JPH11174614A - Silver halide color photosensitive material, processing method therefor, and image forming method using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photosensitive material which has high sensitivity and is excellent in granularity, and by which high grade image information can be presented simply and quickly, a processing method therefor, and an image forming method. SOLUTION: In a silver halide color photosensitive material having a blue sensitive silver halide emulsion layer, a green sensitive silver halide emulsion layer and a red sensitive silver halide emulsion layer on a support, at least one layer of the above silver halide emulsion layers contains at least one kind of emulsion such that 50% or more particles of the total projection area of the silver halide all particles are flat silver halide particles having two or more phases in the interior of the particle, the silver iodide content of the phase with the maximum silver iodide content being less than 15 mol.%, and the silver iodide content of the surface area being 10 mol.% or less. Further the layer contains at least one kind of compound expressed by the formula I. Wherein, R indicates an aliphatic group or an aryl group, and X indicates an atom group needed for forming a lactam ring.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic material, and more particularly, to a silver halide color photographic material having high sensitivity and excellent graininess, a processing method thereof, and an image forming method using the same. It is about.

[0002]

2. Description of the Related Art In recent years, the use of photographing equipment such as cameras has become increasingly widespread, and opportunities for photographing using silver halide color photographic light-sensitive materials have been increasing, and demands for higher sensitivity and higher image quality have been increasing. On the other hand, with the rapid spread of personal computers (PCs) and the spread of the Internet, it is becoming increasingly common to import image information into a personal computer and process it. To capture image information into a personal computer, there is a method of shooting with a digital camera and a method of reading image information of conventional color photographic photosensitive material with a scanner, but the former has a small number of pixels,
There is a problem that the latitude is narrow and the gradation is not smooth, and the latter is that high-quality image data is obtained,
It is excellent in that it can effectively utilize image information of conventional photographic light-sensitive materials accumulated over many years.

However, even when a color photographic light-sensitive material is read by a scanner as described above, the demand for higher image quality is increasing because the magnification is generally high. Since silver halide grains are one of the controlling factors for high sensitivity and high image quality of silver halide color photographic light-sensitive materials, the demand for silver halide emulsions has been increasing more and more in recent years, for example, excellent sensitivity and high sensitivity. An extremely high level of performance is required, for example, having excellent granularity and excellent storage stability.

Techniques for increasing the sensitivity of silver halide emulsions, that is, sensitization techniques, relate to methods for producing silver halide emulsions, techniques for chemically sensitizing silver halide emulsions, and methods for spectrally sensitizing silver halide emulsions. Various methods are known, such as a method for designing a silver halide color light-sensitive material, a method for developing a silver halide color light-sensitive material, and the most preferable and essential method is halogenation. This is to enhance the photosensitive quantum efficiency of the silver particles themselves.

For example, a technique using a core having a high silver iodide content inside a grain is known as the most popular technique for improving the quantum efficiency itself of the sensitivity of silver halide grains. A technique for providing a core having a high content is disclosed in JP-A-63-92942.

JP-A-7-92594 discloses a silver halide grain having a core having a high silver iodide content inside the grain and having a low silver iodide content near the outermost surface of the grain. Technical disclosure has been made.

However, when these grains are used, particularly when the content of silver iodide in the vicinity of the outermost surface of the grains is specified to be low, there arises a problem that although the sensitivity is increased, the graininess is greatly deteriorated. I understood.

Japanese Patent Application Laid-Open (JP-A) No. 61-36746 discloses a technique in which carbonamides are used for a silver halide photographic light-sensitive material.
JP-A-2-34840, U.S. Pat. No. 5,188,92
No. 6, etc. However, even when the carbonamide compounds described in the above-mentioned documents are used in conventional silver halide color photographic light-sensitive materials, effects such as improvement in dispersion stability, image storability and residual colorability are obtained, but silver halide The improvement in graininess of the particles was still insufficient.

Further, as the grain size of silver halide grains is reduced to improve the graininess, the sensitivity tends to decrease, and there is a limit in satisfying both high sensitivity and graininess. Means for satisfying both the graininess have been required.

On the other hand, silver halide color photographic light-sensitive materials require a long processing time to obtain image information, and there is a high demand for a reduction in processing time. In recent years, attempts have been made vigorously to shorten the processing time. However, the results of processing time reduction to date have been limited to color paper processing, and the processing time of color negative films has hardly been realized except for special processing for news reports. From the viewpoint of shortening the total processing time of color negatives and color papers so that customers do not have to wait, it has been particularly desired to reduce the processing time of color films.

As a method of solving such a problem, Japanese Patent Application Laid-Open No. Hei 9-146247 discloses that after color development processing, the processing is terminated without desilvering and the image is read by a scanner to obtain image information. The technology is disclosed,
It has been found that the method described in the above-mentioned patent publication is not easily applicable to a photographic light-sensitive material requiring a high sensitivity, because desensitization due to an optical filter effect due to a coloring material at the time of exposure is remarkable and high sensitivity cannot be obtained.

Further, when a normally used color negative film for photography is read by a scanner without desilvering after development processing, the yellow filter layer and the antihalation layer become obstacles, and only a part of the image can be read. found. In order to solve this problem, it is effective to remove the yellow filter layer or the antihalation layer, or to reduce the amount of the dye used in the yellow filter layer or the antihalation layer. Although image information can be read, it is hard to say that the image is a high-quality image when the magnification is high. In particular, improvement in graininess has been required.

[0013]

SUMMARY OF THE INVENTION Accordingly, a first object of the present invention is to provide a silver halide color photographic material having high sensitivity and improved graininess.

A second object of the present invention is to provide a silver halide color photographic light-sensitive material capable of providing high-quality image information simply and quickly, a processing method thereof, and an image forming method.

[0015]

The above objects of the present invention have been attained by the following items 1 to 3.

1. In a silver halide color photographic material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, at least one of the silver halide emulsion layers is preferably All silver halide in at least one of the silver halide emulsion layers containing at least one compound represented by the following general formula (I) and containing the compound represented by the above general formula (I) The grains having 50% or more of the total projected area of the grains have two or more phases inside the grains, and among these phases, the phase having the highest silver iodide content has a silver iodide content of less than 15 mol%. A silver halide color photographic material comprising tabular silver halide grains having a silver iodide content of 10 mol% or less in the surface region.

[0017]

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In the formula, R represents an aliphatic group or an aryl group, and X represents an atomic group necessary for forming a lactam ring.

2. 2. A method for processing a silver halide color photographic light-sensitive material, wherein the silver halide color photographic light-sensitive material is not desilvered after color development processing.

3. After color developing the silver halide color photographic light-sensitive material described in 1 above, the image information is converted into optical information or an electrical signal while the developed silver and silver halide are held in the light-sensitive material, and the information is converted. Image forming method for obtaining a color image on another recording material based on the

Hereinafter, the present invention will be described in detail.

The tabular silver halide grains of the present invention have two parallel main planes, and have a circle-equivalent diameter of the main plane (a diameter of a circle having the same projected area as the main plane) and a distance between the main planes. The particles have a ratio of the distance (that is, the thickness of the particles), that is, the aspect ratio exceeds 1.

Further, the projection occupied by the tabular silver halide grains of the present invention having an aspect ratio of 8.0 or more in at least one of the silver halide emulsion layers containing the compound represented by the formula (I). The area ratio is preferably 45% or more, more preferably 50% or more, of the projected area of all the tabular silver halide grains.

The diameter of the tabular silver halide grains of the present invention is from 0.3 to 10 μm, preferably from 0.5 to 5.0 μm.
m, more preferably 0.5 to 2.0 μm. The particle thickness is preferably from 0.05 to 0.8 μm.

In the present invention, the measurement of the particle diameter and the particle thickness can be obtained by the method described in US Pat. No. 4,434,226.

The size distribution of the tabular grains of the present invention is obtained by dividing the coefficient of variation of the circle-converted diameter of the main plane (the diameter of a circle having the same projected area as the main plane) by dividing the standard deviation of the diameter distribution by the average diameter. ) Is preferably 30% or less, more preferably 20% or less. In the present invention, the average diameter is a value obtained by arithmetic mean of individual diameters.

The halogen composition of the silver halide grains is preferably silver iodobromide or silver chloroiodobromide.
The average silver iodide content is preferably from 1 to 15 mol%, and from 3 to 1 mol%.
2 mol% is more preferred.

The intergranular distribution of the silver iodide content of the silver halide grains of the present invention is determined by calculating the coefficient of variation of the silver iodide content (the standard deviation of the silver iodide content distribution between grains is expressed by the average silver iodide content). (Divided) is preferably 30% or less, more preferably 20% or less.

The tabular silver halide grains of the present invention have two or more phases inside the grains excluding the surface region. The phase inside the grains as used herein refers to a phase whose halogen composition can be distinguished by XRD or EPMA described later. Among the phases inside the grains in the present invention, the phase having the highest silver iodide content has a silver iodide content of less than 15 mol%, preferably 3 mol% or more and less than 10 mol%. Further, the volume fraction of the phase in the particles is preferably 30% or more and 90% or less, more preferably 30% or more and 60% or less.

In the present invention, the surface region is a region including the surface region of the particle, and is a region having a thickness of about 10 atomic layers.

In the present invention, the silver iodide content in the surface region refers to the XPS method (X-ray photoselect).
ron spectroscopy (X-ray photoelectron spectroscopy).

The silver iodide content according to the XPS method of the present invention can be determined as follows. The sample was cooled to −115 ° C. or less in an ultra-high vacuum of 1 × 10 ⁻⁸ torr or less,
MgKα as an X-ray source voltage 15 kV, X-ray source current 4
Irradiation at 0 mA, Ag3d5 / 2, Br3d, I3d3
/ 2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the surface is determined from the intensity ratio.

The structure relating to the halogen composition in the grains is represented by X
RD (X-ray diffraction analysis), EPMA (Electron)
probe X-ray microanalysis
r: X-ray microanalyzer) or the like.

The maximum silver iodide-containing phase does not include a high iodine-localized region generated by an operation described later for forming dislocation lines excluding the surface region in the present invention.

As a method for producing tabular grains, methods known in the art can be appropriately combined. For example, JP-A Nos. 61-6643, 61-146305 and 62
-157024, 62-18556, 63-9
No. 2942, No. 63-151618, No. 63-163
No. 451, No. 63-220238, No. 63-3112
A known method such as No. 44 can be referred to. For example, p in a liquid phase in which silver halide is formed, which is one type of a double jet method, a double jet method, and a double jet method, is used.
A so-called control double jet method in which Ag is kept constant and a triple jet method in which soluble silver halides having different compositions are independently added can also be used. A forward mixing method can be used, and a method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. If necessary, a silver halide solvent can be used. Silver halide solvents often used include ammonia, thioethers and thioureas. Regarding thioethers, U.S. Pat.
271,157, 3,790,387 and 3,574,628. The mixing method is not particularly limited, and a neutral method using no ammonia, an ammonia method, an acidic method, or the like can be used. However, from the viewpoint of reducing fogging of silver halide grains, it is preferable to use pH (hydrogen). The logarithmic value of the reciprocal of the ion concentration) is 5.5 or less, more preferably 4.5 or less.

The silver halide grains of the present invention contain iodide ions. In this case, there is no particular limitation on the method of adding iodide ions during grain growth, and they may be added as an ion solution such as potassium iodide. Further, for example, it may be added as silver iodide fine particles.

The grain formation using the silver halide fine grains is as follows.
As with the grains disclosed in JP-A-1-183417, JP-A-1-183644, JP-A-1-183645 and the like, grain growth may be performed using only silver halide fine grains. May be supplied by silver halide fine particles. In this case, the iodide ions are preferably supplied by silver halide fine particles. As disclosed in JP-A-5-5966, there are two or more silver halide fine grains used for grain growth, and at least one of them may be composed of only one kind of halogen element.

Further, as described in JP-A-2-16737, an emulsion containing silver halide grains grown in the presence of silver halide grains having a lower solubility than the growing silver halide grains. It is particularly desirable to use silver iodide as the silver halide grain having a small solubility product.

The silver halide grains of the present invention can have dislocation lines described below.

The dislocation of tabular grains is described, for example, in J. Am. F. Ha
Milton, Photo. Sci. Eng. , 11
(1967), 57; Shiozawa, J .; Sc
i. Photo. Sci. Japan, 35 (197
2) Observation can be performed by the method described in 213, that is, a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out so as not to apply enough pressure from the emulsion to generate dislocations on the grains are placed on a mesh for an electron microscope to prevent damage (printout, etc.) by an electron beam. Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particle, the more difficult it is for the electron beam to pass therethrough.
The use of an electron microscope (200 kV) for a thickness of 5 μm allows more clear observation. From the grain photograph obtained by such a method, the position and number of dislocations for each grain when viewed from a direction perpendicular to the main plane can be determined.

The dislocation position of the grains of the present invention does not necessarily have to be at a specific location, but preferably exists at the fringe portion of the tabular grain. It is also preferred that it is present both in the particle fringe portion and inside the particle.

In the present invention, the fringe portion of the tabular grains refers to the outer periphery of the tabular grains. More specifically, in a perpendicular line dropped from the center of gravity of the tabular grain projection surface to each side of the grains as viewed from the principal plane side, Outside of 50% of the length of the perpendicular (side)
Means Among the fringes, it preferably has dislocation lines outside 70%, more preferably outside 80%.

In the present invention, the dislocation line inside the particle means a dislocation line existing in a region other than the above-mentioned fringe portion.

Regarding the number of dislocations in the tabular grains of the present invention, it is preferable that grains containing 5 or more dislocations account for at least 50% of the projected area of all silver halide grains in the emulsion.
It is particularly preferred that it is 0% or more. Further, the number of dislocations is more preferably 10 or more.

When dislocation lines are present in the inside of the grain and the fringe portion, it is preferable that five or more dislocation lines exist in the inside of the grain, and it is more preferable that there are five or more dislocation lines in both the fringe portion and the inside of the grain.

The method of introducing dislocation lines according to the present invention is not particularly limited, but a method of adding an aqueous solution of an iodide ion such as potassium iodide and a water-soluble silver salt solution by a double jet at the position where the dislocation is to be introduced, or A method of adding silver halide fine particles, a method of adding only an iodine ion solution,
The method can be carried out by a method using an iodide ion releasing agent as described in No. 11781. A method of adding an aqueous iodide ion solution and a water-soluble silver salt solution by a double jet,
A method of adding silver iodide fine particles and a method of using an iodide ion releasing agent are preferable, and a method of using silver iodide fine particles is more preferable. The aqueous solution of iodide ions is preferably an aqueous solution of an alkali iodide, and the aqueous solution of a water-soluble silver salt is preferably an aqueous solution of silver nitrate.

The introduction of dislocations is preferably performed after the formation of the maximum silver iodide-containing phase inside the grains, and more preferably after the formation of the phase and before the formation of the adjacent phase.

In the preparation of the whole grains, it is preferable to introduce the silver halide grains at a timing when silver halide grains corresponding to 50 to 95% of the total silver content of the grains are produced.
More preferably, it is introduced at less than 80%.

Next, the compound represented by formula (I) will be described.

The aliphatic group represented by R is an alkyl group, an alkenyl group or an alkynyl group. These aliphatic groups may have a substituent. Preferred substituents include a halogen atom, an aryl group, an alkyloxy group, an aryloxy group and the like. Further, R
The preferred aliphatic group is a group having 7 to 24 carbon atoms, and is a linear or branched alkyl group, a linear or branched alkenyl group, a halogen-substituted alkyl group, an alkyloxyalkyl group, an aryloxy group. Preferred are an alkyl group, an alkylaryloxyalkyl group and the like.

The aryl group represented by R includes
A phenyl group or an α- or β-naphthyl group is preferred. When the aryl group has a substituent, preferred substituents include a linear or branched alkyl group having 1 to 24 carbon atoms, a halogen atom, and a carbon atom having 1 to 24 carbon atoms.
Alkyloxy groups and the like.

X represents an atom group necessary for forming a lactam ring. It is preferably a 4- to 7-membered lactam, and particularly preferably a 5-membered lactam.

The carbon atom forming the lactam ring may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an acylamino group, a sulfonamide group, an alkylthio group, and an arylthio group. , Anilino group, cyano group and the like.

The compound represented by the general formula (I) of the present invention is a compound having both hydrophilicity and lipophilicity and having a surface active function.

By using the compound of the present invention and the tabular silver halide grains of the present invention in the same emulsion layer, the development progress of the tabular silver halide grains of the present invention during color development can be suppressed. Since the initial development is not suppressed and the latent image bleaching does not occur, the number of developed silver is increased, and as a result, a silver halide photographic material having high sensitivity and improved graininess is considered to be obtained. .

Specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited to these.

[0057]

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[0058]

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The compound represented by formula (I) of the present invention is preferably used in the silver halide emulsion layer used in the present invention in an amount of ^{20 to} 600 mg / m ² .

In order to incorporate the compound of the general formula (I) into the silver halide emulsion layer, the compound of the general formula (I) is added to a conventionally known method, for example, a low-boiling solvent such as butyl acetate or ethyl acetate. After dissolving, a method of mixing with a gelatin aqueous solution containing a surfactant, emulsifying and dispersing using a high-speed rotation mixer or a colloid mill or an ultrasonic dispersing machine, and then directly adding the emulsion can be adopted. . Further, after the emulsified dispersion is set, it may be shredded, washed with water, and then added to the emulsion. At this time, a high boiling point solvent such as known dibutyl phthalate and tricresyl phosphate can be used in combination. Preferably, it can be contained in a silver halide emulsion layer together with the coupler by the above-mentioned emulsification dispersion method.

As the coupler used together with the compound of the general formula (I), those represented by the general formula (II) are particularly preferred.

[0062]

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In the formula, Y represents a group which is eliminated by a coupling reaction with an oxidized form of a color developing agent, R ₁ represents a chlorine atom or an alkoxy group, R ₂ represents a substituent, and q represents 1 to 5. Represents an integer of 4, and when q is 2 or more, R ₂ may be the same or different.

In the general formula (II), Y is particularly preferably an arylthio group as a group which is eliminated by a coupling reaction with an oxidized form of the color developing agent represented by Y, and the ortho position of a sulfur atom of the arylthio group is preferred. Are more preferably those having an acylamino group. Acylamino group is -NHC
OR 'is preferred, and R' represents a substituent. Examples of R ′ include an alkyl group such as a methyl group, an ethyl group and a methoxyethyl group, an aryl group such as a phenyl group and a 4-methoxyphenyl group, and a heterocyclic group such as a 2-pyridyl group. Or an alkyl group having a substituent.

In the general formula (II), R ₂ represents a substituent, and q represents an integer of 1 to 4. Examples of the substituent represented by R ₂ include a halogen atom such as chlorine, bromine and fluorine, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, a 2,6-dichlorobenzoylamino group, A benzoylamino group such as a 1,6-dimethoxybenzoylamino group, an alkylsulfonyl group such as a hexadecylsulfonyl group, an acylamino group such as an acetylamino group,
Examples include an alkoxycarbonyl group such as a cyano group, a nitro group, a carboxyl group, an amino group, and an ethoxycarbonyl group, and an alkyl group such as a methyl group, an ethyl group, and an isopropyl group.

Among the magenta couplers represented by the general formula (II), particularly preferred examples include the following general formulas (II-M)
Can be mentioned.

[0067]

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In the formula, Y ₁ has the same meaning as Y in formula (II).

In the general formula (II-M), R ₃ represents a chlorine atom or an alkoxy group. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, t-
Examples thereof include a butyloxy group, a hexyloxy group, and a methoxyethyloxy group.

In the general formula (II-M), R ₁₁ represents a substituent, p represents an integer of 1 to 5, and when p is 2 or more,
₁₁ may be the same or different. Examples of the substituent represented by R ₁₁ include an alkyl group such as a methyl group, an isopropyl group and a trifluoromethyl group, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and a tolyloxy group, chlorine, and bromine. a halogen atom such as fluorine, nitro group, an amino group, and a alkylamino group such as dimethylamino group, at least one of R ₁₁ NH
Substitution at the ortho position of the CO group is preferred.

Specific examples of the magenta coupler represented by formula (II) of the present invention are shown below, but the present invention is not limited to these.

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[0073]

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[0074]

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[0075]

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The silver halide emulsion used in the light-sensitive material of the present invention can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion.

It is advantageous to use gelatin as a binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can contain a plasticizer and a dispersion (latex) of a water-insoluble or hardly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color light-sensitive material.

Further, the development accelerator, the bleaching accelerator, the developer, the silver halide solvent, the toning agent, and the hardening agent are coupled with a colored coupler having a color correcting effect, a competitive coupler and an oxidized form of the developing agent. Compounds that release photographically useful fragments can be used, such as filming agents, fogging agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

The light-sensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an anti-irradiation layer. These layers and / or the emulsion layers may contain dyes which flow out of the light-sensitive material or are bleached during the development processing.

The light-sensitive material may contain a formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color haze inhibitor, a development accelerator, a development retarder and a bleaching accelerator. it can.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In the present invention, a developing method and method
Known conditions and methods can be freely applied regardless of conditions. C, which is the standard processing condition for general color negatives
The development conditions of the -41 process can be preferably applied. Further, it is also possible to develop by spraying or applying a developing solution in an amount substantially penetrating the photosensitive material. Regardless of the method of ejecting the developer, the developer may be ejected while moving a single movable nozzle, or may be ejected using a plurality of fixed nozzles. The injection may be performed while the photosensitive material is fixed and the nozzle is moved, or the injection may be performed while the nozzle is fixed and the photosensitive material is moved. A combination of these may be used.

In the case of performing a developing process for supplying an amount of the developing solution that can substantially penetrate the photosensitive material through the medium carrying the developing solution to the photosensitive material, the medium carrying the developing solution is limited. Alternatively, felt, woven fabric, metal having slits or holes, or the like can be preferably used. A method in which the developer is applied to the photosensitive material by the medium while the developer is sprayed on the photosensitive material or the medium is also preferable.

In the present invention, desilvering refers to bleaching, fixing or bleach-fixing. It is preferable not to perform bleaching and fixing processing in terms of shortening the processing time.

In the present invention, the information of the color image including the information of the developed silver is converted into optical information or an electrical signal, but it may be photoelectrically read and converted into a digital signal. A scanner can be used for this reading. A scanner optically scans a photosensitive material and reflects it,
Alternatively, it is a device for converting the transmission optical density 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.

Light sources for reading image information include a tungsten lamp, a fluorescent lamp, a light emitting diode, a laser beam, and the like.
Tungsten lamps are preferred because they can be used without particular limitation and are inexpensive, and laser beams are preferred because they are stable, have high brightness, and are not easily affected by scattering. The reading method is not particularly limited, but it is preferable to read the transmitted light in terms of sharpness. It is preferable to use a semiconductor image sensor (for example, an area CCD or a CCD line sensor) for the light receiving unit.

In the present invention, an image signal thus read is output to form an image on another recording material. In this case, the output material need not be a photosensitive material, and may be, for example, a sublimation type thermal transfer material, an inkjet material, a full-color direct thermal recording material, a color CRT, a color LCD, or the like.

[0091]

Example 1 Preparation of seed crystal emulsion-1 A seed crystal emulsion was prepared as follows.

JP-B-58-58288, 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. For 2 minutes to form nuclei. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and 90% or more of the total projected area of the silver halide grains had a maximum side ratio of 1.0.
~ 2.0 hexagonal tabular grains. This emulsion is referred to as seed emulsion-1.

(Solution A1) Ossein gelatin 24.2 g Potassium bromide 10.8 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) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide While vigorously stirring 5 l, 2 l each of a 7.06 mol aqueous silver nitrate solution and a 7.06 mol aqueous potassium iodide solution were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

Preparation of Emulsion Em-1 0.178 moles of seed crystal emulsion-1 and 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) in 10% ethanol solution 0.5
4.5% by weight of an aqueous inert gelatin solution 70
0 ml at 75 ° C., pAg 8.9, pH 5.0.
Then, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

(1) A 2.1 mol silver nitrate aqueous solution and 0.1 mol
95 mol of SMC-1 and an aqueous solution of potassium bromide were added to p
Ag was added at 8.9 and pH was maintained at 5.0.

(2) Subsequently, a 1.028 mol aqueous solution of silver nitrate, 0.032 mol of SMC-1 and an aqueous solution of potassium bromide were added while keeping the pAg at 8.9 and the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had an average diameter of 1.36 μm.
m, particles having an aspect ratio of 8.0 or more have a projected area of 50
% Of the grains having the halogen composition shown in Table 1.

When the content of silver iodide on the surface was measured by the method described in this specification, the content of silver iodide in the surface region was 4.5 mol%.

Preparation of Emulsion Em-2 The preparation of Emulsion Em-1 was carried out in the same manner as in Em-1 except that after the step (2), 0.004 mol of SMC-1 was added and the mixture was aged for 15 minutes. Em-2 was prepared.

The obtained emulsion had an average diameter of 1.36 μm.
The emulsion was as shown in Table 1. The silver iodide content in the surface region was 13.1 mol%.

Preparation of Emulsion Em-3 0.178 mol of seed crystal emulsion-1 and 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) in 10% ethanol solution 0.5
4.5% by weight of an aqueous inert gelatin solution 70
0 ml at 75 ° C., pAg 8.9, pH 5.0.
Then, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

(1) A 2.1 mol aqueous solution of silver nitrate and 0.1 mol
95 mol of SMC-1 and an aqueous solution of potassium bromide were added to p
Ag was added at 8.9 and pH was maintained at 5.0.

(2) Subsequently, the solution was cooled to 60 ° C.
g was adjusted to 9.8. Thereafter, 0.071 mol of SM
C-1 was added and aging was performed for 2 minutes (introduction of dislocation lines).

(3) An aqueous solution of 0.959 mol of silver nitrate, 0.030 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 9.8 and the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion had an average diameter of 1.35 μm.
The emulsion was as shown in Table 1. Observation of this emulsion with an electron microscope revealed that 60% of the total projected area of the grains in the emulsion was obtained.
In these particles, five or more dislocation lines were observed both in the fringe portion and inside the particles. The silver iodide content in the surface region is 6.7.
Mole%.

Preparation of Emulsion Em-4 In the preparation of Emulsion Em-3, the amount of silver nitrate added in step (2) was 0.92 mol and the amount of SMC-1 was 0.069.
Emulsion Em-4 in the same manner as Em-3, except that the molar amount was changed to mol.
Was prepared.

The obtained emulsion had an average diameter of 1.33 μm.
The emulsion was as shown in Table 1. Observation of this emulsion with an electron microscope revealed that 60% of the total projected area of the grains in the emulsion was obtained.
In these particles, five or more dislocation lines were observed both in the fringe portion and inside the particles. The silver iodide content in the surface region is 11.
9 mol%.

Preparation of Emulsion Em-5 0.178 mol of seed crystal emulsion-1 and polyisoprene
4.5% by weight containing 0.5 ml of a 10% solution of polyethylene oxy-disuccinate sodium salt in ethanol
Of inert gelatin aqueous solution at 75 ° C.
After adjusting the Ag to 8.9 and the pH to 5.0, particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

(1) A 0.692 mol aqueous solution of silver nitrate, 0.297 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 8.9 and the pH at 5.0.

(2) Subsequently, a 2.295 mol aqueous solution of silver nitrate, 0.071 mol of SMC-1 and an aqueous solution of potassium bromide were added while maintaining the pAg at 8.9 and the pH at 5.0.

(3) After the step of (2), 0.004
Molar SMC-1 was added and aged for 15 minutes.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the step (3), the resultant is subjected to a washing treatment at 40 ° C. using a normal flocculation method, and gelatin is added thereto for re-dispersion.
Was adjusted to 5.8.

The obtained emulsion had an average diameter of 1.15 μm.
The emulsion was as shown in Table 1. Observation of this emulsion with an electron microscope revealed that there were no grains having dislocation lines. The silver iodide content in the surface region was 12.0 mol%.

Preparation of Emulsion Em-6 Em-6 described in Examples of JP-A-7-92594
Comparative emulsion Em-6 was prepared according to the production method of Comparative Example 4.

Emulsions Em-1 to E prepared as described above
Table 1 shows the content of m-6.

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[Table 1]

To each of the above emulsions Em-1 to Em-6, sensitizing dyes SD-5, SD-6 and SD-7 were added, and sodium thiosulfate, selenium sensitizer S-1, chloroauric acid, thiocyanate were added. Potassium acid was added and subjected to chemical sensitization according to a conventional method so as to optimize the fog-sensitivity relationship.

After completion of the chemical sensitization, a stabilizer ST-1 was added to each emulsion.
And antifoggant AF-1. The amount of ST-1 added was 1 g per mole of silver halide, and the amount of AF-1 was 60 mg per mole of silver halide.

On a triacetylcellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side, and a multilayer color photographic light-sensitive material sample 10
1 was created.

The amount of addition indicates the number of grams per 1 m ² unless otherwise specified. Silver halide and colloidal silver were expressed in terms of silver, and sensitizing dyes were expressed in moles per mole of silver.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling organic solvent (Oil-1) 0.12 Gelatin 1.53 Second layer: Intermediate layer Antifouling agent (SC-1) 0.06 High boiling organic solvent (Oil-2) 0.08 Gelatin 0.80 Third layer: Low-sensitivity red-sensitive layer Silver iodobromide emulsion (average diameter 0.38 μm, iodide Silver content 8.0 mol%) 0.43 silver iodobromide emulsion (average diameter 0.27 μm, silver iodide content 2.0 mol%) 0.15 sensitizing dye (SD-1) 2.8 × 10 ^-4 sensitizing dye (SD-2) 1.9 x 10 ^-4 sensitizing dye (SD-3) 1.9 x 10 ^-4 sensitizing dye (SD-4) 1.0 x 10 ^-4 cyan coupler (C-1) 0.56 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.025 Boiling point organic solvent (Oil-1) 0.49 Gelatin 1.14 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average diameter 0.52 μm, silver iodide content 8.0 mol%) 0.89 Silver iodobromide emulsion (average diameter 0.38 μm, silver iodide content 8.0 mol%) 0.22 sensitizing dye (SD-1) 2.3 × 10 ^-4 sensitizing dye (SD-2) 1 0.2 × 10 ^-4 sensitizing dye (SD-3) 1.6 × 10 ^-4 cyan coupler (C-1) 0.45 colored cyan coupler (CC-1) 0.038 DIR compound (D-1) 0 0.019 High-boiling organic solvent (Oil-1) 0.39 Gelatin 1.01 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion (average diameter: 1.00 μm, silver iodide content: 8.0 mol%) 1.27 sensitizing dye (SD-1) 1.3 × 10 -4 sensitizing dye ^{(SD-2) 1.3 × 10} -4 sensitizing dye (SD- ) 1.6 × ^{10 -4} Cyan coupler (C-2) 0.20 Colored cyan coupler (CC-1) 0.034 DIR compound (D-3) 0.002 High-boiling organic solvent (Oil-1) 0. 57 Gelatin 1.10 6th layer: Intermediate layer Color stain inhibitor (SC-1) 0.075 High boiling organic solvent (Oil-2) 0.095 Gelatin 1.00 7th layer: Low sensitivity green-sensitive layer Silver iodide emulsion (average diameter 0.38 μm, silver iodide content: 8.0 mol%) 0.64 Silver iodobromide emulsion (average diameter: 0.27 μm, silver iodide content: 2.0 mol%) 0.21 Sensitizing dye (SD-4) 7.4 × 10 ^-4 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.19 Magenta coupler (M-2) 0.49 Colored magenta coupler (CM-1) 0.12 High boiling organic solvent (Oil- 0.81 gelatin 1.89 8th layer: medium-speed green-sensitive layer silver iodobromide emulsion (average diameter 0.59 μm, silver iodide content 8.0 mol%) 0.76 sensitizing dye (SD-6) ) 1.5 × 10 ^-4 sensitizing dye (SD-7) 1.6 × 10 ^-4 sensitizing dye (SD-8) 1.5 × 10 ^-4 magenta coupler (M-1) 0.043 magenta coupler (M-2) 0.10 Colored magenta coupler (CM-1) 0.039 DIR compound (D-2) 0.021 DIR compound (D-3) 0.004 High boiling organic solvent (Oil-2) 37 Gelatin 0.76 Ninth layer: High-sensitivity green-sensitive layer Emulsion Em-A 1.46 Magenta coupler (M-1) 0.08 Magenta coupler (M-2) 0.133 Colored magenta coupler (CM-2) 0 .014 Cyan Coupler (C-3) 0.01 High Point organic solvent (Oil-2) 0.36 Gelatin 1.08 10th layer: Yellow filter layer Yellow colloidal silver 0.07 Color stain inhibitor (SC-1) 0.18 High boiling organic solvent (Oil-2) 0 .21 gelatin 0.73 eleventh layer: low-sensitivity blue-sensitive layer silver iodobromide emulsion (average diameter 0.59 μm, silver iodide content 8.0 mol%) 0.073 silver iodobromide emulsion (average diameter 0 .38 μm, silver iodide content: 3.0 mol%) 0.16 Silver iodobromide emulsion (average diameter: 0.27 μm, silver iodide content: 2.0 mol%) 0.20 Sensitizing dye (SD-9) 2.1 × 10 ^-4 sensitizing dye (SD-10) 2.8 × 10 ^-4 Yellow coupler (Y-1) 0.89 DIR compound (D-4) 0.008 High boiling organic solvent (Oil- 2) 0.37 gelatin 1.51 12th layer: high-sensitivity blue-sensitive layer silver iodobromide emulsion Diameter 1.00 .mu.m, a silver iodide content of 8.0 mol%) 0.95 Sensitizing dye (SD-9) 7.3 × 10 -4 Sensitizing dye (SD-10) 2.8 × 10 -4 Yellow Coupler (Y-1) 0.16 High boiling organic solvent (Oil-2) 0.093 Gelatin 0.80 13th layer: 1st protective layer Silver iodobromide emulsion (average diameter 0.05 μm, silver iodide content 3.00 mol%) 0.30 Ultraviolet absorber (UV-1) 0.094 Ultraviolet absorber (UV-2) 0.10 Formalin scavenger (HS-1) 0.38 High boiling organic solvent (Oil-1) 0.10 gelatin 1.44 14th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 polymethyl methacrylate (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, dispersing aid SU-2, viscosity modifier V-1, hardener H-1, H-2,
Stabilizer ST-1, dyes AI-1, AI-2, antifoggant AF-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, and Preservative DI-1 was added.

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

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[0127]

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[0130]

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[0133]

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The emulsion Em-A of the ninth layer of the sample 101,
High boiling organic solvent Oil-2 and seventh, eighth and ninth layers
Samples 102 to 132 were prepared by replacing the magenta couplers M-1 and M-2 in the layers as shown in Table 2.

The emulsion was replaced with an equimolar amount of silver halide. The replacement amount of the coupler was replaced with a coupler of 1/2 mole amount of the sum of the mole numbers of M-1 and M-2 in each layer. When using a magenta coupler other than M-1 and M-2,
Compound Oil-3 in an amount corresponding to 30% by weight of the coupler
Was added. The additional layers are a seventh layer, an eighth layer, and a ninth layer.

The high-boiling organic solvent Oil-2 in the ninth layer was replaced with the compound of the general formula (I) of the present invention or the comparative compound by an equivalent weight.

Each of the samples prepared as described above was exposed to light according to the performance evaluation shown below, subjected to color development processing shown below, and the performance was evaluated.

(A) Photosensitivity A sample was subjected to gradation exposure with white light and subjected to the following color development processing. From the characteristic curve of the magenta color image, a minimum density of +0.2 was obtained.
The logarithm of the reciprocal of the exposure amount that gives the density of
The difference (ΔS) between each sample and the reference sample 101 was calculated with reference to 1. Here, the higher the value of ΔS, the higher the sensitivity.

(B) Granularity The portion of the sample whose photographic sensitivity was previously determined, giving a green density of the minimum density + 0.2, was passed through an Eastman Kodak Watten filter (W-99) to have an opening area of 1800.
μm ² (slit width 10 μm, slit length 180 μm)
Scanning with a microdensitometer of 100, and the standard deviation of the variation of
The zero-fold value was obtained, and the value was shown as a relative value with the value of Sample 101 being 100.

The smaller the value, the better the graininess.

<< Development processing step >> Step Processing temperature Processing time Replenishment amount * Color development 38 ± 0.3 ° C. 3 minutes 15 seconds 780 ml Bleaching 38 ± 2.0 ° C. 45 seconds 150 ml Settling 38 ± 2.0 ° C. 1 minute 30 seconds 830 ml Stability 38 ± 5.0 ° C. 60 seconds 830 ml Drying 55 ± 5.0 ° C. 60 seconds − * The replenishment amount is a value per 1 m ² of the photosensitive material.

<Preparation of processing agent> (Composition of color developing solution) Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g Diethylenetetraaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Finish to 0.01 and adjust to pH 10.06 with potassium hydroxide or 20% sulfuric acid.

(Composition of color developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium hydrogen carbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetetraamine pentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and the pH was adjusted using potassium hydroxide or 20% sulfuric acid. Adjust to 10.18.

(Composition of bleaching solution) Water 800 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Alternatively, the pH is adjusted to 4.4 using glacial acetic acid.

(Composition of bleaching replenisher) Water 700 ml 1,3-diaminopropanetetraacetic acid iron (III) ammonium 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.4 with water or glacial acetic acid.

(Composition of Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Water was added to make up to 1.0 liter, and the pH was adjusted to 6.2 with aqueous ammonia or glacial acetic acid.

(Composition of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Water was added to finish to 1.0 liter, and the pH was adjusted to 6.2 using aqueous ammonia or glacial acetic acid.

(Composition of Stabilizing Solution and Stabilizing Replenishing Solution) Water 800 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.5 ml Aqueous ammonia Water was added to make up to 1.0 liter, and the pH was adjusted to 8.0 using ammonia water or 50% sulfuric acid. Adjust to 5.

[0150]

[Table 2]

From the results shown in Table 2, the silver halide photographic light-sensitive material having high sensitivity and improved graininess can be obtained by using the compound represented by formula (I) of the present invention together with the emulsion of the present invention. It can be seen that it can be obtained. It can also be seen that the use of the magenta coupler represented by the general formula (II) further improves the granularity.

Example 2 The samples 123 and 125 prepared in Example 1
Samples 201 and 202 were prepared in the same manner except that the black colloidal silver in the layer and the yellow colloidal silver in the tenth layer were removed. A photograph of a person and a Macbeth color chart was taken for each of the samples thus prepared, and subjected to the processing described below.

<< Development Processing Step >> Step Processing Temperature Processing Time Color Development 38 ± 0.3 ° C. 3 minutes 15 seconds Same developer as in Example 1 Stop 38 ± 2.0 ° C. 30 seconds 1% acetic acid solution Drying 55 ± 5 0.0 ° C for 60 seconds The time required for the treatment is 4
What was 50 seconds could be shortened significantly to 285 seconds.

Image information of the processed sample was read by using a scanner Q-scan manufactured by Konica Corporation, image-processed on a personal computer, and output by a printer PM-700C manufactured by Epson Corporation. When the obtained image was visually evaluated, the sample 202 of the present invention was higher in granularity and higher quality than the comparative sample 201.

[0155]

According to the present invention, a silver halide color photographic light-sensitive material having high sensitivity and excellent graininess can be provided. In addition, a silver halide color photographic light-sensitive material capable of providing high-quality image information simply and quickly, a processing method thereof, and an image forming method can be provided.

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer At least one layer of the compound represented by the following general formula (I), and at least one layer of a silver halide emulsion layer containing the compound represented by the above general formula (I) Grains having at least 50% of the total projected area of all silver halide grains having two or more phases inside the grains, of which the silver iodide content is the largest of each phase. A silver halide color photographic light-sensitive material comprising tabular silver halide grains having a silver content of less than 15 mol% and a silver iodide content of 10 mol% or less in a surface region. Embedded image [Wherein, R represents an aliphatic group or an aryl group, and X represents an atom group necessary for forming a lactam ring. ] 2. A method for processing a silver halide color photographic light-sensitive material, wherein the silver halide color photographic light-sensitive material according to claim 1 is not desilvered after color development processing. 3. After the silver halide color photographic light-sensitive material according to claim 1 is subjected to color development processing, the developed silver and silver halide are held in the light-sensitive material, and the image information is converted into optical information or electric signal. And forming a color image on another recording material based on the information.