JP2003322944A - Silver halide color photographic sensitive material and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method by which high quality and stable performance are ensured in rapid processing under low replenishment. <P>SOLUTION: In the image forming method in which a silver halide color photographic sensitive material is imagewise exposed and subjected to processing comprising a color developing step, a bleach fixing step and a rinsing step, the color developing step is carried out while replenishing a color developing solution with 20-60 ml replenisher solution per 1 m<SP>2</SP>of the silver halide color photographic sensitive material, the silver halide color photographic sensitive material contains compounds of formulae (I) and (II) added by 1.0-100 mg/m<SP>2</SP>and 0.1-5.0 mg/m<SP>2</SP>, respectively, in its production process, at least one of the photosensitive silver halide emulsion layers comprises a silver halide emulsion having ≥90 mol% silver chloride content, and the silver halide color photographic sensitive material is swollen by 10-20 μm film thickness in the color developing solution in the color developing step. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide color photographic light-sensitive material and a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material suitable for low replenishment rapid processing. The present invention relates to an image forming method using the above, particularly to an image forming method capable of obtaining a high image quality and stable performance in a low replenishment rapid processing, and a silver halide photographic color light-sensitive material.

[0002]

2. Description of the Related Art In recent years, digitalization has been remarkably permeated even in the field of color printing using color photographic paper. For example, the digital exposure method by laser scanning exposure can be applied to a color printer from a processed color negative film which has been conventionally used. Compared to the analog exposure method that directly prints, it shows a dramatic increase in the penetration rate. Such a digital exposure method is characterized in that a high image quality can be obtained by performing image processing, and plays an extremely important role in improving the quality of color prints using color printing paper. Further, with the rapid spread of digital cameras, it is also an important factor that color prints with high image quality can be easily obtained from these electronic recording media, and this is expected to bring about a further dramatic spread.

On the other hand, as the color printing method, techniques such as an ink jet method, a sublimation method, and a color xerography have made progress, and the color printing method is being recognized as a color printing method. Among these, the characteristics of the digital exposure method using color photographic paper are high image quality, high productivity, and high image fastness. Further, a system using color photographic paper uses a processing liquid unlike other systems, but it is required to reduce the processing liquid in the environment, and the replenishment amount of the processing liquid has been reduced. It is desirable to extend these features further to provide higher quality photographs more easily and cheaper. In particular, if you receive the recording medium of a digital camera at the store and finish high-quality prints within a short time of about a few minutes and return it on the spot, that is, if you can provide a one-stop service for color printing, color printing paper The superiority of printing is increasing. Further, if the rapid processability of color photographic paper is improved, it is possible to use a printing apparatus that is smaller and cheaper and has high productivity, and it can be expected that the one-stop service for color printing will become more popular. From these points, it is important to enhance the rapid processability of color photographic paper.

In order to enable a one-stop service for color printing using color printing paper, the exposure time is shortened, the so-called latent image time from the exposure to the start of processing is shortened, and the time from processing to drying is shortened. It is necessary to study from various viewpoints such as the above, and it has been proposed from each viewpoint from the past. Among these, the time required to expose one print is much shorter than that of the other, and in the case of ordinary printer capacity used in stores, there is almost no problem.
A design is being considered to make the latent image time as short as possible with a printer. Also, the time from processing to drying has been shortened, and proposals for rapid processing have been made by processing solution composition, processing temperature, stirring conditions of processing solution, ironing of photosensitive materials, devising of drying method, etc. ing. In addition to improving productivity, it is also important to stabilize the quality of color prints. In general, print quality changes with rapid processing, so it is important to design color photographic paper suitable for rapid processing.

As a silver halide emulsion used for color photographic paper, a silver halide emulsion having a high silver chloride content is used because of the demand for rapid processing. Various improvements have been made in order to improve the quality stability of a silver halide photographic light-sensitive material using a silver halide emulsion having a high silver chloride content.

Techniques for improving the storability of silver halide light-sensitive materials having a high silver chloride content have been investigated. JP-A-11
A cyclic ketone having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group described in JP-A-327094, JP-A-11-14301.
Sulfo-substituted catechols and hydroquinones described in JP-A-1 No. 1, and hydroxylamines represented by formula (A) in US Pat. No. 5,556,741.
It is known in JP-A-1-102045 to incorporate various compounds of the water-soluble reducing agents represented by the general formulas (I) to (III). Further, JP-A No. 7-31450 describes that it is effective to use a specific triazine-based compound as a gelatin hardener.

[0007]

Therefore, the inventors of the present invention examined the above technique in order to improve the storability, and found that there was an effect of improving the sensitivity fluctuation due to the storage of the light-sensitive material, but it was not sufficient. there were. Further, when a color paper which has been subjected to scanning exposure is processed by using a processing solution with a small replenishing amount, a new problem of image unevenness occurs.

Therefore, the present invention aims to solve the above-mentioned problems of the prior art and achieve the following objects.
That is, an object of the present invention is to provide an image forming method which can obtain high quality and stable performance in low replenishment rapid processing, and to obtain a silver halide photographic color light-sensitive material suitable for low replenishment rapid processing.

[0009]

Means for solving the problems Means for solving the above problems are as follows. (1) A blue-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a green photosensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a red photosensitive silver halide emulsion layer containing a cyan dye-forming coupler on a support. And a silver halide color photographic light-sensitive material having a photographic constituent layer consisting of at least one of each of a non-photosensitive hydrophilic colloid layer and imagewise exposed, and then subjected to a development process including a color development process, a bleach-fixing process and a rinse process. In the image forming method, the replenishing amount of the color developing solution in the color developing step is 1 m ^{2 of the} silver halide color photographic light-sensitive material.
The amount of the compound represented by the following general formula (I) and the general formula (II) is 1.0% in the production process of the silver halide color photographic light-sensitive material.
It is added in an amount of from 100 mg / m ² to 100 mg / m ² and from 0.1 mg / m ² to 5.0 mg / m ² , and at least one of the photosensitive silver halide emulsion layers has a silver chloride content of 90. The silver halide color photographic light-sensitive material contains a silver halide emulsion in an amount of at least mol%, and the swollen film thickness in the color developing solution in the color developing step is 10 μm.
An image forming method characterized in that the thickness is changed from m to 20 μm.

[0010]

[Chemical 3]

(In the general formula (I), Y represents a carbon atom.
Z represents a carbon atom. R¹, R²Are the same or different
May be a hydroxyl group, an amino group, an alkyl group, respectively.
Ruamino group, anilino group, heterocyclic amino group, acyl group
Mino group, alkylsulfonylamino group, arylsulfo
Nylamino group, heterocyclic sulfonylamino group, alkoxy
Cycarbonylamino group, carbamoylamino group, merca
Group, alkylthio group, arylthio group, heterocyclic group
Represents a group. R³Is a hydrogen atom, Y is connected to a carbon atom
Group, a group connecting Y with an oxygen atom, a group connecting Y with a nitrogen atom
Represents the group R ^FourIs a hydrogen atom, linked with Z and a carbon atom
Group, a group that connects with Z and an oxygen atom, a group that connects with Z and a nitrogen atom.
Represents a group to be bonded. R³And R^FourCooperate with each other to form a ring
May be. )

[0012]

[Chemical 4]

(In the general formula (II), M represents a cation.
R is an atom having an atomic weight of 50 or less, or the total atomic weight is 50.
It represents the following groups. )

(2) The residual amount of the compound represented by the general formula (I) in the silver halide color photographic light-sensitive material is 0.5 mg / m in a period of 1 week to 6 months after the production of the light-sensitive material.
² to 50 mg / m ² (1) above
The image forming method described in 1 ..

(3) The image as described in (1) or (2) above, wherein the total coated silver amount of the silver halide color photographic light-sensitive material is 0.50 to 0.20 g / m ^2. Forming method.

(4) A silver halide emulsion having a silver chloride content of 90 mol% or more and a metal complex represented by the following general formula (III) in at least one of the photosensitive silver halide emulsion layers. The image forming method according to any one of (1) to (3) above, including:

General formula (III) [IrX^I _nL^I _(6-n)]^m- (X in the general formula (III)^IIs a halogen ion or pseudo
Represents a rogen ion. L ^IIs X^IAny ligand different from
Represents n represents an integer of 3 to 5. m is an integer from -4 to +1
Represents a number. )

(5) Any of the above (1) to (4), wherein the silver halide color photographic light-sensitive material contains a hardening agent represented by the following general formula (H-II). An image forming method according to claim 1.

[0019]

[Chemical 5]

(In the general formula (H-II), X ¹ and X ² are each —CH═CH ₂ or —CH ₂ CH ₂ Y, and even if X ¹ and X ² are the same, It may be different.
Y represents a group which is substituted by a nucleophilic group or which can be eliminated by a base in the form of HY (for example, a halogen atom, sulfonyloquine, sulfuric acid monoester, etc.). L is a divalent linking group and may be substituted. )

(6) The color developing step is carried out while the silver halide color photographic light-sensitive material is conveyed at a conveying linear velocity of 4.0 m / min or more.
The image forming method according to any one of (5).

(7) The color developing step is performed for 28 seconds or less and 6 seconds or more, from (1) to (1) above.
The image forming method according to any one of (6).

(8) A silver halide color photographic light-sensitive material of a type in which after imagewise exposure, development processing including a color color development step, a bleach-fixing step and a rinse step is performed.
In the color developing step, the replenishing amount of the color developing solution is ² per 1 m ^{2 of the} silver halide color photographic light-sensitive material.
0-60 ml, the silver halide color photographic light-sensitive material comprises a support and a blue dye-sensitive silver halide emulsion layer containing a yellow dye-forming coupler and a green light-sensitive silver halide emulsion layer containing a magenta dye-forming coupler. , A cyan dye-forming coupler-containing red light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer, each having at least one photographic constituent layer. The compound represented by (II) is added in an amount of 1.0 mg / m ² to 100 mg / m ² and 0.1 mg, respectively.
/ M ² to 5.0 mg / m ² is added, and the residual amount of the compound represented by the general formula (I) is 0.5 mg / m in a period of 1 week to 6 months after the production of the light-sensitive material. ² to 5
A silver halide color photographic light-sensitive material containing 0 mg / m ² of a silver halide emulsion having a silver chloride content of 90 mol% or more in at least one of the light-sensitive silver halide emulsion layers.

(9) The silver halide color photographic light-sensitive material according to the above (8), wherein the compound represented by the general formula (I) is a compound represented by the following general formula (IA). material.

[0025]

[Chemical 6]

(In the general formula (IA), R ¹ and R ² may be the same or different from each other, and R ¹ and R ² in the general formula (I) are respectively the same.
Represents the same meaning as ¹ and R ² . X represents an atomic group necessary for forming a 5- or 6-membered ring in cooperation with two vinyl carbon atoms substituted by R ¹ and R ² and a carbonyl carbon atom. )

(10) The silver halide color photographic light-sensitive material according to the above (8), wherein the compound represented by the general formula (I) is a compound represented by the following general formula (IB). material.

[0028]

[Chemical 7]

(In the general formula (IB), R ¹ and R ² may be the same or different and each has the same meaning as R ¹ and R ² in the general formula (I). R ⁹ and R ^{2 10} , R ¹¹ and R ¹² may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a hydroxyl group, a carboxy group, a sulfo group or an alkoxy group. Group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl Group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamido Group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group.)

(11) The silver halide color photographic light-sensitive material according to the above (8), wherein the compound represented by the general formula (I) is a compound represented by the following general formula (IC). material.

[0031]

[Chemical 8]

(In the general formula (IC), R ¹³ and R ¹⁴ may be the same or different and represent a hydrogen atom or an alkyl group. R ¹³ and R ¹⁴ may together form a ring. .
When forming a ring, the ring formed together with the nitrogen atom when R ¹³ and R ¹⁴ are combined is limited to a saturated ring. R ¹⁵ has 1 carbon atom
4 represents a substituted or unsubstituted alkyl group. R ¹⁶
Represents a hydrogen atom or a hydroxyl group. )

(12) Any of the above (8) to (11), characterized in that the silver halide color photographic light-sensitive material contains a hardening agent represented by the general formula (H-II). The silver halide color photographic light-sensitive material as described in 1.

(13) In any one of the above (8) to (12), wherein the total coated silver amount of the silver halide color photographic light-sensitive material is 0.50 to 0.20 g / m ^2. The described silver halide color photographic light-sensitive material.

(14) A silver halide emulsion having a silver chloride content of 90 mol% or more and a metal complex represented by the general formula (III) in at least one of the light-sensitive silver halide emulsion layers. (8), which is characterized in that
The silver halide color photographic light-sensitive material as described in any of (13).

(15) In the process of producing the silver halide color photographic light-sensitive material, the total amount of the compound represented by the general formula (I) added is 1.0 mg / m ² to 100 mg / m ^2.
The hardener is added to the coating solution added so that 50% or more of the total amount of the hardener coexists with the compound represented by the general formula (I) in the coating solution. The silver halide color photographic light-sensitive material as described in any of (8) to (14) above, which is not used. (16) At least one of the photosensitive silver halide emulsion layers has a silver chloride content of 90 mol% or more, and [IrCl
_The silver halide color photographic light-sensitive material as described in any of (8) to (15) above, which comprises a silver halide emulsion containing ₅ (5-methylazol)] ^2- .

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
In the image forming method of the present invention, a silver halide color photographic light-sensitive material is imagewise exposed and then developed to form an image.

First, a silver halide color photographic light-sensitive material is imagewise exposed on the basis of image information. As an exposure method, a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a semiconductor laser is used as an excitation light source. A digital scanning exposure method using monochromatic high-density light such as a second harmonic light emitting source (SHG) combining a solid-state laser and a nonlinear optical crystal is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) combining a semiconductor laser or a solid-state laser with a nonlinear optical crystal. In particular, it is preferable to use a semiconductor laser in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The maximum wavelength of the spectral sensitivity of the photosensitive material can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG obtained by combining a semiconductor laser with a nonlinear optical crystal
In the light source, the oscillation wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three wavelength regions of blue, green and red. When the exposure time per pixel in such scanning exposure is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ⁻³ seconds or less, more preferably 10 ^−4.
Seconds or less, more preferably 10 ⁻⁶ seconds or less.

As a semiconductor laser light source, specifically, a blue semiconductor laser (2001) having a wavelength of 430 to 450 nm is used.
March, Nichia presentation at the 48th Joint Lecture on Applied Physics), a semiconductor laser (oscillation wavelength: about 940 nm) with LiNbO ₃ S having a waveguide-like inversion domain structure.
470nm blue laser and semiconductor laser (wavelength: about 1060)
nm) having a waveguide-like inversion domain structure
Approximately 53 wavelength converted by O ₃ SHG crystal
0 nm green laser, wavelength about 685 nm red semiconductor laser (Hitachi type No. HL6738MG), wavelength about 650 nm red semiconductor laser (Hitachi type No.
HL6501MG) and the like are preferably used.

In particular, it is preferable to perform imagewise exposure with coherent light of a blue laser having an oscillation wavelength of 430 to 460 nm, and among the blue lasers, it is particularly preferable to use a blue semiconductor laser.

Not limited to the scanning exposure method using these light sources, an exposure method used in a printing system using a normal negative printer or a scanning exposure method using a cathode ray (CRT) can be used. . A cathode ray tube exposure apparatus is simpler and more compact than an apparatus using a laser, and is low in cost. Moreover, the optical axis and color can be easily adjusted. For the cathode ray tube used for image exposure, various light-emitting bodies that emit light in the spectral region are used as necessary. For example, any one of a red light emitting body, a green light emitting body, and a blue light emitting body, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a fluorescent substance that emits light in a yellow, orange, violet, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

Further, when the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, That is, image signals of a plurality of colors may be input to the cathode ray tube to cause the tube surface to emit light. A method of sequentially inputting image signals for each color to sequentially emit light of each color and exposing through a film that cuts colors other than that color (area sequential exposure) may be adopted. Generally, the area sequential exposure is used. But,
Since a high-resolution cathode ray tube can be used, it is preferable for improving image quality.

Then, the imagewise exposed silver halide color photographic light-sensitive material is developed. For the developing treatment, a silver halide color photographic light-sensitive material is subjected to a color developing step using a color developing solution, a bleach-fixing step using a bleach-fixing solution, and a rinse solution (washing water and / or stabilizing solution).
Is included in the rinsing step (washing water and / or stabilizing step), and the silver halide color photographic light-sensitive material is subjected to development processing by being successively dipped in each processing solution in each step. These development processes are not limited to these, and auxiliary processes such as an intermediate water washing process and a neutralization process can be inserted between the processes. The bleach-fixing step is performed by one step using a bleach-fixing solution.

Each of these processing solutions is used while being replenished. In the present invention, the replenishing amount of the color developing solution is 20 to 60 ml, and preferably 20 to 50 ml per 1 m ² of the light-sensitive material. The replenishing amount of the bleach-fixing solution is preferably 25 ml to 45 ml and more preferably 25 to 40 ml per 1 m ² of the light-sensitive material. Further, the replenishing amount of the rinse liquid (washing water and / or stabilizing liquid) is preferably 50 ml to 1000 ml in the whole rinse liquid, and further replenished according to the area of the silver halide color photographic light-sensitive material to be developed. You can also

Here, the color development time (that is, the time for performing the color development step) is preferably 45 seconds or less, more preferably 30 seconds or less, further preferably 28 seconds or less, particularly preferably 25 seconds or less 6 seconds or more, Most preferably, it is 20 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time (that is, the time for performing the bleach-fixing step) is preferably 45 seconds or less, more preferably 30 seconds or less, and further preferably 25 seconds.
It is not more than 6 seconds and not more than 6 seconds, particularly preferably not more than 20 seconds and not less than 6 seconds. The rinsing (washing or stabilizing) time (that is, the time for performing the rinsing step) is preferably 90 seconds or less, more preferably 30 seconds or less, and further preferably 30 seconds or less and 6 seconds or more. The color developing time means the time from the time when the light-sensitive material enters the color developing solution to the time when it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic developing machine, etc., the time during which the photosensitive material is immersed in the color developing solution (so-called in-liquid time), and the photosensitive material leaves the color developing solution to bleach-fix in the next processing step. The color development time is the sum of the time during which the liquid is conveyed in the air (so-called air time). Similarly, the bleach-fixing time refers to the time from when the light-sensitive material enters the bleach-fixing solution until it enters the next washing or stabilizing bath. In addition, rinse (washing or stabilizing)
The time means a time (so-called in-liquid time) during which the light-sensitive material is in the rinsing liquid (washing or stabilizing liquid) and then in the liquid for the drying step.

The developing process is carried out while the silver halide color photographic light-sensitive material is conveyed by the conveying rollers. As the transportation method using the transportation rollers, for example, a method of guiding and transporting in a U shape in each processing liquid bath is suitably applied.
For example, the development processing system disclosed in FIG. 2 of JP-A-11-327109 can be applied to the present specification as it is. Further, in the transportation method using the transportation rollers, a crossover rack structure with a mixing prevention plate attached is preferable in order to shorten the crossover time between the processing liquid baths and prevent mixing of the processing liquids. Further, a squeeze roller for a photosensitive material described in JP-A-11-133564, a photosensitive material processing apparatus described in JP-A-11-327109, and JP-A-11-352655.
It is also preferred to use the processing racks described in the specification.

In the developing process, the effect of improving image unevenness is greater in a processor in which the photosensitive material is conveyed in each processing solution at a higher speed. For this reason, the conveying speed of the photosensitive material in each processing solution (particularly the color developing solution) is preferably a linear speed of 1.5 m / min or more because the effect of improving the image unevenness is further exhibited, and particularly 4.0 m / min. Minutes or more (preferably 4.
0 m / min or more and 20 m / min or less) is preferable because the effect of improving the image unevenness becomes more significant. In general, a processing machine with a higher transport speed has a larger number of processed sheets per unit time, and therefore the present invention is suitable for processing with a larger number of processed sheets per unit time.

The developed silver halide color photographic light-sensitive material is then subjected to a post-treatment such as a drying step. In the drying process, from the viewpoint of reducing the amount of water carried into the image film of the silver halide color photographic light-sensitive material, it is dried by absorbing the water with a squeeze roller or cloth immediately after the development process (rinsing process). It is also possible to hasten it. Further, as a matter of course, it is possible to accelerate the drying by increasing the temperature or changing the shape of the spray nozzle to increase the drying air. Furthermore, JP-A-3-
As described in Japanese Laid-Open Patent Publication No. 157650, the drying can be accelerated by adjusting the blowing angle of the drying air to the photosensitive material or removing the exhausted air.

In this way, an image is output on the silver halide color photographic light-sensitive material.

Other preferred embodiments of the image forming method of the present invention will be described below. The image forming method of the present invention,
It can be preferably used in combination with the exposure and development system described in the following publicly known materials. Examples of the developing system include an automatic printing and developing system described in JP-A-10-333253, and JP-A-2000-102.
Japanese Patent Laid-Open No. 11-2 / 1999.
Recording system including the image reading device described in Japanese Patent No. 15312, Japanese Patent Laid-Open No. 11-88619, and Japanese Patent Laid-Open No. 10-8619.
-202950, an exposure system comprising a color image recording system, a digital photo print system including a remote diagnosis system described in JP-A-10-210206, and US Pat. No. 6,297,873B1. The photo printing system including the image recording device of

The scanning exposure method is described in detail in the patents listed in Table 1 below.

Further, in imagewise exposure, US Pat.
It is preferable to use the band stop filter described in the specification of No. 80,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. Furthermore, European Patent EP0789270A1 and EP0789480.
As described in the A1 specification, before the image information is given, a yellow microdot pattern is pre-exposed in advance,
Copying restrictions may be applied.

Further, in the developing process, Japanese Patent Laid-Open No. 2072/1990 is used.
No. 50, page 26, lower right column, line 1 to page 34, upper right column, line 9, and JP-A-4-97355, page 5, upper left column 1
The processing materials and processing methods described in line 7 to page 18, lower right column, line 20 can be preferably applied. As the preservative used in this developer, compounds described in the patents listed in Table 1 below are preferably used.

Typically, as a color development processing, a minilab "PP350" manufactured by Fuji Photo Film Co., Ltd. and CP48S chemical as a processing agent are used, and a light-sensitive material is subjected to imagewise exposure from a negative film having an average density to prepare a color development replenisher. There is a method in which processing is performed with a processing solution which has been continuously processed until the capacity becomes twice the capacity of the color developing tank.

The chemical of the treating agent may be CP47L manufactured by Fuji Photo Film Co., Ltd.

Hereinafter, a silver halide color light-sensitive material (hereinafter referred to as a light-sensitive material) applied to the image forming method of the present invention.
Will be described (silver halide color photographic light-sensitive material of the present invention).

The light-sensitive material comprises, on a support, a blue light-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a green light-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and a red light-sensitive halogen containing a cyan dye-forming coupler. It has a photographic constituent layer comprising at least one silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer. The silver halide emulsion layer containing the yellow dye-forming coupler is a yellow color-forming layer, the silver halide emulsion layer containing the magenta dye-forming coupler is a magenta color-forming layer, and the silver halide emulsion containing the cyan dye-forming coupler. The emulsion layer functions as a cyan coloring layer. The silver halide emulsion contained in each of the yellow color forming layer, the magenta color forming layer and the cyan color forming layer is sensitive to light in different wavelength regions (for example, light in blue region, green region and red region). It is preferable to have

The light-sensitive material may have an antihalation layer, an intermediate layer and a coloring layer as a non-photosensitive hydrophilic colloid layer described later, if desired, in addition to the yellow coloring layer, the magenta coloring layer and the cyan coloring layer. Good.

The light-sensitive material is subjected to the above-mentioned exposure / development treatment to obtain a compound represented by the following general formula (I) and the following general formula (II) in the production process in order to obtain high quality and stable performance. Each of them is added in a predetermined amount, and at least one of the photosensitive silver halide emulsion layers contains a silver halide emulsion having a silver chloride content of 90 mol% or more.

The compound represented by formula (I) will be described.

[0062]

[Chemical 9]

In formula (I), Y represents a carbon atom. Z
Represents a carbon atom. R ¹ and R ² may be the same or different and each is a hydroxyl group, amino group, alkylamino group, anilino group, heterocyclic amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, heterocyclic sulfonyl group. It represents an amino group, an alkoxycarbonylamino group, a carbamoylamino group, a mercapto group, an alkylthio group, an arylthio group, or a heterocyclic thio group. The alkylamino group has 1 to 40 carbon atoms,
Preferably, it is an alkylamino group having 1 to 22 carbon atoms, for example, dimethylamino, diethylamino, 2-hydroxyethylamino, octylamino, 3- (2,5-di-t
-Amylphenoxy) propylamino, piperidino, morpholino, pyrrolidino. The anilino group is an anilino group having 6 to 24 carbon atoms, and examples thereof include anilino, m-nitroanilino, and N-methylanilino. The heterocyclic amino group is a 5-membered or 6-membered saturated or unsaturated heterocyclic amino group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the hetero ring constituting the ring. The number of atoms and the number of elements may be one or more, for example, 1-phenyltetrazolyl-5-amino, 2
-Tetrahydropyranylamino, 2-pyridylamino,
2-thiazolylamino. The acylamino group is an acylamino group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include acetylamino, 2-methoxypropionylamino, p-nitrobenzoylamino, and 2-ethylhexanoylamino. The alkylsulfonylamino group has 1 to 40 carbon atoms, preferably 1 to 1 carbon atoms.
22 alkylsulfonylamino groups such as methanesulfonylamino, hexadecanesulfonylamino, 2-
Acetylaminoethanesulfonylamino and 2-methoxyethanesulfonylamino. The arylsulfonylamino group is an arylsulfonylamino group having 6 to 24 carbon atoms, such as p-toluenesulfonylamino, 5-
It is t-octyl-2-octyloxybenzenesulfonylamino. The heterocyclic sulfonylamino group is a 5-membered or 6-membered saturated or unsaturated heterocyclic sulfonylamino group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms and constitutes a ring. The number of heteroatoms and the kinds of elements to be used may be one or more, for example, thiazole-2-sulfonylamino. The alkoxycarbonylamino group has 2 to 40 carbon atoms,
Preferred is an alkoxycarbonylamino group having 2 to 22 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, and 3-methanesulfonylpropoxycarbonylamino. The carbamoylamino group is a carbamoylamino group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include carbamoylamino, N-methylcarbamoylamino, N, N-diethylcarbamoylamino and N-2-methanesulfonamidoethyl. It is carbamoylamino. Alkylthio group has 1 carbon
To 40, preferably an alkylthio group having 1 to 22 carbon atoms, and examples thereof include methylthio, ethylthio and 2-phenoxyethylthio. Arylthio group has 6 to 24 carbon atoms
An arylthio group of, for example, phenylthio, 2-
Carboxyphenylthio and 4-cyanophenylthio. As the heterocyclic thio group, an oxygen atom having 1 to 5 carbon atoms,
A 5-membered or 6-membered saturated or unsaturated heterocyclic thio group containing at least one nitrogen atom or a sulfur atom, wherein the number of heteroatoms constituting the ring and the kind of element are one or more; Also, for example, 2-benzothiazolylthio,
2-pyridylthio.

In the general formula (I), R ³ is a hydrogen atom, a group connecting Y to a carbon atom, a group connecting Y to an oxygen atom, Y
Represents a group connecting with a nitrogen atom. The group connecting Y with a carbon atom is an alkyl group, an aryl group, a heterocyclic group, a cyano group, a carboxy group, a carbamoyl group, an aryloxycarbonyl group, or an acyl group. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good. More specifically,

The alkyl group is a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl and 2-hydroxy. Ethyl, 3-hydroxypropyl, benzyl, 2-methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl. , 3-carbamoylpropyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, n-hexyl, 2-hydroxypropyl,
4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-carbamoylaminobutyl, 4-carbamoylbutyl, 2-carbamoyl-1-methylethyl and 4-nitrobutyl.
The aryl group is an aryl group having 6 to 24 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocyclic ring containing 1 or more oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The number of the elements may be one or more, and examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl and pyrazolyl. Carbamoyl group has 1 to 4 carbon atoms
0, preferably a carbamoyl group having 1 to 22 carbon atoms, such as carbamoyl, N, N-dimethylcarbamoyl, N
-Ethylcarbamoyl. The aryloxycarbonyl group is an aryloxycarbonyl group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonyl, 2-methylphenoxycarbonyl, and 4-acetamidophenoxycarbonyl. The acyl group is an acyl group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include acetyl, benzoyl and 4-chlorobenzoyl.

The group connecting Y with an oxygen atom is an alkoxy group, an aryloxy group or a silyloxy group.
These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good. More specifically, the alkoxy group is an alkoxy group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include methoxy, ethoxy, 2-methoxyethoxy, and 2-methanesulfonylethoxy. The aryloxy group is an aryloxy group having 6 to 24 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy and m- (3
-Hydroxypropionamido) phenoxy. The silyloxy group is a silyloxy group having 3 to 40 carbon atoms, preferably 3 to 22 carbon atoms, and examples thereof include trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy. The group connecting Y with a nitrogen atom is an amino group, an alkylamino group, or an anilino group. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good. More specifically, the alkylamino group is an alkylamino group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include dimethylamino, diethylamino and 2-hydroxyethylamino. The anilino group is an anilino group having 6 to 24 carbon atoms, and examples thereof include anilino, m-nitroanilino, and N-methylanilino.

In the general formula (I), R ⁴ is a hydrogen atom, a group connecting with Z and a carbon atom, a group connecting with Z and an oxygen atom, Z
Represents a group connecting with a nitrogen atom. The details are synonymous with R ³ .

In the general formula (I), R ³ and R ⁴ may combine with each other to form a ring. In the compound represented by the general formula (I), it is preferable that R ³ and R ⁴ cooperate with each other to form a ring, and among them, the compound represented by the following general formula (IA) is preferable.

[0069]

[Chemical 10]

[0070] In the general formula (IA), R ¹ and R ² may be the same or different from each other, each in the general formula (I) R ¹
And R ² have the same meaning. X represents an atomic group necessary for forming a 5- or 6-membered ring in cooperation with two vinyl carbon atoms substituted by R ¹ and R ² and a carbonyl carbon atom.

The general formula (IA) will be described in more detail. In formula (IA), R ¹ and R ² may be the same or different and each has the same meaning as described above. X together with two vinyl carbon atoms substituted by R ¹ and R ² and a carbonyl carbon atom constitute a 5- or 6-membered ring. The 5- or 6-membered ring may be a heterocyclic ring in which the element constituting the ring itself may be only a carbon atom or an oxygen atom, a nitrogen atom, a sulfur atom or the like in addition to the carbon atom. Specific examples of the atomic group represented by ^{X, -O -, - CR 5} (R 6) -,
^{-C (R 7) =, -} C (= O) -, - N (R 8) -, - N
=, -S- can be mentioned.

Here, R ⁵ and R ⁶ may be the same or different and each is a hydrogen atom, a halogen atom, an alkyl group,
Aryl group, heterocyclic group, cyano group, nitro group, hydroxyl group, carboxy group, sulfo group, alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group , Alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, Heterocyclic thio group, sulfinyl group, phosphonyl group,
It represents an aryloxycarbonyl group or an acyl group. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good. R ⁷ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxy group, a sulfo group, a carbamoyl group, a sulfamoyl group, a sulfonyl group or an acyl group. These are alkyl groups, alkenyl groups, alkynyl groups, aryl groups, hydroxyl groups, nitro groups, cyano groups, halogen atoms or other oxygen atoms, nitrogen atoms,
It may be substituted with a substituent formed by a sulfur atom or a carbon atom. R ⁸ is an alkyl group, an aryl group,
Heterocyclic group, hydroxyl group, alkoxy group, aryloxy group, acylamino group, amino group, alkylamino group, anilino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group, sulfamoyl group , A sulfonyl group, an aryloxycarbonylamino group, an imide group, an aryloxycarbonyl group, and an acyl group. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good.

Each group represented by R ⁵ , R ⁶ , R ⁷ and R ⁸ will be described in more detail. The halogen atom is, for example, a fluorine atom or a chlorine atom. Alkyl group has 1 to 4 carbon atoms
0, preferably a linear, branched or cyclic alkyl group having 1 to 22 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, t-butyl, 2-hydroxyethyl, 3-hydroxypropyl, benzyl, 2- Methanesulfonamidoethyl, 3-methanesulfonamidopropyl, 2-methanesulfonylethyl, 2-methoxyethyl, cyclopentyl, 2-acetamidoethyl, 2-carboxyethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 2,3-dihydroxy. Propyl, 3,
4-dihydroxybutyl, n-hexyl, 2-hydroxypropyl, 4-hydroxybutyl, 2-carbamoylaminoethyl, 3-carbamoylaminopropyl, 4-
Carbamoylaminobutyl, 4-carbamoylbutyl,
2-carbamoyl-1-methylethyl and 4-nitrobutyl.

The aryl group is an aryl group having 6 to 24 carbon atoms, and examples thereof include phenyl, naphthyl and p-methoxyphenyl. The heterocyclic group is a 5-membered or 6-membered saturated or unsaturated heterocyclic ring containing 1 or more oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, and the number of heteroatoms constituting the ring. The number of the elements may be one or more, and examples thereof include 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzotriazolyl, imidazolyl and pyrazolyl. The alkoxy group is an alkoxy group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include methoxy, ethoxy, 2-methoxyethoxy, and 2-methanesulfonylethoxy. The aryloxy group is an aryloxy group having 6 to 24 carbon atoms, and examples thereof include phenoxy, p-methoxyphenoxy and m- (3
-Hydroxypropionamido) phenoxy. The acylamino group is an acylamino group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, for example, acetamide,
2-methoxypropionamide and p-nitrobenzoylamide.

The alkylamino group has 1 to 4 carbon atoms.
0, preferably an alkylamino group having 1 to 22 carbon atoms, such as dimethylamino, diethylamino and 2-hydroxyethylamino. Anilino group has 6 to 6 carbon atoms
The 24 anilino groups are, for example, anilino, m-nitroanilino, and N-methylanilino. The ureido group is a ureido group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include ureido, methylureido, N, N-diethylureido, and 2-metalsulfonamidoethylureido.

The sulfamoylamino group has 0 carbon atoms.
-40, preferably a C2-C22 sulfamoylamino group, for example, dimethylsulfamoylamino, methylsulfamoylamino, 2-methoxyethylsulfamoylamino. Alkylthio group has 1 carbon
To 40, preferably an alkylthio group having 1 to 22 carbon atoms, and examples thereof include methylthio, ethylthio and 2-phenoxyethylthio. Arylthio group has 6 to 24 carbon atoms
Arylthio groups of, for example, phenylthio, 2,
-Carboxyphenylthio and 4-cyanophenylthio. 2 carbon atoms as the alkoxycarbonylamino group
To 40, preferably an alkoxycarbonylamino group having 2 to 22 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, and 3-methanesulfonylpropoxycarbonylamino.

The sulfonamide group has 1 to 4 carbon atoms.
0, preferably a sulfonamide group having 1 to 22 carbon atoms, such as methanesulfonamide, p-toluenesulfonamide, and 2-methoxyethanesulfonamide. The carbamoyl group is a carbamoyl group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, for example, carbamoyl,
They are N, N-dimethylcarbamoyl and N-ethylcarbamoyl. The sulfamoyl group has 0 to 40 carbon atoms,
Preferably, it is a sulfamoyl group having 0 to 22 carbon atoms, and examples thereof include sulfamoyl, dimethylsulfamoyl, and ethylsulfamoyl. C1 as a sulfonyl group
To 40, preferably an aliphatic or aromatic sulfonyl group having 1 to 22 carbon atoms, for example, methanesulfonyl,
They are ethanesulfonyl, 2-chloroethanesulfonyl, benzenesulfonyl and p-toluenesulfonyl. The alkoxycarbonyl group is an alkoxycarbonyl group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, for example,
Methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl. The heterocyclic oxy group is a 5-membered or 6-membered saturated or unsaturated heterocyclic oxy group having at least one oxygen atom, nitrogen atom, or sulfur atom having 1 to 5 carbon atoms, which is a hetero ring constituting a ring. The number of atoms and the number of elements may be one or more, and examples thereof include 1-phenyltetrazolyl-5-oxy, 2-tetrahydropyranyloxy, and 2-pyridyloxy.

The azo group is an aromatic azo group having 6 to 40 carbon atoms, preferably 6 to 22 carbon atoms, for example, phenylazo, 2-hydroxy-4-propanoylphenylazo,
They are 4-sulfophenylazo and 4-methylimidazolylazo. The acyloxy group is an acyloxy group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include acetoxy, benzoyloxy, and 4-hydroxybutanoyloxy. Carbamoyloxy group has 1 carbon atom
-40, preferably a carbamoyloxy group having 1 to 22 carbon atoms, such as N, N-dimethylcarbamoyloxy,
They are N-methylcarbamoyloxy and N-phenylcarbamoyloxy.

The silyl group is a silyl group having 3 to 40 carbon atoms, preferably 3 to 22 carbon atoms, and examples thereof include trimethylsilyl, isopropyldiethylsilyl and t-butyldimethylsilyl. The silyloxy group has 3 to 4 carbon atoms
0, preferably a silyloxy group having 3 to 22 carbon atoms, such as trimethylsilyloxy, triethylsilyloxy and diisopropylethylsilyloxy. The aryloxycarbonylamino group is an aryloxycarbonylamino group having 7 to 24 carbon atoms, and examples thereof include phenoxycarbonylamino, 4-cyanophenoxycarbonylamino, and 2,6-dimethoxyphenoxycarbonylamino. The imide group is an imide group having 4 to 40 carbon atoms, and examples thereof include N-succinimide and N-phthalimide. As the heterocyclic thio group, an oxygen atom having 1 to 5 carbon atoms,
A 5-membered or 6-membered saturated or unsaturated heterocyclic thio group containing at least one nitrogen atom or a sulfur atom, wherein the number of heteroatoms constituting the ring and the kind of element are one or more; Also, for example, 2-benzothiazolylthio,
2-pyridylthio.

The sulfinyl group has 1 to 40 carbon atoms,
Preferably, it is an aliphatic or aromatic sulfinyl group having 1 to 22 carbon atoms, such as methanesulfinyl, benzenesulfinyl and ethanesulfinyl. The phosphonyl group is an aliphatic or aromatic phosphonyl group having 2 to 40 carbon atoms, preferably 2 to 22 carbon atoms, and examples thereof include methoxyphosphonyl, ethoxyphosphonyl, and phenoxyphosphonyl. The aryloxycarbonyl group has 7 to 7 carbon atoms.
24 aryloxycarbonyl groups such as phenoxycarbonyl, 2-methylphenoxycarbonyl, 4-
It is acetamidophenoxycarbonyl. The acyl group is an acyl group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, and examples thereof include acetyl, benzoyl and 4-chlorobenzoyl.

In the general formula (IA), the 5- or 6-membered ring constituted by two vinyl carbon atoms substituted by X and R ¹ and R ² and a carbonyl carbon atom is saturated or non-substituted. The saturated ring may be condensed. Specific examples of the 5- or 6-membered ring formed by the two carbonyl carbon atoms substituted by X and R ¹ and R ² and the carbonyl carbon atom include a furanone ring, a dihydropyrone ring, a pyranone ring, and cyclo. Pentenone ring, cyclohexenone ring, pyrrolinone ring,
Examples thereof include a 1,5-dihydropyrrole-2-one ring, a pyrazolone ring, a pyridone ring, an azacyclohexanone ring, and a uracil ring.

Among the compounds represented by the general formula (IA), the compound represented by the general formula (IB) is preferable.

[0083]

[Chemical 11]

In the general formula (IB), R ¹ and R ² may be the same or different from each other, and R ¹ and R ² in the general formula (I) are respectively the same.
Represents the same meaning as ¹ and R ² . R ⁹ , R ¹⁰ , R ¹¹ and R ¹²
May be the same as or different from each other, and each has the general formula (I
It has the same meaning as R ⁵ described in A).

R ¹ , R ² , R ⁹ in the general formula (IB),
Preferred combinations of R ¹⁰ , R ¹¹ and R ¹² will be described below. R ^1, R ² are each a hydroxyl group may be the same or different from each other, an amino group, an alkylamino group, an anilino ^{group, R 9, R 1 0,} R 11, R 12 are either the same or different from each other However, a combination in which each is a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group, a carboxy group, a sulfo group or an alkoxy group is preferable. These may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents formed by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. Good. The compound represented by the following general formula (IC) is more preferable as the general formula (IB).

[0086]

[Chemical 12]

In formula (IC), R ¹³ and R ¹⁴ may be the same or different and each represents a hydrogen atom or an alkyl group. R ¹³ and R ¹⁴ may together form a ring. When forming a ring, the ring formed together with the nitrogen atom when R ¹³ and R ¹⁴ are combined is limited to a saturated ring. R ¹⁵ represents a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R ¹⁶ represents a hydrogen atom or a hydroxyl group. General formula (IC)
The number of carbon atoms of the compound represented by is preferably 25 or less.

Preferred specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0089]

[Chemical 13]

[0090]

[Chemical 14]

[0091]

[Chemical 15]

The compound represented by the general formula (I) is described in US Pat. No. 2,936,308, Journal of American Chemical Society, Vol. 75, p. 316 (19).
53), Synthesis 4, Vol. 176 (1972).

The compounds represented by the general formula (I) can be used alone or in combination of two or more kinds.

The compound represented by formula (I) can be used in any layer in the light-sensitive material. That is, a photosensitive layer (blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, red-sensitive silver halide emulsion layer), non-photosensitive layer (eg protective layer, non-photosensitive fine grain silver halide emulsion layer,
It can be used in any of an intermediate layer, a filter layer, an undercoat layer and an antihalation layer), but is preferably used in an emulsion layer.

The compound represented by the general formula (I) has a storability of the light-sensitive material and an unevenness of an image obtained by processing the light-sensitive material, and is 1.0 in the process of manufacturing the light-sensitive material.
It has to be added in an amount of from 100 mg / m ² to 100 mg / m ² , and from 1.5 mg / m ² to 90 mg / m ²
Is preferable, and it is more preferable that 200 mg to 50 g is added per mol of silver halide in the light-sensitive material. The residual amount of the compound represented by formula (I) is preferably 0.5 mg / m ² to 50 mg / m ² in the period of 1 week to 6 months after the production of the light-sensitive material, and 0.6 mg / M ² to 48 mg / m ² , more preferably 100 mg to 25 g per mol of silver halide in the light-sensitive material.
The period of 1 week to 6 months after the production of the light-sensitive material is generally the period during which the light-sensitive material is actually exposed and developed. That is, since the photosensitive material is manufactured by applying the coating solution, the photosensitive material is actually exposed / developed because the photosensitive material is subjected to the steps of cutting into a desired size, packaging and transportation. It is about 6 months from a week. Although it may be exposed and developed after a longer period of time, taking the color print market as an example, it is a special case when a long period of time after 6 months has passed, and most of the It is developed.

The compound represented by formula (I) can be added at any time during the production of the light-sensitive material (silver halide grain formation, physical ripening, chemical ripening, during coating solution preparation, etc.). However, it is preferable to add it at least during the preparation of the coating liquid, or it may be added during the preparation of a plurality of coating liquids. It is also possible to add in multiple times during these steps. For compounds that are more soluble at higher or lower pH when dissolved in water,
It may be added at high or low pH and added. Regarding the method of adding the compound represented by the general formula (I), they may be added directly, or may be added by dissolving them in a water-soluble solvent such as water, methanol or ethanol or a mixed solvent thereof. Alternatively, they may be added by emulsion dispersion.

Particularly, the compound represented by the general formula (I) is
It is preferable to add it after dissolving in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof.

Here, the residual amount of the compound represented by the general formula (I) is 20 at 35 ° C. and 45% RH in the dark.
Measured after being stored for a day. Since the residual amount of the compound represented by the general formula (I) in the light-sensitive material stored under this condition is almost the same as the residual amount after 6 months storage, this condition can be adopted as the accelerated test condition.

On the other hand, the residual amount of the compound represented by the general formula (I) is measured by the reverse phase high performance liquid chromatogram (reverse phase HPLC) method as follows, for example, Tosoh Corporation.
It can be measured under the following conditions using the high-thickness gradient basic system 1. Regarding the reversed-phase high performance liquid chromatogram method, specifically, "REVERSED-P
HASE HIGH-PERFORMANCE LIQ
UID CHROMATO GRAPHY "John
Wiley & Sons, Inc. (Published in 1982). -Extraction Conditions- The photosensitive material 3.5 x 15 cm was extracted with 4.0 ml of pure water (dark room, ultrasonic wave was applied for 5 minutes). 50 μl of extract is added to H
Injection into PLC measuring device. -HPLC condition-Column: Capcellpak C18 manufactured by Shiseido Co., Ltd.
UG-120 * (A) and (B) were adjusted to pH 7 by adding tetrahydrogen n-butylammonium phosphate. Eluent flow rate: 1.0 ml / min ((A) + (B)) Gradient: Time (min) 0 15 20 25 (B) Concentration (%) 10 10 90 90 Detection: UV absorbance measurement (310 nm) Other conditions: It is possible to measure the standard solution of the compound to be measured in advance, create a calibration curve of the detected amount and concentration, obtain the concentration in the extract, and further calculate the content per unit area of the photosensitive material. it can.

The compound represented by formula (I) is necessary for improving the storage stability of the light-sensitive material. On the other hand, for example, the use of sulfo-substituted catechols and hydroquinones described in JP-A-11-143011, which is a conventionally known finding, also improves the storage stability, but the effect is insufficient, and at the same time image unevenness occurs. It ’s going to get a lot worse,
In the present invention, the compound represented by formula (I) is required.

The compound represented by the following general formula (II) will be described.

[0102]

[Chemical 16]

In the general formula (II), M represents a cation, and hydrogen ion, alkali metal ion (eg sodium ion, potassium ion), ammonium ion, 4-substituted ammonium ion (eg tetramethylammonium ion, tetraethylammonium ion) and Silver ions are preferred.

In the general formula (II), R represents a group having an atomic weight of 50 or less or a total atomic weight of 50 or less, and specific examples thereof include a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group (a methyl group, an ethyl group). , Propyl group), alkoxy groups (methoxy group, ethoxy group), carboxyl group, hydroxyl group, amino group, and these groups have a total atomic weight of 5
You may have a substituent in the range of 0 or less. Preferred as R are a hydrogen atom, a chlorine atom and a methyl group, and a hydrogen atom is more preferred.

The compound represented by the general formula (II) is added in an amount of 0.1 m in the process of producing a light-sensitive material in order to suppress the storability of the light-sensitive material and the unevenness of an image obtained by processing the light-sensitive material.
It is necessary to add g / m ² to 5.0 mg / m ^2, and 0.12 mg / m ² to 4.9 mg / m ²
It is more preferable to add. Also, from 1 mg to 2700 m per mol of silver halide contained in the light-sensitive material.
g is preferably added. The compound of the general formula (II) can be added at any time during the production of the light-sensitive material (silver halide grain formation, physical ripening, chemical ripening, during preparation of coating solution, etc.), but at least preparation of coating solution. It is preferable to add it to the inside, and it is also possible to separately add to a plurality of coating liquids being prepared.

The compound represented by the general formula (II) can be used in any layer in the light-sensitive material. That is, a photosensitive layer (blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, red-sensitive silver halide emulsion layer), non-photosensitive layer (eg protective layer, non-photosensitive fine grain silver halide emulsion layer,
It can be used in any of an intermediate layer, a filter layer, an undercoat layer and an antihalation layer), but is preferably used in an emulsion layer.

In the compound represented by the general formula (II), the total atomic weight of the atoms represented by R or the atomic weight of the groups is 5
When it is larger than 0, the storage stability is deteriorated and the image unevenness is insufficiently suppressed.

The photosensitive material has a swelled film thickness of 10 μm to 20 μm in the color developing solution in the above color developing process in order to improve the image unevenness and to achieve both the development progress and the drying speed. 11 μm
˜19 μm, more preferably 12 μm-18
It is preferably μm. The swelled film thickness is measured by immersing the dried light-sensitive material in the color developing solution used in the color developing process under the temperature conditions in the case of actual processing, swelling and reaching a sufficient equilibrium state. Can be measured at. In the present invention, the swollen film thickness falls within the above range when the photosensitive material is actually subjected to color development processing from 1 week to 6 months after coating. In addition, there is no particular limitation for setting the swollen film thickness of the light-sensitive material in the above range, but for example, it is preferable to use a specific hardener as the hardener described later.

In order to obtain stable photographic performance, the light-sensitive material is provided with at least one of the following photosensitive silver halide emulsion layers in order to obtain stable photographic performance, especially when low-replenishment rapid processing (development processing) is performed by laser scanning exposure. It is preferable to contain at least one selected from the metal complexes represented by the formula (III).

Regarding the metal complex represented by the general formula (III),
Explain. General formula (III) [IrX^I _nL^I _(6-n)]^m- X in the general formula (III)^IIs a halogen ion or pseudohalo
Represents a gen ion. L ^IIs X^IAny ligand different from
Represent n represents an integer of 3 to 5. m is an integer from -4 to +1
Represents

In formula (III), X ^I is preferably fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, isocyanate ion, thiocyanate ion, hydroxide ion, nitrate ion, Nitrite ion or azide ion is preferred, and chloride ion and bromide ion are particularly preferred. L ^I is not particularly limited as long as it is an arbitrary ligand different from X ^I, and may be an inorganic compound or an organic compound, and may have a charge or no charge. Although it is good, it is preferably an uncharged inorganic compound or organic compound.

Among the metal complexes represented by the general formula (III), the metal complex represented by the following general formula (IIIA) is preferable. In the general formula _{^{(IIIA) [IrX IA n L}} IA (6-n)] m- formula (IIIA), X ^IA represents a halogen ion or a pseudohalogen ion. L ^IA represents any inorganic ligand different from X ^IA . n; represents an integer of 3 to 5. m is -4 to +
Represents an integer of 1.

In formula (IIIA), X ^IA is represented by formula (III)
Is the same as X ^I , and L ^IA is preferably water or OC.
N, ammonia, phosphine and carbonyl are preferable, and water is particularly preferable.

Among the metal complexes represented by the general formula (III), the metal complex represented by the following general formula (IIIB) is more preferable. In the general formula _{^{(IIIB) [IrX IB n L}} IB (6-n)] m- formula (IIIB), X ^IB represents a halogen ion or a pseudohalogen ion. L ^IB represents a ligand in which a chain or cyclic hydrocarbon has a mother structure or a part of carbon or hydrogen atoms of the mother structure is replaced with another atom or atomic group. n represents an integer of 3 to 5. m represents an integer of -4 to +1.

In the general formula (IIIB), X ^IB is the general formula (I)
Is the same as X ^I of, and L ^IB is a ligand in which a chain or cyclic hydrocarbon is a mother structure or a part of carbon atoms or hydrogen atoms of the mother structure is replaced with another atom or atomic group. However, cyanide ion is not included. A heterocyclic compound is preferable as L ^IB , more preferably a complex having a 5-membered ring compound as a ligand, and among the 5-membered ring compound, at least one nitrogen atom and at least one sulfur atom have a 5-membered ring skeleton structure. The compound contained therein is more preferable.

Among the metal complexes represented by the general formula (III), the metal complex represented by the following general formula (IIIC) is more preferable. General formula (IIIC) [IrX ^IC _n L ^IC _(6-n) ] ^{m-In the} general formula (IIIC), X ^IC represents a halogen ion or a pseudohalogen ion. L ^IC is a 5-membered ring ligand and represents a ligand containing at least one nitrogen atom and at least one sulfur atom in the ring skeleton. However, it may have an arbitrary substituent on a carbon atom in the ring skeleton. n represents an integer of 3 to 5. m represents an integer of -4 to +1.

In the general formula (IIIC), X ^IC is the general formula (III)
Is the same as X ^{I in (1) above,} and is preferably a compound having a thiadiazole skeleton as L ^ID . The optional substituent on the carbon atom in the ring skeleton in L ^IC is preferably a substituent having a smaller volume than the n-propyl group. As a substituent, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a formyl group, a thioformyl group, a hydroxyl group, a mercapto group,
Amino group, hydrazino group, azido group, nitro group, nitroso group, hydroxyamino group, carboxyl group, carbamoyl group, fluoro group, chloro group, bromo group and iodo group are preferable.

Among the metal complexes represented by the general formula (III), the metal complex represented by the following general formula (IIID) is particularly preferable.

General formula (IIID) [IrX ^ID _n L ^ID _(6-n) ] ^{m-In the} general formula (IIID), X ^ID represents a halogen ion or a pseudohalogen ion. L ^ID is a 5-membered ring ligand and represents a ligand containing at least two nitrogen atoms and at least one sulfur atom in the ring skeleton. However, it may have an arbitrary substituent on a carbon atom in the ring skeleton. n represents an integer of 3 to 5. m represents an integer of -4 to +1.

In the general formula (IIID), X ^ID is the general formula (III)
^Which is the same as X ^I and preferably has a thiadiazole as a skeleton as L ^ID , provided that a substituent other than hydrogen is bonded to a carbon atom in the compound. The optional substituent on the carbon atom in the ring skeleton in L ^ID is preferably halogen (fluorine, chlorine, bromine, iodine), methoxy group, ethoxy group, carboxyl group, methoxycarboxyl group, acyl group, acetyl group, chloro. Formyl group, mercapto group, methylthio group, thioformyl group, thiocarboxy group, dithiocarboxy group, sulfino group, sulfo group, sulfamoyl group, methylamino group, cyano group, isocyanato group, cyanato group, isocyanato group, thiocyanato group, isocyanato group , A hydroxyamino group, a hydroxyimino group, a carbamoyl group, a nitroso group, a nitro group, a hydrazino group, a hydrazono group or an azido group, more preferably a halogen (fluorine, chlorine, bromine, iodine), a chloroformyl group, a sulfino group. , Sulfo group, sulfamo Group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isocyanato group, hydroxyimino group, nitroso group, nitro group, or an azido group. Among them, chlorine, bromine, chloroformyl group, isocyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group and isocyanato group are particularly preferable. n is preferably 4 or 5, and m is preferably -2 or -1.

Preferred specific examples of the metal complex represented by the general formula (III) are shown below, but the invention is not limited thereto. [IrCl ₅ (H ₂ O)] ^2- [IrCl ₄ (H ₂ O) ₂ ] ^- [IrCl ₅ (H ₂ O)] ^- [IrCl ₄ (H ₂ O) ₂ ] ⁰ [IrCl ₅ (OH)] ^3- [IrCl ₄ (OH) ₂ ] ^2- [IrCl ₅ (OH)] ^2- [IrCl ₄ (OH) ₂ ] ^2- [IrCl ₅ (O)] ^4- [IrCl ₄ (O) ₂ ] ^5- [IrCl ₅ (O)] ^3- [IrCl ₄ (O) ₂ ] ^4- [IrBr ₅ (H ₂ O)] ^2- [IrBr ₄ (H ₂ O) ₂ ] ^- [IrBr ₅ (H ₂ O)] ^- [IrBr ₄ (H ₂ O) ₂ ] ⁰ [IrBr ₅ (OH)] ^3- [IrBr ₄ (OH) ₂ ] ^2- [IrBr ₅ (OH)] ^2- [IrBr ₄ (OH) ₂ ] ^2- [IrBr ₅ (O)] ^4- [IrBr ₄ (O) ₂ ] ^5- [IrBr ₅ (O)] ^3- [IrBr ₄ (O) ₂ ] ^4- [IrCl ₅ (OCN)] ^3- [IrBr ₅ (OCN)] ^3- [IrCl ₅ (thiazole)] ^2- [IrCl ₄ (thiazole) ₂ ] ^- [IrCl ₃ (thiazole) ₃ ] ⁰ [IrBr ₅ (thiazole)] ^2- [IrBr ₄ (thiazole) ₂ ] ^- [IrBr ₃ (thiazole) ₃ ] ⁰ [IrCl ₅ (5-methylthiazole)] ^2- [IrCl ₄ (5-methylthiazole) ₂ ] ^- [IrBr ₅ (5-methylthiazole)] ^2- [IrBr ₄ (5-methylthiazole) ) ₂ ] ^- [IrCl ₅ (5-chlorothiadizole)] ^2- [IrCl ₄ (5-chlorothiadizole) ₂ ] ^- [IrBr ₅ (5-chlorothiadizole)] ^2- [IrBr ₄ (5-chlorothiadizole) ₂ ] ^- [IrCl ₅ (2-chloro-5-fluorothiadiazole)] ^2- [IrCl ₄ (2-chloro-5-fluorothiadiazole) ₂ ] ^- [IrBr ₅ (2-c hloro-5-fluorothiadiazole)] ^2- [IrBr ₄ (2-chloro-5-fluorothiadiazole) ₂ ] ^- [IrCl ₅ (2-Bromo-5-chlorothiadiazole)] ^2- [IrCl ₄ (2-Bromo-5-chlorothiadiazole) ) ₂ ] ^- [IrBr ₅ (2-Bromo-5-chlorothiadiazole)] ^2- [IrBr ₄ (2-Bromo-5-chlorothiadiazole) ₂ ] ^-

Further, an iridium compound other than the metal complex represented by the general formula (III) can be further contained. As the iridium compound, a hexacoordinated complex having six ligands and iridium as a central metal is preferable because it can be uniformly incorporated into the silver halide crystal. As one preferable embodiment of iridium used in the present invention, a hexacoordinated complex having Ir as a central metal and having Cl, Br or I as a ligand is preferable, and Ir in which all six ligands are Cl, Br or I is A hexacoordination complex having a central metal is more preferable. In this case, Cl, Br or I may be mixed in the hexacoordinated complex. Cl, B
It is particularly preferable that the hexacoordination complex having Ir as a central metal and having r or I as a ligand is contained in the silver bromide-containing phase in order to obtain a hard gradation by exposure to high illuminance.

In the following, all 6 ligands were Cl, Br.
Further, specific examples of the hexacoordinated complex of Ir having Ir as a central metal will be given, but iridium that can be used in the present invention is not limited thereto. [IrCl ₆ ] ^2- [IrCl ₆ ] ^3- [IrBr ₆ ] ^2- [IrBr ₆ ] ^3- [IrI ₆ ] ^3-

It is also preferable to contain a metal complex represented by the following general formula (IV) in addition to the metal complex represented by the general formula (I).

The metal complex represented by the general formula (IV) will be described. General formula (IV) [MX ^II _n L ^II _(6-n) ] ^m-In general formula (IV), M is Cr, Mo, Re, Fe, Ru,
Represents Os, Co, Rh, Pd, or Pt. X ^II represents a halogen ion. L ^II represents any ligand different from X ^II . n represents an integer of 3 to 6. m represents an integer of -4 to +1.

Preferred examples of X ^II in the general formula (IV) include a fluoride ion, a chloride ion, a bromide ion, and an iodide ion, and among them, a chloride ion and a bromide ion are particularly preferred. L ^II may be an inorganic compound or an organic compound as long as it is an arbitrary different ligand, and may have a charge or no charge, but is an uncharged inorganic compound. It is preferable.
L ^II is preferably H ₂ 0, NO or NS.

Among the metal complexes represented by the general formula (IV), the metal complex represented by the following general formula (IVA) is preferable. General formula (IVA) [M ^IIA X ^IIA _n L ^IIA _(6-n) ] ^{m-in the} general formula (IVA), M ^IIA ; Re, Ru, Os, or R
represents h. X ^IIA represents a halogen ion. L ^IIA is M
^{When IIA} is Re, Ru or Os, it represents NO or NS, and when M ^IIA is Rh, it represents H ₂ O, OH or O. n
Represents an integer of 3 to 6. m represents an integer of -4 to +1.

In formula (IVA), X ^IIA is represented by formula (IV)
Same as X ^II .

Specific preferred examples of the metal complex represented by the general formula (IV) are shown below, but the invention is not limited thereto. [ReCl ₆ ] ^2- [ReCl ₅ (NO)] ^2- [RuCl ₆ ] ^2- [RuCl ₆ ] ^3- [RuCl ₅ (NO)] ^2- [RuCl ₅ (NS)] ^2- [RuBr ₅ (NS )] ^2- [OsCl ₆ ] ^4- [OsCl ₅ (NO)] ^2- [OsBr ₅ (NS)] ^2- [RhCl ₆ ] ^3- [RhCl ₅ (H ₂ O)] ^2- [RhCl ₄ (H ₂ O) ₂ ] ^- [RhBr ₆ ] ^3- [RhBr ₅ (H ₂ O)] ^2- [RhBr ₄ (H ₂ O) ₂ ] ^- [PdCl ₆ ] ^2- [PtCl ₆ ] ^2-

Here, the metal complexes represented by the general formulas (I) to (II) (including other iridium compounds) are anions, and when they form a salt with a cation, they form a counter cation in water. Those that are easily dissolved are preferred. Specifically, alkali metal ions such as sodium ion, potassium ion, rubidium ion, cesium ion and lithium ion, ammonium ion, and alkylammonium ion are preferable. These metal complexes should be used by dissolving them in a mixed solvent of water and an appropriate organic solvent that can be mixed with water (eg, alcohols, ethers, glycols, ketones, esters, amides, etc.). You can These iridium complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻³ mol, and preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻⁵ mol per mol of silver during grain formation. Most preferred.

The above metal complex is added directly to the reaction solution at the time of silver halide grain formation, or to an aqueous solution of a halide for forming silver halide grains, or a solution other than the above, to form a grain formation reaction. It is preferably incorporated into the silver halide grain by adding it to the solution. Further, it is also preferable to physically ripen fine particles in which an iridium complex has been incorporated into the grains and incorporate them into the silver halide grains. Further, these methods may be combined and contained in the silver halide grains.

When these metal complexes are incorporated into silver halide grains, they may be made to exist uniformly inside the grains. JP-A-4-208936 and JP-A-2-1252
As disclosed in JP-A-45-45 and JP-A-3-188437, it is also preferable that the layer is present only in the particle surface layer, and the complex is present only inside the particle and a layer not containing the complex is added to the particle surface. Is also preferable. Also, US Pat. Nos. 5,252,451 and 5,256,53
As disclosed in No. 0, it is also preferred to physically ripen the fine particles in which the complex is incorporated into the particles to modify the surface phase of the particles. Further, these methods may be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the above complex is contained, but a hexacoordinated complex in which all six ligands are Cl, Br or I with Ir as the central metal has a silver bromide concentration maximum part. It is preferable to contain it.

In addition to the above metal complexes, other metal ions can be doped inside and / or on the surface of the silver halide grains. The metal ion used is preferably a transition metal ion, among which iron, ruthenium, osmium, rhodium, lead, cadmium, or zinc is preferable. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion, thiocyanate, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thiol ion. It is preferable to use a nitrosyl ion, and it is also preferable to use a nitrosyl ion coordinated with any of the above-mentioned metal ions of iron, ruthenium, osmium, rhodium, lead, cadmium, or zinc. It is also preferably used in the molecule. Further, an organic compound can be used as the ligand, and preferred organic compounds include a chain compound having a main chain having 5 or less carbon atoms and / or a 5-membered or 6-membered heterocyclic compound. . More preferable organic compound is a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom to a metal, and particularly preferably furan,
Thiophene, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, triazole, furazan, pyran, pyridine, pyridazine, pyrimidine, pyrazine, and compounds having these compounds as a basic skeleton and substituents introduced into them are also included. preferable.

The combination of a metal ion and a ligand is preferably an iron ion or a ruthenium ion and a cyanide ion. In the present invention, it is preferable to use these compounds in combination. In these compounds, the cyanide ion preferably occupies the majority of the coordination numbers to the central metal iron or ruthenium, and the remaining coordination sites are thiocyan, ammonia, water, nitrosyl ion, dimethyl sulfoxide, pyridine, It is preferably populated with pyrazine or 4,4′-bipyridine. Most preferably, all six coordination sites of the central metal are occupied by cyanide ions to form a hexacyanoiron or hexacyanoruthenium complex. Complexes having these cyanide ions as ligands are added in an amount of 1 × 10 ⁻⁸ mol to 1 mol per 1 mol of silver during grain formation.
It is preferable to add ^{x10 -2} mol, and most preferable to add 1 x 10 ^-6 mol to 5 x 10 ^-4 mol. When ruthenium and osmium are the central metals, it is also preferable to use nitrosyl ion, thionitrosyl ion, or water molecule and chloride ion together as ligands. It is more preferable to form a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachloroaqua complex, and it is also preferable to form a hexachloro complex. These complexes are preferably added in an amount of 1 × 10 ⁻¹⁰ to 1 × 10 ⁻⁶ mol, and more preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁶ mol per mol of silver during grain formation. That is.

The silver halide emulsion will be described in detail below. The grain shape of the silver halide emulsion is not particularly limited,
A cubic or 14-sided crystal grain having substantially {100} faces (these may have rounded grain vertices and higher-order faces), an octahedral crystal grain, and a main surface of { 1
It is preferably composed of tabular grains having an aspect ratio of 2 or more and having a {00} plane or a {111} plane. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of particles. In the present invention, it is more preferable that the silver halide grains in all the image forming layers are cubic grains, tetradecahedral grains or tabular grains having an aspect ratio of 3 or more.

The silver halide emulsion must have a silver chloride content of 90 mol% or more, and from the viewpoint of rapid processability, the silver chloride content is preferably 93 mol% or more.
It is more preferably 5 mol% or more. The silver bromide content is preferably 0.1 to 7 mol% and more preferably 0.5 to 5 mol% because it has a high contrast and excellent latent image stability. The silver iodide content is preferably 0.02 to 1 mol% because of high sensitivity and high contrast under high illuminance exposure.
0.05 to 0.50 mol% is more preferable, and 0.07 to
Most preferred is 0.40 mol%. The silver halide grains contained in the silver halide emulsion are preferably silver iodobromochloride grains, and more preferably silver iodobromochloride grains having the above halogen composition. Further, the silver halide grains in all the image forming layers are preferably the silver halide grains of the present invention.

The silver halide emulsion (grain) preferably has a silver bromide-containing phase and / or a silver iodide-containing phase. Here, the silver bromide- or silver iodide-containing phase means a portion where the concentration of silver bromide or silver iodide is higher than that of the surrounding area.
The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings may change continuously or may change sharply. Such a silver bromide or silver iodide-containing phase is
A layer having a substantially constant concentration may be formed at a certain portion within the particle, or a local maximum point without spreading may be formed. The local silver bromide content of the silver bromide-containing phase is preferably 5 mol% or more, more preferably 10 to 80 mol%, and most preferably 15 to 50 mol%. The local silver iodide content of the silver iodide containing phase is 0.3.
It is preferably at least mol%, more preferably from 0.5 to 8 mol%, most preferably from 1 to 5 mol%. Further, such a silver bromide- or silver iodide-containing phase may be present in a plurality of layers in each grain,
Each may have a different silver bromide or silver iodide content, but each has at least one content phase.

It is important that the silver bromide-containing phase or silver iodide-containing phase of the silver halide emulsion is in a layer form so as to surround the grains. One of the preferred embodiments is that the silver bromide-containing phase or the silver iodide-containing phase formed in a layer surrounding the grains has a uniform concentration distribution in the orbiting direction of the grains in each phase. However, in the silver bromide-containing phase or the silver iodide-containing phase that is layered so as to surround the grain, the maximum or minimum point of the silver bromide or silver iodide concentration exists in the orbiting direction of the grain, and the concentration distribution May have. For example, when the layer has a silver bromide-containing phase or a silver iodide-containing phase near the surface of the grain so as to surround the grain, the concentration of silver bromide or silver iodide at the corner or edge of the grain is different from that on the main surface. There are cases. Also,
In addition to the silver bromide-containing phase and the silver iodide-containing phase that are layered so as to surround the grain, a silver bromide-containing phase or an iodide that does not completely surround the grain and exists in a specific part of the surface of the grain. There may be a silver halide containing phase.

When the silver halide emulsion contains a silver bromide-containing phase, the silver bromide-containing phase is preferably formed in layers so that the silver bromide-containing phase has a maximum silver bromide concentration inside the grain. When the silver halide emulsion contains a silver iodide-containing phase, the silver iodide-containing phase is preferably formed in layers so that the surface of the grain has a maximum silver iodide concentration.
Such a silver bromide-containing phase or a silver iodide-containing phase is composed of 3% or more and 30% or less of the grain volume in terms of increasing the local concentration with a smaller silver bromide or silver iodide content. It is preferable that the amount of silver is 3% or more and 15% or less.

The silver halide emulsion preferably contains both a silver bromide-containing phase and a silver iodide-containing phase. In that case, even if the silver bromide-containing phase and the silver iodide-containing phase are at the same location on the grain,
Although it may be at a different location, it is preferable to be at a different location from the viewpoint of facilitating control of particle formation. Further, the silver bromide-containing phase may contain silver iodide, and conversely, the silver iodide-containing phase may contain silver bromide. In general, the iodide added during the formation of high silver chloride grains is more likely to exude to the grain surface than bromide, so that the silver iodide-containing phase is likely to be formed in the vicinity of the grain surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase are at different positions in the grain, it is preferable that the silver bromide-containing phase is formed inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided further outside the silver iodide-containing phase near the grain surface.

The silver bromide content or the silver iodide content increases as the silver bromide-containing phase or the silver iodide-containing phase is formed inside the grain. There is a risk of impairing processability. Therefore, it is preferable that the silver bromide-containing phase and the silver iodide-containing phase are adjacent to each other in order to concentrate these functions for controlling the photographic effect near the surface in the grain. From these points, the silver bromide-containing phase is formed at any of the positions of 50% to 100% of the grain volume and the silver iodide-containing phase is at any of the positions of 85% to 100% of the grain volume measured from the inside. It is preferable to form a crab. The silver bromide-containing phase is 70% to 95% of the grain volume.
It is more preferable that the silver iodide-containing phase is formed at any position of 90% to 100% of the grain volume.

The introduction of the bromide or iodide ion to contain silver bromide or silver iodide in the silver halide emulsion may be carried out by adding a solution of bromide salt or iodide salt alone or by adding a solution of silver bromide or a solution of silver salt. A bromide salt or iodide salt solution may be added together with the addition of the chloride salt solution. In the latter case, the bromide salt or iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the bromide salt or iodide salt and the high chloride salt. The bromide salt or iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth bromide salt or iodide salt.
Alternatively, it can be introduced by cleaving bromide ion or iodide ion from the organic molecule described in US Pat. No. 5,389,508. Fine silver bromide grains or fine silver iodide grains can also be used as another bromide or iodide ion source.

The addition of the bromide salt or iodide salt solution is
The particle formation may be concentrated in one period, or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fog. When the iodide ion is introduced inside the emulsion grains, the increase in sensitivity is small. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 85%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. When the addition of the iodide salt solution is completed slightly inside the grain surface, an emulsion having higher sensitivity and lower fog can be obtained. On the other hand, the bromide salt solution is preferably added to the outside of 50% of the grain volume, more preferably outside of 70%.

The distribution of the bromide or iodide ion concentration in the grain in the depth direction was measured by etching / TOF-SIMS.
(Time of Flight-Secondary
ryIon Mass Spectrometry) method, for example, TRIFTII manufactured by Phi Evans
Type TOF-SIMS can be used for measurement. TOF-SI
Regarding the MS method, specifically, “Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectrometry” edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (1
999). Etching / TOF
When the emulsion grains are analyzed by the SIMS method, it can be analyzed that the iodide ions are exuded toward the grain surface even after the addition of the iodide salt solution is completed inside the grains. In the emulsion of the present invention, it is preferable that the iodide ion has a maximum concentration on the surface of the grain and the iodide ion concentration is attenuated toward the inner side in the analysis by the etching / TOF-SIMS method. It is preferable to have a maximum concentration inside. The local concentration of silver bromide can also be measured by an X-ray diffraction method if the silver bromide content is high to some extent.

The silver halide emulsion preferably comprises grains having a monodisperse grain size distribution. The variation coefficient of the spherical equivalent diameter of all grains of the silver halide emulsion is preferably 20% or less, more preferably 15% or less, and 1
It is more preferably 0% or less. The coefficient of variation of the sphere-equivalent diameter is expressed as a percentage of the standard deviation of the sphere-equivalent diameter of each particle with respect to the average of the sphere-equivalent diameters. At this time, the above monodisperse emulsions may be blended in the same layer for the purpose of obtaining a wide latitude, or a plurality of yellow, magenta or cyan image forming layers may be provided so that each layer has a different sphere equivalent diameter. It is also preferable to perform multi-layer coating using each of the above. In the present invention, the light-sensitive material may contain silver halide grains other than the silver halide grains defined in the present invention. Specifically, the silver halide grains defined in the present invention are the total projections of all grains. 50% or more of the area is preferably silver halide grains defined in the present invention, and 8
It is more preferably 0% or more. Here, in the present specification, the equivalent sphere diameter is represented by the diameter of a sphere having a volume equal to the volume of each particle.

The equivalent spherical diameter of the silver halide emulsion (grain) is
The silver halide grains in the yellow image forming layer are preferably 0.70 μm to 0.30 μm,
More preferably, it is 0.68 μm to 0.32 μm. The average spherical equivalent diameter of the silver halide grains in the magenta and cyan image forming layers is 0.40 μm to 0.20 μm, respectively.
Is preferable, and 0.38 μm to 0.22 μm is more preferable.

The sustained electron release time of the silver halide emulsion is 10
It is preferably between ^-5 and 10 seconds. Here, the term "electron sustained release time" refers to the time until a photoelectron generated in a silver halide crystal is trapped in an electron trap in the crystal and exposed again when the silver halide emulsion is exposed to light. . If the electronic controlled release time is shorter than 10 ^-5 seconds, it is difficult to obtain a high-sensitivity and high-contrast gradation in high-illuminance exposure. Cause The electron sustained release time is more preferably 10 ⁻⁴ to 10 seconds, most preferably 10 ⁻³ to 1 second.

The sustained electron release time can be measured by the double pulse photoconductivity method. A microwave photoconductivity method or a radio wave photoconductivity method is used to perform a first short-time exposure and then a second fixed short-time exposure. Electrons are trapped in the electron trap in the silver halide crystal by the first exposure, and when the second exposure is given immediately after that, the electron trap is clogged and the second photoconduction signal becomes large. If the two exposure intervals are set sufficiently and the electrons trapped in the electron trap have already been emitted in the first exposure, the photoconduction signal of the second emission returns to the original magnitude. If the exposure interval dependency of the second photoconductive signal intensity is taken by changing the exposure interval of two times, it becomes 2
It is possible to measure how the intensity of the photoconductive signal of the eye is decreasing. This represents the sustained release time of photoelectrons from the electron trap. The sustained release of electrons may continue to occur for a certain period of time after the exposure, but it is preferable that the sustained release is observed within 10 ⁻⁵ seconds to 10 seconds. 10 ^-4 seconds to 10
More preferably, sustained release is observed during 10 seconds, 10 ⁻³
More preferably, sustained release is observed between seconds and 1 second.

The silver halide emulsion is preferably subjected to gold sensitization known in the art. This is because the gold sensitization can increase the sensitivity of the emulsion and reduce fluctuations in photographic performance when scanning exposure is performed with a laser beam or the like. For gold sensitization, various inorganic gold compounds, gold (I) complexes having inorganic ligands and gold (I) compounds having organic ligands can be used. Examples of the inorganic gold compound include chloroauric acid or a salt thereof,
As the gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate compound such as potassium dithiocyanate (I) potassium or a compound such as a gold dithiosulfate compound such as trisodium dithiosulfate (I) sodium is used. it can.

Examples of the gold (I) compound having an organic ligand (organic compound) include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, for example, bis (1,4,5-trimethyl). -1,2,4-Triazolium-3-thiolate) aurate (I) tetrafluoroborate, an organic mercapto gold (I) complex described in JP-A-11-218870, for example, potassium bis (1-)
[3- (2-Sulfonatobenzamido) phenyl]-
(5-mercaptotetrazole potassium salt) aurate (I) pentahydrate, a gold (I) compound coordinated with a nitrogen compound anion described in JP-A-4-268550, for example,
Bis (1-methylhydantoinato) gold (I) sodium salt tetrahydrate can be used. As the gold (I) compound having these organic ligands, those synthesized and isolated in advance are used, and in addition, an organic ligand and an Au compound (for example, chloroauric acid or a salt thereof) are mixed. Due to
It can be added to the emulsion without being generated and isolated. Further, an organic ligand and an Au compound (for example, chloroauric acid or its salt) may be separately added to the emulsion to generate a gold (I) compound having an organic ligand in the emulsion. Further, gold (I) thiolate compounds described in U.S. Pat. No. 3,503,749, JP-A-8-69074,
Gold compounds described in JP-A-8-69075 and JP-A-9-269554, US Pat. Nos. 5,620,841 and 59.
No. 12112, No. 5620841, No. 5939245
No. 5,912,111 described above can also be used. The addition amount of these compounds may vary in a wide range depending on the case, but it is 5 × 10 ⁻⁷ to 1 mol of silver halide.
It is 5 × 10 ⁻³ mol, preferably 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol.

It is also possible to use colloidal gold sulfide, and the manufacturing method thereof is described in Research Disclosure, 3715.
4), Solid State Ionics (Solid
State Ionics, Vol. 79, pp. 60-66,
Published 1995, Compt. Rend. Hebt. Se
ances Acad. Sci. Sect. B No. 263
Vol., Page 1328, published in 1966, etc. The above-mentioned Research Disclosure describes a method of using thiocyanate ions in the production of colloidal gold sulfide, but a thioether compound such as methionine or thiodiethanol can be used instead.

Various sizes of colloidal gold sulfide can be used, and those having an average particle diameter of 50 nm or less are preferably used, the average particle diameter of 10 nm or less is more preferable, and the average particle diameter of 3 nm or less is further preferable. This particle size is T
It can be measured from an EM photograph. The composition of the colloidal gold sulfide may be Au ₂ S ₁ or a composition with excess sulfur such as Au ₂ S _{1 to} Au ₂ S ₂ , and a composition with excess sulfur is preferable. Au ₂ S _1.1 ~Au ₂ S _1.8 is more preferred.

The composition analysis of this colloidal gold sulfide can be carried out, for example, by taking out the gold sulfide particles and determining the gold content and the sulfur content by using an analytical method such as ICP or iodometry. The presence of gold ions and sulfur ions (including hydrogen sulfide and its salts) dissolved in the liquid phase in the gold sulfide colloid affects the composition analysis of gold sulfide colloid particles. The analysis is performed after separation. The addition amount of the gold sulfide colloid may vary widely depending on the case, but 5 × 10 ^-7 ~5 × 10 ^-3 mol as per mole of silver halide gold atoms, preferably 5 × 10 ^-6 ~5 × 10 ^{- 4} mol.

In the silver halide emulsion, chalcogen sensitization as well as gold sensitization can be performed with the same molecule.
Molecules capable of releasing Ch ⁻ can be used. Here, Au represents Au (I), and Ch represents a sulfur atom, a selenium atom, or a tellurium atom. Examples of the molecule capable of releasing AuCh ⁻ include a gold compound represented by AuCh-L. Here, L represents an atomic group forming a molecule by bonding with AuCh. Further, one or more ligands may be coordinated with Au along with Ch-L. Also, A
When a gold compound represented by uCh-L is reacted in a solvent in the presence of silver ions, AgAuS when Ch is S, AgAuSe when Ch is Se, and AgAu when Ch is Te.
It has a feature that Te is easily generated. Examples of such a compound include those in which L is an acyl group. In addition, compounds represented by the general formula (AuCh
1), compounds represented by the general formula (AuCh2) and the general formula (AuCh3).

General Formula (AuCh1) R ₁ —X—M-ChAu In the general formula (AuCh1), Au represents Au (I), and C
h represents a sulfur atom, a selenium atom, or a tellurium atom, M represents a substituted or unsubstituted methylene group, X represents an oxygen atom, a sulfur atom, a selenium atom, or NR ₂ , and R ₁ is bonded to X. Represents an atomic group (eg, an organic group such as an alkyl group, an aryl group, or a heterocyclic group) constituting a molecule, and R ₂ represents a hydrogen atom and a substituent (eg, an organic group such as an alkyl group, an aryl group, or a heterocyclic group). Group). R ₁ and M may combine with each other to form a ring.

In formula (AuCh1), Ch is preferably a sulfur atom or a selenium atom, X is preferably an oxygen atom or a sulfur atom, and R ₁ is preferably an alkyl group or an aryl group. Examples of more specific compounds include Au (I) salts of thiosugars (gold thioglucose such as α-gold thioglucose, gold peracetylthioglucose, gold thiomannose, gold thiogalactose, gold thioarabinose),
Examples include Au (I) salts of selenosugars (gold peracetylselenoglucose, gold peracetylselenomannose, etc.), Au (I) salts of tellurosugars, and the like. Where thio sugar, seleno sugar,
Telluro sugar means that the anomeric hydroxyl group of the sugar is SH.
Represents a compound in which a group, a SeH group and a TeH group are replaced.

General Formula (AuCh2) W ₁ W ₂ C = CR ₃ ChAu In the general formula (AuCh2), Au represents Au (I), and C
h represents a sulfur atom, a selenium atom, or a tellurium atom, R ₃ and W ₂ represent a substituent (for example, a hydrogen atom, a halogen atom,
And an organic group such as an alkyl group, an aryl group and a heterocyclic group), and W ₁ represents an electron-withdrawing group having a positive Hammett's substituent constant σp value. R ₃ and W ₁ , R ₃ and W ₂ , W
₁ and W ₂ may combine with each other to form a ring.

In the general formula (AuCh2), Ch is preferably a sulfur atom or a selenium atom, and R ₃ is
A hydrogen atom and an alkyl group are preferred, and W ₁ and W ₂ are preferably electron-withdrawing groups having a Hammett's substituent constant σp value of 0.2 or more. Examples of more specific compounds include (N
C) ₂ C = CHSAu, (CH ₃ OCO) ₂ C = CHSA
u, such as _{CH 3 CO (CH 3 OCO)} C = CHSAu the like.

General Formula (AuCh3) W ₃ -E-ChAu In the general formula (AuCh3), Au represents Au (I), and C
h represents a sulfur atom, a selenium atom, or a tellurium atom, E represents a substituted or unsubstituted ethylene group, and W ₃ represents an electron-withdrawing group having a positive Hammett's substituent constant σp value. In the compound represented by the formula (AuCh3), Ch
Is preferably a sulfur atom or a selenium atom, and E
Is preferably an ethylene group having an electron-withdrawing group having a positive Hammett's substituent constant σp value, and W ₃ is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.2 or more. preferable. The addition amount of these compounds can be varied over a wide range depending on the case, but it is 5 per mol of silver halide.
× 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 3 × 10 ^{−6 to} 3
It is × 10 ^-4 mol.

For the silver halide emulsion, the above gold sensitization can be performed by another sensitizing method such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound. May be combined with. Especially, it is preferable to combine with sulfur sensitization and selenium sensitization.

To the silver halide emulsion, various compounds or their precursors are added for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. You can As specific examples of these compounds, those described on pages 39 to 72 of JP-A No. 62-215272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

In the silver halide emulsion, the hydroxamic acid derivative described in JP-A No. 11-109576 and JP-A No. 11-143011 can be used in combination with the compound represented by formula (I) in order to improve its storage stability. Sulfo-substituted catechols and hydroquinones (for example, 4,5
-Dihydroxy-1,3-benzenedisulfonic acid, 2,
5-dihydroxy-1,4-benzenedisulfonic acid,
3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof, etc., US Pat.
Hydroxylamines represented by the general formula (A) in US Pat. No. 5,556,741 (US Pat. No. 5,556,741 at column 4, line 56 to column 11, line 22: The water-soluble reducing agents represented by the general formulas (I) to (III) in JP-A No. 11-102045 are also preferably applied in the present application and incorporated as a part of the specification of the present application in the present invention. Preferably used.

The silver halide emulsion contains a spectral sensitizing dye for the purpose of imparting so-called spectral sensitivity, which exhibits photosensitivity in a desired light wavelength region. Examples of the spectral sensitizing dye used for spectral sensitization in the blue, green and red regions include F.I. M. H
Armor by Heterocyclic compo
unds-Cyanine dyes and rel
arated compounds (John Wile
y & Sons [New York, London
n] Published in 1964). As specific examples of compounds and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used.
Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-123340 is known.
The spectral sensitizing dyes described in JP-A No. 1993-242242 are very preferable from the viewpoints of stability, strength of adsorption, temperature dependence of exposure and the like.

The addition amount of these spectral sensitizing dyes is in a wide range depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, it is in the range of 1.0 × 10 ⁻⁶ mol to 5.0 × 0 ⁻³ mol.

The light-sensitive material will be described in more detail below. Photosensitive material preferably has a total Coating amount of gelatin in the photographic component layers is 6.0~3.0g / m ^2, and still more preferably from 5.5~3.5g / m ^2. Further, it is more preferable that the total coating設銀amount is preferably 0.50~0.20g / m ^2, a 0.46~0.24g / m ^2.

A hardener can be generally used in the light-sensitive material, but in the present invention, among the hardeners, a vinyl sulfone type hardener represented by the following general formula (H-II) is preferably contained. preferable.

[0167]

[Chemical 17]

In formula (H-II), X ¹ and X ² are each-
CH = CH ₂ or is any of -CH ₂ CH ₂ Y,
X ¹ and X ² may be the same or different. Y represents a group which is substituted by a nucleophilic group or which can be eliminated by a base in the form of HY (for example, a halogen atom, sulfonyloquine, sulfuric acid monoester, etc.). L is a divalent linking group and may be substituted.

Specific examples of X ¹ and X ^{2 in} the general formula (H-II) include the groups shown below.

[0170]

[Chemical 18]

Of these, the following groups are preferable.

[0172]

[Chemical 19]

In the general formula (H-II), L includes an alkylene group, an arylene group, or a divalent linking group formed by combining one or more of these groups with the following bonds. . Where R ^{1 in the} bond shown below
Is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms,
It represents an aralkyl group having 1 to 15 carbon atoms.

[0174]

[Chemical 20]

In general formula (H-II), in particular, when L has two or more bonds shown below, R ^{1 s} thereof may bond to each other to form a ring.

[0176]

[Chemical 21]

In formula (H-II), L may have a substituent, and the substituent is a hydroxyl group. Alkoxyl group, carbamoyl group, sulfamoyl group. Examples thereof include an alkyl group and an aryl group. Further, the substituent may be further substituted with one or more groups represented by X ³ —SO ₂ —. Here, X ³ has the same meaning as X ¹ and X ^{2 in} formula (H-II).

In the general formula (H-II), typical examples of L include the groups shown below. However, in the example, a to v
Represents an integer of 1 to 6, and only d may be 0. Among them, d, k, l and p are preferably 1 to 3, and a to w are preferably 1 or 2 except d, k, l and p. R ¹ is a hydrogen atom, having 1 to
6 is preferable, and a hydrogen atom, a methyl group, or an ethyl group is particularly preferable.

[0179]

[Chemical formula 22]

Specific examples of the vinyl sulfone type hardener represented by the general formula (H-II) are shown below, but the invention is not limited thereto.

[0181]

[Chemical formula 23]

[0182]

[Chemical formula 24]

By using the hardener of the general formula (H-II), the amount of the compound represented by the general formula (I) remaining in the light-sensitive material increases, and the storage stability is improved accordingly. Turn into. Japanese Unexamined Patent Publication (Kokai) No. 7-311450 describes that use of a specific triazine-based compound as a gelatin hardener is effective for storage stability. However, in the present invention,
The triazine-based hardener showed less improvement in storability than the case where the hardener represented by the general formula (H-II) was used. Further, when the hardener represented by the general formula (H-II) is not used, the swollen film thickness of the light-sensitive material becomes large by using the compound represented by the general formula (I). Although image unevenness may worsen, it is preferable to use the hardener represented by the general formula (H-II) because the swelled film thickness of the photosensitive material can be prevented from increasing and the image unevenness can be further improved. .

Incidentally, in combination with a hardener represented by the general formula (H-II), for example, JP-A-62-215272, 1
Paragraph 46, upper right side, line 8 to lower right column, line 2 and 147 of the same paragraph
The hardeners described in line 6 on the lower right side of item to line 4 on the lower left column of item 155 can be used in combination.

In the light-sensitive material, the amount of the hardener used may vary depending on the purpose of use of the light-sensitive material, but is generally 0.0 with respect to gelatin generally used as a hydrophilic colloid.
1 to 20 wt% is preferable, 0.05 to 10 wt%
Is more preferable. The hardener is preferably added to the coating solution used when the photosensitive material is produced by coating, immediately before coating. A plurality of coating liquids corresponding to the respective layers are used for coating the light-sensitive material of the present invention, but the hardener may be added to any coating liquid, or may be added to a plurality of coating liquids. . The hardener is added to the coating solution in which the compound represented by the general formula (I) is added in the above range in the process of producing the light-sensitive material in an amount of 50% or more (preferably 80% or more) of the total addition amount. Is preferably added so as not to coexist with the compound represented by the general formula (I) in the coating liquid. Specifically, it is preferable to add it to at least one type of coating liquid that does not contain the compound represented by the general formula (I), and more preferably, a plurality of coatings that do not contain the compound represented by the general formula (I). It is to add the liquid separately. Further, the amount of the hardener added to the coating liquid not containing the compound represented by the general formula (I) is preferably 50% or more, more preferably 80% or more of the total amount added.

For the light-sensitive material, conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as the photographic support. As the transparent support, a transparent film such as a cellulose nitrate film or a polyethylene terephthalate film, and a polyester or NDCA of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) are used.
A polyester having terephthalic acid and EG and an information recording layer such as a magnetic layer is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers and containing a white pigment such as titanium oxide in at least one of the water resistant resin layers (laminate layer) is preferable.

Preferred examples of the reflective support include those having a polyolefin layer having fine pores on the paper base on which the silver halide emulsion layer is provided. The polyolefin layer may be composed of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no microvoids (eg polypropylene, polyethylene) and is on a paper substrate. It is more preferable to use a polyolefin (for example, polypropylene or polyethylene) having micropores on the near side. The density of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is preferably 0.40 to 1.0 g / ml, more preferably 0.50 to 0.70 g / ml. Also, the thickness of these multi-layer or one-layer polyolefin layers located between the paper base and the photographic constituent layers is 10
˜100 μm is preferable, and 15 to 70 μm is more preferable. The thickness ratio of the polyolefin layer to the paper substrate is preferably 0.05 to 0.2, more preferably 0.1 to 0.15.

It is also preferable to provide a polyolefin layer on the opposite side (rear surface) of the paper base from the photographic constituent layer from the viewpoint of increasing the rigidity of the reflection support. In this case, the polyolefin layer on the back surface has a matte surface. Preferred are polyethylene or polypropylene, with polypropylene being more preferred. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further has a density of 0.
It is preferably 7 to 1.1 g / ml. Regarding the preferred embodiment of the polyolefin layer provided on the paper substrate in the reflective support of the present invention, see JP-A-10-
No. 333277, No. 10-333278, No. 11-52513, No. 11-65024,
EP0880065 and EP0880066
The examples described in the specification are included.

Further, it is preferable to contain a fluorescent whitening agent in the water resistant resin layer. Also, a hydrophilic colloid layer containing the fluorescent whitening agent dispersed therein may be separately formed. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent can be used, and more preferably, a benzoxazolylnaphthalene-based or benzoxazolyl-stilbene-based fluorescent whitening agent. The amount used is not particularly limited, but preferably 1 to 10
It is 0 mg / m ² . When mixed with a water resistant resin, the mixing ratio is preferably 0.0005 to 3 mass% with respect to the resin.
And more preferably 0.001 to 0.5 mass%.

The reflection type support may be a transmission type support or a reflection type support as described above, on which a hydrophilic colloid layer containing a white pigment is coated. Further, the reflective support may be a support having a specular reflective or type II diffuse reflective metal surface.

As a support used for the light-sensitive material, a white polyester support for display or a support provided on a support having a layer containing a white pigment on a side having a silver halide emulsion layer is used. May be. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

In the light-sensitive material, a hydrophilic colloid layer is added in order to improve the sharpness of an image, European Patent EP0,
The dyes which can be decolorized by the treatment (in particular, oxonol dyes) described on pages 27 to 76 of the specification of 337,490A2 are added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more. Alternatively, the water-resistant resin layer of the support may contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated with a divalent to tetravalent alcohol (eg, trimethylolethane). preferable.

In the light-sensitive material, a hydrophilic colloid layer is used for the purpose of preventing irradiation or halation and improving safety of safelight, etc., European Patent EP03374.
It is preferable to add a dye (in particular, an oxonol dye or a cyanine dye) which can be decolorized by the treatment described on pages 27 to 76 of the specification of 90A2. Furthermore, European patent E
The dyes described in P0819977 are also preferably added to the present invention. Some of these water-soluble dyes may deteriorate color separation and safelight safety when the amount used is increased. Examples of dyes that can be used without deteriorating color separation include JP-A-5-127324 and JP-A-5-12732.
Water-soluble dyes described in JP-A No. 5 and JP-A No. 5-216185 are preferable.

In the light-sensitive material, a colored layer that can be decolorized by a treatment in place of the water-soluble dye or in combination with the water-soluble dye is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to install a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength range used for exposure (400 nm to 700 nm in ordinary printer exposure).
In the visible light region of nm, the wavelength of the scanning exposure light source used in the case of scanning exposure), the optical density value at the wavelength having the highest optical density is preferably 0.2 or more and 3.0 or less. It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

In order to form the colored layer, a conventionally known method can be applied. For example, the dyes described in JP-A-2-282244, from page 3, upper right column to page 8,
-7931 gazette, page 3, upper right column to page 11, lower left column, a method of incorporating a hydrophilic colloid layer in the form of a solid fine particle dispersion, a method of mordanting an anionic dye with a cationic polymer, a dye A method of adsorbing to a fine particle such as silver halide and fixing it in a layer, JP-A-1-239
A method using colloidal silver as described in Japanese Patent No. 544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at least at pH 6 or less, but is substantially water-soluble at least at pH 8 or more is disclosed in Japanese Patent Laid-Open No. 2-308244, pages 4-13. Further, for example, a method of mordanting an anionic dye on a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. For the preparation of colloidal silver as a light absorber, see US Pat. No. 2,688,
601 and 3,459,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

The light-sensitive material is used as a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, and the like. Among them, the color photographic paper is preferably used. In the present invention, the color photographic paper is required to have at least one yellow color forming silver halide emulsion layer, at least one magenta color forming silver halide emulsion layer and at least one cyan color forming silver halide emulsion layer. Are these silver halide emulsion layers in order from the support to the yellow color forming silver halide emulsion layer,
These are a magenta color forming silver halide emulsion layer and a cyan color forming silver halide emulsion layer.

However, a layer structure different from this may be adopted. The silver halide emulsion layer containing the yellow coupler may be arranged at any position on the support, but when the yellow coupler-containing layer contains silver halide tabular grains, the magenta coupler-containing silver halide It is preferably coated at a position farther from the support than at least one of the emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color due to a sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated at a position farthest from the support as compared with other silver halide emulsion layers. It is preferably provided. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a central layer of other silver halide emulsion layers, and from the viewpoint of reducing photofading, a cyan coupler-containing silver halide emulsion layer. Is preferably the bottom layer. Further, each of the yellow, magenta and cyan color forming layers may be composed of two layers or three layers. For example, JP-A-4-75055 and 9-1.
As described in 14035, 10-246940, US Pat. No. 5,576,159, etc.,
It is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color forming layer.

Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied in the light-sensitive material, and processing methods and processing additions applied for processing the light-sensitive material. As the agent, JP-A-62-2
Those described in Japanese Patent No. 15272, JP-A-2-33144 and European Patent EP0,355,660A2, and particularly those described in European Patent EP0,355,660A2 are preferably used. . Furthermore, JP-A-5-34889 and 4-35924.
9, gazette 4-313753 gazette, and gazette 4-2703.
No. 44, No. 5-66527, No. 4-3454.
No. 8, No. 4-145433, No. 2-854, No. 1-158431, No. 2-90145, No. 3-19439, No. 2-93641, and European Patent Publication No. The silver halide color photographic light-sensitive material and its processing method described in the specification of 0520457 A2 and the like are also preferable.

Particularly, in the present invention, the above-mentioned reflection type support, silver halide emulsion, further different metal ion species doped in silver halide grains, storage stabilizer for silver halide emulsion or antifoggant. , Chemical sensitization method (sensitizer), spectral sensitization method (spectral sensitizer), cyan, magenta, yellow coupler and its emulsion dispersion method, color image storability improver (anti-staining agent or anti-fading agent), As for the dye (colored layer), the type of gelatin, the layer structure of the photosensitive material and the coating pH of the photosensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applicable.

[0200]

[Table 1]

Other cyan, magenta and yellow couplers used in the light-sensitive material are disclosed in JP-A-6-61.
No. 2-215272, page 91, upper right column, line 4 to 12
Page 1, upper left column, line 6, line 3 of JP-A-2-33144
Page top right column, line 14 to page 18 top left column, end line and page 30, top right column, line 6 to page 35, bottom right column, line 11 and EP0355, 66
0A2, page 4, lines 15-27, page 5, 30
Lines to the end of page 28, pages 45 to 29, 31 to 47
The couplers described on page 23, line 63 to page 63, line 50 are also useful. In addition, the general formula (II) of WO98 / 33760
In addition, (III) and the compound represented by the general formula (D) of JP-A-10-221825 may be added, which is preferable.

A pyrrolotriazole coupler is preferably used as a cyan dye-forming coupler (sometimes simply referred to as "cyan coupler") usable in a light-sensitive material, and it is represented by the general formula (I) in JP-A-5-313324. Or a coupler represented by (II) and JP-A-6-3479.
The couplers represented by formula (I) in JP-A-60, as well as the exemplified couplers described in these patents are particularly preferable. Phenol-based and naphthol-based cyan couplers are also preferable, and for example, a cyan coupler represented by the general formula (ADF) described in JP-A-10-333297 is preferable. As cyan couplers other than the above, European Patents EP0488248 and EP049119
Pyrroloazole-type cyan couplers described in 7A1 and 2,5-described in US Pat. No. 5,888,716.
Diacylaminophenol coupler, US Pat. No. 4,8
73,183 and 4,916,051 and a pyrazoloazole type cyan coupler having an electron-withdrawing group and a hydrogen bonding group at the 6-position, particularly JP-A-8-1
No. 71185, No. 8-311360, No. 8-
The pyrazoloazole type cyan coupler having a carbamoyl group at the 6-position described in JP-A-339060 is also preferable.

In addition to the diphenylimidazole type cyan coupler described in JP-A-2-33144, a 3-hydroxypyridine type cyan coupler described in European Patent EP 0333185A2 (the couplers listed as specific examples ( 42) A 4-equivalent coupler having a chlorine-eliminating group to make it a 2-equivalent compound, or a coupler (6)
And (9) are particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8 and 3 listed as specific examples among them).
4 is particularly preferred), European Patent EP 0456226A1
, A pyrrolopyrazole-type cyan coupler described in
The pyrroloimidazole type cyan coupler described in European Patent EP 0484909 can also be used.

Among these cyan couplers, the pyrroloazole type cyan coupler represented by the general formula (I) described in JP-A No. 11-228138 is particularly preferable, and paragraphs 0012 to 0059 of the patent are described. Including the exemplified cyan couplers (1) to (47) are directly applied to the present application and are preferably incorporated as part of the specification of the present application.

Examples of magenta dye-forming couplers (sometimes simply referred to as "magenta couplers") usable in the light-sensitive material include 5-pyrazolone-based magenta couplers and pyrazoloazoles described in the above-mentioned publicly known documents. A magenta coupler is used. Among them, a secondary or tertiary alkyl group as described in JP-A-61-65245 has a pyrazolotriazole ring of 2, in terms of hue, image stability, color developability and the like. Pyrazolotriazole couplers directly linked to the 3 or 6-positions, pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-A-61-65246, JP-A-61-147254. And a pyrazoloazole coupler having an alkoxyphenyl sulfonamide ballast group as described above and European Patent No. 226,84. A Pat and the first 294,785
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in A specification. Particularly, as a magenta coupler, it is disclosed in Japanese Patent Laid-Open No. Hei 8
Pyrazoloazole couplers represented by formula (M-I) described in JP-A-122984 are preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application,
It is incorporated as part of the specification of the present application. In addition to this, European Patent No. 854384 and European Patent No. 88464
Pyrazoloazole couplers having a steric hindrance group at both the 3- and 6-positions described in No. 0 are also preferably used.

As the yellow dye-forming coupler (sometimes referred to simply as "yellow coupler") usable in the light-sensitive material, in addition to the compounds described in the above table, the acyl group described in European Patent EP 044969A1 is used. Acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure, malondianilide type yellow coupler having a cyclic structure described in European Patent No. EP 0482552A1, EP 953870A1 and EP 953871A1. Calligraphy, ibid. 953872
No. A1, No. 953873, No. 9A1, No. 9
No. 5,118,599. Pyrrole-2 or 3-yl or indol-2 or 3-ylcarbonylacetic acid anilide type couplers described in US Pat. No. 5,387,5A1 and No. 953875A1. An acylacetamide type yellow coupler having a dioxane structure is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The coupler which can be used in the light-sensitive material can be used in the presence (or absence) of the high boiling point organic solvent described in the above table.
Loadable latex polymers (eg US Pat. No. 4,
No. 203,716) or by dissolving with a water-insoluble polymer soluble in an organic solvent to emulsify and disperse in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449 at columns 7 to 15 and International Publication WO88 / 00723 at pages 12 to 30. The homopolymers or copolymers mentioned may be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

Known color mixing inhibitors can be used in the light-sensitive material, and among them, those described in the following patents are preferable. For example, high molecular weight redox compounds described in JP-A-5-333501, WO98 / 3
Phenidone and hydrazine compounds described in US Pat. No. 3,760, US Pat. No. 4,923,787 and the like, JP-A-5-249637 and JP-A-10-2821515.
The white couplers described in Japanese Patent Publication No. 19629142A1 and the like can be used. Further, particularly when the pH of the developing solution is raised to accelerate the development, German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 84297.
It is also preferable to use the redox compounds described in Japanese Patent No. 5A1, German Patent 1980846A1 and French Patent No. 2760460A1.

In the light-sensitive material, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as an ultraviolet absorber. For example, the compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or the non-photosensitive layer. For example, JP-A-46-33
No. 35, No. 55-152776, JP-A-5-
No. 197074, No. 5-232630, No. 5
No. 307232, No. 6-211813, No. 8-53427, No. 8-234364, No. 8-239368, No. 9-31067, No. 10-15898, No. 10- 147577, 10-182621, and German Patent No. 1973.
The compounds described in 9797A specification, EP 711804A specification, JP-A-8-501291, etc. can be used.

As the binder or protective colloid that can be used in the light-sensitive material, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably 5 ppm or less, more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 m.
g / m ² or less.

In order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material is provided with an antibacterial / antifungal agent as described in JP-A-63-271247. It is preferable to add it. Further, the film pH of the light-sensitive material is preferably 4.0 to 7.0, more preferably 4.
0 to 6.5.

The photosensitive material preferably has a film thickness of 3 μm to 7.5 μm in a dry state as a whole in order to satisfy development progress, fixing bleaching property, and residual color.
Further, it is preferably 3 μm to 6.5 μm. The dry film thickness can be evaluated by measuring the change in film thickness before and after peeling of the dry film or by observing the cross section with an optical microscope or an electron microscope.

In the light-sensitive material, a surfactant can be added to the light-sensitive material from the viewpoints of improving coating stability, preventing static electricity generation, adjusting charge amount and the like. Examples of surfactants include anionic surfactants, cationic surfactants, betaine surfactants, and nonionic surfactants.
The one described in JP-A-333492 may be mentioned. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. Particularly, a fluorine atom-containing surfactant can be preferably used. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but preferably in combination with other conventionally known surfactants. The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10 ^{−5 to} 1 g / m ² , and preferably 1 × 10 5.
^-4 to 1 x 10 ^-1 g / m ² , and more preferably 1 x 10 ^-3 to.
It is 1 × 10 ^-2 g / m ² .

[0214]

EXAMPLES The present invention will be described below in greater detail by giving Examples, but the present invention is not limited thereto.

[Example 1] (Preparation of emulsions BH) In a standard method of simultaneously adding and mixing silver nitrate and sodium chloride into a stirred aqueous gelatin solution,
A cubic high silver chloride emulsion having a sphere-equivalent diameter of 0.55 μm and a coefficient of variation of 10% was prepared. However, K ₄ [Ru (CN) ₆ ] was added from the time when the addition of silver nitrate was 80% to the time when it was 90%. When the addition of silver nitrate was 90% completed, potassium iodide (0.3 mol% per mol of the finished silver halide) was added. Further, from the time when the addition of silver nitrate was 92% to the time when 98% was added, K ₂ [Ir (5-methy
lthiazole) Cl ₅ ] was added. The emulsion thus obtained was desalted and gelatin was added thereto to redisperse it.
Sodium thiosulfonate, sensitizing dye A and additional dye B were added to this emulsion in an amount of 3 × 10 3 per mol of silver halide.
^-4 mol each, and sodium thiosulfate pentahydrate and a gold sulfide colloidal dispersion were used as sulfur sensitizers and aged so as to be optimum. Further, 1-phenyl-5-mercaptotetrazole and 1- (5-methylureidophenyl)-
5-Mercaptotetrazole was added. The emulsion thus obtained was designated as Emulsion BH. (Preparation of Emulsion B-L) Emulsion B-H was prepared by changing only the addition rates of silver nitrate and sodium chloride to give a spherical equivalent diameter of 0.45 μm.
A cubic high silver chloride emulsion having m and a coefficient of variation of 10% was prepared.
The obtained emulsion was designated as Emulsion BL.

[0216]

[Chemical 25]

(Preparation of Emulsion GH) A cubic high silver chloride emulsion having a sphere-equivalent diameter of 0.35 μm and a coefficient of variation of 10% was prepared by simultaneously adding and mixing silver nitrate and sodium chloride in a stirred aqueous gelatin solution. Prepared. However, when the addition of silver nitrate was 80% to 90%, K ₄ [Ru
(CN) ₆ ] was added. From the time when the addition of silver nitrate was 80% to the time when it was 100%, potassium bromide (4 mol% per mol of the finished silver halide) was added.
When the addition of 90% of silver nitrate was completed, potassium iodide (0.2 mol% per mol of the finished silver halide) was added. From the time of addition of silver nitrate of 92% to that of 95%, K ₂ [Ir (5-methylthiaz
ole) Cl ₅ ]. Further addition of silver nitrate is 92
% To 98%, K ₂ [Ir (H
₂ O) Cl ₅ ]. The emulsion thus obtained was desalted and gelatin was added thereto to redisperse it. Sodium thiosulfonate was added to this emulsion, and sodium thiosulfate pentahydrate was used as a sulfur sensitizer and bis (1,2) was used as a gold sensitizer.
4,5-Trimethyl-1,2,4-triazolium-3
-Thiolate) Aurate (I) Aged optimally with tetrafluoroborate. Further sensitizing dye C,
1-phenyl-5-mercaptotetrazole, 1- (5
-Methylureidophenyl) -5-mercaptotetrazole and potassium bromide were added. The emulsion thus obtained was designated as Emulsion GH. (Preparation of Emulsion G-L) Emulsion G-H was prepared by changing only the addition rates of silver nitrate and sodium chloride to obtain an equivalent spherical diameter of 0.28 μm.
A cubic high silver chloride emulsion having m and a coefficient of variation of 10% was prepared.
The obtained emulsion was designated as Emulsion GL.

[0218]

[Chemical formula 26]

(Preparation of Emulsion RH) A cubic high silver chloride emulsion having a sphere-equivalent diameter of 0.35 μm and a coefficient of variation of 10% was prepared by simultaneously adding and mixing silver nitrate and sodium chloride in a stirred aqueous gelatin solution. Prepared. However, when the addition of silver nitrate was 80% to 90%, K ₄ [Ru
(CN) ₆ ] was added. From the time when the addition of silver nitrate was 80% to the time when it was 100%, potassium bromide (4.3 mol% per mol of the finished silver halide) was added. When the addition of 90% of silver nitrate was completed, potassium iodide (0.15 mol% per mol of finished silver halide) was added. 95% addition of silver nitrate from 95%
%, K ₂ [Ir (5-methylthyl
iazole) Cl ₅ ] was added. Further, from the time when the addition of silver nitrate was 92% to the time when 98% was added, K ₂ [Ir
(H ₂ O) Cl ₅ ] was added. The emulsion thus obtained was desalted and gelatin was added thereto to redisperse it. Sodium thiosulfonate was added to this emulsion, and sodium thiosulfate pentahydrate as a sulfur sensitizer and bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate) as a gold sensitizer were added. ) Aurate (I) tetrafluoroborate was used for optimal aging. Further, sensitizing dye H, 1-phenyl-5-mercaptotetrazole, 1
-(5-Methylureidophenyl) -5-mercaptotetrazole, Compound I and potassium bromide were added.
The emulsion thus obtained was designated as Emulsion RH. (Preparation of Emulsion RL) Emulsion RH was prepared by changing only the addition rates of silver nitrate and sodium chloride to obtain a sphere-equivalent diameter of 0.28 μm.
A cubic high silver chloride emulsion having m and a coefficient of variation of 10% was prepared.
The obtained emulsion was designated as emulsion RL.

[0220]

[Chemical 27]

[0221]

[Chemical 28]

(Preparation of Photosensitive Material) After a corona discharge treatment was applied to the surface of a support having both sides of paper coated with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. Layers to a seventh photographic constituent layer were sequentially coated to prepare a sample of a silver halide color photographic light-sensitive material having the following layer structure. The coating liquid for each photographic constituent layer was prepared as follows.

-Preparation of coating solution for first layer-Yellow coupler (ExY) 57 g, color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
21 g of solvent (Solv-1) and 80 m of ethyl acetate
22 g of a 23.5% by mass gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate.
Emulsified and dispersed in 0 g by a high-speed stirring emulsifying machine (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion B-1 were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

-Preparation of Second Layer to Seventh Layer Coating Liquid-The coating liquids for the second to seventh layers were prepared in the same manner as the first layer coating liquid. (HA) was added as a gelatin hardener for each layer so that the total amount was 0.15 g / m ² . Further, Ab-1, Ab-2, Ab-3, and Ab-4 were added to each layer in a total amount of 15.0 mg / m ² , 60.0 mg / m ² ,
It was added to a 5.0 mg / m ² and 10.0 mg / m ^2.

[0225]

[Chemical 29]

[0226]

[Chemical 30]

To the red-sensitive emulsion layer, 0.05 g / m ^{2 of a} copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200,000-400000) was added. In addition, the following dyes (the amount in parentheses represents the coating amount) were added to prevent irradiation.

[0228]

[Chemical 31]

-Layer Structure- The structure of each layer is shown below. Numbers are coating amount (g / m ² )
Represents The silver halide emulsion represents the coating amount in terms of silver. Support polyethylene resin laminated paper [white pigment (TiO ₂ ; polyethylene resin on the first layer side;
Content 16% by mass, ZnO; content 4% by mass) and fluorescent whitening agent (4,4′-bis (5-methylbenzoxazolyl) stilbene. Content 0.03% by mass), bluish dye ( Ultramarine)] First layer (blue-sensitive emulsion layer) 1: 1 (silver ratio) mixture of emulsions BH and BL 0.25 gelatin 1.25 yellow coupler (ExY-1) 0.58 colors Image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv -1) 0.21

[0230]   Second layer (color mixing prevention layer)     Gelatin 0.99     Color mixing inhibitor (Cpd-4) 0.09     Color image stabilizer (Cpd-5) 0.018     Color image stabilizer (Cpd-6) 0.13     Color image stabilizer (Cpd-7) 0.01     Solvent (Solv-1) 0.06     Solvent (Solv-2) 0.22

[0231]   Third layer (green sensitive emulsion layer)     Emulsion GH and GL 1: 1 (silver ratio) mixture 0.14     Gelatin 1.36     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.14     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-4) 0.002     Color image stabilizer (Cpd-6) 0.09     Color image stabilizer (Cpd-8) 0.02     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.11     Solvent (Solv-4) 0.22     Solvent (Solv-5) 0.20

[0232]   Fourth layer (color mixing prevention layer)     Gelatin 0.71     Color mixing prevention layer (Cpd-4) 0.06     Color image stabilizer (Cpd-5) 0.013     Color image stabilizer (Cpd-6) 0.10     Color image stabilizer (Cpd-7) 0.007     Solvent (Solv-1) 0.04     Solvent (Solv-2) 0.16

[0233]   Fifth layer (red sensitive emulsion layer)     Emulsion RH and RL 1: 1 (silver ratio) mixture 0.12     Gelatin 1.11.     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-1) 0.05     Color image stabilizer (Cpd-6) 0.06     Color image stabilizer (Cpd-7) 0.02     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-14) 0.01     Color image stabilizer (Cpd-15) 0.12     Color image stabilizer (Cpd-16) 0.03     Color image stabilizer (Cpd-17) 0.09     Color image stabilizer (Cpd-18) 0.07     Solvent (Solv-5) 0.15     Solvent (Solv-8) 0.05

[0234]   Sixth layer (UV absorption layer)     Gelatin 0.46     UV absorber (UV-B) 0.45     Solvent (Solv-7) 0.25

[0235]   Seventh layer (protective layer)     Gelatin 1.00     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.02     Surfactant (Cpd-13) 0.01

[0236]

[Chemical 32]

[0237]

[Chemical 33]

[0238]

[Chemical 34]

[0239]

[Chemical 35]

[0240]

[Chemical 36]

[0241]

[Chemical 37]

[0242]

[Chemical 38]

[0243]

[Chemical Formula 39]

[0244]

[Chemical 40]

The sample thus obtained was used as sample 1
It was set to 01. According to Table 2, catechol-3,5-disulfonate disodium, 1- (5-methylureidophenyl) -5-mercaptotetrazole, 1-phenyl-5-mercaptotetrazole and compounds in silver emulsion for sample 101 according to Table 2. Samples in which the addition amount of I-4 was changed and (HII-1) was replaced in place of the hardener (HA) in an equimolar amount were prepared in the same manner, and samples 102 to 112 were prepared.
And

[0246]

[Table 2]

To examine the photographic characteristics of these samples, the following exposure and development processing A was carried out to evaluate the swollen film thickness, storability and unevenness. In addition, the swollen film thickness in the color development processing solution in the following development processing was examined. The results are shown in Table 3.

-Exposure / Development Treatment A- Each sample was processed into a roll having a width of 127 mm, and was subjected to vertical exposure by a laser exposure method shown below using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd. A sample having a size of 12 × 8.9 cm was subjected to grayscale gradation exposure such that the color densities of yellow, magenta, and cyan were approximately equal, and then the sample was automatically conveyed for development processing. In this developing process, a continuous process (running test) was performed until replenishment of twice the capacity of the color developing tank. This was a process using this running liquid, and this was designated as color development process A. However, the transport speed of the sample in color development processing A was set to a linear velocity of 1.2 m / min. As for the sample 102, the replenishing amount in the color developing step was 63 ml and 30 m per 1 m ² of the light-sensitive material.
The image formation changed to 1 was also performed.

—Laser Exposure Method— As a laser light source, a blue semiconductor laser (2001
March 1994, presented by Nichia at the 48th Joint Lecture on Applied Physics) wavelengths of 430-450 nm or semiconductor lasers (oscillation wavelength of about 940 nm) with SHG crystals of LiNbO ₃ having a waveguide-like inversion domain structure. About 470 nm converted and taken out, about 530 nm wavelength-converted and taken out by a semiconductor laser (oscillation wavelength about 1060 nm) by a SHG crystal of LiNbO ₃ having a waveguide-like inversion domain structure, and a red semiconductor laser (Hitachi type No. .HL6738MG) wavelength of about 685 nm
Or red semiconductor laser (Hitachi type No. HL6
501 MG) and a wavelength of about 650 nm was used. The laser light of each of the three colors was moved in a direction perpendicular to the scanning direction by a polygon mirror so that the sample could be sequentially scanned and exposed. Fluctuations in the amount of light due to the temperature of the semiconductor laser are suppressed by using a Peltier device to keep the temperature constant. The effective beam diameter is 80 μm,
The scanning pitch is 42.3 μm (600 dpi), and 1
The average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds.

-Color development processing A-Processing step Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45 ml Bleach-fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds-Rinse (3) ** 38.0 ° C 20 seconds-Rinse (4) ** 38.0 ° C 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Fuji Photo A phosphorus screening system RC50D manufactured by Film Co., Ltd. is installed in the rinse (3), and the rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the same tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and temperature control circulation was performed for 10 hours a day. (Rinsing was performed from the tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank liquid] [Replenisher] 800 ml water 800 ml Dimethylpolysiloxane-based surfactant 0.1g 0.1g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8g 8.8g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0g 10.0g 4,5-dihydroxybenzene-1,3- Sodium disulfonate 0.5g 0.5g Potassium chloride 10.0g- Potassium bromide 0.040g 0.010g Triazinylaminostilbene fluorescent 2.5g 5.0g Whitening agent (Hakkor FWA-SF / Showa Kagaku) Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                     8.5g 11.1g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-ami No-4-aminoaniline / 3/2 sulfuric acid monohydrate                                     5.0 g 15.7 g Potassium carbonate 26.3g 26.3g Add water 1000 ml 1000 ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                   10.15 12.50

[0252] [Bleach fixer] [Tank solution] [Replenisher] Water 700 ml 600 ml Ethylenediaminetetraacetate Iron (III) ammonium                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g m-carboxybenzenesulfinic acid                                     8.3g 16.5g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium thiosulfate (750 g / l)                           107.0 ml 214.0 ml Ammonium sulfite 16.0 g 32.0 g Ammonium bisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted with 25 ° C / acetic acid and ammonia)                                     6.0 6.0

[0253] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μS / cm or less)                             1000 ml 1000 ml pH 6.5 6.5

-Swelled film thickness-The swelled film thickness in the color developing solution in the above-mentioned development processing is as described above for each of the sample (1 W) after 1 week at 25 ° C. and the sample (6M) after 6 months. Examined.

-Preservability-Exposure / development treatment was carried out for each of the samples which had been stored at 25 ° C for 1 week and 6 months after coating. In addition, gradation exposure is performed using the shortest laser light in the exposure process, the yellow density of each sample after the process is measured, a characteristic curve is obtained, and an exposure amount (E) giving a color density of 0.7 is obtained. Each sample was obtained, and 1 / E was defined as S. Let S (1W) and S (6M) be S in the sample after one week and in the sample after 6 months. The value of S (6M) / S (1W) was obtained in order to estimate the performance variation due to the progress of the sample. The closer this value is to 1, the better the storage stability of the unexposed sample.

-Mura-Exposure / development treatment was carried out on each of the sample (1 W) that had been stored for 1 week at 25 ° C and the sample (6M) that had been stored for 6 months after coating. Using the digital information recorded by the digital camera, each sample was exposed and developed as described above, and each condition (1
Make 10 color prints for each W, 6M,
The unevenness of the print was visually observed and evaluated as follows. A Very good with almost no streaky unevenness B 1 to 10 out of 10 samples showing slight streaky unevenness
There are three. C 1 out of 10 samples with clearly visible streaky spots
~ 3 sheets, which is inferior in color print quality. D Most of the samples clearly show streaky unevenness,
Unacceptable color print quality.

[0257]

[Table 3]

From the results shown in Table 3, it was found that image unevenness was particularly aggravated by reducing the replenishment amount of the color developing solution, and it was confirmed that Compound I-4 (the compound represented by the general formula (I)) and 1-
Phenyl-5-mercaptotetrazole (general formula (II)
It can be seen that the photographic performance (image unevenness and storability) can be favorably maintained by subjecting the light-sensitive material containing the compound represented by the formula (4) in a specific range to the above-mentioned exposure and development treatment.

Example 2 With respect to the sample 110 of Example 1, the amount of I-4 added was changed to 4 mg / m ² and HA or (HII-1) was used as a hardening agent. I
-4 was replaced with the coating liquid as shown in Table 4, and sample 2 was added.
01 to 204 were produced and evaluated in the same manner as in Example 1.
In addition, the sample that had been kept at 25 ° C for 1 week after coating was further tested at 35 ° C for 4 weeks.
The same evaluation as in Example 1 was performed on the sample stored for 20 days under 5% RH. The results are shown in Table 5.

[0260]

[Table 4]

[0261]

[Table 5]

As is clear from the results shown in Table 5, at 35 ° C. 4
It can be seen that the 20-day storage condition under 5% RH corresponds well to 6-month storage. In addition, the sample 201 prepared by adding the compound (I-4) and the hardener to the same coating solution was (I-
The residual amount of 4) is small, the swollen film thickness is large, and the performance is not satisfactory, but from Samples 202 to 204, the proportion of the hardener coexisting with the compound (I-4) in the coating liquid should be reduced. It is also effective to use a vinyl sulfone compound as a hardener.

Example 3 The sample 204 of Example 2 is
As a gelatin hardener for each layer, the total amount of (HII-1) was 0.
09g / m by adding ² to become so, to change the amount of various compounds, samples 301, further changing the layer configuration as shown below
Was produced.

[0264] -Layer structure-   First layer (blue sensitive emulsion layer) Emulsion B-H and BL mixture of 4: 6 (silver ratio) 0.14     Gelatin 0.75     Yellow coupler (ExY-2) 0.34     Color image stabilizer (Cpd-1) 0.04     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-3) 0.04     Color image stabilizer (Cpd-8) 0.01     Solvent (Solv-1) 0.13

[0265]   Second layer (color mixing prevention layer)     Gelatin 0.60     Color mixing inhibitor (Cpd-19) 0.09     Color image stabilizer (Cpd-5) 0.007     Color image stabilizer (Cpd-7) 0.007     UV absorber (UV-C) 0.05     Solvent (Solv-5) 0.11

[0266]   Third layer (green sensitive emulsion layer) Emulsion GH and GL 7: 3 (silver ratio) mixture 0.14     Gelatin 0.73     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.05     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-7) 0.008     Color image stabilizer (Cpd-8) 0.07     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.009     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.06     Solvent (Solv-4) 0.11     Solvent (Solv-5) 0.06

[0267]   Fourth layer (color mixing prevention layer)     Gelatin 0.48     Color mixing prevention layer (Cpd-4) 0.07     Color image stabilizer (Cpd-5) 0.006     Color image stabilizer (Cpd-7) 0.006     Ultraviolet absorber (UV-C) 0.04     Solvent (Solv-5) 0.09

[0268]   Fifth layer (red sensitive emulsion layer) Emulsion RH and RL 3: 7 (silver ratio) mixture 0.12     Gelatin 0.59     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-7) 0.01     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-15) 0.19     Color image stabilizer (Cpd-18) 0.04     Ultraviolet absorber (UV-7) 0.02     Solvent (Solv-5) 0.09

[0269]   Sixth layer (UV absorption layer)     Gelatin 0.32     Ultraviolet absorber (UV-C) 0.42     Solvent (Solv-7) 0.08   Seventh layer (protective layer)     Gelatin 0.70     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.01     Surfactant (Cpd-13) 0.01     Polydimethylsiloxane 0.01     Silicon dioxide 0.003

[0270]

[Chemical 41]

A sample in which the amount of each compound added was changed as shown in Table 6 to Sample 301 was also prepared in the same manner.
It was set to 02 to 308.

[0272]

[Table 6]

The produced sample was exposed and developed according to the following exposure and development process B and evaluated in the same manner as in Examples 1 and 2. The results are shown in Table 7.

-Exposure / Development Process B- Minilab printer processor PP3 manufactured by Fuji Photo Film Co., Ltd. so that the sample of the above-mentioned photosensitive material can be processed into a roll having a width of 127 mm and the processing time and the processing temperature can be changed.
Image-wise exposure was performed on a sample of a light-sensitive material from a negative film having an average density by using an experimental processor modified from 50, and the volume of the color developing replenisher used in the following processing step was 0.5 times the volume of the color developing tank. Continuous processing (running test) was performed until it became. This was designated as color development processing B. The sample conveyance speed in the color development step was set to a linear velocity of 4.4 m / min.

—Color Development Processing B— Processing Step Temperature Time Replenishment Amount ^* Color Development 45.0 ° C. 15 seconds 35 mL Bleach-fix 40.0 ° C. 15 seconds 35 mL Rinse (1) 40.0 ° C. 8 seconds − Rinse (2) 40 0.0 ° C 8 seconds-Rinse (3) ** 40.0 ° C 8 seconds-Rinse (4) 38.0 ° C 8 seconds 121mL Dry 80.0 ° C 15 seconds (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material * * Fuji Photo Film Co., Ltd. phosphorus screening system RC50D is attached to the rinse (3), and the rinse liquid is taken out from the rinse (3) and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the same tank is supplied to the rinse, and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinse was a 4-tank countercurrent system from (1) to (4).

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] Water 800mL 600mL Optical brightener (FL-1) 5.0 g 8.5 g Triisopropanolamine 8.8g 8.8g Sodium p-toluenesulfonate 20.0 g 20.0 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Sodium sulfite 0.10g 0.50g Potassium chloride 10.0g- 4,5-dihydroxybenzene- Sodium 1,3-disulfonate 0.50 g 0.50 g Disodium-N, N-bis (sulfonate Ethyl) hydroxylamine 8.5 g 14.5 g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl ) Aniline, 3/2 sulfate, monohydrate                                 10.0 g 22.0 g Potassium carbonate 26.3g 26.3g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6

[0277] [Bleach fixer] [Tank solution] [Replenisher] Water 800mL 800mL Ammonium thiosulfate (750 g / mL)                                   107 mL 214 mL Succinic acid 29.5g 59.0g Ethylenediaminetetraammonium iron (III) acetate                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g Nitric acid (67%) 17.5g 35.0g Imidazole 14.6g 29.2g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Add water to the total volume 1000 mL 1000 mL pH (25 ° C, adjusted with nitric acid and aqueous ammonia) 6.00 6.00

[0278] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL pH (25 ° C) 6.5 6.5

[0279]

[Chemical 42]

[0280]

[Table 7]

As is clear from the results of Table 7, Example 1
It can be seen that the effect of the present invention can be obtained even in the processes of lower replenishment, rapid processing, and processing in which the photosensitive material is being conveyed at a higher speed than those of Nos.

[0282]

As described above, according to the present invention, an image forming method capable of obtaining high quality and stable performance in low replenishment rapid processing, and a silver halide photographic color light-sensitive material suitable for low replenishment rapid processing are obtained. You can

Claims (2)

[Claims] 1. A yellow dye-forming coupler on a support.
Containing blue-sensitive silver halide emulsion layer, magenta dye forming agent
Puller-containing green Photosensitive-containing silver halide emulsion layer, cyan color
A red-sensitive silver halide emulsion layer containing an element-forming coupler and
At least one non-photosensitive hydrophilic colloid layer
Silver halide color photograph having a single photographic constituent layer
After imagewise exposure of the light-sensitive material, color development process, bleaching
Image type that undergoes development processing including fixing and rinsing steps
In the composition method, the color development step is
The replenishment amount of the color developing solution is the silver halide color photographic light-sensitive material.
1m charge²The above halogen is performed at 20 to 60 ml per
The silver halide color photographic light-sensitive material has the following
The compounds represented by the general formula (I) and the general formula (II) are respectively
1.0 mg / m²From 100 mg / m²And 0.1 mg /
m²To 5.0 mg / m²Is added in an amount
At least one of the light-sensitive silver halide emulsion layers is chlorinated.
Including a silver halide emulsion having a silver content of 90 mol% or more,
The silver halide color photographic light-sensitive material is colored in the above-mentioned color.
The swollen film thickness in the color developing solution in the developing process is 1
Image forming method characterized in that the diameter is changed from 0 μm to 20 μm
Law. [Chemical 1] (In the general formula (I), Y represents a carbon atom. Z represents a carbon atom.
Represents R¹, R²May be the same or different from each other
Hydroxyl group, amino group, alkylamino group,
Anilino group, heterocyclic amino group, acylamino group, al
Killsulfonylamino group, arylsulfonylamino
Group, heterocyclic sulfonylamino group, alkoxycarbonyl
Luamino group, carbamoylamino group, mercapto group,
Represents a lulylthio group, an arylthio group, and a heterocyclic thio group.
You R³Is a hydrogen atom, a group connecting Y with a carbon atom, Y
And a group connecting with an oxygen atom, a group connecting with a nitrogen atom with Y
Represent R ^FourIs a hydrogen atom, a group connecting with Z and a carbon atom,
Group connecting with Z and oxygen atom, group connecting with Z and nitrogen atom
Represents R³And R^FourEven though they form a ring together
Good. ) [Chemical 2] (In the general formula (II), M represents a cation. R represents an atomic weight.
Represents 50 or less atoms or groups with a total atomic weight of 50 or less
You ) 2. A color development process after imagewise exposure,
In a silver halide color photographic light-sensitive material of a type which is subjected to a development process including a bleach-fixing step and a rinse step, in the color development step, the replenishment amount of the color developing solution is 20 per 1 m ^{2 of the} silver halide color photographic light-sensitive material. ~
The above silver halide color photographic light-sensitive material is formed on a support by using a blue light-sensitive silver halide emulsion layer containing a yellow dye-forming coupler, a green light-sensitive silver halide emulsion layer containing a magenta dye-forming coupler, and cyan. The dye-forming coupler-containing red light-sensitive silver halide emulsion layer and the non-light-sensitive hydrophilic colloid layer each have at least one photographic constituent layer, and in the production process thereof, the above-mentioned general formula (I) and the above-mentioned general formula (II) ) Is represented by 1.0 mg / m ² to 100 mg / m ² and 0.1 mg / m ² respectively.
is the amount added from the m ² becomes 5.0 mg / m ^2, after the amount of residual manufacturing photosensitive materials of the compound represented by the general formula (I) 1
0.5 mg / m ² to 50 mg in the period from week to 6 months
/ M ² and at least one of the light-sensitive silver halide emulsion layers contains a silver halide emulsion having a silver chloride content of 90 mol% or more, and a silver halide color photographic light-sensitive material.