thickness of the tabular grains of the present invention is from 0.03 to 1.0 µm, more preferably from 0.05 to 0.5 µm. The tabular silver halide grains used in the present invention preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 25% or less, more preferably 20%. These are:

Further, taking into account the factors of the aspect ratio and the thickness of the grains, the flatness represented by the following equation: A = ECD / b2 is preferably 20 or more. Here, ECD indicates the average projected diameter (μm) of tabular grains, and b is the thickness of the grains. Here, the average projected diameter represents the number average of the diameter of a circle having an area equal to the projected area of the tabular grains.

Further, the distribution of the halogen content of each grain in the tabular silver halide grain emulsion used in the present invention is preferably small. Specifically, (standard deviation of halogen content / average halogen content) ×
When the width of the distribution is defined by 100 = the width (%) of the halogen content, it is preferably 25% or less, more preferably 20% or less.

The silver halide grains used in the present invention are:
The silver halide grains may have a core / shell type structure having at least two layer structures having substantially different halogen compositions or a uniform composition. The average silver iodide content of the silver halide emulsion according to the present invention is preferably 20 mol% or less,
More preferably, it is 0.1 to 10 mol%. In the present invention, so-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is preferably from 0.2 to 2.0 mol% based on the silver amount, and the conversion may be carried out during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a solubility product with silver smaller than the halogen composition on the grain surface before the halogen conversion is usually added. The fine particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

The grain size of the silver halide used in the present invention is preferably 1/3 or less of the above filter pitch width. It is not preferable that the particle size has a size that extends over adjacent filter pitches, since color turbidity occurs. In particular, when tabular grains are used, it is important to appropriately select an average aspect ratio such that the particle diameter becomes 1/3 or less, more preferably 1/4 or less, with respect to the filter pitch.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, gold, platinum, and the like, which are known for an emulsion for a normal type light-sensitive material, are used. A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, JP-A-3-110555).
No., Japanese Patent Application No. 4-75798).

As the chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer and a selenium sensitizer are preferably used. As sulfur sensitizers, thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate,
Examples include cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like. The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect size, and the like, but 5 × 10 ^{−10 to} 5 × 10 ⁻ per mol of silver halide. A range of ⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferred.

As the gold sensitizer, various gold complexes other than chloroauric acid, gold sulfide and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of gold compound used is
Although it is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., it is usually preferred that the amount is 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).
issue). Further, an antifoggant described later can be added after the completion of chemical sensitization. Specifically, Japanese Patent Application Laid-Open No. 5-4583
No. 3, JP-A-62-40446. The pH at the time of chemical sensitization is preferably 5.3 to 1
0.5, more preferably 5.5 to 8.5, and pAg
Is preferably 6.0 to 10.5, more preferably 6.8.
９9.0. The coating amount of the photosensitive silver halide used in the present invention is 1 mg to 10 g / m ² in terms of silver.
Range.

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-59-180550, JP-A-64-13546
And sensitizing dyes described in JP-A-5-45828 and JP-A-5-45834.

These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is particularly used for the purpose of controlling the wavelength of supersensitization or spectral sensitization. Often used. 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
And those described in JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening.
Nos. 6,225,666 before and after the nucleation of silver halide grains. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or one solution of a surfactant. The amount of addition is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The hydrophilic protective colloid used for preparing the silver halide emulsion and the silver halide photographic light-sensitive material of the present invention are described in Product Licensing Index, Vol. 92, P108, "Vehicles". In addition to conventional gelatin used in silver halide emulsions, gelatin derivatives such as acetylated gelatin and phthalated gelatin, water-soluble cellulose derivatives and other synthetic or natural hydrophilic polymers are included.

In the present invention, an organic metal salt may 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 0.05 to 3 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 0.1 g / m ² .
４4 g / m ² is suitable.

In the light-sensitive material of the present invention, various antifoggants or photographic stabilizers and precursors thereof can be used. Specific examples thereof include U.S. Pat. Nos. 5,089,378, 4,500,627 and 4,614,702, JP-A-64-13564, pages (7) to (9), (57)-(71) and (8)
1) to (97), U.S. Pat. No. 4,775,610,
Nos. 4,626,500 and 4,983,494
And JP-A-62-174747 and JP-A-62-23914.
No. 8, JP-A-1-150135 and 2-110557
No. 2-178650, Research Disclosure RD17643 (1978) (24)-(25)
Page, RD18716, RD308119 and the like. These compounds are 5 × per mole of silver
It is preferably 10 ^-6 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-5 mol.
１1 × 10 ^-2 mol is preferably used.

Couplers preferably used in the present invention (couplers which react with an oxidized developing agent to form a dye),
Among the two equivalent couplers that are particularly preferably used,
The coupler represented by the following general formula [I] will be described as an example, but the coupler used in the present invention is not limited thereto.

[0058]

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In the formula, Cp represents a coupler residue, * represents a coupling position of the coupler, and X is released when a dye is formed by coupling with an oxidized form of an aromatic primary amine color developing agent. Represents an atom or group.

Among the coupler residues represented by Cp, representative yellow coupler residues are described in US Pat. Nos. 2,298,443, 2,407,210, 2,875,057, and 2,875,057. No. 3,048,194, No. 3,265,506, No. 3,447,928 and "Falbukplaaine Literat Ulverzicht Agfa Mittling (Band II)" @ Far
bkupleleine Liteturube
rsiecht Agfa Mitteilung (B
and II) @ 112-126 (1961). Among these, acylacetanilides,
For example, benzoylacetanilide and pivaloylacetanilide are preferable.

Representative magenta coupler residues are described in US Pat. Nos. 2,369,489 and 2,343,727.
Nos. 03, 2,311,082, 2,600,78
8, 2,908,573 and 3,062,653
Nos. 3,152,896 and 3,519,429
No. 3,725,067, 4,540,654
No. JP-A-59-162548 and the aforementioned Agfa
Mitteilung (Band II) 126-156
Page (1961). Of these, pyrazolone or pyrazoloazole (eg, pyrazoloimidazole, pyrazolotriazole, etc.) are preferred.

Representative cyan coupler residues are described in US Pat. Nos. 2,367,531 and 2,423,730.
No. 2,474,293, 2,772,162
No. 2,895,826, 3,002,836
No. 3,034,892, No. 3,041,236 and the aforementioned Agfa Mittelung (Band)
II) pages 156 to 175 (1961). Of these, phenols and naphthols are preferred.

The leaving atom or group represented by X includes, for example, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group,

[0064]

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(X ₁ represents a group of atoms necessary for forming a 5- or 6-membered ring together with at least one atom selected from nitrogen, carbon, oxygen, nitrogen and sulfur in the formula) A monovalent group such as an acylamino group or a sulfonamide group and a divalent group such as an alkylene group;
In the case of a valent group, X forms a dimer.

Specific examples will be described below.

Halogen atom: each atom such as chlorine, bromine and fluorine

[0068]

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[0069]

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[0070]

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[0071]

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Pyrazolyl, imidazolyl, triazolyl, tetrazolyl,

[0073]

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[0074]

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As the 2-equivalent yellow coupler, those represented by the following general formulas [II] and [III] are preferable.

[0076]

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In the general formulas [II] and [III], R ₁ and R ₂
Represents a hydrogen atom or a substituent, k and l represent 1 to 5,
When k and l are 2 or more, each R ₁ and each R ₂ may be the same or different, and X has the same meaning as X in the general formula [I].

Examples of the substituents and substituents represented by R ₁ and R ₂ include, for example, a halogen atom, an alkyl, cycloalkyl, aryl, and heterocyclic group bonded directly or via a divalent atom or group. Is mentioned.

Examples of the above divalent atom or group include an oxygen atom, a nitrogen atom, a sulfur atom, carbonylamino,
Examples include aminocarbonyl, sulfonylamino, aminosulfonyl, amino, carbonyl, carbonyloxy, oxycarbonyl, ureylene, thioureylene, thiocarbonylamino, sulfonyl, and sulfonyloxy.

The above-mentioned alkyl, cycloalkyl, aryl and heterocycle as examples of the substituent represented by R ₁ and R ₂ include those having a substituent. Examples of the substituent include a halogen atom, nitro, cyano, alkyl, alkenyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, carboxy, sulfo, sulfamoyl, carbamoyl, acylamino, ureido, urethane, and sulfonamide , Heterocycle, arylsulfonyl, alkylsulfonyl, arylthio, alkylthio, alkylamino, anilino, hydroxy, imide, acyl and the like.

In the 2-equivalent yellow coupler, X includes those exemplified in the general formula [I].

[0082]

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(X ₁ has the same meaning as X ₁ described above).

The general formula [II] includes a case where a dimer or more is formed with R ₁ or X, and the general formula [III] includes a case where a dimer or more is formed with R ₁ , R ₂ or X. Including the case where a multimer is formed.

As the 2-equivalent magenta coupler, those represented by the following general formulas [IV], [V], [VI] and [VII] are preferable.

[0086]

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In the above general formulas [IV] to [VII], R ₃ represents a substituent, and R ₁ , R ₂ , X and l represent the general formulas [II] and [II]
I] has the same meaning as R ₁ , R ₂ , X and l, and when l is 2 or more, each R ₂ may be the same or different.

[0088] Examples of R _1, R ₂ are, include those exemplified as R _1, R ₂ in the general formula (III), as R _3, for example alkyl, cycloalkyl, aryl, each group of hetero ring, These include those having a substituent, and examples of the substituent include those exemplified as the substituents of each group exemplified as R ₁ and R ₂ in the general formula [II]. .

In the 2-equivalent magenta coupler, examples of X include those exemplified in the general formula [I], and include an alkylthio group, an arylthio group, an aryloxy group, an acyloxy group,

[0090]

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(X ₁ is as defined above for X ₁ ), and an alkylene group is particularly preferred.

The general formulas [IV] and [V] are represented by R ₂ , R ₃
Or X, including the case of forming a dimer or more multimer,
The general formulas [VI] and [VII] include cases where R ₁ , R ₂ or X forms a dimer or more multimer.

As the 2-equivalent cyan coupler, those represented by the following formulas [VIII], [IX] and [X] are preferable.

[0094]

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[0095] Formula [VIII], in [IX], [X] have the same meaning as R _2, R ₃ is R _2, R ₃ in the general formula (IV), R ₄ represents a substituent, m is 1 to 3, n is 1 or 2, p is 1 to 5, and when m, n, and p are 2 or more, each R ₂ may be the same or different.

Examples of R ₂ and R ₃ include those exemplified in the general formula [IV], and examples of R ₄ include those exemplified as R ₃ in the general formula [IV]. In the 2-equivalent cyan coupler, examples of X include those represented by the general formula [I]
And a halogen atom, an alkoxy group, an aryloxy group, and a sulfonamide group are particularly preferable.

The general formulas [VIII] and [X] represent R ₂ , R ₃
Or, the case where X forms a dimer or more multimer is included, and the general formula [IX] includes the case where R ₂ , R ₃ , R ₄ or X forms a dimer or more multimer.

Specific examples of the coupler preferably used in the present invention, in particular, a 2-equivalent coupler are shown below, but are not limited thereto.

[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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In the present invention, the addition amount of the 2-equivalent yellow coupler is preferably from 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol / m.
² , more preferably 1 × 10 ⁻⁴ to 2 × 10 ⁻³ mol / m ² , particularly preferably 2 × 10 ⁻⁴ to 2 × 10 ⁻³ mol / m ² , and addition of a 2-equivalent magenta coupler. The amount is preferably 2 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / m ² , more preferably 5 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / m ² , especially 1 × 10 ⁻⁴ mol / m ^2. The amount of the 2-equivalent cyan coupler is preferably 5 × 10 ⁻⁵ to 1 × 10 ⁻³ mol / m ^2.
2 × 10 ⁻³ mol / m ² , more preferably 1 × 10 ⁻³ mol / m ^{2
-4 to} 2 × 10 ^-3 mol / m ² , especially 2 × 10 ^-4 to 2
× 10 ^-3 mol / m ² is preferred.

To add the coupler of the present invention to a silver halide emulsion, the coupler is dissolved in a high-boiling solvent together with a low-boiling solvent if necessary, mixed with an aqueous gelatin solution containing a surfactant, and mixed with a high-speed rotary mixer. , A colloid mill, an ultrasonic dispersing machine, a capillary type emulsifying apparatus and the like. Examples of the high boiling point solvent used at this time include carboxylic esters, phosphoric esters, carboxylic amides, ethers, substituted hydrocarbons, and the like. Specifically, dibutyl phthalate, diisooctyl Phthalic acid ester, dimethoxyethyl phthalic acid ester, di-butyl adipate, diisooctyl adipate, tributyl citrate, butyl laurate, disebacate, tricresyl phosphate, tributyl phosphate , Triisooctyl phosphate, N, N-diethylcaprylic amide, N, N-dimethylpalmitic amide, butylpentadecylphenyl ether, ethyl-2,4-di-te
rt-butylphenyl ether, dioctyl succinate, dioctyl maleate and the like. Examples of the low boiling point solvent include ethyl acetate, butyl acetate, cyclohexane, and butyl propionate.

In the present invention, a coupler capable of forming a dye having an infrared absorption by reacting with an oxidized form of a developing agent (hereinafter also referred to as an infrared color coupler) can be preferably used as the coupler. For example, a compound represented by the following general formula [IRK-I] or [IRK-II] can be used.

[0136]

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[Wherein, R ¹¹ represents an alkyl group, an alkoxy group, a phenoxy group, or a halogen atom, and R ¹² represents an alkyl group, a phenyl group, an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group,
Represents a sulfamoyl group. R ¹³ represents a hydrogen atom / substituent, and n1 represents an integer of 1, 2, or 3. X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of a color developing agent. ]

[0138]

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[Wherein, V represents an aryl group, and W represents an alkyl group. X represents a hydrogen atom or a group which can be removed by reaction with an oxidized form of a color developing agent. In the general formulas [IRK-I] and [IRK-II], R ¹¹ and R ¹²
And the alkyl group represented by W include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc. Is mentioned. These alkyl groups further include a halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), an alkoxy group (for example, methoxy group, ethoxy group,
1,1-dimethylethoxy group, hexyloxy group, dodecyloxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), alkoxycarbonyl group (eg, Methoxycarbonyl group, ethoxycarbonyl group,
Butoxycarbonyl group, 2-ethylhexylcarbonyl group, etc.), aryloxycarbonyl group (for example, phenoxycarbonyl group, naphthyloxycarbonyl group, etc.),
Alkenyl group (eg, vinyl group, allyl group, etc.), heterocyclic group (eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, morpholyl group, piperidyl group, piperazyl group, pyrimidyl group, pyrazolyl group, furyl group Alkynyl group (for example, propargyl group), amino group (for example, amino group, N, N-dimethylamino group, anilino group, etc.), hydroxy group, cyano group, sulfo group, carboxyl group, sulfonamide group ( For example, it may be substituted by a methylsulfonylamino group, an ethylsulfonylamino group, a butylsulfonylamino group, an octylsulfonylamino group, a phenylsulfonylamino group, or the like.

Examples of the alkoxy group represented by R ¹¹ and R ¹² include, for example, methoxy, ethoxy, butoxy, octyloxy, dodecyloxy, isopropyloxy, t-butyloxy, 2-ethylhexyloxy and the like. Is mentioned. These groups can be substituted by the alkyl groups represented by R ¹¹ and R ¹² and the groups shown as the substituents of the alkyl groups.

Examples of the aryloxy group represented by R ¹¹ include a phenyloxy group and a naphthyloxy group. These groups may be substituted by same substituents represented by R ¹³ to be described later.

Examples of the halogen atom represented by R ¹¹ include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom.

Examples of the alkoxycarbonyl group represented by R ¹² include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a t-butyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group and a dodecyloxycarbonyl group. Can be
These groups can be substituted by the same groups as the alkyl groups represented by R ¹¹ and R ¹² and the groups shown as the substituents of the alkyl group.

The aryloxycarbonyl group represented by R ¹² includes, for example, a phenyloxycarbonyl group, a naphthyloxycarbonyl group and the like. These groups may be substituted by same substituents represented by R ¹³ to be described later.

As the carbamoyl group represented by R ¹² ,
Examples thereof include a methylcarbamoyl group, a propylcarbamoyl group, a t-butylcarbamoyl group, a 2-ethylhexylcarbamoyl group, a pentadecylcarbamoyl group, a dibutylaminocarbonyl group, and an N-methyl-N- (2-ethylhexyl) aminocarbonyl group. These groups can be substituted by the same groups as the alkyl groups represented by R ¹¹ and R ¹² and the groups shown as the substituents of the alkyl group.

Examples of the sulfamoyl group represented by R ¹² include a methylsulfamoyl group, a propylsulfamoyl group, a t-butylsulfamoyl group, a 2-ethylhexylsulfamoyl group, a pentadecylsulfamoyl group, Dibutylaminosulfonyl group, dioctylaminosulfonyl group, N-methyl-N- (2-ethylhexyl)
And an aminosulfonyl group. These groups are represented by R
It can be substituted by the same groups as the alkyl groups represented by ¹¹ and R ¹² and the substituents of the alkyl groups.

The aryl groups represented by V and R ¹² include
Examples include a phenyl group and a naphthyl group. These groups may be substituted by same substituents represented by the following R ^13.

[0148] The substituent represented by R ^13, although anything may if a group substitutable on the benzene ring, such as an alkyl group (e.g., methyl group, an ethyl group, a propyl group, an isopropyl group, tert- butyl group, Pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc., alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aryl group (eg, phenyl group) , Naphthyl group, etc.), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group , A tetrazolyl group, etc.), a halogen atom (for example, chlorine atom, bromine Atom, iodine atom, fluorine atom, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group, etc.) An aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), an alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryl Oxycarbonyl group (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (for example,
Methylsulfonylamino group, ethylsulfonylamino group, butylsulfonylamino group, hexylsulfonylamino group, cyclohexylsulfonylamino group, octylsulfonylamino group, dodecylsulfonylamino group, phenylsulfonylamino group, etc., sulfamoyl group (for example, aminosulfonyl group) , Methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl Group), a ureido group (eg, a methylureido group, an ethylureido group, a pentylureido group, a cyclohexylureido group, Kuchiruureido group, dodecyl ureido group, a phenyl ureido group, Nafuchiruureido group,
2-pyridylaminoureido group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthyl) Carbonyl group, pyridylcarbonyl group, etc.), carbamoyl group (for example, aminocarbonyl group,
Methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl Group, 2-pyridylaminocarbonyl group, etc.), amide group (for example, acetamido group, ethylcarbonylamino group, propylaminocarbonyl group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, Dodecylcarbonylamino group, benzoylamino group, naphthylcarbonylamino group, etc.), sulfonyl group (for example, methylsulfonyl group An ethylsulfonyl group, a butylsulfonyl group, a cyclohexylsulfonyl group, a 2-ethylhexylsulfonyl group, a dodecylsulfonyl group, a phenylsulfonyl group, a naphthylsulfonyl group, a 2-pyridylsulfonyl group, and the like; an amino group (for example, an amino group, an ethylamino group, Dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, etc.), cyano group, nitro group, carboxyl group, hydroxy group, etc. . These groups are represented by R ¹¹ , R ¹²
And the same groups as the alkyl groups represented by and the groups shown as the substituents of the alkyl group.

X represents a hydrogen atom or a group capable of leaving by reaction with an oxidized form of the color developing agent. Examples of the group capable of leaving off by reaction with the oxidized form of the color developing agent represented by X include, for example, Halogen atom, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, alkylthio group, arylthio group, heterocyclic thio group,

[0150]

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(X ₁ represents an atom group required to form a 5- or 6-membered ring together with at least one atom selected from the group consisting of nitrogen, carbon, oxygen, nitrogen and sulfur in the formula) , An acylamino group, a sulfonamide group and the like.

Specific examples will be described below.

[0153]

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[0154]

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[0155]

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[0156]

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[0157]

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Examples of the compounds represented by the general formula [IRK-I] or [IRK-II] are shown below, but are not limited thereto.

[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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In the present invention, a silver halide light-sensitive material,
The monochrome image forming silver halide light-sensitive material preferably has a colored coupler. Colored couplers are well known in the field of color photography, have a hue even in an unreacted state, and may form a dye image such as yellow, magenta, cyan, or black by a coupling reaction with a color developing agent. , May be colorless. Generally, it refers to an unreacted hue having a different hue after color development. The colored coupler is a yellow colored magenta coupler,
There are magenta colored cyan couplers and yellow colored cyan couplers.

Yellow colored magenta couplers are described in JP-A-49-123625, JP-A-49-131448, JP-A-52-42121, JP-A-52-102723, and JP-A-52-102723.
No. 5,525,172, U.S. Pat. Nos. 2,763,552, 2,801,171 and 3,519,429.

Magenta colored cyan couplers are described in JP-A-50-123341, JP-A-55-65957 and JP-A-55-65757.
-94347, JP-B-42-11304, 44-
No. 32461, No. 48-17899, No. 53-347
No. 33, U.S. Pat. Nos. 3,034,892 and 1,08
The compound can be synthesized with reference to the method described in US Pat.

The yellow colored cyan coupler is disclosed in JP-B-61-52827, US Pat. No. 3,763,170.
No. 4,004,929, JP-A-61-72244.
And the methods described in JP-A Nos. 61-273543, 4-144, 4-151655, and the like.

The present invention relates to a photosensitive silver halide, at least one of the developing agents represented by formulas (1) to (5),
A compound (coupler) that forms a dye by a coupling reaction with an oxidized form of the developing agent, a sparingly soluble metal salt compound,
And a silver halide light-sensitive material composed of a plurality of photographic constituent layers containing a binder and a processing material containing a complex-forming compound in the presence of water, followed by heating and developing to form an image. .

Among them, the complex-forming compound reacts with the hardly soluble metal salt compound described below to release an alkali, and both have an effect as a base precursor.
Since the base is released by the reaction of the two components, these can be separately incorporated into the photosensitive material and the processing material, so that the base precursor is excellent in stability and excellent.

The complex-forming compound used in the present invention is a compound which forms a complex salt having a stability constant of 1 or more in log K with a metal ion constituting a sparingly soluble metal salt compound described later.

Next, examples of preferred complex forming compounds are listed (where M ⁺ represents an alkali metal ion, a substituted or unsubstituted guanidinium ion, an amidinium ion or a quaternary ammonium ion). The invention is not limited to this.

[0173]

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[0174]

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[0175]

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[0176]

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These complex forming compounds can be used alone or in combination of two or more. It can be used in combination with a known base or base precursor described below.

In the present invention, the hardly soluble metal salt compound and the compound which forms a complex with the metal ion constituting the hardly soluble metal salt compound (hereinafter referred to as a complex forming compound) are
The pH of the image forming reaction system can be increased by allowing the photosensitive material and the processing material to contain one or the other, and exposing the photosensitive material to heat and bonding the material to the processing material in the presence of water.

The image forming reaction system in the present invention means a region where an image forming reaction occurs. Specifically, layers belonging to each of the photosensitive material and the processing material can be mentioned. When two or more layers are present, they may be all or one layer.

Examples of the hardly soluble metal salt compound used in the present invention include carbonates, phosphates, silicates, borates having a solubility in water (the number of grams of a substance dissolved in 100 g of water) of 0.5 or less. Double salts of these compounds such as acid salts, aluminates, hydroxides, oxides, and basic salts are included.

Preferred specific examples are listed below. Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate (CaMg (CO ₃ ) ₂ ), magnesium oxide, zinc oxide, tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, magnesium hydroxide , Calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide, manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, calcium aluminate , Basic zinc carbonate (2ZnCO ₃ .3Zn (OH) _2.
H ₂ O), basic magnesium carbonate (3MgCO ₃ .Mg)
_{(OH) 2 · 3H 2 O} ), basic nickel carbonate (NiCO
_{3 · 2Ni (OH) 2)} , basic bismuth carbonate (Bi
₂ (CO3) O ₂ · H ₂ O), basic cobalt carbonate (2C
oCO ₃ .3Co (OH) ₂ ), aluminum magnesium oxide.

The compounds preferably used as the hardly soluble metal salt compounds are zinc or aluminum oxides, hydroxides and basic carbonates, and more preferably zinc oxide, zinc hydroxide and basic zinc carbonate. In the present invention, one kind of the hardly soluble metal salt compound may be used, or a plurality of kinds of the hardly soluble metal salt compounds may be used in combination.

General formulas (1), (2), (3), (4) and (5), which are color developing agents preferably used in the present invention.
The compound represented by is described.

In the general formula (1), R ^{1 to} R ⁴ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylcarbamoyl group, arylcarbamoyl group, carbamoyl group, alkylsulfamoyl group, Represents an arylsulfamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, or an acyloxy group. In R ^{1 to} R ⁴ , R
² and R ⁴ are preferably hydrogen atoms. R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (2), Z represents an atomic group forming an aromatic ring. R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (3), R ⁵ represents an alkyl group, an aryl group or a heterocyclic group. R ⁶ represents a substituted or unsubstituted 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 , R ⁸ , R ⁹ , and R ¹⁰ represent a hydrogen atom or a substituent, and R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may combine with each other to form a double bond or a ring.

In the general formula (4), Z represents an atomic group forming an aromatic ring. R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (5), R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group. R ⁶ represents a substituted or unsubstituted 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 , R ⁸ , R ⁹ , and R ¹⁰ represent a hydrogen atom or a substituent, and R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may combine with each other to form a double bond or a ring.

General formulas (1), (2), (3), (4),
The compound represented by the formula (5) is a color developing agent. In the present invention, these compounds are incorporated in the light-sensitive material, and are themselves oxidized by developing a silver salt. Coupling produces a dye. Among these, the compound of the general formula (1) or (4) is particularly preferably used. Hereinafter, these compounds will be described in detail.

The compound represented by the general formula (1) is a compound generally called sulfonamidophenol. Where R
^{1 to} R ⁴ are each a hydrogen atom, a halogen atom (for example, chloro or bromo), an alkyl group (for example, methyl, ethyl, isopropyl, butyl, t-butyl), an aryl group (for example, phenyl, tolyl) Group, xylyl group),
Alkylcarbonamide group (for example, acetylamino group,
Propionylamino group, butyroylamino group, arylcarbonamide group (eg, benzoylamino group), alkylsulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (eg, benzenesulfonylamino group, toluene Sulfonylamino group), alkoxy group (for example, methoxy group, ethoxy group, butoxy group), aryloxy group (for example, phenoxy group), alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group, tolylthio group) Group), alkylcarbamoyl group (for example, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, (Holylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (eg, methylsulfamoyl group, dimethylsulfamoyl group) Group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group, piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfoyl group) Famoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), Ali Rusulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (eg, phenoxycarbonyl group) , An alkylcarbonyl group (eg, an acetyl group, a propionyl group, a butyroyl group), an arylcarbonyl group (eg, a benzoyl group, an alkylbenzoyl group), or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group). These substituents include those further having a substituent. Among R ^{1 to} R ⁴ , R ² and R ⁴ are preferably a hydrogen atom. Further, it is preferable that the sum of the Hammett constant σp values of R ^{1 to} R ⁴ is 0 or more.

R ⁵ is an alkyl group (for example, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group,
A stearyl group), an aryl group (e.g., phenyl, tolyl, xylyl, 4-methoxyphenyl, dodecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl, 4-dodecyloxyphenyl, 3,5-di-
(Methoxycarbonyl) group) or a heterocyclic group (eg, a pyridyl group).

These substituents include those further having a substituent.

The compound represented by the general formula (2) is a compound generally called sulfonylhydrazine. The compound represented by the general formula (4) is a compound generally called carbamoylhydrazine.

In the formula, Z represents an atomic group forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinazoline ring, a quinoxaline ring and the like are preferable.

In the case of a benzene ring, the substituent is
Alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), halogen atom (for example, chloro group,
Bromyl 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) A famoyl group, a piperidylsulfamoyl group, a morpholylsulfamoyl group), an arylsulfamoyl group (for example, a phenylsulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
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, acetyl group, Examples thereof include a propionyl group, a butyroyl group) and an arylcarbonyl group (for example, a benzoyl group and an alkylbenzoyl group). The sum of the Hammett constant σp values of the above substituents is 1 or more. These substituents include those further having a substituent.

The compound represented by the general formula (3) is a compound generally called sulfonylhydrazone. The compound represented by the general formula (5) is a compound generally called carbamoylhydrazone.

In the formula, R ⁶ represents a substituted or unsubstituted 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 tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom. R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ represent a hydrogen atom or a substituent, and R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may combine with each other to form a double bond or a ring.

The specific examples of the compounds represented by formulas (1) to (5) are shown below, but the compounds of the present invention are not limited thereto.

[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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[0214]

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[0215]

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[0216]

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[0219]

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[0218]

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[0219]

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[0220]

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[0221]

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[0222]

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These developing agents preferably used in the present invention are used in an amount of 0.05 to 10 mmol / m 2 per color-forming layer.
It is preferable to use ² . A more preferred amount is 0.1.
The amount is 1 to 5 mmol / m ² , and the particularly preferred amount is 0.1 to 5 mmol / m ² .
² to 2.5 mmol / m ² .

In the silver halide photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. Colloidal silver fine particles have often been used in the yellow filter layer and antihalation layer of conventional color light-sensitive materials. However, it is necessary to provide a bleaching step to remove the colloidal silver after developing the light-sensitive material. For the purpose of the present invention, which requires simple processing, a light-sensitive material which does not require a bleaching step is preferable. Therefore, in the present invention, it is preferable to use a dye, in particular, a dye which decolors or elutes and transfers during development processing and has a small contribution to the density after processing, instead of colloidal silver. When the dye is decolored or removed at the time of development, the amount of the dye remaining after the processing is 1/3 or less, preferably 1/10 or less immediately before coating, and the dye component is developed at the time of development. May be eluted or transferred into a processing material, or may be converted to a colorless compound by reacting during development.

As the binder for the constituent layers of the photosensitive material, hydrophilic binders are preferably used. Examples include Research Disclosure RD17643, RD1871
6, RD308119 and JP-A-64-13546, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferable, for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, pullulan, natural compounds such as polysaccharides such as carrageenan, and polysaccharides. Synthetic polymer compounds such as vinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer are exemplified. Also, U.S. Patent No. 4,960,681, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or (M hydrogen atom or an alkali metal) -SO ₃ M vinyl monomer having A homopolymer or a copolymer of the vinyl monomers or other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate, potassium acrylate, etc.) is also used. These binders can 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 light-sensitive material of the present invention is preferably hardened with a hardener. U.S. Pat.
No. 678,739, column 41, 4,791,042
No., JP-A-59-116655 and JP-A-62-24526.
No. 1, No. 61-18942, No. 61-249054
No. 61-245153, JP-A-4-218044
And the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid and polymer hardeners (compounds described in JP-A-62-234157). Among these hardeners, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. 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.

The hydrophilic protective colloid used for preparing the silver halide photographic light-sensitive material of the present invention includes the above-mentioned Product Licensing Index, Vol.
As described in "Vehicles", gelatin derivatives such as acetylated gelatin and phthalated gelatin, water-soluble cellulose derivatives, and other synthetic or natural hydrophilic compounds, in addition to the gelatin used for ordinary silver halide emulsions Polymers may be mentioned.

In the silver halide photographic light-sensitive material of the present invention, various techniques and additives known in the art can be used, if necessary. For example, it is possible to provide various auxiliary layers such as a photosensitive silver halide emulsion layer, a protective layer, the filter layer, an antihalation layer, various intermediate layers, an undercoat layer, a crossover light cut layer, and a backing layer. it can. Specifically, an undercoat layer as described in U.S. Pat. No. 5,051,335, JP-A-1-1677838, JP-A-61-7838
Intermediate layer having a solid pigment as described in JP-A-20943, JP-A-1-120553, JP-A-5-34884, and JP-A-2-348;
Intermediate layers having a reducing agent or a DIR compound as described in US Pat. No. 6,634, U.S. Pat.
No. 139,919 and JP-A-2-23544, an intermediate layer having an electron transfer agent, JP-A-4-24924.
Various chemical sensitizers, noble metal sensitizers, photosensitive dyes, supersensitizers, couplers, etc. are contained in these layers such as a protective layer having a reducing agent as described in No. 5 or a layer obtained by combining them.
High boiling point solvent, antifoggant, stabilizer, development inhibitor, bleaching accelerator, fixing accelerator, color mixture inhibitor, formalin scavenger, color tone, hardener, surfactant, thickener, plasticizer, slipping agent , An ultraviolet absorber, an anti-irradiation dye, a filter light-absorbing dye, a sunscreen, a polymer latex, a heavy metal, an antistatic agent, a matting agent and the like can be contained by various methods.

These additives described above are described in more detail in Research Disclosure, Vol. 176, Item.
/ 17643 (December 1978), 184 Volume
m / 18431 (August 1979), same volume 187 Ite
m / 18716 (November 1979) and 308 I
tem / 308119 (December 1989).

[0230] Of the above, the types of compounds shown in the three Research Disclosures and their locations are listed in Table 1 below.

[0231]

[Table 1]

As a suitable support that can be used in the present invention, synthetic plastic films such as polyolefins such as polyethylene and polypropylene, polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalate and polyvinyl chloride can also be preferably used. Syndiotactic polystyrenes are also preferred. These can be obtained by polymerizing according to the methods described in JP-A-62-117708 and JP-A-1-46912. Further, a support which can be used in the light-sensitive material of the present invention includes a paper support such as photographic base paper, printing paper, baryta paper, resin-coated paper and a support provided with a reflective layer on the above-mentioned plastic film.
No. 253195 (pages 29 to 31). 28 of the aforementioned RD17643
Also, those described on page 187, page 647, right column to page 648, left column, and page 879, page 879, page 879 can be preferably used. Syndiotactic polystyrenes are also preferred. These are disclosed in JP-A-62-1117708.
And JP-A-1-46912 and 1-178505. These supports include U.S. Pat. No. 4,141,73.
As described in No. 5, by applying a heat treatment of Tg or less, it is possible to use a material which is less likely to have a curl. The surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and the emulsion undercoat layer. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Further, the publicly known technology No. 5 (issued by Aztec Co., Ltd. on March 22, 1991)
The supports described on pages 4-149 can also be used. A transparent support such as polyethylene dinaphthalenedicarboxylate or a support on which a transparent magnetic substance is applied can be used.

Examples of the support which can be used for the light-sensitive material according to the present invention include, for example, the aforementioned RD17643-28.
RD308119, page 1009 and Product Licensing Index, Vol. 92, p.
and "upports".

When the light-sensitive material of the present invention is used in a heat development process described later, it is necessary to use a support capable of withstanding the processing temperature.

As the support, for example, Japanese Patent Application Laid-Open No.
No. 24645, No. 5-40321, No. 6-35092
Photographic information can also be recorded using a support having a magnetic recording layer described in Japanese Patent Application Laid-Open Nos. 5-58221 and 5-106979.

The light-sensitive material of the present invention containing the above-mentioned various additives and the following processing materials used for heat development can be coated on the above-mentioned or the following support by a method known in the art. .

The development processing of the light-sensitive material of the present invention is carried out by RD176
43, pages 28-29, RD18716, page 647 and RD308119, XVII, which can be carried out by methods widely used in the market.

One of the preferred processing modes of the light-sensitive material of the present invention
One is a heat development process. In the heat development, it is preferable to use a processing material different from the photosensitive material. Examples of the treatment material include a sheet having a treatment layer containing a base and / or a base precursor on a support (hereinafter also referred to as a treatment sheet). It is preferable that the treatment layer is composed of a hydrophilic binder. After the photosensitive material is imagewise exposed, the photosensitive material and the processing material are bonded on the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material and heated to form an image. 1/1 of water required for maximum swelling of all coating films constituting photosensitive material and processing material
A method of performing color development by supplying water equivalent to 0 to 1 times to a photosensitive material or a processing material, and then bonding and heating the same is preferably used. Further, it is also possible to use a method in which the auxiliary developer is incorporated in the photosensitive material or the processing material as required, or is applied together with water.

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)
553-555, April 1978, video information 4
Page 0, Nabletts Handbook of P
photography and Reprograph
y 7th Ed. (Vna Nostrand an
d Reinhold Company) 32-33
, U.S. Patent Nos. 3,152,904 and 3,30
Nos. 1,678, 3,392,020, 3,4
57,075, British Patent Nos. 1,131,108 and 1,167,777, and Research Disclosure, June 1978, pp. 9-15 (RD1702).
9). The heating temperature in the thermal development step is about 5
0 ° C to 250 ° C, but especially 60 ° C to 150 ° C is useful.

A heat solvent may be added to the light-sensitive material of the present invention for the purpose of promoting thermal development. The hot solvent is a compound that liquefies when heated and has an action of promoting image formation.
At room temperature, it is preferably white and in a solid state, and it is desired that volatility during heating is small. Preferred melting point is 70
１７０170 ° C. Examples include U.S. Pat.
47,675 and 3,667,959, and organic compounds having polarity. Specifically, amide derivatives (benzamide and the like), urea derivatives (methyl urea, ethylene urea and the like), and sulfonamide derivatives (Japanese Patent Publication No. 1-40974 and 4-137)
No. 01), polyol compounds (sorbitols), and polyethylene glycols. In addition, as a thermal solvent that can be used in the present invention, for example, US Pat. No. 3,347,675,
No. 3,438,776, No. 3,666,477
Nos. 3,667,959, RD17643, JP-A-51-19525, 53-24829, and 5
Nos. 3-60223, 58-118640, 58-
Nos. 198038, 59-68730, 59-84
No. 236, No. 59-229556, No. 60-1424
No. 1, No. 60-191251, No. 60-232525
Nos. 61-52643, 62-42153, 62-44737, 62-78554 and 62-
No. 136645, No. 62-139545, No. 63-5
No. 3548, No. 63-161446, JP-A No. 1-22
No. 4751, No. 1-2227150, No. 2-863,
Compounds described in JP-A-2-120739 and JP-A-2-123354 can be exemplified. Further, as a specific example of a preferred thermal solvent used in the present invention,
JP-A-2-297548, TS-1 to TS-21 described on page 8, upper left to page 9, upper left. The thermal solvents of the present invention can be used in combination of two or more.

The processing material used in the heat development step of the present invention contains a base and / or a base precursor, and also shuts off air during heat development and prevents volatilization of the material from the light-sensitive material. And a function to supply materials for processing other than base to the photosensitive material, and to remove materials (YF dye, AH dye, etc.) in the photosensitive material that become unnecessary after development or unnecessary components generated during development. Can also. The processing material may have a desilvering function. For example, when a part or all of the silver halide and / or the developed silver is soluble when the photographic material is superposed with the imagewise exposed post-processing material, the processing material may contain a fixing agent as a silver halide solvent. You can leave it.

As the support and the binder for the processing material, the same materials as those for the light-sensitive 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, and U.S. Pat. No. 4,50,626, columns 58 to 59, JP-A-61-88256, pages 32-41,
Examples include mordants described in Nos. 2-244043 and 62-244036. U.S. Pat.
463,079 may be used. Further, the above-mentioned thermal solvent may be contained.

When performing thermal development using a processing material, it is preferable to use a small amount of water for the purpose of promoting development, promoting transfer of a processing material, and promoting diffusion of unnecessary substances. As described above, when a method of generating a base with a combination of a basic metal compound which is hardly soluble in water and a metal ion constituting the basic metal compound and a complex forming compound is employed, it is essential to use water. is there. The water may contain an inorganic alkali metal salt or organic base, a low-boiling solvent, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, a fungicide, or a bactericide. Any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the thermal developing apparatus using the photosensitive material and the processing material of the present invention, water may be used up or circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. Also, JP-A-63-144354
No., No. 63-144355, No. 62-38460,
The apparatus described in JP-A-3-210555 or water may be used. Water can be applied to the photosensitive material, the processing material, or both. The amount used is 1/10 to 1 times the amount required for maximally swelling the entire coating film (excluding the back layer) of the photosensitive material and the processing material. As a method of applying this water, for example,
The method described in JP-A-253159 (5) and JP-A-63-85544 is preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in a photosensitive material or a processing material or both in advance in the form of a hydrate. The temperature of the water to be applied is as described in
The temperature may be 30 ° C to 60 ° C as described in, for example, Japanese Patent No. 85544.

When the photosensitive material of the present invention is thermally developed, a known heating means can be applied, for example, a method of contacting with a heated heat block or a surface heater, or a method of contacting with a heat roller or a heat drum. A method of contacting with an infrared or far-infrared lamp heater, a method of passing through an atmosphere maintained at a high temperature, a method of using a high-frequency heating method, or the like can be used. In addition, a method in which a heat-generating conductive substance such as a carbon black layer is provided on the back surface of the photosensitive material or the image receiving member, and Joule heat generated by energization may be applied. The elements described in JP-A-61-145544 can be used as the heat-generating elements. 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 is disclosed in JP-A-62-25315.
Nos. 9 and 61-147244 (page 27) can be applied. The heating temperature is preferably from 70C to 100C.

For processing the silver halide photographic light-sensitive material of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-75247 and JP-A-59-17747.
No. 59-181353, No. 60-18951,
Japanese Utility Model Application Laid-Open No. 62-25944, Japanese Patent Application No. 4-277517.
Nos. 4,243,072, 4,244,693, 6-164421, and 6-164422 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. .

In the heat development processing of the present invention, the processing material may contain a development stopping agent, and the development stopping agent may act simultaneously with the development. The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-253.
No. 159, pages (31) to (32). Further, a combination in which a zinc salt of mercaptocarboxylic acid described in Japanese Patent Application No. 6-190529 or the like is contained in a light-sensitive material and the above-mentioned complex-forming compound is contained in a processing member is advantageous.
Similarly, a silver halide printout inhibitor may be included in the processing material, and the function may be developed simultaneously with the development. Examples of the printout inhibitor include monohalogen compounds described in JP-B-54-164 and JP-A-53-164.
No. 46020 described in JP-A-48-20
No. 45228, compounds in which a halogen is bonded to an aliphatic carbon atom, and polyhalogen compounds represented by tetrabromoxylene described in JP-B-57-8454. Further, a development inhibitor such as 1-phenyl-5-mercaptotetrazole described in British Patent No. 1,005,144 is also effective. In addition, Japanese Patent Application No. 6-33
The viologen compound described in No. 7531 is also effective. The use amount of the printout inhibitor is preferably 10
^-4 to 1 mol / Ag mol, particularly preferably 10 ^-3 to 10 ^-1
Mol / Ag mol.

In the heat development process of the present invention, a silver oxidizing agent acting as a bleaching agent is contained in the processing material in order to remove the developed silver generated in the photosensitive material by the heat development. These reactions can take place. Further, after the development of the image formation is completed, the second processing material containing a silver oxidizing agent may be bonded to the photosensitive material to remove the developed silver. However, it is preferable that the developed silver is not bleached during processing because the processing is simple.

Another preferred processing mode of the light-sensitive material of the present invention is an activator processing. Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material, and development processing 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.). Activator treatment is described in European Patent Nos. 545,491A1 and 565,16.
This is exemplified in known literature such as 5A1. The pH of the activator treatment liquid used in the present invention is preferably 9 or more, more preferably 10 or more.

When the light-sensitive material of the present invention is subjected to an activator treatment, an auxiliary developer is preferably used. Here, the auxiliary developer is a substance having an action of promoting the transfer of electrons from the color developing agent to the silver halide in the development process of silver halide development. The auxiliary developer may be added to the activator processing solution, or may be incorporated in the photosensitive material in advance. A method of developing with an aqueous alkali solution containing an auxiliary developer is described in RD17643, 28-29.
Pp. 18716, 651 left column to right column, and 307
105, pages 880-881.

The auxiliary developing agent in the present invention is preferably an electron-emitting compound represented by the general formula (ETA-I) or the general formula (ETA-II) according to the Kendall-Peltz rule. Among them, those represented by (ETA-I) are particularly preferred.

[0251]

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In the general formulas (ETA-I) and (ETA-II), R ^{51 to} R ⁵⁴ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

R ^{55 to} R ^{59 each} represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic oxy group. Group, silyloxy group, acyloxy group, amino group, anilino group, heterocyclic amino group, alkylthio group, arylthio group, heterocyclic thio group, silyl group, hydroxyl group,
Nitro group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group,
Cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group,
Represents a sulfamoylamino group, an alkylsulfinyl group, an arenesulfinyl group, an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, a sulfo group, a phosphinoyl group, and a phosphinoylamino group.

Q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different from each other. R ⁶⁰ represents an alkyl group or an aryl group.

Formula (ETA-I) or (ETA-II)
Specific examples of the compound represented by the following include compounds (ETA-1) to (ETA-32) described in P26 to 30 of Japanese Patent Application No. 10-44518 by the present applicant.

When the auxiliary developer is incorporated in the light-sensitive material, the auxiliary developer may be incorporated in the form of a precursor in order to enhance the storage stability of the light-sensitive material. The auxiliary developer precursor used herein is described in JP-A-1-13855.
No. 6 can be mentioned. These compounds are dissolved in an appropriate solvent such as water, alcohols, acetone, dimethylformamide, and glycols, or in the form of fine solid dispersion or dissolved in a high boiling organic solvent such as tricresyl phosphate. It can be added and dispersed by dispersing fine particles in a hydrophilic binder. These auxiliary developer precursors may be used in combination of two or more, or may be used in combination with an auxiliary developer.

In the light-sensitive material and the processing material of the present invention, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of slipperiness, antistatic, acceleration of development and the like. Specific examples of the surfactant are known in the art No. 5 (March 22, 1991, Aztec Co., Ltd.), 136-13.
8 pages, JP-A-62-173463 and JP-A-62-1834.
No. 57, etc. The photosensitive material may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, improving peelability, and the like. Representative examples of the organic fluoro compounds are described in JP-B-57-9053, columns 8-17,
Hydrophobic surfactants such as fluorine-based surfactants described in JP-A Nos. 1-20944 and 62-135826, oily fluorine-containing compounds such as fluorine oil, and solid fluorine-containing compounds such as tetrafluoroethylene resin Compounds.

It is preferable that the photosensitive material and the processing material have 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 the like.
As the polyorganosiloxane, polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. 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 light-sensitive material and the processing material of 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 agents are ZnO, TiO ₂ , SnO ₂ , A
l ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, Mo
The volume resistivity of at least one selected from O ₃ and V ₂ O ₅ is 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm.
Fine particles of the following crystalline metal oxides having a particle size of 0.001 to 1.0 μm or composite oxides thereof, and fine particles of sol, metal oxides or composite oxides thereof. The content in the photosensitive material is 5 to 500 mg /
m ² is preferred, and particularly preferably 10 to 350 mg / m ²
It is. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.

The constitutions of the light-sensitive material and the processing material (including the back layer) include various materials for the purpose of improving film properties such as stabilization of dimensions, prevention of curling, prevention of adhesion, prevention of cracking of the film, and prevention of pressure fluctuation. 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 and the processing material of the present invention preferably contain 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 simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio) 0.3 μm) ), Polystyrene particles (0.25 μm), colloidal silica (0.03
μm). Specifically, JP-A-61-882
No. 56, page 29. In addition, benzoguanamine resin beads, polycarbonate resin beads, A
JP-A Nos. 63-274944 and 6
There is a compound described in 3-274952. Other Research Disclosures RD17643, RD1871
6, compounds described in RD308119 and the like can be used.

Next, a film cartridge in which a photosensitive material can be loaded will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, patrone may contain various antistatic agents, such as carbon black, metal oxide particles, nonions,
Anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A-1-312537,
No. 3,12,538. Especially 25 ° C, 25
The resistance at% RH is preferably 1012Ω or less.

Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light-shielding properties. The size of the patrone may be the same as the current 135 size, and it is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to reduce the size of the camera. The volume of the patrone case is 30 cm ³ or less, preferably 25 cm ^3.
cm ³ or less. Weight of plastic used for patrone and patrone case is 5g
~ 15 g is preferred.

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 cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in U.S. Pat. Nos. 4,834,306 and 5,226,61.
No. 3.

The light-sensitive material of the present invention can be used by loading it on a commercially available film unit with a lens.

The light-sensitive material of the present invention is disclosed in Japanese Patent Application No.
No. 58427, No. 10-170624, No. 10-18
It can be used preferably by being loaded into a film unit with a lens described in JP-A-8984.

As a film unit with a lens, a film unit loaded with a sheet film can be preferably used instead of a conventional roll film. The sheet-like photographic film is loaded in the unit so that it can be exposed in advance so as to keep a substantially single plane. That is, the film is not wound in a roll. In one embodiment of the film unit with a lens according to the present invention, when photographing a plurality of sheets, the position of the lens is sequentially moved within a plane parallel to the plane formed by the sheet-like photographic film, and photographing is performed. The sheet film is fixed and does not move until all frames have been shot. Therefore, compared to a conventional film unit with a lens using a roll film, since there is no member for winding up, the camera can be designed to be thin.

The exposure area on a photographic film per frame is preferably 50 mm ^{2 to} 300 mm ² . This makes it possible to use a lens with a short focal length. Such a short focal length lens has a large depth of field even when a lens with a small aperture value (that is, a bright lens) is used. It is possible to shoot an in-focus image from a distance close to infinity. Further, since it is possible to take a picture even in a dark place, it is possible to take a picture indoor without a strobe.

In the present invention, the EV value of the film unit with a lens is preferably 6.5 or more and less than 11. A more preferred EV value is 7.5 or more and less than 10. In the present invention, the EV value (exposure value) is the same as a general definition, and refers to a value indicating the ability of a camera to transmit a light amount by a combination of an aperture value (F) and a shutter speed (Tsec). It is represented by the following equation.

2 EV = F ² / T That is, EV = 3.32 log 10 (F ² / T) The aperture value and shutter speed for obtaining the Ev value in the above range are as follows. A preferred aperture value in the present invention is 2 or more and less than 8.5, and more preferably 2.5 or less.
It is at least 6.5 and less than 6.5, particularly preferably at least 2.8 and less than 5.6. Shutter speed is 1/250 second or more
The time is 5 seconds or less, particularly preferably 1/100 seconds or more and 1/50 seconds or less. The lens of the film unit with a lens according to the present invention preferably has a focal length of about 5 to 20 mm.

When the light-sensitive material of the present invention is used as a light-sensitive material for photographing, it is common to directly photograph landscapes, people, and the like using a camera or the like. The case where the above-described lens-attached film unit is used by being mounted thereon is similar to this.
In addition, the photosensitive material of the present invention is a method of exposing through a reversal film or a negative film using a printer or a stretching machine, a method of scanning and exposing an original image through a slit or the like using an exposing device of a copying machine, etc. Methods of scanning and exposing a light emitting diode, various lasers (laser diode, gas laser, etc.) and the like via an electric signal (JP-A-2-129625, JP-A-5-15-1)
No. 76144, No. 5-199372, No. 6-1270
No. 21, etc.), a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, and a plasma display, and exposing directly or via an optical system.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No.4, such as natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
500,626, column 56, JP-A-2-53378,
The light source and the exposure method described in JP-A-2-54672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can exhibit nonlinearity between localization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, and BaB ₂ O ₄ Such as inorganic compounds,
Urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM);
Compounds described in JP-A-53462 and JP-A-62-210432 can be preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type, and the like are known, and any of them is useful.

The image information is obtained by dividing an image signal obtained from a video camera, an electronic still camera, or the like, a television signal represented by the Nippon Television Signal Standard (NTSC), or an original image into a plurality of pixels such as a scanner. Image signal,
Images produced using a computer represented by CG and CAD can be used.

The silver halide color light-sensitive material of the present invention comprises
In order to extract a luminance signal and a color signal of a digital color image, a photosensitive layer for recording luminance information (hereinafter, also referred to as a luminance information photosensitive layer) and a photosensitive layer for recording color information (hereinafter, referred to as a luminance layer). Color information recording layers) may be independently provided.

First, a photosensitive layer for recording luminance information will be described. The photosensitive layer for recording luminance information has the function of controlling the brightness information of the subject image and the texture of the image, and it is possible to control these characteristics according to the purpose and application mainly by adjusting the spectral sensitivity distribution. it can. In conventional silver halide color light-sensitive materials, if the spectral sensitivity distribution is greatly changed, it has a serious effect on hue reproducibility and a practical color image cannot be obtained. In silver halide color photosensitive materials, hue information can be extracted from the color information recording layer, so the spectral sensitivity distribution of the luminance information photosensitive layer can be selected from the visible light region as well as the invisible wavelength region without affecting the hue reproduction of the subject. can do.

The preferred form of the color information photosensitive layer in the photosensitive material is a stripe or mosaic color separation color filter array layer from the object side, and then a photosensitive layer having color sensitivity to the entire visible light. Is the case. In this case, the color separation color filter array layer is RGB.
Various configurations can be adopted to separate subject information into three primary colors, for example, a method of arranging three color filters of yellow, green, and cyan in a mosaic pattern or a stripe pattern, or a method of red, green , And a method of arranging three blue filters in a mosaic pattern or a stripe pattern. Examples of the method of arranging the filters in a mosaic form include a lattice arrangement method represented by a Bayer arrangement and an arrangement in which triangles, hexagons, and circles are spread. The arrangement of each color may be regular or completely random.

Next, a preferred coating position of the luminance information photosensitive layer will be described. The coating position of the luminance information photosensitive layer is preferably located closer to the subject than the color information photosensitive layer.
That is, the color information photosensitive layer and the luminance information photosensitive layer are applied in this order from the transparent support side and then exposed from the luminance information photosensitive layer side, or the luminance information photosensitive layer and the color information photosensitive layer are applied in order from the transparent support side. An embodiment in which the transparent support side and the subject are exposed in a form opposite to each other, or a mode in which the luminance information photosensitive layer and the color information photosensitive layer are coated with the transparent support and then exposed from the luminance photosensitive layer side is preferable. . In particular, when the color information photosensitive layer is composed of a stripe or mosaic color separation color filter array layer and a photosensitive layer having color sensitivity to the entire visible light, the luminance information photosensitive layer and the transparent support are arranged from the subject side. , A color filter array layer, and a photosensitive layer having sensitivity to the entire visible light.

In the photosensitive material, luminance signal information is extracted from the formed image of the luminance information photosensitive layer, and R and R for extracting color signal information from the formed image of the color information photosensitive layer are extracted.
It is necessary to extract the G and B three-color separation image information. Therefore, in order to read luminance information independently of the formed image of the color information photosensitive layer, it is preferable that the formed image of the luminance information photosensitive layer is a color image having a different hue from the formed image of the color information photosensitive layer. .

Therefore, the silver halide color photographic material preferably contains four types of couplers which react with the oxide of the color developing agent to form dyes having different spectral absorption shapes. Although it is more preferable that these four types of spectral absorption shapes have a small overlap of the absorption shapes,
For this purpose, a coupler having absorption at an infrared wavelength (also referred to as an infrared coupler) can be used in addition to a yellow coupler, a magenta coupler, and a cyan coupler used in conventional color light-sensitive materials.

When the color information photosensitive layer is composed of a stripe or mosaic color separation color filter array layer and a photosensitive layer having color sensitivity to visible light as a whole, the above-mentioned infrared coupler is used in the luminance information photosensitive layer. It is preferable to adopt a mode in which an infrared absorbing image is formed by using the color information photosensitive layer, and an image that blocks the entire visible light region is formed in the photosensitive layer having color sensitivity to the entire visible light of the color information photosensitive layer. The image that blocks the entire visible light region here is not limited as long as it has a function of forming a substantially black image. For example, a blackened silver image obtained by development may be used. Alternatively, a substantially black image may be formed by using a plurality of types of couplers which react with a developing agent to form a dye. In particular, a method of forming a substantially black image by using a mixture of three types of couplers of yellow, magenta, and cyan can obtain a black image having no absorption in an infrared region. Interference with luminance information due to an image is small and can be preferably used.

The image of the present invention formed through the developing step is preferably obtained by converting image information into electrical signals in at least four wavelength regions by a transmission type image reading device (a so-called film scanner). The method will be described.

As a light receiving element (semiconductor image sensor) used in the present invention, a one-dimensional line sensor in which monochrome CCDs having sensitivity in a visible light region and an infrared region are arranged in a line, or a monochrome CCD is arranged in two dimensions vertically and horizontally. An area sensor or the like can be used.

The light source used for the scanner is not particularly limited as long as it has an emission wavelength of visible light and infrared light. For example, a fluorescent lamp filled with a rare gas such as xenon gas or several kinds of high-brightness LEDs are used. Can be used in combination.

The four wavelengths are selected, for example, between the light source and the monochrome CCD when the light source is a continuous light source, or between the spectral absorption of a color coupler or each color of the color filter when the photosensitive material includes a color filter array unit. This can be performed by inserting a color separation filter selected according to the spectral absorption shape. When a high-luminance LED of a primary color emission type such as blue, green, red, or infrared is used as a light source, four wavelengths can be selected by switching the LED light source.

[0285] In addition, the four 1
For the next image information, extract the purest luminance information, red separation information, green separation information, and blue separation information as much as possible by removing the crosstalk component due to the silver image in the case where the absorption of the coupler does not spread or fixation is not performed. Is preferred.

[0286] (expressed as L ₀₎ In this way the luminance information signal extracted, (expressed as B) blue color separation signals, (expressed as G) green degradation signal, B of the red separation signals (denoted R)
An RGB digital color image is produced using the signal, the G signal, and the R signal. Subsequently, only the color information is extracted from the RGB digital color image. The color information can be extracted, for example, by converting the RGB image information into Lab image information or Luv image information.

As an example, a case where the information is converted into Lab information will be described. Lab is CIE (Commiss)
ion Internationale de I'E
clairage: International Commission on Illumination) L * a * b *
(Hereinafter also referred to as Lab) is an abbreviation of a display system, where L represents lightness information and ab represents hue and saturation of a color. This image information conversion process can be easily performed by using, for example, image processing software Photoshop manufactured by Adobe.

After the RGB image is converted into the Lab image in this manner, the brightness information L is discarded and replaced by the brightness information signal (L ₀ ) extracted from the brightness information photosensitive layer. Image L ₀ ab can be obtained. At this time, in order to obtain a better image, L
It is preferable to appropriately adjust the gradation and contrast of the ₀ image.

An image obtained by the present invention can be read using a scanner or the like and converted into electronic image information. In the present invention, the scanner is a device that optically scans a photosensitive material and converts the optical density of reflection or transmission into image information. When scanning, it is common to scan the required area of the photosensitive material by moving the optical part of the scanner in a direction different from the direction of movement of the photosensitive material, and it is recommended that the photosensitive material be fixed. Then, only the optical part of the scanner may be moved, or only the photosensitive material may be moved to fix the optical part of the scanner. Alternatively, a combination of these may be used.

When reading the image information of the image generated in the photosensitive material, the entire surface is irradiated with light in a wavelength region where at least three dyes can be absorbed or slit scanning is performed, and the amount of reflected light or transmitted light is obtained. Is preferable. In this case, it is preferable to use diffused light, because information such as a matting agent and a scratch on the film can be removed as compared with the use of parallel light. Further, it is preferable that a semiconductor image sensor (for example, an area type CCD or a CCD line sensor) is used for the light receiving unit. Also, the presence or absence of a processing sheet at the time of image reading does not matter.

The image data thus obtained can be viewed using various image display devices. As the image display device, an arbitrary device such as a color or monochrome CRT, a liquid crystal display, a plasma light emitting display, and an EL display is used.

In the present invention, an image signal thus read can be output to form an image on another recording material. The output material is silver halide photosensitive material,
Various hard copy devices are used. For example, various systems such as an ink jet system, a sublimation type thermal transfer system, an electrophotographic system, a cycolor system, a thermoautochrome system, a method of exposing a silver halide color paper, and a silver halide heat development system are used. The effect of the present invention is sufficiently exhibited by any of the methods.

Although the main object of the present invention is to capture image information obtained by development as digital data, it is a conventional method to convert photographed information into a print material such as color paper in an analog manner. It can also be used after exposure.

[0294]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 The sample No. 1 described in the example of JP-A-10-207000 was used. According to the preparation method of No. 109, a multilayer silver halide photosensitive sample 101 having a photosensitive layer was prepared. That is,
On a triacetyl cellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to prepare a multilayer color photographic material sample 101.

The amount of addition is expressed in grams per m ² .
However, silver halide and colloidal silver were converted to the amount of silver, and sensitizing dyes (indicated by SD) were shown in moles per mole of silver.

First Layer (Antihalation Layer) Black Colloidal Silver 0.16 UV-1 0.3 CM-1 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33 Second Layer (Intermediate) Layer) AS-1 0.160 OIL-1 0.20 Gelatin 0.69 Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 SD-12 37 × 10 ^-5 SD-2 1.2 × 10 ^-4 SD-3 2.4 × 10 ^-4 SD-4 2.4 × 10 ^-6 CA 0.32 CC-1 0.038 OIL- 2 0.28 AS-2 0.002 Gelatin 0.73 Fourth layer (medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 SD-1 4.5 × 10 ^{-5 SD-2 2.3 × 10 -4} SD-3 4.5 × 10 -4 C-24 0.52 CC-1 0.06 DI-1 0.047 IL-2 0.46 AS-2 0.004 Gelatin 1.30 Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 SD-1 3.0 × 10 ^-5 SD-2 1.5 × 10 ^-4 SD-3 3.0 × 10 ^-4 C-24 0.047 CB 0.09 CC-1 0.036 DI-1 0.024 OIL- 2 0.27 AS-2 0.006 Gelatin 1.28 6th layer (intermediate layer) OIL-1 0.29 AS-1 0.23 Gelatin 1.00 7th layer (Low sensitivity green color-sensitive layer) Silver bromide a 0.19 Silver iodobromide b 0.062 SD-4 3.6 × 10 ^-4 SD-5 3.6 × 10 ^-4 M-40 0.18 CM-1 0.033 OIL-1 0.22 AS-2 0.002 AS-3 0.05 Gelatin 0.61 8th layer (intermediate layer) OIL-1 0.26 AS-1 0.054 Gelatin 0.80 Ninth layer (medium-speed green-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 SD-6 3.7 × 10 ^-4 SD-7 7.4 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-40 0.17 MA 0.33 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL- 1 0.73 AS-3 0.035 AS-2 0.003 Gelatin 1.80 10th layer (high-sensitivity green color-sensitive layer) Silver iodobromide f 1.19 SD-6 4.0 × 10 ^-4 SD-7 8.0 × 10 ^-5 SD-8 5.0 × 10 ^-5 M-40 0.065 CM-2 0.026 CM-1 0.022 DI-3 0.003 DI-2 0.003 OIL-1 0.19 OIL-2 0.43 AS-3 0.017 AS-2 0.014 Gelatin 1.23 11th layer (yellow filter Yellow layer colloidal silver 0.05 OIL-1 0.18 AS-1 0.16 gelatin 1.00 twelfth layer (low-sensitivity blue-sensitive layer) silver iodobromide b 0.22 silver iodobromide a 0.08 Silver iodobromide h 0.10 SD-9 6.5 × 10 ^-4 SD-10 2.5 × 10 ^-4 Y-5 0.77 DI-4 0.017 OIL-1 0.31 AS -2 0.002 Gelatin 1.29 13th layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.41 Silver iodobromide i 0.67 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^-4 Y-5 0.23 OIL-1 0.10 AS-2 0.004 Gelatin 1.20 Fourteenth layer (first protective layer) Silver iodobromide j 0.30 UV-10 0.055 UV-2 0.110 OIL-2 0.30 Gelatin 1.32 15th layer (second protective layer) PM-1 0.15 PM-20 04 WAX-1 0.02 AI-1 0.001 Gelatin 0.55 characteristic of the silver iodobromide Show below (one side length of a cube having the same volume as the average particle diameter).

Emulsion No. Average grain size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 Silver iodobromide b 0.40 8.0 1.4 Silver iodobromide c 0.60 7.0 3.1 Silver iodobromide d 0.74 7.0 5.0 Silver iodobromide e 0.60 7.0 4.1 Silver iodobromide f 0.65 8.7 6. 5 Silver iodobromide g 0.40 2.0 4.0 Silver iodobromide h 0.65 8.0 1.4 Silver iodobromide i 1.00 8.0 2.0 2.0 Silver iodobromide j 0.0. 05 2.0 1.0 The above-mentioned sensitizing dyes were added to each of the above emulsions (excluding emulsion j), and after ripening, triphosphine selenide, sodium thiosulfate, chloroauric acid, and potassium thiocyanate were added. In accordance with a conventional method, fog and chemical sensitization were performed so as to optimize the sensitivity relationship.

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1, two kinds of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 100,000, inhibitors AF-3, AF-4, AF-5,
Hardeners H-1, H-2 and preservative D-1 were added.

The structures of the compounds used in the above samples are shown below.

Thus, a photosensitive material sample 101 was prepared.

Further, an 8 μm B, G, R stripe filter layer was formed on a transparent PET support having a thickness of 122 μm, and layers having the following compositions were sequentially formed thereon from the support side to form a multilayer silver halide. A photosensitive material sample 102 was produced. In the following, unless otherwise specified, the coating amount is g / m ² , and silver halide is converted to metallic silver,
The sensitizing dye is represented by the number of moles per mole of silver halide.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.21 High boiling organic solvent (Oil-2) 0.12 Colored coupler (CM-1) 0.20 Colored Coupler (CC-1) 0.04 Gelatin 1.53 Second layer: Intermediate layer Gelatin 0.80 Third layer: Low sensitivity emulsion layer Silver iodobromide g 1.84 Sensitizing dye (SD-3) 2.4 × 10 ^-4 sensitizing dye (SD-2) 2.1 × 10 ^-4 sensitizing dye (SD-1) 1.9 × 10 ^-4 sensitizing dye (SD-6) 1.7 × 10 ^-4 yellow Coupler (Y-5) 0.26 Magenta coupler (M-40) 0.21 Cyan coupler (C-24) 0.32 High boiling organic solvent (Oil-3) 0.72 Gelatin 2.10 4th layer: Medium Sensitive emulsion layer Silver iodobromide e 2.81 Sensitizing dye (SD-3) × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 -4 Sensitizing dye (SD-1) 1.6 × 10 -4 Sensitizing dye (SD-6) 1.3 × 10 -4 Yellow Coupler (Y-5) 0.20 Magenta coupler (M-40) 0.16 Cyan coupler (C-24) 0.24 High boiling organic solvent (Oil-3) 0.55 Gelatin 2.20 Fifth layer: High Sensitive emulsion layer Silver iodobromide d 2.91 sensitizing dye (SD-3) 1.8 × 10 ^-4 sensitizing dye (SD-2) 1.0 × 10 ^-4 sensitizing dye (SD-1) 1 0.3 × 10 ^-4 sensitizing dye (SD-6) 1.0 × 10 ^-4 Yellow coupler (Y-5) 0.12 Magenta coupler (M-40) 0.08 Cyan coupler (C-24) 16 High boiling organic solvent (Oil-3) 0.33 Gelatin 1.60 Sixth layer: First protective layer Silver iodobromide j 0.30 Ultraviolet absorber (U -1) 0.09 UV absorber (UV-2) 0.10 High boiling point solvent (Oil-2) 0.10 Gelatin 1.44 7th layer: 2nd protective layer PM-1 (average particle size 2 μm) 0 .15 PM-2 (average particle size: 3 μm) 0.04 Slip agent (WAX-1) 0.02 Gelatin 0.55 In addition to the above composition, coating aids SU-1, SU-2,
SU-3, dispersion aid SU-4, viscosity modifier V-1, stabilizer ST-1, dye AI-1, antifoggant AF-3, weight average molecular weight: 10,000 and weight average molecular weight: 10
20,000 polyvinylpyrrolidone (AF-1,
2) Hardeners H-1, H-2 and preservative D-1 were added.

The structure of the compound used in the above sample is shown below.

[0305]

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[0306]

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[0307]

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[0308]

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[0309]

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[0310]

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[0311]

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[0312]

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[0313]

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<Evaluation Method> The obtained sample was subjected to wedge exposure for sensitometry (1/1) using neutral white light.
(200 seconds), the Polarchrome CS was subjected to monochrome development, and the other samples were evaluated for relative sensitivity and granularity by C-41 development (Kodak).

Sensitivity The density of the developed sample was measured using green light, and the result was obtained as the relative value of the reciprocal of the exposure amount giving a density of Dmin (minimum density) +0.15.
The value (relative sensitivity) was set to 00 (relative to 100,
Higher values indicate higher sensitivity).

Dmax (maximum color density) The maximum value Dmax of the magenta density when the development processing time of the C-41 development processing was changed as shown in Table 2 was obtained, and the development processing time of the sample 101 was 3 minutes 15 seconds. Dm for
ax was set to a value of 100 (a value closer to 100 indicates better processing stability).

Granularity A magenta density of Dmin + 0.5 was applied to the aperture scanning area 180
The value was indicated by a relative value of a standard deviation (RMS value) of a change in density value generated when scanning was performed with a microdensitometer of 0 μm ² . The smaller the RMS value is, the better the graininess is and the more effective it is. The RMS value of the sample 101 was shown as a value with respect to 100 (a value smaller than 100 indicates an improvement).

Sharpness For each photosensitive material sample, a short-wave chart was exposed using white light, and Polarchrome CS was monochrome-developed. The other samples were subjected to C-41 development processing (manufactured by Kodak). 2
After performing as described, the microelectronics and meter (R
DM-5 type AR; manufactured by Konica Corporation)
The density is measured with a slit having a width of 2 μm and a width of 2 μm, and the resolving power with respect to the input is obtained as a percentage.
on Transfer Function) values were determined. Specifically, the MTF of the green photosensitive layer was determined, and the MTF at a spatial frequency of 30 lines / mm was set to 1 for the MTF value of the sample 101.
The value was set to 00 (a value larger than 100 indicates a higher resolution).

[0319]

[Table 2]

As is evident from Table 2, the photosensitive material sample 102 of the present invention has higher sensitivity and better granularity and sharpness than the comparative polar chrome CS, and is comparable to the comparative sample 101 (ordinary color negative film photosensitive material). It can be seen that the same or higher image quality can be obtained.

Further, even when the development processing time of the C-41 development processing was varied, the Dmax density variation was small, and it can be seen that the sample 102 of the present invention had higher processing stability than the comparative sample 101.

That is, the present invention (mainly claims 1 and 2 of the present invention)
Or the invention described in 3), it was found that a high-quality filter photosensitive material which can be developed by a color negative developing process widely used in the market can be obtained. It was also found that the filter photographic material of the present invention had high development processing stability.

Example 2 <Preparation of seed emulsion T-1> Seed emulsion T-1 having two parallel twin planes was prepared by the following method.

(A-1 solution) Ossein gelatin 38.0 g Potassium bromide 11.7 g Finished with water to 34.0 L.

(Solution B-1) Finish to 3815 ml with 810.0 g of silver nitrate water.

(C-1 solution) Potassium bromide 567.3 g Finished to 3815 ml with water.

(D-1 solution) Ossein gelatin 163.4 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) Is made up to 3961 ml with 5.5 ml of a 10% methanol solution of water.

(E-1 solution) Sulfuric acid (10%) 91.1 ml (F-1 solution) 56% acetic acid aqueous solution Required amount (G-1 solution) Ammonia water (28%) 105.7 ml (H-1 solution) Potassium hydroxide aqueous solution (10%) Required amount Using a stirring device described in JP-A-62-160128, 3
Solution E-1 was added to solution A-1 which was vigorously stirred at 0 ° C. Then, 279 ml each of solution B-1 and solution C-1 were added at a constant rate for 1 minute by a double jet method to obtain silver halide nuclei. Was generated.

Thereafter, the solution D-1 was added, the temperature was raised to 60 ° C. over 31 minutes, the solution G-1 was further added, the pH was adjusted to 9.3 with the solution H-1, and 6.5 minutes. Aging was performed. Thereafter, the pH was adjusted to 5.8 with the F-1 solution, and then the remaining B-1 solution and the C-1 solution were subjected to a double jet method to obtain a pH of 37.
Min, and desalted immediately by a conventional method. When this seed emulsion was observed with an electron microscope, two parallel
ECD with two twin planes (projected area circle converted particle size) = 0.
This was a monodispersed tabular seed emulsion having a particle size distribution of 72 μm and a variation coefficient of 16%.

<Preparation of Tabular Grain Emulsion Em-1> Emulsion Em-1 was prepared using Seed Emulsion T-1 and the following solutions.

(A-2 solution) Ossein gelatin 519.9 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) ) Of 10% methanol solution 4.5 ml Seed emulsion T-1 Equivalent to 5.3 moles Make up to 18.0 l with water.

(Solution B-2) 2,787 ml of a 3.5N silver nitrate aqueous solution (solution C-2) 1020 g of potassium bromide 29.1 g of potassium iodide The mixture was made up to 2500 ml with water.

(D-2 solution) Potassium bromide 618.5 g Potassium iodide 8.7 g Make up to 1500 ml with water.

(E-2 solution) Potassium bromide 208.3 g Make up to 1000 ml with water.

(F-2 solution) 56% acetic acid aqueous solution Required amount (G-2 solution) Potassium bromide 624.8 g Finish up to 1500 ml with water.

(H-2 solution) A fine grain emulsion comprising 3.0% by weight of gelatin and silver iodide grains (ECD = 0.05 µm), corresponding to 0.672 mol, is prepared as follows.

Containing 0.254 mol of potassium iodide
To 9942 ml of 0% gelatin solution, 3092 ml of an aqueous solution containing 10.59 mol of silver nitrate and 10.59 mol of potassium iodide were added at a constant speed over 35 minutes to form fine particles. The temperature during the formation of fine particles is controlled at 40 ° C, pH,
EAg was determined.

(I-2 solution) 10 ml of an aqueous solution containing 1.4 × 10 ⁻⁶ mol of thiourea dioxide per mol of silver halide (J-2 solution) Sodium ethylthiosulfonate per mol of silver halide. Aqueous solution containing 3 × 10 ⁻⁵ mol 100 ml (K-2 solution) 10% aqueous potassium hydroxide solution Required amount A-2 solution was added to the reaction vessel, and while stirring vigorously at 75 ° C., B-2 solution and C Solution 2 and Solution D-2 were added by the simultaneous mixing method according to the combination shown in Table 3,
Seed crystals were grown to prepare Em-1. Here, B-
The addition rates of the second liquid, the second liquid C-2, and the second liquid D-2 are changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate, and the generation of small particles other than the growing seed particles and the growth are performed. The deterioration of the particle size distribution due to Ostwald ripening between the particles was prevented.

First, the first growth was carried out by controlling the solution temperature in the reaction vessel to 75 ° C., the pAg to 8.9, and the pH to 5.8. In this first addition, 6 of solution B-2
5.8% was added. Thereafter, the solution J-2 was added, the solution temperature in the reaction vessel was lowered to 40 ° C. in 30 minutes, and the pAg was raised to 1
The solution was adjusted to 0.3, the entire amount of the H-2 solution was added at a constant speed for 2 minutes, and the second addition was immediately performed. The second addition was performed while controlling the solution temperature in the reaction vessel at 40 ° C., the pAg at 10.3, and the pH at 5.0, and all the remaining solution B-2 was added. For controlling pAg and pH, Solution E-2, Solution F-2 and Solution K-2 were added as necessary.

After the particles are formed, desalting is performed according to the method described in JP-A-5-72658, and gelatin is added and dispersed, and pAg 8.06, pH 5.0 at 40 ° C.
8 were obtained. The silver iodide content of this emulsion was 5.3%. When the silver halide grains in this emulsion were observed with an electron microscope, the ECD (grain equivalent to projected area circle) = 1.
The particles were hexagonal tabular monodisperse silver halide grains having an average aspect ratio of 7.0 and a variation coefficient of particle size distribution of 50 μm and a variation coefficient of 14%.

[0341]

[Table 3]

<Chemical sensitization and spectral sensitization> Em-1 was divided into small portions, and the following spectral sensitizing dyes were added to each of them. Further, optimal amounts of sodium thiocyanate, sodium thiosulfate,
Triethylthiourea, chloroauric acid, 1- (3-acetamidophenyl) -5-mercaptotetrazole (AF-
5) was added and heated to 50 ° C. After ripening for each of the optimum reaction times, the mixture was cooled, and a stabilizing agent ST-1 and an antifoggant AF-5 were added thereto to obtain a red-sensitive silver halide emulsion.
1, green-sensitive silver halide emulsion-1 and blue-sensitive silver halide emulsion-1 were obtained. The types and amounts of sensitizing dyes added to each emulsion are as follows. The addition amount was shown as an addition amount per mole of silver halide.

Red-sensitive silver halide emulsion-1 Sensitizing dye (SD-1) 0.04 mmol Sensitizing dye (SD-2) 0.07 mmol Sensitizing dye (SD-3) 0.04 mmol Sensitizing dye (SD-4) 0.13 mmol green-sensitive silver halide emulsion-1 sensitizing dye (SD-5) 0.04 mmol sensitizing dye (SD-6) 0.03 mmol sensitizing dye (SD-7) 0 .17 mmol sensitizing dye (SD-8) 0.02 mmol sensitizing dye (SD-9) 0.02 mmol sensitizing dye (SD-10) 0.02 mmol blue-sensitive silver halide emulsion-1 sensitizing dye (SD-11) 0.19 mmol Sensitizing dye (SD-12) 0.06 mmol Also, a silver iodide content of 3 mol% and an ECD (in terms of projected area circle) were prepared in basically the same manner as in the above Preparation Examples. Particle size) = 0.5
9, average aspect ratio 3.4, particle size distribution variation coefficient 16
% Of a silver halide emulsion containing monodispersed silver iodobromide tabular grains in the same manner as in the red-sensitive silver halide emulsion-1, the green-sensitive silver halide emulsion-1, and the blue-sensitive silver halide emulsion-1. By performing spectral sensitization and chemical sensitization, a red-sensitive silver halide emulsion-2, a green-sensitive silver halide emulsion-2, and a blue-sensitive silver halide emulsion-2 were obtained. The types and amounts of sensitizing dyes added to each emulsion are as follows. The addition amount was shown as an addition amount per mole of silver halide.

Red-sensitive silver halide emulsion-2 Sensitizing dye (SD-1) 0.08 mmol Sensitizing dye (SD-3) 0.08 mmol Sensitizing dye (SD-4) 0.42 mmol Green-sensitive halogen Silver halide emulsion-2 Sensitizing dye (SD-5) 0.04 mmol Sensitizing dye (SD-6) 0.15 mmol Sensitizing dye (SD-7) 0.35 mmol Sensitizing dye (SD-9) 0 0.05 mmol Blue-sensitive silver halide emulsion-2 Sensitizing dye (SD-11) 0.38 mmol Sensitizing dye (SD-12) 0.11 mmol The sensitizing dyes used here are shown below.

[0345]

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[0346]

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<Preparation of Photosensitive Material 201 (Comparative)> Using the silver halide emulsion thus obtained, a photographic component layer having the following composition was formed on a subbed transparent PEN base (85 μm thick). A comparative photosensitive material 201 having a multilayer structure was prepared by coating sequentially. The amount of each material added is indicated in units of mg / m ² as the coating amount per 1 m ^2. However, silver halide was expressed in terms of silver.

First layer (antihalation layer) Gelatin 800 Ultraviolet absorber (UV-1) 200 High boiling point solvent (OIL-2) 200 Zinc hydroxide 500 Dye (AI-1) 280 Dye (AI-2) 240 Dye (AI-3) 400 Second layer (cyan coloring layer) Gelatin 1000 Red-sensitive silver halide emulsion-1 350 Red-sensitive silver halide emulsion-2 290 Color developing agent (A-64) 520 Cyan coupler (C-1) 230 Cyan coupler (C-2) 160 High boiling solvent (OIL-1) 460 High boiling solvent (OIL-2) 130 Antifoggant (AF-6) 1 Third layer (intermediate layer) Gelatin 800 Dye (AI-2) ) 160 additive (HQ-2) 20 high boiling point solvent (OIL-2) 60 water-soluble polymer (PS-1) 60 zinc hydroxide 500 4th layer (Maze) Color-forming layer) Gelatin 1800 Green-sensitive silver halide emulsion-1 350 Green-sensitive silver halide emulsion-2 290 Color developing agent (A-64) 520 Magenta coupler (M-1) 400 High boiling solvent (OIL-1) 460 High boiling solvent (OIL-2) 90 Antifoggant (AF-6) 1 Water-soluble polymer (PS-1) 20 Fifth layer (intermediate layer) Gelatin 800 Dye (AI-1) 320 Additive (HQ-1) Reference Signs List 6 Additive (HQ-2) 20 High boiling solvent (OIL-1) 75 Zinc hydroxide 300 6th layer (yellow color-forming layer) Gelatin 3200 Blue-sensitive silver halide emulsion-1 670 Blue-sensitive silver halide emulsion-2 550 Color developing agent (A-64) 520 Yellow macapra (Y-1) 1060 High boiling solvent (OIL-1) 450 High boiling solvent (OIL-2) 300 Antifoggant (AF-6) 2 Water-soluble polymer (PS-1) 40 7th layer (intermediate layer) Gelatin 1500 Water-soluble polymer (PS-1) 60 Zinc hydroxide 700 8th layer (protective layer) Gelatin 1000 Matt Agent (WAX-1) 200 Water-soluble polymer (PS-1) 120 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, viscosity modifier V-1,
Stabilizers ST-1, ST-2, antifoggant AF-1, A
F-2, AF-3, AF-4, AF-5, hardener H-
1, H-2, H-3, H-4 were added. Also, F-
2, F-3, F-4 and F-5 each having a total amount of 15.
^{0mg / m 2, 60.0mg / m} 2, 50.0mg / m 2
And 10.0 mg / m < ² > and distributed to each layer. The materials used above are as follows.

[0349]

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[0350]

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[0351]

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[0352]

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[0353]

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[0354]

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<Preparation of Photosensitive Material 202> The silver halide emulsion obtained above was used to prepare an 8 μm B.I. G. FIG. A photographic material layer having the following composition was sequentially coated on the same surface of the support having the R stripe filter layer as the filter, to prepare a photosensitive material 202 having a multilayer structure. The amount of each material added is indicated in units of mg / m ² as the coating amount per 1 m ^2. However, silver halide was expressed in terms of silver.

First layer (undercoat layer) Gelatin 800 Ultraviolet absorber (UV-1) 200 High boiling point solvent (OIL-2) 200 Second layer (high sensitivity color forming layer) Gelatin 1700 Red-sensitive silver halide emulsion-1 1000 Green-sensitive silver halide emulsion-1 1000 Blue-sensitive silver halide emulsion-1 1000 Color developing agent (A-64) 450 Cyan coupler (C-1 ') 160 Magenta coupler (M-1') 90 Yellow coupler (Y-) 1 ′) 210 High-boiling solvent (OIL-1) 350 High-boiling solvent (OIL-2) 85 Antifoggant (AF-6) 2 Water-soluble polymer (PS-1) 40 Third layer (low-sensitivity color-forming layer) Gelatin 3300 Red-sensitive silver halide emulsion-2 500 Green-sensitive silver halide emulsion-2 500 Blue-sensitive silver halide emulsion-2 500 Color developing agent (A- 4) 900 Cyan coupler (C-1 ') 320 Magenta coupler (M-1') 180 Yellow coupler (Y-1 ') 420 High boiling solvent (OIL-1) 700 High boiling solvent (OIL-2) 170 Antifogging Agent (AF-6) 2 Water-soluble polymer (PS-1) 20 Fourth layer (antihalation layer) Gelatin 800 Dye (AI-1) 280 Dye (AI-2) 240 Dye (AI-3) 400 Fifth layer (Base generation layer) Gelatin 1200 Additive (HQ-2) 20 High boiling point solvent (OIL-2) 60 Water-soluble polymer (PS-1) 60 Zinc oxide 1630 Zinc hydroxide 400 6th layer (protective layer) Gelatin 500 Matt Agent (WAX-1) 200 Water-soluble polymer (PS-1) 120 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, stabilizer ST-1, S
T-2, antifoggants AF-1, AF-2, AF-3,
AF-4, AF-5, hardeners H-1, H-2, H-3,
H-4 was added. The total amount of F-2, F-3, F-4 and F-5 was 15.0 mg / m ² , 60.0%, respectively.
^{mg / m 2, 50.0mg / m} 2 and 10.0mg / m ²
Was added to each layer. The materials used above are as follows.

[0357]

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<Preparation of photosensitive material 203> Photosensitive material 202
In the preparation of, a color developing agent (A-64), a cyan coupler (C-1 '), a magenta coupler (M-1'), and a yellow coupler (Y-
1 ') except that the photosensitive material 201 is changed as follows.
A photosensitive material 203 was produced in exactly the same manner as described above.

Photosensitive material 203: [Second layer] Color developing agent (A-64) → Color developing agent (A-12)
0) Cyan coupler (C-1 ′) → Cyan coupler (C-
2 ′) Magenta coupler (M-1 ′) → Magenta coupler (M
-2 ') Yellow coupler (Y-1') → Yellow coupler (Y
-2 ') [Third layer] Color developing agent (A-64) → Color developing agent (A-12)
0) Cyan coupler (C-1 ′) → Cyan coupler (C-
2 ′) Magenta coupler (M-1 ′) → Magenta coupler (M
-2 ') Yellow coupler (Y-1') → Yellow coupler (Y
-2 ')

[0360]

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<Preparation of processing sheet P-1> Subtracted transparent P
A layer having the following composition was sequentially applied on an EN base (thickness: 85 μm) to prepare a treated sheet P-1. The amount of each material added is indicated in units of mg / m ² as the coating amount per 1 m ^2. The materials used are described above, and those not present are shown below.

Addition amount (mg / m ² ) of first layer Gelatin 460 Water-soluble polymer (PS-2) 20 Surfactant (SU-3) 23 Hardener (H-5) 360 Second layer Gelatin 2400 Water-soluble Polymer (PS-3) 360 Water-soluble polymer (PS-1) 700 Water-soluble polymer (PS-4) 600 High boiling point solvent (OIL-3) 2000 Guanidine picolinate 2400 Hydantoin potassium 160 Potassium quinolinate 225 Sodium quinolinate 180 Interface Activator (SU-3) 24 Third layer Gelatin 2400 Water-soluble polymer (PS-1) 700 Water-soluble polymer (PS-3) 360 Water-soluble polymer (PS-4) 600 Guanidine picolinate 2150 Surfactant (SU- 3) 24 fourth layer gelatin 220 water-soluble polymer (PS-2) 60 Soluble polymer (PS-3) 200 Potassium nitrate 12 Antifoggant (AF-4) 20 Matting agent (PM-2) 10 Surfactant (SU-3) 7 Surfactant (SU-5) 7 Surfactant (SU) -6) 10 Hardener (H-5) 370

[0363]

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<Evaluation of Samples> The photosensitive materials 202 and 203 produced as described above were exposed to 1000 lux of neutral white light from the support side for 1/100 second through an optical wedge and exposed. . 15 ml / m ² of 40 ° C. warm water was applied to the surface of each photosensitive material, and the processing sheet P-1 and the respective film surfaces were overlapped with each other, and then heat-developed at 85 ° C. for 30 seconds using a heat drum. After the processing, the photosensitive material and the processing sheet were peeled off, and a wedge-shaped image as a monochrome black-and-white negative image was obtained on the photosensitive material. As a comparison, a color image was obtained by performing the same processing except that the heat development time was changed to 45 seconds for the photosensitive material 201. The obtained images were evaluated for sensitivity and granularity as described below (same as in Example 1).

<Evaluation Method and Evaluation Criteria> Sensitivity Wedge exposure for sensitometry (1/200 second) was performed using green light (G).
It was obtained as a relative value of the reciprocal of the exposure amount giving a density of n (minimum density) +0.15, and was shown as a value (relative sensitivity) with the sensitivity of the sample 201 being 100 (the larger the value, the higher the value of 100). Sensitivity).

Granularity Wedge exposure for sensitometry (1/200 second) was performed using green light (G), and after the heat development, Dmi
The density of n + 0.5 was indicated by a relative value of a standard deviation (RMS value) of a fluctuation of a density value generated when scanning was performed with a microdensitometer having an opening scanning area of 1800 μm 2. The smaller the RMS value is, the better the graininess is and the more effective it is. Sample 2
The RMS value of 01 is shown as a value of 100 (a value smaller than 100 indicates an improvement).

The results are shown in Table 4.

[0368]

[Table 4]

As is clear from Table 4, the light-sensitive material of the present invention (mainly the structure of the invention according to claim 5, 6, 7 or 9 of the present invention) has a simplified layer structure and a rapid development process. Nevertheless, it was found that similar image quality was obtained.

Example 3 <Preparation of photosensitive materials 301 and 302>
The following photographic constituent layers were sequentially coated on the surface opposite to the photographic constituent layer of No. 03 with the support interposed therebetween to prepare photosensitive materials 301 and 302 having photographic constituent layers on both sides. The amount of each material added is indicated in units of mg / m ² as the coating amount per 1 m ^2. However, silver halide was expressed in terms of silver.

Layer 1a (undercoat layer) Gelatin 800 Ultraviolet absorber (UV-1) 200 High boiling solvent (OIL-2) 200 Layer 2a (photosensitive layer) Gelatin 1700 Red-sensitive silver halide emulsion-1 1000 Green Sensitive silver halide emulsion-1 1000 Blue-sensitive silver halide emulsion-1 1000 Color developing agent (A-5) 450 Infrared coupler (IRK-II-8) 250 High boiling solvent (OIL-1) 350 High boiling solvent ( OIL-2) 85 Antifoggant (AF-6) 2 Water-soluble polymer (PS-1) 40 Layer 3a (base generating layer) Gelatin 1200 High boiling solvent (OIL-2) 60 Water-soluble polymer (PS-1) 60 zinc oxide 1630 4th layer (protective layer) gelatin 500 matting agent (WAX-1) 200 water-soluble polymer (PS-1) 120 In addition to the Narubutsu, coating aids SU-1, SU-
2, SU-3, dispersing aid SU-4, stabilizer ST-1, S
T-2, antifoggants AF-1, AF-2, AF-3,
AF-4, AF-5, hardeners H-1, H-2, H-3,
H-4 was added. The total amount of F-2, F-3, F-4 and F-5 was 7.5 mg / m ² and 30.0 m, respectively.
g / m ^2, it was added by distributing to each layer so that 25.0 mg / m ² and 5.0 mg / m ^2. The used materials are the same as in the case of the second embodiment.

<Evaluation of Samples> Evaluation of Sensitivity The photosensitive materials 202 and 203 produced in Example 2 and the photosensitive materials 301 and 302 produced in Example 3 were cut into a 35 mm negative film size, punched, and processed into a cartridge.
Furthermore, the human being and the Macbeth chart were photographed by changing the setting sensitivity at the time of photographing from ISO 100 to 3200, respectively.

For each of the light-sensitive materials 202 and 203, hot water of 40 ° C. was applied to the surface of the light-sensitive material at a rate of 15 ml / m ^2, and the processing sheet P-1 and the respective film surfaces were overlapped with each other. After thermal processing at 85 ° C. for 30 seconds, and after processing, the photosensitive material and the processing sheet were peeled off, and a wedge-shaped image as a monochrome black-and-white negative image was obtained on the photosensitive material.

For each of the light-sensitive materials 301 and 302, warm water of 40 ° C. was applied to both surfaces of the light-sensitive material at a rate of 15 m per side.
1 / m ^2, and the processing sheet P-1 was sandwiched from both sides so that the film surfaces of the processing sheet P-1 were overlapped with each other, and was thermally developed at 85 ° C. for 30 seconds using a heat drum. After the processing, the photosensitive material and the processing sheet were peeled off, and a wedge-shaped image as a monochrome black-and-white negative image was obtained on the photosensitive material.

Next, the light-sensitive materials 202 and 203 obtained above
For each monochrome monochrome negative image, a wedge-shaped image, a red separation filter (Gelatin filter No. W26, manufactured by Eastman Kodak Co.), a green separation filter (No. W99), or a blue separation filter (No. W98). Placed between the light source and the sample, 20
R, G, and B color-separated negative images were obtained using a monochrome CCD camera (KX4 manufactured by Eastman Kodak Company) of 48 × 2048 pixels. After the obtained image is subjected to the gradation inversion process,
After appropriately adjusting the contrast of the three color separation images, 3
The three images were combined to obtain an RGB color image.

On the other hand, the light-sensitive material 30 of the present invention obtained above was obtained.
The wedge-shaped image, which is a monochrome black-and-white negative image of each of Nos. 1 and 302, was processed using a red separation filter (Gelatin Filter No. W2 manufactured by Eastman Kodak Company).
6), a green separation filter (No. W99) or a blue separation filter (No. W98) was placed between the light source and the sample, and an infrared cut filter (DR manufactured by Kenko Co., Ltd.)
Filter) pre-installed monochrome CCD
Was used to obtain a separated negative image for extracting R, G, and B color information. Separately, an infrared light transmission filter (gelatin filter No. W89B manufactured by Eastman Kodak Co.) was arranged between the light source and the sample without using an infrared light cut filter (DR filter manufactured by Kenko).
A negative image for extracting luminance information was obtained using a 0,000 pixel monochrome CCD camera.

After the obtained image is subjected to gradation inversion processing, an RGB color image is prepared from a decomposed image for extracting color information, and further, the RGB color image is converted to a color image by using Adobe Photoshop image editing software Photoshop. L
Converted to ab image. Thereafter, the Lab image was replaced with an image for extracting luminance information read using an infrared light transmission filter, and then subjected to RGB image conversion processing again to obtain a color image of the present invention.

The RGB images corresponding to the respective photosensitive materials 202, 203, 301, and 302 obtained by changing the set sensitivity at the time of photographing from ISO 100 to 3200 were confirmed on a CRT (cathode ray tube).

As a result, the ISO setting value at which the image descriptive power was the most excellent in each sample was the light-sensitive materials 202 and 20.
3 is ISO 400, and photosensitive materials 301 and 302 are ISO 1600. The light-sensitive materials 301 and 302 of the present invention (mainly the structure of the invention described in claims 1 and 2 of the present invention) are provided by replacing a luminance information image with luminance information obtained from an infrared region. It was found that the sensitivity was excellent for 203.

Example 4 Preparation of Photosensitive Materials 401 and 402 Instead of the first to fourth layers on the side of the support having a filter layer in the photosensitive materials 301 and 302, layers having the following compositions were sequentially applied. Other than that, photosensitive materials 401 and 402 having photographic constituent layers on both sides were prepared.
The amount of each material added was mg / m ² , and silver halide and colloidal silver were expressed in terms of silver.

First layer (undercoat layer) Gelatin 800 Ultraviolet absorber (UV-1) 200 High boiling point solvent (OIL-2) 200 Second layer (intermediate layer) Gelatin 1600 Water-soluble polymer (PS-1) 401 5-Diphenyl-3-pyrazolidone 1558 Third layer (emulsion layer) Gelatin 1700 Red-sensitive silver halide emulsion-1 750 Green-sensitive silver halide emulsion-1 750 Antifoggant (AF-6) 2 Water-soluble polymer (PS- 1) 60 4th layer (halation layer) Gelatin 1000 Water-soluble polymer (PS-1) 80 Dye (AI-1) 280 Dye (AI-2) 240 Dye (AI-3) 400 High boiling point solvent (OIL-2) Reference Signs List 60 additive (HQ-2) 20 fifth layer (base generating layer) gelatin 800 water-soluble polymer (PS-1) 100 zinc oxide 1630 hydroxyl Zinc 400 6th layer (protective layer) Gelatin 500 Matting agent (WAX-1) 200 Water-soluble polymer (PS-1) 120 Evaluation of Samples The same processing and evaluation as in the case of the photosensitive materials 301 and 302 were carried out. The photosensitive materials 401 and 402 (mainly the constitutions of the invention described in claims 1, 2 and 4 of the present invention (embodiments of a black-and-white developing agent and an embodiment of black-and-white color development)) are particularly subjected to digital image conversion processing. It was found that photographic performance equivalent to 301 and 302 was obtained.

[0382]

According to the present invention, it is possible to provide a color filter silver halide light-sensitive material which is capable of forming an image with a versatile current color negative developing system, and which is suitable for processing stability and rapid processing.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hideaki Haraga 1st Sakuracho, Hino-shi, Tokyo Konica Stock Company In-house F-term (reference) 2H016 AD02 BA00 BB02 BC01 BC03 BD00 BE01 BE02 BE03 BK00 2H023 AA00 BA04 CD06 FD00

Claims (12)

[Claims] 1. A coupler having a mosaic or striped filter layer having at least two regions having different spectral sensitivity characteristics on a support and reacting with an oxidized form of a developing agent to form a dye, and a halogen. A silver halide photosensitive material having at least one photosensitive layer containing a silver halide emulsion. 2. The silver halide light-sensitive material according to claim 1, wherein said coupler is at least one of an yellow coupler, a magenta coupler and a cyan coupler. 3. A method for processing a silver halide light-sensitive material, comprising subjecting the silver halide light-sensitive material according to claim 1 to color development processing. 4. A mosaic or striped filter layer having at least two regions having different spectral sensitivity characteristics on a support, and at least one photosensitive layer containing a silver halide emulsion and a developing agent is provided. A silver halide photosensitive material characterized by having: 5. The silver halide photosensitive material according to claim 1, wherein at least one photosensitive layer contains a color developing agent. 6. The color developing agent of the following general formula (1):
The silver halide light-sensitive material according to claim 5, which is at least one of the compounds represented by (5). Embedded image [Wherein, R ^{1 to} R ⁴ are each 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, aryloxycarbonyl Represents an alkylcarbonyl group, an arylcarbonyl group, or an acyloxy group. R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group. R ⁶ represents a substituted or unsubstituted alkyl group. X
Represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl- or aryl-substituted tertiary nitrogen atom. R ⁷ ,
R ^8, R ^9, R ¹⁰ represents a hydrogen atom or a substituent, R ^7,
R ⁸ , R ⁹ and R ¹⁰ may combine with each other to form a double bond or a ring. Z represents an atomic group forming an aromatic ring. ] 7. An image forming method comprising: exposing the silver halide photosensitive material according to claim 5 or 6 to heat development to form an image. 8. An image forming method, wherein an image is formed by subjecting the silver halide photosensitive material according to claim 5 to activator processing. 9. The image forming method according to claim 7, wherein the heat development is performed using a processing sheet. 10. The silver halide emulsion according to claim 1, wherein 50% or more of the total projected area of the silver halide grains contained in the silver halide emulsion is tabular grains having an aspect ratio of 2 or more. 7. The silver halide light-sensitive material according to item 5 or 6. 11. The silver halide photosensitive material according to claim 1, wherein the photosensitive layer comprises two or more layers. 12. The silver halide light-sensitive material according to claim 11, wherein said filter layer is provided between two or more light-sensitive layers.