JP2948666B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing a color light-sensitive material suitable for rapid processing, and more particularly to a method for developing a color light-sensitive material for photography capable of rapid processing with excellent color reproduction processing stability. It is.

[0002]

BACKGROUND OF THE INVENTION In recent years, in the field of silver halide color photographic light-sensitive materials, ultra-high sensitivity represented by ISO-1600 to 3200 and small format represented by disc films have been developed to achieve high image quality. Is required. Therefore, the demand for silver halide color photographic light-sensitive materials is becoming increasingly severe, and a higher level of demand is required for a wide range of photographic performances such as higher sensitivity, excellent graininess, high sharpness, low fog, and a wide exposure range. It has been done.

At present, a so-called negative-positive system for photographing a color photograph with a color negative film, stretching the photograph on a color paper and performing color printing is widely used.

One of the reasons is that a color negative film has a very wide exposure latitude, has a low probability of failure at the time of photographing, and can be easily taken by a general user without specialized knowledge. Unlike color reversal film and color paper, color negative film is a photosensitive material that requires strict control of gradation over a wider exposure range.If this gradation is poor, color reproducibility and tone reproduction of dye images are poor. The print quality is deteriorated and the color tone is broken when printed.

[0005] Dyes used in color photography are different from block dyes which are ideal in the subtractive color method, that is, those having photosensitivity only in a specific wavelength region, and exhibit considerable irregular absorption in other regions of the spectrum. Since it has light and therefore absorbs part of the light that it does not want to absorb, sufficient color reproduction cannot be achieved as it is. Therefore, for example, in a color negative film, masking using a colored coupler for correcting the irregular absorption is performed, thereby realizing good color reproducibility.

Further, negative spectral sensitivity correction based on the principle of the three primary colors of the subtractive color method and the characteristics of the human eye is performed, and an inter-image effect is used to emphasize a pure color.

Hitherto, it has been well known to use a DIR compound which releases a development inhibitor as an image quality improver such as the gradation, sharpness, granularity and color reproducibility of such a color image.

Further, in addition to a technique for improving image characteristics by using a DIR compound, silver iodide is contained in silver halide grains to improve image quality by utilizing the effect of suppressing the development of iodine ions released during development. Techniques for measuring gradation are also well known.

A photographic negative film using a silver iodobromide emulsion makes full use of the advantages of silver iodide, such as high sensitivity and interlayer effect, but it contains a silver iodide for development. Making it difficult to shorten.

That is, iodine ions accumulated in the desilvering solution have a fatal disadvantage that they significantly delay the bleaching and fixing of silver, hinder the speeding up of processing and the reduction in replenishment.

As a result, a negative effect is brought about in terms of suitability for short-time processing of color development, which is rapidly spreading in recent years, that is, so-called rapid processing.

On the other hand, an emulsion having a high silver chloride content is advantageous in shortening each process of development and bleach-fix. However, silver chloride-containing emulsions are easily hardened, and have graininess,
It tends to have poor color reproducibility.

In addition to color negative films,
The gradation of various color photographic light-sensitive materials is very easily affected by fluctuations in development processing conditions, and it is recognized that deterioration of color reproduction and tone reproduction is particularly important.

Japanese Patent Application Laid-Open No. 60-156059 discloses that a silver halide grain having substantially no photosensitivity is contained between two emulsion layers having different photosensitivity in order to improve the development progress of a color photographic light-sensitive material. A technique of providing a layer has been proposed. Further, JP-A-60-128429 discloses that a non-photosensitive silver halide grain is contained in an outer layer of a photosensitive silver halide emulsion layer farthest from a support. Discloses a technique for reducing the influence of process variability.

However, these prior arts are also insufficient and have not yet sufficiently improved the processing stability, and there has been a strong demand for a solution together with the above-described inhibition of the development processing.

A color photographic light-sensitive material using a silver halide emulsion containing silver chloride is excellent in rapid development, but is inferior in color reproducibility and is not generally used in color photographic materials for photography.

[0017]

SUMMARY OF THE INVENTION It is an object of the present invention to rapidly process a color image having excellent color reproducibility by using a silver halide emulsion containing silver chloride and to obtain a stable and stable process without any processing fluctuation. An object of the present invention is to provide a method for developing a silver color photographic light-sensitive material.

[0018]

The present inventors have made intensive studies and have found that the object of the present invention is achieved as follows.

That is, the processing method of the silver halide color photographic light-sensitive material according to the present invention comprises the steps of: providing at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer on a transparent support. When the silver halide emulsion layer
Both have multiple layers with the same color sensitivity and different photographic sensitivity.
In the method for processing a silver halide color photographic light-sensitive material, the silver halide color photographic light-sensitive material has an average silver chloride content of 10 mol% in the photosensitive silver halide emulsion layer.
In addition to the above, from the start to the end of color development,
The ratio D (R / B) of the effective color density of the red-sensitive silver halide emulsion layer to the blue-sensitive silver halide emulsion layer and / or the effective color development of the green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer. The iodine-containing halogen is used so that the color development processing in which the concentration ratio D (G / B) is in the range of 0.2 to 1.1 is performed.
Antioxidation products of silver halide emulsions, DIR couplers, and developing agents
A compound capable of scavenging the oxide in response, or
It has a compound capable of releasing these precursors .

In the present invention, the effective color density refers to a color density from the minimum color density.

The ratio of the effective color density of the red-sensitive layer, green-sensitive layer and blue-sensitive layer in the present invention is determined according to the following method.

The ratio of the effective color density of the red-sensitive layer, green-sensitive layer and blue-sensitive layer in the present invention is determined according to the following method. The photosensitive material is subjected to sensitometric exposure using white light, and then subjected to color development processing. With respect to the obtained samples, the sensitometric densities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer are measured using red light, green light, and blue light, respectively. Regarding the sensitometry of the obtained sample, the ratios of the green and red effective color densities to the blue effective color densities (color densities from the minimum color densities) at the same exposure point are D (G / B) and D (G / B). R / B).

Hereinafter, the present invention will be described in detail.

The silver halide color photographic light-sensitive material according to the present invention has a plurality of light-sensitive silver halide emulsion layers on a support, and two or more layers composed of emulsions having different photographic characteristics.
These are the things that exist. For example, as the example thereof, red-sensitive, green-sensitive, there are multiple layers der that have different color sensitivities, such as blue-sensitive. In the present invention, the same color sensitivity
Having a plurality of layers having different photographic sensitivity sex, as an example of that includes the sensitive layer, mid layer, a different photographic sensitivity while having substantially the same color sensitivity as low sensitivity layer Refers to multiple layers. Here, substantially the same color sensitivity to say, for example, blue-sensitive, green-sensitive, may be a same In terms of red-sensitive, need not be exactly the same spectral sensitivity characteristics.

A preferred maximum spectral sensitivity wavelength of each layer is, for example, 400 to 500 nm for a blue-sensitive layer and 520 for a green-sensitive layer.
To 580 nm, and the red-sensitive layer is at 570 to 650 nm.

In the present invention, a particularly preferred layer structure is a layer structure comprising a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer each having one to three layers having different sensitivities. It is suitable for a color photographic light-sensitive material having such a layer structure.

In the present invention, the dried film thickness of the entire photographic constituent layers (all layers except the support) is preferably 30 μm or less, but the processing stability and rapid processing suitability are most effectively exhibited. In order to achieve this, the dry film thickness is particularly preferably 10 to 25 μm.

The silver halide grains used in the light-sensitive material according to the present invention contain 10 mol% or more of silver chloride. The silver chloride content is preferably at least 50 mol%, particularly preferably at least 80 mol%.

The components other than silver chloride are preferably silver bromide or silver iodide, and the silver halide emulsions include silver chlorobromide, silver chloride and silver chloroiodobromide.

When the silver halide emulsion according to the present invention comprises a solid solution crystal such as silver chlorobromide or silver chloroiodobromide, silver bromide or silver iodide is localized at a specific portion of the silver halide grain crystal. Are preferred.

When the silver halide emulsion according to the present invention is silver chlorobromide, it is preferable that the silver bromide is localized at the vertex of the silver halide crystal or in the vicinity thereof. Such a silver halide emulsion is prepared by adsorbing a sensitizing dye or an inhibitor onto silver chloride or silver chlorobromide crystal grains and then ripening by adding silver bromide fine particles, or adding a water-soluble bromide solution. It can be obtained by addition and halogen substitution.

Further, when the silver halide emulsion is silver chloroiodobromide, the silver iodide is preferably localized inside the grains.

A silver halide emulsion in which silver iodide is localized inside the grains can be obtained by depositing silver chloride or silver chlorobromide on a core containing silver iodide. For the deposition of silver chloride or silver chlorobromide, a known silver halide crystal growth method such as a double jet method or Ostwald ripening method can be used.

The core preferably has a silver iodide content of at least 10 mol%, more preferably 15 to 40 mol%.
It is.

The core is preferably silver iodobromide. The above silver halide emulsion is disclosed in JP-A-64-694.
No. 1, No. 64-26839 and JP-A-1-12184.
No. 8, No. 1-138550, and the like.

When the silver halide grains according to the present invention contain silver iodide, the content relative to the whole grains is 20 mol%.
Or less, more preferably 12 mol% or less, and particularly preferably 0 to 5 mol%.

The silver halide grains according to the present invention may be normal crystals such as cubic, tetradecahedral or octahedral, or twins such as tabular, and particularly preferably octahedral or tabular. The shape of the crystal can be controlled by appropriately selecting pAg, pH, and the like during mixing. Also, 8
Planar or tabular grains are described, for example, in JP-A-58-11935.
No. 58-11936, No. 58-11937, No. 58-108528, No. 62-163046, No. 6
As can be seen in JP-A-3-41845 and JP-A-63-212932, it can be obtained by growing crystals on silver halide grains in the presence of an adsorptive sensitizing dye or inhibitor.

The silver halide grains according to the present invention preferably have an average grain size of 0.05 to 10 μm, more preferably 0.1 to 5 μm, particularly preferably 0.2 to 3 μm.

The silver halide grains according to the present invention can be used in combination with other silver halide grains as long as the effects of the present invention are not impaired. At this time, the silver halide grains according to the invention are preferably at least 30% by weight, more preferably at least 50%, particularly preferably at least 80%.

The localization of halogen in the silver halide grains is X
It can be confirmed by examining sections of silver halide grains dispersed in a resin by a X-ray microanalysis method or a line diffraction method.

The silver halide emulsion according to the present invention is preferably monodisperse.

In the present invention, the term "monodispersity" means that the weight of silver halide contained within a range of ± 20% of the particle size around the average particle size d is 70% or more of the total weight of silver halide. , Preferably 80% or more, more preferably 90% or more.

The average particle size d herein is defined as the particle diameter d ₁ when the product n ₁ × d ₁ ³ of the frequency n ₁ and d ₁ ³ particles having a particle size d ₁ is maximized. (Three significant digits and the least significant digit are rounded off to the nearest whole number.) The particle size referred to here is the diameter when the projected image of the particle is converted into a circular image having the same area.

The particle size can be determined by, for example, dispersing the particles so as not to overlap on a flat sample stage, photographing them with an electron microscope at a magnification of 10,000 to 50,000 times, and photographing the particle diameter on the print or the projection time. It can be obtained by measuring the area.
(The number of measured particles is indiscriminately 1000 or more.) Particularly preferred highly monodispersed emulsions of the present invention are defined by the following formula: standard deviation of particle size / average particle size × 100 = width of distribution (%). The distribution area is less than 20%,
It is more preferably at most 15%.

Here, the method for measuring the particle size is in accordance with the above-mentioned measuring method, and the average particle size is an arithmetic mean.

Average particle size = Σd ₁ n ₁ / Σn _{1 In the} silver halide color light-sensitive material according to the present invention using the silver chloride-containing emulsion, the light sensitivity of the blue-sensitive layer, green-sensitive layer and red-sensitive layer The silver bromide content of the silver halide emulsion is preferably higher in the order of the blue-sensitive layer, the green-sensitive layer, and the red-sensitive layer.

When each color-sensitive layer comprises a plurality of layers having different sensitivities, at least one of the layers may have the above relationship.
It is preferable that the above relationship exists between all layers. The difference in the silver bromide content of each sensitive layer is more preferably 2 mol% or more, and more preferably 5 mol% or more.

A feature of the present invention is that a color photographic light-sensitive material using the above-mentioned silver halide emulsion can be rapidly processed, and excellent quality can be stably obtained in terms of color reproduction even with processing fluctuations. As a result of intensive studies, the present inventors have studied the color development process and the factors that determine color reproducibility of a color photosensitive material using the silver halide emulsion containing silver chloride, and have studied the present invention as follows. Was found to be achieved. That is, when the color photosensitive material using the silver chloride emulsion containing silver chloride is exposed to white light and color-developed, the D (R / B) and / or D (G / B) is set to 0.2 to 1. It has been found that controlling to 1 makes the interlayer effect more conspicuous and improves color reproducibility. More preferably, it is set to 0.3 to 0.9 .

The above control is performed by the constitution or composition of the photosensitive material according to the present invention.

In the present invention, the following materials according to the present invention
Therefore , the interlayer effect generated is such that when a layer having the interlayer effect (for example, a cyan layer) is exposed to light at a specific wavelength (red wavelength), the layer that receives the interlayer effect (for example, the magenta layer) has an interlayer effect. Can be used in such a manner that the color development is suppressed in accordance with the color development of the layer (cyan layer) giving the color. In this way, unnecessary color development in another layer is suppressed at the same time as the necessary exposure in one layer, and as a result, the color purity is increased and the color reproducibility is improved.

As a material for producing an interlayer effect, the present invention
In light of this, there are iodine-containing silver halide emulsions, compounds capable of reacting with oxidized products of DIR couplers and developing agents to scavenge the oxides, or compounds capable of releasing these precursors. Specific examples of such compounds are described in Japanese Patent Application No. 62-162618.

As DIR couplers, for example, US Pat. No. 953,454 and US Pat. No. 3,227,5
No. 54, No. 3,615,506, No. 3,617,29
No. 1, No. 3,701,783, No. 3,833,500
No. 4,095,984 and 4,149,886
No. 4,286,054, No. 4,359,521
JP-A-52-90932, JP-A-56-116029
And U.S. Patent Nos. 4,248,962 and 4,409,323.
And JP-A-57-154234 and JP-A-58-16294.
No. 9, No. 58-205150, No. 59-195643
Nos. 59-206834 and 59-206636
DI described in JP-A-59-210440, etc.
An R coupler can be preferably used.

Examples of the DIR compound include, for example, US Pat. Nos. 3,632,345, 3,928,041, 3,938,996, 3,958,993, and 3,961,959. Nos. 4,046,574, 4,052,213, 4,171,223, 4,186,012, JP-A-52-65433, JP-A-52-130327, and 57- Compounds described in JP-A-128335 and pages 52 to 9 of Japanese Patent Application No. 61-44544.
Exemplary compounds (D-1) to (D-93) described on page 5 can be preferably used.

Compounds which can react with an oxidation product of a developing agent to scavenge the oxide include, for example, British Patent 1,
546,837, JP-A-52-150631
Nos. 57-111536 and 51-111537
No. 57-138636, No. 60-185950
No. 60-203943, No. 60-21944
No. 60-214358, No. 61-53643,
No. 61-84646, No. 61-86751, No. 61
-102646, 61-102647, 61-
No. 107245, No. 61-113060, No. 61-2
No. 31553, No. 61-233741, No. 61-23
Nos. 6550, 61-236551, 61-238
No. 057, No. 61-240240, No. 61-2490
No. 52, No. 62-81638, No. 62-205346
And No. 62-287249.

As the support of the silver halide color photographic light-sensitive material in the present invention, a transparent cellulose acetate film having a thickness of 10 to 200 μm, a polyethylene terephthalate film or the like may be used.

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

Various photographic additives such as an antifoggant and a stabilizer can be added to the photosensitive silver halide emulsion. It is advantageous to use gelatin as a binder for the emulsion.

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

A coupler is used in the light-sensitive silver halide emulsion layer of the color photographic light-sensitive material according to the present invention. There are no particular restrictions on the type of coupler.

Further, by coupling with a colored coupler having a color correcting effect, a competitive coupler and an oxidized form of a developing agent, a developer, a silver halide solvent, a toning agent, a hardener, an antifoggant, a chemical Compounds that release photographically useful fragments can be used, such as sensitizers, spectral sensitizers, and desensitizers.

Auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation layer can be provided on the light-sensitive material. In these layers and / or the emulsion layers, dyes which flow out of the light-sensitive material or are bleached during the development processing may be contained.

To the light-sensitive material, a formalin scavenger, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fogging inhibitor, a development accelerator, a development retarder, a bleaching accelerator and the like can be added.

The photosensitive material according to the present invention is particularly useful as a negative photosensitive material.

In order to obtain a dye image using the light-sensitive material according to the present invention, generally known color photographic processing can be performed after exposure.

In the method for processing a light-sensitive material of the present invention, it is preferable to perform processing in an alkaline bath having a pH of 7.0 to 12.0 immediately before color development processing. More preferably, pH 9.0 to 11.
0.

The color developing agent used in the color developing solution according to the present invention is preferably an aromatic primary amine-based compound.
-Phenylenediamine color developing agents are preferred.

These color developing agents are used in a concentration of preferably 0.1 to 30 g, more preferably 1 to 15 g, per liter of the color developing solution.

To obtain a dye image using the light-sensitive material according to the present invention, color photographic processing is performed after exposure. The color photographic processing generally includes a color developing step, a bleaching step, a fixing step, a rinsing step and, if necessary, a stabilizing step, but a processing step using a bleaching solution and a process using a fixing solution. Instead of the process, the bleach-fixing process can be performed using a one-bath bleach-fixing solution, or a one-bath developing bleach-fixing solution capable of performing color development, bleaching and fixing in one bath is used. A monobus processing step can also be performed. Also,
Instead of the rinsing step, a rinsing alternative stabilization step can be performed.

A pre-hardening treatment step, a neutralization step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed in combination with these treatment steps. In these processes, a color developing agent or a precursor thereof may be contained in the photosensitive material in place of the color developing process, and an activator process may be performed in which the developing process is performed with an activator solution. Beta processing can be applied. Among these processes, representative processes are shown below. (These processes are the final process, the washing process,
Either a washing treatment step and a stabilization treatment step, or a stabilization treatment or a stabilization treatment alternative to washing. )-Color development processing step-Bleaching processing step-Fixing processing step-Color development processing step-Bleaching and fixing processing step-Pre-hardening processing step-Color development processing step-Stop fixing processing step-Rinse processing step-Bleaching processing step-Fixing Processing step-Rinse step-Post-hardening step-Color development step-Rinse step-Supplementary color development step-Stop processing step-Bleaching step-Fixing step-Activator step-Bleaching and fixing step- Activator processing step-Bleaching processing step-Fixing processing step-Mono bath processing step-Preprocessing-Color development processing step-Bleaching processing step-Fixing processing step Note that "Washing processing step" in the above representative processing step is replaced with " A washing substitute stabilization process "may be performed.

The processing temperature is usually selected in the range of 10 ° C. to 65 ° C., but may be higher than 65 ° C. Preferably, the treatment is performed at 25 to 45 ° C.

The color developing solution is an alkali agent usually used in the developing solution, for example, sodium hydroxide, potassium hydroxide,
Ammonium hydroxide, sodium carbonate, potassium carbonate,
It may contain sodium sulfate, sodium metaborate or borax, etc., and may further contain various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or as development regulators such as citrazic acid. And hydroxylamine or sulfite as a preservative. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, dimethylformamide and dimethylsulfoxide can be appropriately contained.

The pH of the color developing solution is usually 7 or more, preferably about 9 to 13.

The color developing solution used in the present invention may optionally contain, as an antioxidant, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol,
Hydroxamic acid, pentose or hexose, pyrogallol-1,3-dimethyl ether and the like may be contained.

In the color developer, various chelating agents can be used in combination as a sequestering agent. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid;
Organic phosphonic acids such as -hydroxyethylidene-1,1'-diphosphonic acid; aminopolyphosphonic acids such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid; oxycarboxylic acids such as citric acid or gluconic acid; 2-phosphonobutane-1 And polyhydroxy compounds such as phosphonocarboxylic acids such as 1,2,4-tricarboxylic acid and polyphosphoric acids such as tripolyphosphoric acid and hexametaphosphoric acid.

The bleaching step may be performed simultaneously with the fixing step as described above, or may be performed individually.
As the bleaching agent, a metal complex salt of an organic acid is preferably used.For example, a polycarboxylic acid, an aminopolycarboxylic acid or an organic acid such as oxalic acid or citric acid, to which a metal ion such as iron, cobalt or copper is coordinated. Is used. The most preferred organic acids among the above organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′, N′-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and iminodiacetic acid. , Dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylene diamine tetrapropionic acid, phenylenediamine tetraacetic acid, and the like.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

[0077] These bleaching agents are preferably 5-450 g.
/ L, more preferably 20 to 250 g / l.

As the bleaching solution, in addition to the bleaching agent as described above, a solution having a composition containing a sulfite as a preservative can be used if necessary. Further, the bleaching solution may be a solution containing a composition containing a large amount of a halide such as ammonium bromide, which contains an iron (III) complex salt of ethylenediaminetetraacetate. Examples of the halide include, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide,
Potassium iodide, ammonium iodide and the like can also be used.

Examples of the bleaching solution include JP-A-46-280, JP-B-45-8506 and JP-B-46-556, Belgian Patent No. 770,910, JP-B-45-8836 and JP-A-45-8836.
-9854, JP-A-54-71634, and JP-A-49-71634.
Various bleaching accelerators described in JP-A-42349 and the like can be added.

The pH of the bleaching solution is used at 2.0 or more.
Generally, it is used at 4.0 to 9.5, preferably at 4.5.
~ 8.0, most preferably between 5.0 and 7.0.

A fixing solution having a commonly used composition can be used. As a fixing agent, a compound capable of forming a water-soluble complex salt by reacting with silver halide used in a normal fixing process, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and potassium thiocyanate , Sodium thiocyanate,
Typical examples thereof include thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount of 5 g / l or more, which can be dissolved, but generally used in an amount of 70 to 250 g / l.
A part of the fixing agent can be contained in the bleaching solution, and conversely, a part of the bleaching agent can be contained in the fixing solution.

The bleaching solution and the fixing solution include various pHs such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. Buffering agents can be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, defoaming agents or surfactants can be added.
Also, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acid or nitro alcohol, stabilizers such as nitrates, hardening agents such as water-soluble aluminum salts, An organic solvent such as methanol, dimethylsulfamide, dimethylsulfoxide and the like can be appropriately contained.

The fixing solution is used at pH 3.0 or higher, but is generally used at 4.5 to 10, preferably 5 to 9.5.
And most preferably from 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above-mentioned bleaching process. Preferred compounds and the concentrations in the processing solution are the same as those in the above-mentioned bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above-mentioned bleaching agent, and if necessary, a solution having a composition containing a sulfite as a preservative is applied. Also, a bleach-fixing solution having a composition in which a small amount of a halide such as ammonium bromide is added in addition to the ethylenediaminetetraacetate (III) complex salt bleaching agent and the silver halide fixing agent, or a halogen such as ammonium bromide. A special bleach-fixing solution having a composition containing a large amount of a compound can also be used. As the halide, besides ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used. it can.

As the silver halide fixing agent that can be contained in the bleach-fixing solution, the fixing agents described in the above fixing step can be exemplified. The concentration of the fixing agent and the pH buffer and other additives that can be contained in the bleach-fixing solution are the same as those in the fixing step.

The pH of the bleach-fixing solution is used at 4.0 or higher, but it is generally used at 5.0 to 9.5, preferably 6.0 to 8.5, and most preferably 6.5. ~
8.5.

The stabilizing solution used for a color negative photosensitive material, such as a stabilizing solution used after the water washing process and a washing alternative stabilizing solution used in place of the water washing, are used. Can be used without particular limitation.

In the silver halide color photographic light-sensitive material used in the present invention, the silver halide emulsion is preferably a silver halide emulsion.
The one described in Disclosure 308119 (hereinafter abbreviated as RD308119) can be used. The following table shows the locations. [Item] [Page of RD308119] Iodine structure Item 993 IA Manufacturing method Item 993 IA and 994 E Crystal habit Normal crystal 993 IA Twin twin 〃 Epitaxial ハ ロ ゲ ン Halogen composition uniform 993 IB Uniform Not 〃 Halogen conversion 994 IC section 置換 Substitution 〃 Metal-containing 994 ID section Monodisperse section 995 IF Solvent addition 潜 Latent image formation position Surface 999 IG section Inside 〃 Applicable photosensitive material negative 990 IH section Positive (including internal fog grains) 用 い る Using a mixture of emulsions Section 995 IJ Desalting Section 995 II-A In the present invention, the silver halide emulsion obtained by physical ripening, chemical ripening and spectral sensitization is used. use. Additives used in such a process are described in Research Disclosure No. 17643, No. 1 18716 and no. 308
119 (hereinafter RD17643 and RD1871 respectively)
6 and RD308119).

The following table shows the locations described. [Item] [Page of RD308119] [RD17643] [RD18716] Chemical sensitizer Section 996 III-A 23 648 Spectral sensitizer 996 IV-AA, B, C, D, H, H, I, J Section 23-24 648-9 Supersensitizer 996 IV-AE, Item J 23-24 648-9 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 Known photographic materials usable in the present invention. Additives are also described in Research Disclosure, supra. The following table shows relevant descriptions. [Item] [Page of RD308119] [RD17643] [RD18716] Anti-turbidity agent 1002 VII-I 25 650 Dye image stabilizer 1001 VII-J 25 Whitening agent 998 V 24 UV absorber 1003 VIII C, Section XIII C 25-26 Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 650 Lubricant 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer (contained in photosensitive material) Item 1011 XX-B Various couplers are used in the photosensitive material used in the present invention. Can be used, and specific examples thereof are described in the above-mentioned Research Disclosure. The following table shows relevant descriptions. [Item] [RD308119 page] [RD 17643] [RD 18716] Yellow coupler 1001 VII-D VII C-G Magenta coupler 1001 VII-D VII C-G cyan coupler 1001 VII-F VII C- Item G DIR coupler 1001 Item VII-F Item VIIF BAR coupler 1002 Item VII-F Other useful residue releasing coupler 1001 Item VII-F Alkali-soluble coupler 1001 Item VII-E The additive used in the present invention is RD308119. XIV
Can be added by the dispersion method described in the above.

In the present invention, the aforementioned RD17643
Page 28, RD1877164 pages 7-8 and RD308
The supports described in XIX 19 can be used.

The light-sensitive material of the present invention includes the aforementioned RD3081
An auxiliary layer such as a filter layer or an intermediate layer described in section 19 VII-K can be provided.

The light-sensitive material of the present invention is obtained by using the above-mentioned RD30811.
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in Section VII-K can be employed.

The present invention can be applied to various color light-sensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. .

The light-sensitive material of the present invention, other than the above,
RD17643, pages 28 to 29, RD18716
The development can be carried out by a usual method described on page 647 and XVII of RD308119.

[0096]

According to the present invention, a silver halide emulsion containing silver chloride is used to rapidly process a color image having excellent color reproducibility and to obtain a stable and stable image without processing fluctuation. A method for developing a silver color photographic light-sensitive material can be provided.

[0097]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples.

(Preparation of EM-1) Silver chlorobromide emulsion EM-1
Was adjusted as follows. The following (Solution A) and (Solution B) were simultaneously added to 1000 ml of a 2% aqueous gelatin solution kept at 40 ° C. over 30 minutes while controlling pAg = 6.6 and pH = 2.0. Solution) and (D Solution) with pAg =
7.3 and pH = 5.8 were added simultaneously over 180 minutes.

At this time, the control of pAg is described in JP-A-59-4.
No. 5437, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide. (Solution A) Sodium chloride 1.03 g Potassium bromide 0.006 g Add water 50 ml (Solution B) Add silver nitrate 3 g water 50 ml (Solution C) Sodium chloride 103.0 g Potassium bromide 0.63 g Add water 600 ml (Solution D) 300 g of silver nitrate Water was added, and after the addition of 600 ml, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., Ltd., followed by mixing with an aqueous gelatin solution and averaging. Particle size 0.70μ
m, coefficient of variation of particle size distribution: 7%, silver chloride content: 99.7
A mol% monodisperse cubic emulsion EM-1 was obtained.

Further, the halide compositions of Solution A and Solution C were arbitrarily changed from the above-mentioned method for preparing EM-1, and Solution C and Solution D were changed.
The pAg, pH, mixing time, and amount added at the time of addition of the solution were arbitrarily changed to obtain monodispersed cubic emulsions of EM-2 to 27 shown in Table 1.

Further, the above emulsion is composed of sodium thiosulfate,
Optimum chemical sensitization with chloroauric acid and ammonium thiocyanate.

[0102]

[Table 1]

[0103] In all the following examples Example 1, the addition amount of the silver halide color photographic material in particular shows the number of grams per 1 m ² unless otherwise noted. Further, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye was represented by the number of moles per mole of silver.

On a triacetylcellulose film support, each layer having the following composition was sequentially applied from the support side. 101 was created.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling solvent (Oil-1) 0 .20〃 (Oil-2) 0.20 Gelatin 1.6 Second layer: Intermediate layer (IL-1) Gelatin 1.3 Third layer: Low sensitivity red-sensitive emulsion layer (RL) EM-30. 4 EM-4 0.3 Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) ) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.50 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) ) 0.07 DIR compound (D-1) 0.006 DIR compound (D-2) 0.01 High boiling point solution (Oil-1) 0.55 Gelatin 1.0 Layer 4: High Sensitivity Red-sensitive emulsion layer (R-H) EM-2 0.9 Sensitizing dye (S-1) 1.7 × 10 -4 ( mol / Silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan Coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2) 0.02 High boiling solvent (Oil-1) 0.25 Gelatin 1.0 Fifth layer: intermediate Layer (IL-2) Gelatin 0.8 Sixth layer: low-sensitivity green-sensitive emulsion layer (GL) EM-3 0.6 EM-4 0.2 Sensitizing dye (S-4) 6.7 × 10 ⁴ (mol / mole of silver) sensitizing dye (S-5) 0.8 × 10 -4 ( mol / mole of silver) magenta coupler (M-1) 0.17 〃 (M-2) 0 43 colored magenta coupler (CM-1) 0.10 DIR compound (D-3) 0.02 high boiling point solvent (Oil-1) 0.70 gelatin 1.0 7th layer: high-sensitivity red-sensitive emulsion layer (G- H) EM-2 0.9 Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ (mol / silver 1 (Mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.03 〃 (M-2) 0.13 Colored magenta coupler (CM-1) 0.04 DIR compound (D-3) 0.004 High boiling point solvent (Oil-2) 0.35 Gelatin 1.0 Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (HS- 1) 0.07〃 (HS-2) 0.07〃 (HS-3) 0.12 High boiling point solvent ( Oil-2) 0.15 gelatin 1.0 Ninth layer: low-sensitivity blue-sensitive emulsion layer (BL) EM-3 0.25 EM-4 0.25 sensitizing dye (S-9) 5.8 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.60 〃 (Y-2) 0.32 DIR compound (D-1) 0.003 〃 (D-2) 0.006 High boiling point Solvent (Oil-2) 0.18 Gelatin 1.3 10th layer: High-sensitivity blue-sensitive emulsion layer (BH) EM-1 0.5 Sensitizing dye (S-9) 5.8 × 10 ^-4 ( Mol / silver 1 mol) {(S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 ８ (Y-2) 0.10 High boiling point solvent (Oil) -2) 0.05 gelatin 1.0 11th layer: 1st protective layer (PRO-1) Fine silver chloride particles (average particle size 0.06 μm) 0.3 UV absorption Absorbent (UV-1) 0.07〃 (UV-2) 0.1 Additive (HS-1) 0.2〃 (HS-2) 0.1 High boiling solvent (Oil-2) 0.05〃 (Oil-3) Gelatin 1.0 12th layer: 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Gelatin 0.5 In addition to the above composition, each layer has a coating aid Su-2, a dispersion aid Su-1, hardeners H-1 and H-2, and a dye AI-
1. AI-2 was added as appropriate.

[0106]

Embedded image

[0107]

Embedded image

[0108]

Embedded image

[0109]

Embedded image

[0110]

Embedded image

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

Next, the sample No. Sample No. 101 shown in Table 2 was used for Sample No. 101 instead of the emulsion of each photosensitive emulsion layer. 101 to 104 were produced.

[0115]

[Table 2]

After the sample thus prepared was subjected to sensitometric exposure using white light, it was processed in the following development processing A by changing only the color development time as shown in Table 3.

The sensitometric densities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer of each of the obtained samples were measured using red light, green light, and blue light.

For the sensitometry of each of the obtained samples, the total average (D (G) of the ratios of the green and red effective color densities to the blue effective color densities (color densities from the minimum color densities) at each exposure point was obtained. / B) and D (R / B)).
Table 3 shows the obtained results.

Further, to the same sample, a green separation exposure was uniformly applied to the sample, and a red separation exposure for sensitometry was further applied. Then, in the development processing A, the color development time was processed at 2 minutes. . The evaluation was based on the degree to which the green density when the red density was 1.0 was lower than the green density when the minimum red density was applied. In this case, the larger the reduction width (△ DG), the better the color reproducibility (△ DG). The decrease width (△ DG) is the same as that of sample N
o. The relative value when the value of 101 was set to 100 was displayed.

Table 3 shows the results.

Processing A Processing step (38 ° C.) Color development Developed Table 3 Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixing 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Each processing The composition of the processing solution used in the process is as follows.

<Color developing solution> 4-amino-3-methyl-
N-ethyl-N- (β-hydroxyethyl) aniline.
Sulfate 4.7
5g anhydrous sodium sulfite
4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 3
7.5 g sodium bromide
1.3 g Nitriloacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter. (PH = 10.1) <Bleaching solution> Ethylenediaminetetraacetate ammonium salt 100 g Ethylenediamine-4-acetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Add water to make 1 liter, and use ammonia water to make pH 6.0. Adjust to

<Fixing Solution> 175.0 g of ammonium thiosulfate 8.5 g of anhydrous sodium sulfite 2.3 g of sodium metasulfite 2.3 g of water was added to make 1 liter, and the pH was adjusted to 6.0 with acetic acid.

<Stabilizing Solution> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica) 7.5 ml Add water to make 1 liter.

[0125]

[Table 3]

As is clear from Table 3, the comparative sample N in which the ratio of the effective color densities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer did not fall within the range of 0.2 to 1.1, particularly in the early stage of development.
o. In particular, D (R / B) values of 101, 102, and 104 are small, and the color reproducibility is poor.

On the other hand, from the start of development, the red-sensitive layer
The ratio of each effective color density of the green sensitive layer and the blue sensitive layer is 0.2 to
1.1 of the present invention within the range of No. 1.1. It can be seen that 103 has much better color reproducibility than the comparison.

Example 2 Sample No. 1 used in Example 1 Exposure was performed on 101 to 104 in the same manner as in Example 1, and in the same manner as in Example 1, the color reproducibility (ΔDG), red-sensitive layer, green-sensitive layer, and blue sensitivity were determined by the following processing methods B and C in the same manner as in Example 1. Layer effective color density ratio (D
(G / B) and D (R / B)). Processing B, C
Are shown in Table 4. As a result, the same result as in Example 1 was obtained.

[0129]

[Table 4]

Processing B Processing Step Color development time (Table 4) Temperature 40 ° C. (Same as Processing A except for the color development step and color developer) <Color developer> 4-Amino-3-methyl-N- (β- Hydroxyethyl) aniline sulfate 11.1 g Anhydrous sodium sulfite 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 30.0 g Sodium bromide 1.3 g Nitrilo trisulfate trisodium salt (1 water (Salt) 2.5 g Water was added to make 1 liter. (PH = 10.2) Processing C Processing Step Temperature Time Color Development 38.0 ± 0.3 ° C Table 4 Bleaching and Fixing 35.0 ± 0.5 ° C 45 seconds Stabilization 30-34 ° C 90 seconds Drying 60 ８０80 ° C. for 60 seconds Color developing solution pure water 800 ml triethanolamine 10 g N, N-diethylhydroxylamine 5 g potassium bromide 0.02 g potassium chloride 2 g potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1. 0 g ethylenediaminetetraacetic acid 1.0 g catechol-3,5-diphosphonic acid disodium 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 9 g fluorescent brightener (4 , 4'-diaminostilbenzylsulfonic acid derivative) 1.0 g Potassium carbonate 27 g Water was added to make the total volume 1 liter, pH 10 Adjust to .10.

Bleaching and fixing solution Ferric ammonium ammonium diaminetetraacetate dihydrate 60 g Ethylenediaminetetraacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 1000 ml Ammonium sulfite (40% aqueous solution) 27.5 ml Adjust the pH to 5.7 with potassium or glacial acetic acid.

Stabilizing solution 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene 1,1-diphosphonic acid 2.0 g ethylenediaminetetraacetic acid 1.0 g hydroxylation Ammonium (20% aqueous solution) 3.0 g Fluorescent whitening agent (4,4'-diaminostilbenzyl sulfonic acid derivative) 1.5 g Water was added to a total volume of 1 liter, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide. Adjust.

Example 3 Sample No. 1 used in Example 1 The color reproduction (ΔDG) and the ratio of the effective color densities of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer were performed in exactly the same manner as in Example 1 except that the processing 103 was performed in the processing A and the processing D described below. (D (G / B), D (R /
B)) was determined. Note that the color reproducibility (ΔDG) of sample 103
Is expressed as a relative value with respect to the value of 100. Table 5 shows the obtained results.

Processing D Processing step (38 ° C.) Alkaline bath 1 minute Color development Developed as shown in Table 5 Bleaching 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 Second drying The composition of the processing solution used in each processing step is as follows. The processing after the color development process is completely the same as the processing A.

<Alkaline bath> Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitriloacetic acid / 3 sodium salt (monohydrate) 2.5 g Add water and add 1 liter And adjust the pH to 10.1.

<Color developing solution> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.75 g Sodium sulfite anhydrous 4.25 g Hydroxylamine 1/2 sulfate 2.0 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitriloacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter. (PH = 10.1) <Bleaching solution> Ethylenediaminetetraacetate ammonium salt 100 g Ethylenediamine4-acetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Add water to make 1 liter, and use ammonia water to make pH 6.0. Adjust to

<Fixing Solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 using acetic acid.

<Stabilizing Solution> Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica) 7.5 ml Add water to make 1 liter.

[0139]

[Table 5]

As is clear from Table 5, in the present invention,
It can be seen that the color reproducibility is improved by passing an alkaline bath before the color development process.

Example 4 Sample No. 1 used in Example 1 The third layer for 103,
Instead of the emulsion used in the fourth layer, EM
-26, EM-27, EM-25 for the 10th layer,
The coupler and DIR used in each photosensitive emulsion layer
In the same manner as in Sample No. 1 except that the coupler and the DSR compound were used instead of the compound as shown in Table 6, 401 was created. Further, the sample No. Sample No. 401 was prepared in exactly the same manner as in Sample No. 401 except that the DSR compound was changed as shown in Table 6. 4
02 was created.

Further, the material No. 401, NO. 402 is processed in the same manner as in Examples 1, 2 and 3, and the color reproducibility (ΔDG), the ratio of the effective color densities of the red-sensitive layer, the green-sensitive layer, and the blue-sensitive layer (D (G / G / B) and D (R / B)) were found to improve the color reproducibility in the present invention as in Examples 1, 2, and 3.

[0143]

[Table 6]

[0144]

Embedded image

[0145]

Embedded image

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-63-63044 (JP, A) JP-A-63-212932 (JP, A) JP-A-61-100751 (JP, A) JP-A-55- 29882 (JP, A) JP-A-3-13843 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 7/30 G03C 1/035 G03C 7/20

Claims (3)

(57) [Claims] 1. A transparent support having at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer ,
A method for processing a silver halide color photographic light-sensitive material having a plurality of layers having different sensitivities with different color sensitivities , wherein the silver halide color photographic light-sensitive material is an average of the light-sensitive silver halide emulsion layer. The silver chloride content is 10 mol% or more, and the ratio D (R / B) of the effective color density of the red-sensitive silver halide emulsion layer to the blue-sensitive silver halide emulsion layer from the start to the end of color development. And / or a color development process in which the ratio D (G / B) of the effective color density of the green-sensitive silver halide emulsion layer to the blue-sensitive silver halide emulsion layer is in the range of 0.2 to 1.1. Iodine-containing silver halide emulsion,
Reacts with an oxidation product of an IR coupler or a developing agent to cause the oxidation.
Compounds that can scavenge substances or their precursors
A method of processing a silver halide color photographic light-sensitive material, characterized by having a compound capable of releasing sir . 2. A method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the Br content of the light-sensitive silver halide emulsion layer is red-sensitive layer <green-sensitive layer <blue-sensitive layer. 3. The method according to claim 1, wherein the pH is from 7.0 to 1.
A method for processing a silver halide color photographic light-sensitive material, which is subjected to color development processing after processing in an alkaline bath of 2.0.