JPH05307238A - Color reverse picture forming method - Google Patents

Abstract

PURPOSE:To reduce a waste soln., to enhance the maximum coloring density with a high sensitivity and to improve color reproducibility by using a silver halide emulsion having a specified halogen composition and a silver bromide- localized phase. CONSTITUTION:This color photographic sensitive material has a layer contg. a silver halide emulsion consisting of >=90mol% silver chloride, <=10mol% silver bromide and 0mol% silver iodide or at least a layer contg. a silver halide emulsion consisting of >=88mol% silver chloride, <=10mol% silver bromide and 0.1-2mol% silver iodide. The silver halide grain in the emulsion has a silver bromide localized phase contg. >=20mol% silver bromide. Picture exposure, black-and-white development, reversing processing, color development and desilverization are carried out by using the color photographic sensitive body.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color reversal image forming method. In particular, the present invention relates to an image forming method with less waste liquid and improved color reproducibility.

[0002]

2. Description of the Related Art A color reversal film and a color reversal paper using a reversal process are known as a method for directly obtaining a positive image without passing through a negative image. These light-sensitive materials are required to have sufficient sensitivity and exposure latitude because they need to be directly photographed. Further, in order to improve color reproducibility and sharpness, an emulsion having a large developing effect is required. Therefore, silver iodobromide, which is advantageous for these, has been used as a photosensitive silver halide.

However, silver iodobromide releases bromine ions and iodine ions into a developing solution upon development, and these accumulated ions suppress development, so that the development delays with an increase in processing amount, which is an unfavorable result. Was invited. Therefore, in order to stabilize the development performance, it was necessary to add a cumulative amount of the inhibitor to the developing solution in advance and further increase the replenishment amount to apparently reduce the development delay due to continuous processing. .. As a result, the light-sensitive material using silver iodobromide inevitably has a large amount of waste liquid as compared with the light-sensitive material using silver halide which releases a small amount of the suppressive substance.

While environmental problems are becoming serious,
Various innovations have been made to the photographic development waste liquid. For example, a so-called low replenishment method that uses a small amount of a concentrated replenisher to reduce the amount of waste liquid, or a so-called reclaiming method that removes the development inhibitor from the collected waste liquid and reuses the consumed developing agent and other components is put to practical use. Came. However, these methods have a limit in reducing the amount of waste liquid because they involve an increase in fluctuations in processing liquid performance and photographic performance. Further, there is a problem that the cost of the waste liquid recycling facility is high and it is difficult to introduce it.

[0005]

Under the circumstances as described above, a light-sensitive material using silver chloride has been attracting attention because the release of the suppressing substance is small in principle. In recent years, in a system such as color paper that uses only color development, rapid processing is possible with a photosensitive material using silver chloride-based silver halide and a special processing agent that take advantage of such advantages, and a small amount of waste liquid is possible. The system was put into practical use. On the other hand, a system in which color development is followed by color development such as a color reversal process cannot be put to practical use due to some unfavorable phenomena caused by using a silver chloride emulsion. In particular, in a system in which black and white development is followed by color development, the use of a silver chloride silver halide emulsion causes a problem that sensitivity and maximum color density are reduced, and color reproducibility is deteriorated due to a reduction in development effect. ..

The use of a silver chloride silver halide emulsion in a color reversal (positive type) light-sensitive material is disclosed in JP-A-63-38.
No. 556, No. 63-318557, No. 64-7037.
No. 64-61742, No. 64-86140, and JP-A No. 2-214857. However, none of them describes reduction of waste liquid and improvement of sensitivity and reduction of maximum color density.

JP-A 64-26837, JP-A 1-1
05940, 1-183643 and 1-18
Japanese Patent No. 3647 describes that a photographic light-sensitive material excellent in rapid processability can be obtained by using a silver chloride-based silver halide emulsion having a silver bromide localized phase.
However, these photographic light-sensitive materials are mainly used for negative type color image formation in which only color development is performed, and are not directly applicable to color reversal (positive type) image formation.

An object of the present invention is to provide a color reversal image forming method in which the amount of waste liquid is small, the sensitivity is high, the maximum color density is high, and the color reproducibility is improved.

[0009]

The present invention provides chlorine, bromine,
A layer containing a silver halide emulsion consisting of silver halide having an iodine content of 90 mol% or more, 10 mol% or less, and 0 mol%, or a chlorine, bromine, or iodine content of 88 mol%, respectively. Mol% or more and 10 mol% or less, 0.
Silver bromide localization having at least one layer containing 1 to 2 mol% of silver halide emulsion and silver halide grains contained in the silver halide emulsion having a silver bromide content of 20 mol% or more. Provided is a color reversal image forming method for forming a color reversal image on a photographic light-sensitive material by image exposure processing, black-and-white development processing, reversal processing, color development processing and desilvering processing using a color photographic light-sensitive material having a phase. It is preferable that the silver halide grains have a cubic or tetradecahedral shape, and the silver bromide localized phase is present at least at one of the vertices of the edges of the cubic or tetradecahedron or in the vicinity thereof. The silver halide grains are preferably formed by mixing host grains and grains having a grain size smaller than that of the host grains and having a silver bromide content of 20 mol% or more and ripening. .. Furthermore, the image forming method of the present invention can be carried out in the following modes.

(1) The processing solution for the black-and-white development processing contains substantially no bromine ion and sulfite ion. (2) The processing solution for the black and white development process contains 5 × 10 5 chlorine ions.
^{-3 to} 1 × 10 ^-1 mol / liter. (3) The processing solution for the black and white development processing does not substantially contain thiocyanate ions. (4) The processing solution for color development processing contains substantially no thiocyanate ion. (5) The processing solution for color development process contains 5 × 10 5 salt ions.
^{-3 to} 1 × 10 ^-1 mol / liter. (6) The processing solution for black and white development processing and the processing solution for color development processing do not substantially contain bromine ions.

[0011]

According to the study of the present inventors, in the image forming method of the color reversal processing system for obtaining the color image by performing the color development after the black and white development, the silver halide having the above specific halogen composition and the silver bromide station. It has been found that the above objects can be achieved by using an emulsion. That is, according to the image forming method of the present invention, the amount of waste liquid is small, the sensitivity is high, the maximum color density is high, and the color reproducibility is improved.

DETAILED DESCRIPTION OF THE INVENTION The silver halide emulsion used in the color reversal light-sensitive material of the present invention has chlorine, bromine and iodine contents of 90 mol% or more and 10 mol% respectively.
Hereinafter, a silver halide emulsion consisting of silver halide of 0 mol% (hereinafter referred to as "silver chloride emulsion"), or a content of chlorine, bromine or iodine is 88 mol% or more and 10 mol% or less, respectively. 0.1 to 2 mol% of silver halide emulsion (hereinafter referred to as "silver iodochloride emulsion"). The silver halide emulsion having these halogen compositions is a silver chloride-based silver halide emulsion containing substantially no silver bromide.

The term "substantially free of silver bromide" means that the molar content of silver bromide is 10 mol% or less. It is preferably 5 mol% or less, more preferably 2 mol% or less. Silver chloride emulsion is at least 90
A high-silver-chloride silver chloride emulsion in which at least mol% is silver chloride. The molar content of silver chloride is preferably 95 mol% or more, more preferably 98 mol% or more. The silver iodochloride emulsion is a high silver chloride silver iodochloride emulsion having a silver iodide content of 0.1 to 2 mol% and comprising at least 90 mol% of silver chloride. The molar content of silver chloride is preferably 94 mol% or more, more preferably 97 mol% or more.

Next, the localized silver bromide phase will be described. The silver halide grains used in the present invention must have a localized phase of 20 mol% or more in terms of silver bromide content. Such a localized phase having a high silver bromide content may be arranged freely according to the purpose. The localized phase may be inside the silver halide grain, on the surface or subsurface, and may be divided into the inside and the surface or subsurface. In addition, the localized phase is
It may have a layered structure which surrounds the silver halide grains inside or on the surface.

Regarding the arrangement of the silver bromide localized phase, the silver halide grains have a cubic or tetradecahedral shape, and the silver bromide localized phase is located at or near the apex of the cubic or tetradecahedral ridge. It is preferably present in at least one place. This localized phase is locally epitaxially grown. The above "vertex or its vicinity" means 1 of the diameter of a circle having the same area as the projected area of silver halide grains.
The length is / 3 (preferably ⅕) as one side, and is within the area of a square whose one core is the apex of particles (intersection of edges in the case of cubic normal crystal particles).

The silver bromide content of the localized phase needs to exceed 20 mol%, but if the silver bromide content is too high, desensitization is caused when pressure is applied to the light-sensitive material, and processing is performed. The sensitivity and gradation may change significantly due to changes in the composition of the liquid. Therefore, the silver bromide content of the localized phase is preferably in the range of 20 to 70 mol%, more preferably in the range of 20 to 60 mol%, and particularly preferably in the range of 30 to 50 mol%. The silver bromide content of the localized phase can be determined by X-ray analysis method (described in "Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis" Maruzen) or XPS method ("Surface analysis, -IMA, Auger electron / photoelectron"). Application of spectroscopy- "described in Kodansha) can be used for analysis.

By examining the halogen composition of the host grain and the new phase by the X-ray analysis method and by examining the average halogen composition of the surface by the XPS method, the extent to which the new phase richer in silver bromide than the host grain on the entire surface is measured. Whether it accounts for
It can be roughly estimated.

Further, in order to identify the existence position of a new phase richer in silver bromide than the host grain and to measure the proportion of the new phase in the vicinity of the apex of the grain, observation with an electron microscope is carried out. In addition to EDX (Energy Dispersiv
e X-ray analysis) method, and can be measured using an EDX spectrometer equipped in a transmission electron microscope. This measuring method is concretely described in "Electronic Denry Microanalysyl" by Keiyoshi Soejima, Nikkan Kogyo Shimbun (issued in 1987).

The silver bromide localized phase is preferably composed of 0.1 to 20% silver, and preferably 0.5 to 7% silver of the total amount of silver constituting the silver halide grains. Is more preferable. The interface between such a localized phase of silver bromide and the other phase may have a clear phase boundary, or may have a short transition region in which the halogen composition gradually changes.

Various methods can be used for forming such a silver bromide localized phase. For example, a soluble silver salt and a soluble halogen salt can be reacted by a one-sided mixing method or a simultaneous mixing method to form a localized phase. Further, the localized phase can be formed also by using a so-called conversion method including a process of converting already formed silver halide into silver halide having a smaller solubility product. Alternatively, the localized phase can be formed by adding fine silver bromide particles and recrystallizing them on the surface of the silver chloride-based particles.

The preferred method for preparing the silver halide emulsion used in the present invention will be described below.

(1) The host grains of the silver halide emulsion are
It is preferably cubic or tetradecahedral crystal grains having substantially (100) faces (these may have rounded corners and higher-order faces). The average grain size of the host silver halide grains is preferably 0.2 to 2 μm.

The grain size distribution of the host silver halide grains is preferably monodisperse. A monodisperse emulsion has a variation coefficient (S / r) of 0.25 with respect to the grain size of silver halide grains.
The emulsion has the following grain size distribution. Here, r is the average particle size, and S is the standard deviation regarding the particle size.

The above-mentioned grain size is a diameter corresponding to a projected area when a silver halide emulsion is microscopically photographed by a usual method (for example, electron microscopic photography). The diameter equivalent to the projected area is defined as the diameter of a circle equal to the projected area of silver halide grains. Therefore, even when the shape of the silver halide grains is other than spherical (for example, cubic, octahedral, tetrahedral, tabular, and potato-like), the average grain size r and its standard deviation S can be obtained as described above. .. For the measurement of these particle sizes, see “The Theory of the Photogr” by TH James et al.
aphic Process ", 3rd edition, pp. 36-43, published by Macmillan, Inc. (described in 1966. The coefficient of variation is 0.
It is preferably 20 or less, more preferably 0.15 or less, and most preferably 0.10 or less.

(2) Next, bromine ions or high silver bromide fine particles are supplied to the host silver halide grains to form a new silver halide phase richer in silver bromide on the surface of the host silver halide grains. Precipitate. In the case of bromide ion, this process proceeds in a process called "halogen conversion" by the exchange reaction with the halogen ion on the surface of the host silver halide grain. When high silver bromide fine grains are used, a reaction called “recrystallization” is attempted between the host silver halide grains and the high silver bromide fine grains to form crystals having a more stable composition. Although the above two kinds of reactions are completely different, in both reactions, the vicinity of the apex of the host grain can be selected as the formation site of a new phase richer in silver bromide. Halogen conversion or recrystallization is carried out by a compound that adsorbs to a silver halide such as a sensitizing dye (see, for example, JP-A 64-268.
37, 64-26838 and 64-2684.
It is preferable to carry out the reaction in the presence of a compound represented by the formula [I], [II] or [III] described in No. 0 of each publication.

In the process of silver halide grain formation or physical ripening, even if cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt, etc. coexist. Good. In particular, the iridium salt is used in an amount of 10 ^-9 to 10 ^-4 mol / mol, more preferably 10 ^-8 to 10 ^-5 mol / mol, based on silver halide. This is particularly useful in order to obtain rapid developability and stability at a high illuminance or a low illuminance outside the proper exposure illuminance range, as compared with an emulsion prepared without using an iridium salt. In the present invention, it is preferred that at least 50% of all iridium salts be co-deposited during the deposition of the silver bromide localized phase. Emulsions doped with a large amount of polyvalent impregnated ions as disclosed in JP-A-62-260137 are preferable for improving reciprocity law failure and can be used in the silver chloride emulsion of the present invention.

In any case, the chloride concentration after the formation of the particles of the present invention is preferably 5 mol / liter or less.
A concentration of 07-3 mol / l is particularly preferred. The temperature at the time of grain formation is 10 to 95 ° C, preferably 40 to 90 ° C. The pH at the time of particle formation is not particularly limited, but may be neutral to
A weakly acidic range is preferable.

The silver halide salt emulsion is usually used for coating after physical ripening, desalting and chemical ripening after grain formation. Well-known silver halide solvents (for example, ammonia, Rhodan Kali or U.S. Pat. No. 3,271,157, JP-A-51-12360, 53-82408, 53).
No. 144319, No. 54-100717 and No. 5
Physical ripening in the presence of thioethers and thione compounds described in JP-A-4-155828 gives a monodisperse emulsion having a regular crystal form and a nearly uniform grain size distribution. In order to remove the soluble silver salt from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method or the like is used.

The average grain size of silver halide grains (in the case of spherical grains or grains close to spheres, the grain size is represented by the grain diameter, and in the case of cubic grains, the edge length is represented by the grain size) It is preferably 2 μm or less and 0.2 μm or more, and particularly preferably 1 μm or less and 0.2 μm or more. The particle size distribution may be narrow or wide. A so-called monodisperse silver halide emulsion having a value obtained by dividing the standard deviation of the grain size distribution by the average grain size within 0.15, particularly preferably within 0.10. In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodisperse silver halide emulsions having different grain sizes are mixed or separated in the same layer in the emulsion layers having substantially the same color sensitivity. It is preferred to coat the layers in multiple layers. 2 more
It is also preferable to use more than one kind of monodisperse silver halide emulsion or a combination of monodisperse emulsion and polydisperse emulsion as a mixture or multilayer. In the present invention, it is particularly preferable to use two or more monodisperse emulsions in a mixed or multilayer form.

As the protective colloid used in the preparation of the silver chloride emulsion used in the present invention and as the binder of the other hydrophilic colloid layers, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. it can. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate, starch derivatives, etc .; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymer of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, and polyvinylpyrazole. You can In addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Phot. Japan,
Oxygen-treated gelatin as described in No. 16, P30 (1966) may be used, and a hydrolyzate or oxygen hydrolyzate of gelatin may also be used.

The emulsion of the present invention is used after grain formation and chemical ripening. For chemical ripening, a gold sensitization method using a gold compound is described, for example, in US Pat. No. 2,448,060.
And the methods described in the respective specifications of No. 3320069 and No. 3320069 can be applied. As the gold sensitizer used in the present invention, a gold complex salt, for example, a compound described in US Pat. No. 2,399,083 can be preferably used.
Of these, potassium chloroaurate, potassium aurithiocyanate, auric trichloride, sodium aurithiosulfate and 2-orthosulfobenzothiazole methochloride are particularly preferred. The content of the gold sensitizer in the silver halide grain layer is 10 ^-9 to 10 ^-3 mol, and especially 10 ^-8 to 10 mol per mol of silver halide.
^-4 mol is preferred. TH Ham to strengthen gold sensitization
es "The Theory of the Photographic Process" 4th
Edition, (Macmillan Co. Ltd., New York, 1977), page 155, in combination with thiocyanate,
Further, it is also useful to use a tetra-substituted thiourea compound in combination as described in JP-B-59-11892.

In the present invention, it is preferable to use sulfur sensitization together with gold sensitization. As the sulfur sensitizer to be used, thiosulfates, thioureas, thiazoles, rhodanines and other compounds (specific examples: US Pat. No. 157494)
No. 4, No. 2410689, No. 2278947, No. 2
728686, 3656955, and 403092
No. 8 and No. 4067740). Of these, thiosulfates, thioureas, and rhodanines are particularly suitable. The amount of sulfur sensitizer is
The optimum amount can be selected according to the conditions such as the temperature of particle size chemical sensitization, pAg and pH. 10 ⁻⁷ to 10 ⁻³ mol, preferably 5 × 10 ⁻⁷ to 1 mol per mol of silver halide
0 ^-4 mol, more preferably 5 x 10 ^-7 to 10 ^-5 mol is used. The chemical sensitization temperature is pA in the range of 30 ° C to 90 ° C.
The value of g is 5 or more and 10 or less, and the pH of 4 or more can be appropriately selected.
In the present invention, a sensitizing method using a metal such as iridium, platinum, rhodium or palladium (eg US Pat. No. 24480)
No. 60, No. 2566245 and No. 2566263, each), a selenium sensitization method using a selenium compound,
Alternatively, a reduction sensitization method using tin salts, thiourea dioxide, polyamine and the like (eg, US Pat. Nos. 2,487,850 and 25,186).
No. 98 and No. 2521925).

Next, the main processing steps of the color image forming method of the present invention will be described in more detail.

[Black and White Development Processing] The black and white developing solution (processing solution) used in the present invention contains a developing agent. Examples of the developing agent include dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-). Pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol), ascorbic acid and 1,2,3,4
-A fused heterocyclic compound of a tetrahydroquinoline ring and an indole ring (described in U.S. Pat. No. 4067872) can be mentioned. As the developing agent, two or more kinds of compounds may be used in combination. A particularly preferred combination is the case where dihydroxybenzenes and 3-pyrazolidones are used together. The amount of developing agent used is 1 × per liter of black and white developer.
It is 10 ^{−5 to} 1 mol. In the black and white developing solution, in addition to the developing agent, a preservative (eg, sulfite, bisulfite), a silver halide solvent, a buffer (eg, carbonate, boric acid, borate,
Alkanol amines), alkaline agents (eg hydroxides, carbonates), solubilizers (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid), sensitizers (eg , Quaternary ammonium salts), development accelerators (eg, thioether compounds), surfactants, defoamers, film hardening agents, viscosity imparting agents, antifoggants, swelling inhibitors (eg sodium sulfate, potassium sulfate), A chelating agent or the like can be added. The sulfite used as the preservative also acts as a silver halide solvent. Examples of silver halide solvents other than sulfite include potassium thiocyanate, sodium thiocyanate, potassium sulfite, sodium sulfite, potassium disulfite, sodium disulfite, potassium thiosulfate, sodium thiosulfate and 2-
Mention may be made of methylimidazole. The amount of the silver halide solvent used is, as thiocyanate ions, 0.0 to 0.02 mol per liter of the black and white developing solution. In particular, the amount of silver halide solvent used is preferably 0.005 mol or less. The sulfite ion is preferably used in an amount of 0.0 to 1 mol, and more preferably 0.0 to 0.1 mol, per liter of the black and white developing solution. The concentration of bromine ions contained in the black-and-white developing solution (processing solution) is preferably 1 × 10 ⁻³ mol / l or less,
More preferably, it is 5 × 10 ⁻⁴ mol / l or less. The concentration of sulfite ion is preferably 1 × 10 ^-1 mol / l or less, more preferably 2 × 10 ^-2 mol / l or less. Furthermore, Rodin ions contained in the black and white developing solution (processing solution) is preferably 1 × 10 ^-2 mol / l or less, it is 1 × 10 ^-3 mol / l or less, more preferably. The black-and-white developing solution (processing solution) preferably contains chlorine ions in an amount of 5 × 10 ⁻³ mol / l or more and 1 × 10 ⁻¹ mol / l or less, and 5 × 10 ⁻³ mol / l or more. It is more preferable that the content is 2 × 10 ^-2 mol / l or less. Examples of the antifoggant include
Alkali metal salts of halogen (eg, potassium bromide, sodium bromide, potassium iodide), nitrogen-containing heterocyclic compounds (eg, benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, hydroxyazaindolizine), mercapto-substituted heterocyclic compound (eg, 1-phenyl-5-mercapto) And tetramer, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole) and mercapto-substituted aromatic compounds (eg, thiosalicylic acid). The antifoggant may be added to the photographic material. In that case, the antifoggant is eluted from the photographic material in the black-and-white developing process and accumulated in the black-and-white developing solution. The amount of antifoggant used is 0.001 to 0.05 per liter of black and white developer.
It is preferably molar. Examples of the chelating agent include aminopolycarboxylic acid (eg, ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid) and phosphonic acid (eg, nitrilo-N). , N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid). As the chelating agent, two or more kinds of compounds may be used in combination. The amount of the chelating agent used is preferably 0.1 g to 20 g, and more preferably 0.5 g to 10 g per liter of the black and white developer. The pH value of the black and white developer is preferably 8.5 to 11.5, and more preferably 9.0 to 10.5. Black and white developer replenishment amount is 1m for photographic material
50 to 500 ml per ² is preferable,
More preferably, it is 50 to 150 ml.
The processing time of the black and white development step is preferably 10 seconds to 120 seconds, more preferably 10 seconds to 45 seconds. The treatment temperature is preferably 30 ° C to 50 ° C, more preferably 35 ° C to 45 ° C. In the black and white development process, a water washing process is performed after the black and white development process. In the water washing step, in order to reduce the replenishment amount, it is preferable to use a multi-stage countercurrent method with two or more tanks. Replenishment may be reduced to other treatment bath levels (in this case,
Called a rinse bath). The replenishment amount of wash water is 1
It is preferably 0.5 to 10 liters per m ² . In the case of a rinse bath, the replenishing amount is preferably 50 ml to 2 liters per 1 m ² of the photographic material, and more preferably 100 ml to 500 ml. If necessary, an oxidizing agent, a chelating agent, a buffering agent, a bactericidal agent or the like can be added to the treatment liquid of the rinse bath.

[Reversal Processing] In the color image forming method of the present invention, the reversal processing is performed after the black and white development processing. The reversal process includes a chemical fogging process or a reversal exposure process. The reverse exposure step is preferred. In the case of the chemical fogging process, a fogging agent such as tin ion complex salt is used. The reversal processing and the color development processing may be performed in the same step by adding a fogging agent to the color developing solution described later. In the case of the reversal exposure step, the entire surface of the photographic photosensitive material is exposed at 100 lux for 10 seconds or more.

[Color Developing Treatment] The color developing solution is usually an alkaline aqueous solution of an aromatic primary amine type color developing agent. A p-phenylenediamine compound is preferable as the developing agent. Examples of p-phenylenediamine compounds include 3-methyl-4-amino-N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl- Four
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, phosphates, p-toluenesulfonate,
Mention may be made of tetraphenyl borate and p- (t-octyl) benzene sulfonate. The developing agent is
It is preferable to use 1.0 g to 15 g, and more preferably 3.0 g to 8.0 g, per liter of the color developing solution. Color developers include, in addition to the developing agent, buffers (eg, alkali metal carbonates, borates and phosphates), preservatives (eg, hydroxylamine, diethylhydroxylamine, triethanolamine, catechol- 3,5-disulfonate, sulfite, bisulfite), organic solvent (eg, diethylene glycol, triethylene glycol), dye-forming coupler, competitive coupler (eg, citrazinic acid, J acid, H acid), nucleating agent (Eg, sodium boron halide), auxiliary developing agent (eg, 1-phenyl-3-pyrazolidone), viscosity imparting agent, development accelerator, antifoggant, chelating agent and the like can be added. Examples of the antifoggant and the chelating agent are the same as the examples of the additives for the black and white developing solution described above. Examples of the development accelerator include benzyl alcohol, pyridinium compounds (JP-B-44-9503, and US Pat. No. 264860).
4 and 3171247), cationic dyes (eg, phenosafranine), nitrates (eg, thallium nitrate, potassium nitrate), polyethylene glycol and derivatives thereof (Japanese Patent Publication No. 44-9304, and US Pat. No. 2,533,990). No. 2531832, No. 2
No. 57127 and No. 2950970), polythioethers and thioether compounds (described in US Pat. No. 3,012,242). The pH value of the color developing solution is preferably 9 or more, more preferably 9.5 to 12.0, and particularly preferably 10.0 to 11.5. The replenishing amount of color developer is 25 per 1 m ^{2 of} photographic material.
The volume is preferably ml to 500 ml, more preferably 50 to 150 ml. The processing temperature in the color developing step is preferably 30 ° C to 50 ° C, more preferably 31 ° C to 45 ° C. The concentration of bromine ion contained in the color developing solution (processing solution) is 1
The amount is preferably × 10 ^-3 mol / l or less, more preferably 5 × 10 ^-4 mol / l or less. The concentration of sulfite ion is preferably 1 × 10 ⁻² mol / l or less, more preferably 5 × 10 ⁻³ mol / l or less. Further, it is preferable that the color developing solution (processing solution) contains chlorine ions in an amount of 5 × 10 ⁻³ mol / l or more and 1 × 10 ⁻¹ mol / l or less.

[Desilvering Treatment] The desilvering treatment comprises an adjusting step, a water washing step, a bleaching step, a fixing step, a bleach-fixing step, a water washing alternative stabilizing step and the like. As a method of replenishing the treatment liquid in each step, the replenishment liquid in each bath can be individually replenished. When the bleach-fixing treatment is carried out after the bleaching treatment, the overflow solution of the bleaching bath may be introduced into the bleach-fixing bath and the bleach-fixing bath may be supplemented with only the fixing solution. As the bleaching agent used in the bleaching step or the bleach-fixing step, aminopolycarboxylic acid iron (II
I) Complex salts are typical. Examples of preferred bleaching agents are ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, diethylenetriaminepentaacetic acid,
Mention may be made of cyclohexanediaminetetraacetic acid, cyclohexanediaminetetraacetic acid disodium salt, iminodiacetic acid and 1,3-diaminopropanetetraacetic acid. Aminopolycarboxylic acid iron (III) complex salt is iron (III)
Salt and aminopolycarboxylic acid may be added to the treatment liquid to form an iron (III) complex salt in the treatment liquid. Two or more kinds of aminopolycarboxylic acids may be used in combination. In addition, the aminopolycarboxylic acid may be used in an excessive amount (as long as the iron (III) complex salt is formed). In addition to the iron (III) complex salt, metal ion complex salts other than iron such as cobalt and copper may be added to the bleaching solution or the bleach-fixing solution. The amount of bleach used per liter of bleaching solution is preferably 0.1 mol to 1 mol,
More preferably, it is 0.2 to 0.5 mol. The pH of the bleaching solution is preferably 4.0 to 8.0, more preferably 5.0 to 6.5.
The amount of bleach used per liter of bleach-fixing solution is 0.0
The amount is preferably 5 to 0.5 mol, more preferably 0.1 to 0.3 mol. The pH of the bleach-fixing solution is preferably 5 to 8, and more preferably 6 to 7.5. Bleaching accelerators can be added to the bleaching bath, the bleach-fixing bath or the conditioning bath. Examples of bleaching accelerators include mercapto compounds (JP-A-53-141623 and US Pat. No. 3893).
No. 858 and British Patent No. 1138842), compounds having a disulfide bond (JP-A-53-53).
95630), thiazolidine derivatives (described in JP-B-53-9854), isothiourea derivatives (described in JP-A-53-94927), thiourea derivatives (JP-B-45-8506 and 49-26586). Descriptions in each publication), thioamide compounds (JP-A-49-423)
No. 49), dithiocarbamate salts (Japanese Patent Laid-Open No. Sho 5)
5-26506) and alkyl mercapto compounds (eg, trithioglycerin, α, α′-thiodipropionic acid, δ-mercaptobutyric acid). The alkylmercapto compound may have a substituent such as a hydroxyl group, a carboxyl group, a sulfonic acid group, and an amino group (which may further have a substituent such as an alkyl group and an acetoxyalkyl group). The amount of the bleaching accelerator used is determined in consideration of the type of photographic material, processing temperature and processing time. Mercapto compounds, compounds having a disulfide bond, when using a thiazolidine derivative or isothiourea derivative as bleach accelerator, the treatment liquid 1 is preferred to liters per 10 ^-5 to 10 ^-1 moles, 10 ^-4 to 5 × 10 ^- It is more preferable to use ² mol. In addition to the bleaching agent and the bleaching accelerator, a rehalogenating agent, an inorganic acid having a pH buffering ability, an organic acid or a salt thereof can be added to the bleaching solution. Examples of the rehalogenating agent include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) and chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Examples of acids or salts having pH buffering ability include nitrates (eg, sodium nitrate, ammonium nitrate), boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid,
Mention may be made of phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid.

Examples of the fixing agent used in the fixing step or the bleach-fixing step include thiosulfates (eg, sodium thiosulfate, ammonium thiosulfate), thiocyanates (eg, sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate). , Thiourea and thioethers. The amount of the fixing agent used per liter of the bleach-fixing solution is preferably 0.3 mol to 3 mol, more preferably 0.5 mol to 2 mol. The amount of fixer used per liter of fixer is 0.5
It is preferably from 4 to 4 mol, more preferably from 1 to 3 mol. The pH of the fixing solution is preferably 6 to 10, and more preferably 7 to 9. Known additives such as sulfites, bisulfites, buffers, chelating agents, and sulfinic acids may be added to the fixer or the bleach-fixer. Further, ammonium halide (eg, ammonium bromide) or an alkali metal salt of halogen (eg, sodium bromide, sodium iodide) may be added to the fixing solution or the bleach-fixing solution. When the fixing solution or the bleach-fixing solution is diluted with the overflow solution of the bleaching bath, it is preferable that the respective components of the fixing solution or the bleach-fixing solution have a relatively high concentration. Considering the dilution with the overflow liquid, the amount of the discharged liquid can be reduced and the burden of the recovery process can be reduced. The replenishing amount of the bleaching solution, the fixing solution and the bleach-fixing solution is 3 per 1 m ² of the photographic material.
0 ml to 500 ml is preferred, 50 ml
It is more preferable that the volume is from about 150 ml.

In the desilvering process, finally, a washing step or a washing-stabilizing alternative step is carried out. Known additives can be added to the washing water used in the washing step, if necessary.
Examples of additives include chelating agents (eg, inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid), bactericides, fungicides, hardeners and surfactants. The water washing step may use two or more tanks. Further, the washing water may be saved by multi-stage countercurrent washing (for example, 2 to 9 steps). The stabilizing solution used in the stabilizing step as a substitute for washing has a function of stabilizing the dye image. Examples of the stabilizing solution include a solution having a buffering capacity of pH 3 to 6 and a solution containing an aldehyde (eg, formaldehyde). If necessary, a chelating agent, a bactericidal agent, a mildew-proofing agent, a hardener, a surfactant and the like can be added to the stabilizing solution. Two or more tanks may be used in the washing-replacement stabilizing step. The stabilizing liquid may be saved by multi-stage countercurrent water washing (for example, 2 to 9 stages). A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, a nitrogen stirrer, an air stirrer and the like may be provided in the treatment bath of each step as described above, if necessary. ..

The color photographic material used in the present invention will be described below. The color photographic material has a silver halide emulsion layer containing a yellow coupler, a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a cyan coupler on a support. The photosensitive wavelengths of the silver halide emulsion layers are different from each other. The emulsion layer is usually sensitive to visible light, specifically blue light, green light and red light. In conventional color photographic materials, the blue-sensitive silver halide emulsion layer contains a yellow coupler, the green-sensitive silver halide emulsion layer contains a magenta coupler, and the red-sensitive silver halide emulsion layer contains a cyan coupler. The arrangement of silver halide emulsion layers is generally in the order of a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer from the support side. Of course, the emulsion layer may have photosensitivity outside the visible region. Further, combinations of the sensitivity of the emulsion layers and couplers other than the above, and arrangement of the photosensitive layers other than the above are also possible. Further, each emulsion layer may have a two-layer structure of a high sensitivity emulsion layer and a low sensitivity emulsion layer. In a normal color photographic material, layers having various functions (eg, antihalation layer, intermediate layer, ultraviolet absorbing layer, protective layer) are provided in addition to the silver halide emulsion layer.

The coating amount of the silver halide emulsion is preferably 0.1 g / m ² to 1.5 g / m ^{2 in} terms of silver, and is 0.1 g / m ^{2 to} 1.0 g / m ^2. Is more preferable. Phenolic compounds may be added to the silver halide emulsion layers for the purpose of improving the photographic properties of color photographic materials. As the phenol compound, a hydroquinone compound is particularly preferable. Regarding the hydroquinone compound, JP-A-55-43521 and JP-A-56-109344.
Nos. 57-22237 and 60-172040.
The respective publications and US Pat. No. 2,701,197 are described. The phenolic compound can be added to the photographic material as an aqueous alkaline solution. Further, it may be dissolved in a high boiling point oil and added to the photographic material as an emulsion. The phenol compound is preferably used in a coating amount of 10 ^{−4 to} 1 g / m ² .

The photographic material used in the present invention contains a yellow coupler, a magenta coupler and a cyan coupler for forming a color image. Various compounds are already known for these couplers. In the present invention, the type of coupler is not particularly limited. The yellow coupler is preferably a pivaloyl or pyrazoloallol compound. For yellow couplers, Japanese Patent Publication No. 58-107
39, and US Pat. Nos. 3,933,501 and 39.
73968, 4022620, 4248961
No. 43, 14023, 4326024, 44
01752, 4511649 and British Patent 1425
020, 1476760 and European Patent 2494.
No. 73A is described in each specification. Magenta coupler
5-Pyrazolone and pyrazoloazole compounds are preferred. For the magenta coupler, see JP-A-55-1.
18034, 60-33552, 60-357.
No. 30, No. 60-43659, No. 60-185951
And 61-72238, U.S. Pat. No. 306
1432, 3725067 and 4310619.
No., No. 4351897, No. 4500630, No. 45
No. 40654, No. 4556630, and European Patent 7363.
6, International Publication No. W088 / 04795, and Research Disclosure No. 24220 (19)
June 1984) and No. 24230 (6 June 1984)
Month). The cyan coupler is preferably a phenol type compound or a naphthol type compound. Regarding cyan couplers, JP-A-61-42658 and US Pat. Nos. 2,369,929, 2,772,162 and 2801.
No. 171, No. 2895826, No. 3446622,
No. 3758308, No. 3772002, and No. 4052
No. 212, No. 4146396, No. 4228233,
No. 4254212, No. 4296199, No. 4296
No. 200, No. 4327173, No. 4333999,
No. 4334011, No. 4427767, No. 4451
No. 559, No. 4690888, No. 4775616,
West German Patent Publication 3329729, European Patent 121365
No. A and No. 249453A are described in each specification.
As another coupler which can be added to a photographic material, a colored coupler for correcting unnecessary absorption of a coloring dye (Japanese Patent Publication No. 57-39413, U.S. Pat.
04909, 4138258, 4163670.
And British Patent No. 1146368, and Research Disclosure 17643 VII-G
), A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling (US Pat. No. 47.
No. 74181), a coupler having as a leaving group a dye precursor that reacts with a developing agent to form a dye (described in U.S. Pat. No. 4,777,120), and a coupler in which a coloring dye has an appropriate diffusibility (U.S. Pat.
37, British Patent 2125570, West German Patent Publication 32
34533 and EP 96570), polymerized dye forming couplers (US Pat.
No. 451820, No. 4080211, No. 436728
No. 2, No. 4,409,320, No. 4,576,910, and British Patent No. 2,102,173), and a DIR coupler (Japanese Unexamined Patent Publication Nos. 57-151944, 57-154234, 57-154234) that releases a development inhibitor upon coupling. 60-184248, 63-37346 and 63-37350, US Pat. Nos. 4,248,962 and 4782012, and Research.
Disclosure magazine 17643, Item VII-F), couplers that release a nucleating agent or a development accelerator imagewise during development (JP-A-59-157638 and JP-A-5-157638).
9-170840 and British Patent 20971
Nos. 40 and 2131188 each), competitive couplers (US Pat. No. 4,130,427), multi-equivalent couplers (US Pat. Nos. 4,283,472 and 4,338).
No. 393 and No. 4310618 each description), D
IR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing compound or DIR
Redox-releasing redox compound (JP-A-60-185)
950 and 62-24252), a coupler that releases a dye that recolors after withdrawal (EP 173).
No. 302A and No. 313308A).
Bleach accelerator releasing coupler (Japanese Patent Laid-Open No. 61-201247, and Research Disclosure 1144)
9 and 24241), a ligand-releasing coupler (described in US Pat. No. 4,553,477), and a leuco dye-releasing coupler (described in JP-A-63-75747). The coupler used in the present invention is preferably added to the photographic material using a high boiling solvent (preferably having a boiling point of 175 ° C. or higher).
Specifically, the coupler is dissolved in a high boiling point solvent, and the solution is emulsified in an aqueous liquid such as a silver halide emulsion. Examples of the high boiling point solvent include phthalic acid esters (eg, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4
-Di-t-amylphenyl) phthalate, bis (2,4)
-Di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tri Cyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate), benzoic acid esters (eg, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl) -P-hydroxybenzoate), amides (eg, N, N-diethyldodecane amide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone), a Call acids (e.g., isostearyl alcohol), phenols (e.g., 2,4-di -tert-
Amylphenol), aliphatic carboxylic acid esters (eg, bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg, N, N-dibutyl) -2-butoxy-5
-Tert-octylaniline) and hydrocarbons (eg, paraffin, dodecylbenzene, diisopropylnaphthalene). As an auxiliary solvent for a high boiling point solvent, the boiling point is 30 ° C. or higher, preferably 50 ° C. to 160 ° C.
You may use the organic solvent of. Examples of co-solvents include
Mention may be made of ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

Other additives usable in photographic materials are described in Research Disclosure Nos. 17643 and 18716. The relevant parts are summarized below. ──────────────────────────────────── Additive RD17643 RD18716 ────────── ────────────────────────── Chemical sensitizer page 23 648 right column Sensitivity enhancer page 648 right column Spectral sensitizer, strong color Sensitizer, page 23-24, page 648, right column-page 649, right column Whitening agent, page 24, antifoggant and stabilizer, page 24-25, page 649, right column-light absorber, filter dye, page 25-26, page 649, right column Page 650 right column and UV absorber anti-staining agent page 25 right column page 650 left column to right column dye image stabilizer page 25 hardener 26 page 651 left column binder 26 page 651 left column plasticizer, lubricant Page 27, page 650, right column, coating aids and surfactants, pages 26-27, page 650, right column, antistatic agent Page 27 Page 650 Right column ──────────────────────────────────── In addition, In order to prevent deterioration, a compound which reacts with formaldehyde to be immobilized may be added to the photographic material. Such compounds are disclosed in US Pat. Nos. 4411987 and 44355.
No. 03 There is a description in each specification. Hydroquinones releasing development inhibiting compounds (described in JP-A-64-546 and US Pat. Nos. 3,379,529 and 3639417) or naphthoquinones releasing development inhibiting compounds (Research Disclosure 1826).
No. 4 (described in June 1979) may be added to the photographic material. Preservatives or fungicides can also be added to the photographic materials. Examples of preservatives and fungicides include 1,2-benzisothiazolin-3-one, n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5.
Mention may be made of dimethylphenol, 2-phenoxyethanol and 2- (4-thiazolyl) benzimidazole. Preservatives and antifungal agents are described in JP-A Nos. 63-257747, 62-272248 and 1-80941.

There is no particular limitation on the support used for the photographic material. Regarding the support, Research Disclosure 17643, page 28 and 18716, 64.
It is described in the right column on page 7 to the left column on page 648. In the color photographic material used in the present invention, the total thickness of all hydrophilic colloid layers on the side having the silver halide emulsion layer is preferably 28 μm or less, more preferably 20 μm or less, and 12 μm or less. It is particularly preferable that
The film swelling rate (T _1/2 ) is preferably 30 seconds or less, more preferably 20 seconds or less. The film swelling speed is defined as the time required to reach half the film thickness, where 90% of the maximum swollen film thickness reached when the film is treated with a color developer at 30 ° C. for 3 minutes and 15 seconds is taken as the saturated film thickness. .. The film thickness can be measured using a selometer (swelling meter). For the film swelling rate, see A. Green et al.
et al), Photographic Science and
Engineering (Photogr. Sci. Eng.), Volume 19, 2
No. 9, pp. 124-129. The film swelling rate is
It can be adjusted by adding a hardening agent to gelatin which is a binder, or by changing the aging condition after coating. The swelling rate is preferably 150 to 400%. The method of the present invention can be preferably applied to positive color image formation using a color reversal film for slides or a television and a color reversal paper.

[0045]

【Example】

[Example 1] "Preparation of emulsion EM-1" 6.49 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and N, N'-dimethylimidazolidine-2-thione (1% aqueous solution) was added to 3.2.
ml was added. While stirring vigorously, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.04 mol of potassium bromide and 0.16 mol of sodium chloride were mixed in this solution.
Added and mixed at 2 ° C. Subsequently, an aqueous solution containing 0.8 mol of silver nitrate, 0.16 mol of potassium bromide, 0.64 mol of sodium chloride, 2.0 mg of potassium hexacyanoferrate (II) trihydrate and potassium hexachloroiridium (IV) ate. An aqueous solution containing 1.0 mg was added and mixed at 52 ° C. with vigorous stirring. One minute after the addition of the aqueous silver nitrate solution and the aqueous halogen alkali solution was completed, 95 mg of each of red sensitizing dyes-1, 2, and 3 was added.

After keeping at 52 ° C. for 15 minutes, desalting and washing with water were performed. Further, 90.0 g of lime-processed gelatin was added and triethylthiourea was added, and optimum chemical sensitization was carried out so as to obtain a surface latent image type emulsion. The obtained silver chlorobromide (silver bromide 20 mol%) emulsion was designated as emulsion EM-1.

[0047]

[Chemical 1]

[0048]

[Chemical 2]

[0049]

[Chemical 3]

[Preparation of Emulsion EM-2] 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and N,
3.2 ml of N′-dimethylimidazolidine-2-thione (1% aqueous solution) was added. Silver nitrate was added to this solution in an amount of 0.
An aqueous solution containing 2 mol and an aqueous solution containing 0.004 mol of potassium bromide and 0.196 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.8 mol of silver nitrate, 0.016 mol of potassium bromide, 0.764 mol of sodium chloride, 2.0 mg of potassium hexacyanoferrate (II) trihydrate and 1 mg of potassium hexachloroiridium (IV) ate. An aqueous solution containing 0.0 mg was added and mixed at 52 ° C. with vigorous stirring. One minute after the addition of the aqueous silver nitrate solution and the aqueous halogen alkali solution was completed, 95 mg of each of red sensitizing dyes-1, 2, and 3 was added.

After keeping at 52 ° C. for 15 minutes, desalting and washing with water were performed. Further, 90.0 g of lime-processed gelatin was added and triethylthiourea was added, and optimum chemical sensitization was carried out so as to obtain a surface latent image type emulsion. The obtained silver chlorobromide (silver bromide 2 mol%) emulsion was designated as emulsion EM-2.

[Preparation of Emulsion EM-3] 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and N,
3.2 ml of N′-dimethylimidazolidine-2-thione (1% aqueous solution) was added. To this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.05 mol of silver nitrate and an aqueous solution containing 0.02 mol of potassium bromide, 0.03 mol of sodium chloride and 2.0 mg of potassium hexacyanoferrate (II) trihydrate were vigorously stirred. Added and mixed at 52 ° C. One minute after the addition of the silver nitrate aqueous solution and the sodium chloride aqueous solution was completed, the red sensitizing dyes-1, 2 and 3 were each added in an amount of 95 m.
g was added.

After being kept at 52 ° C. for 15 minutes, an aqueous solution containing 0.75 mol of silver nitrate and 0.75 of sodium chloride were further added.
Molar and potassium hexachloroiridium (IV) 1.
An aqueous solution containing 0 mg was added and mixed at 40 ° C. with vigorous stirring. Then, desalting and water washing were performed. Further, 90.0 g of lime-processed gelatin was added and triethylthiourea was added, and optimum chemical sensitization was carried out so as to obtain a surface latent image type emulsion. The obtained silver chlorobromide (silver bromide 2 mol%) emulsion was designated as emulsion EM-3.

[Preparation of Emulsion EM-4] 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and N,
3.2 ml of N′-dimethylimidazolidine-2-thione (1% aqueous solution) was added. To this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. Then, an aqueous solution containing 0.75 mol of silver nitrate and an aqueous solution containing 0.75 mol of sodium chloride and 2.0 mg of potassium hexacyanoferrate (II) trihydrate were added and mixed at 52 ° C. with vigorous stirring. One minute after the addition of the aqueous silver nitrate solution and the aqueous sodium chloride solution was completed, 95 mg of each of red sensitizing dyes-1, 2 and 3 was added.

After being kept at 52 ° C. for 15 minutes, an aqueous solution containing 0.05 mol of silver nitrate, 0.02 mol of kalim bromide, 0.03 mol of sodium chloride and 1.0 mg of potassium hexachloroiridium (IV) ate were further contained. The aqueous solution was added and mixed at 40 ° C. with vigorous stirring. Then, desalting and water washing were performed. Furthermore, lime-processed gelatin 90.
0 g was added, triethylthiourea was added, and optimum chemical sensitization was performed so that a surface latent image type emulsion was obtained. The obtained silver chlorobromide (silver bromide 2 mol%) emulsion was designated as emulsion EM-4.

"Preparation of Emulsion EM-5" To a 3% aqueous solution of lime-processed gelatin, 3.3 g of sodium chloride was added, and N,
3.2 ml of N′-dimethylimidazolidine-2-thione (1% aqueous solution) was added. To this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. Then, an aqueous solution containing 0.775 mol of silver nitrate, 0.775 mol of sodium chloride and hexacyanoiron (II)
An aqueous solution containing 2.0 mg of potassium acid trihydrate was added and mixed at 52 ° C. with vigorous stirring. One minute after the addition of the aqueous silver nitrate solution and the aqueous sodium chloride solution was completed, 95 mg of each of red sensitizing dyes-1, 2 and 3 was added.

After being kept at 52 ° C. for 15 minutes, an aqueous solution containing 0.025 mol of silver nitrate, 0.02 mol of kalim bromide, 0.005 mol of sodium chloride and 1.0 mg of potassium hexachloroiridium (IV) ate were further contained. The aqueous solution was added and mixed at 40 ° C. with vigorous stirring. afterwards,
It was desalted and washed with water. Furthermore, lime-processed gelatin 9
0.0 g was added, triethylthiourea was added, and optimum chemical sensitization was carried out so as to obtain a surface latent image type emulsion. The obtained silver chlorobromide (silver bromide 2 mol%) emulsion was used as emulsion EM-5.
And

"Preparation of Emulsion EM-6" To a 3% aqueous solution of lime-processed gelatin, 3.3 g of sodium chloride was added, and N,
3.2 ml of N′-dimethylimidazolidine-2-thione (1% aqueous solution) was added. To this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. Then, an aqueous solution containing 0.75 mol of silver nitrate, 0.75 mol of sodium chloride, 2.0 mg of potassium hexacyanoferrate (II) trihydrate and hexachloroiridium (I
V) An aqueous solution containing 1.0 mg of potassium acid was added and mixed at 52 ° C. with vigorous stirring. One minute after the addition of the aqueous silver nitrate solution and the aqueous sodium chloride solution was completed, 95 mg of each of red sensitizing dyes-1, 2 and 3 was added.

After maintaining at 52 ° C. for 15 minutes, an ultrafine silver bromide emulsion (grain size 0.05 μm) was further added in an amount containing 2 mol% of silver bromide with respect to silver chloride, and the mixture was heated to 58 ° C. The temperature was raised and aged for 10 minutes. Then, desalting and water washing were performed. Further, 90.0 g of lime-processed gelatin was added and triethylthiourea was added, and optimum chemical sensitization was carried out so as to obtain a surface latent image type emulsion. The obtained silver chlorobromide (silver bromide 2 mol%) emulsion was designated as emulsion EM-6.

The grain shape, grain size and grain size distribution of the thus prepared 6 types of silver halide emulsions EM-1 to EM-6 were determined from electron micrographs. The silver halide grains contained in the emulsions EM-1 to EM-6 were all cubic. The particle size is represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution is the standard deviation of the particle size divided by the average particle size. The halogen composition of the emulsion grains was then determined by measuring X-ray analysis from the silver halide crystals. Using the monochromatic CuKaα ray as a radiation source, the analysis angle of the analysis line from the (200) plane was measured in detail. An analysis line from a crystal having a uniform halogen composition gives a single peak, whereas an analysis line from a crystal having a localized phase having a different composition gives a plurality of peaks corresponding to those compositions. The halogen composition of the silver halide constituting the crystal can be determined by calculating the lattice constant from the analyzed angle of the measured peak. Further, the position of the silver bromide localized phase was determined by an electron micrograph and EDX method. The results are shown in Table 1.

[0061]

[Table 1] Table 1 ──────────────────────────────────── Halogen particle size Main peak Sub peak Silver bromide Localized phase silver halide emulsion shape μm (distribution) (%) (%) Localized phase formation position ───────────────────────── ──────────── EM-1 (Comparative example) Cube 0.51 (0.08) Cl 80 None None None None EM-2 (Comparative example) Cube 0.50 (0.08) Cl 98 None None None EM-3 ( The present invention) Cube 0.51 (0.07) Cl 99 Cl80 to 90 Yes Inside particle EM-4 (Invention) Cube 0.49 (0.09) Cl 99 Cl80 to 90 Yes Particle corner EM-5 (Invention) Cube 0.49 (0.09) Cl100 Cl61 ~ 90 Yes Particle Corner EM-6 (Invention) Cube 0.49 (0.09) Cl100 Cl80 ~ 90 Yes Particle Corner ─────────────────────────── ──────────

A photographic light-sensitive material was prepared by coating the following emulsion layer and protective layer on a paper support laminated on both sides with polyethylene. The components of each layer below are shown by the coating amount (g / m ² ). However, for silver halide, the coating amount in terms of silver is shown. The compounds used to make the photographic light-sensitive material are
This is shown in Example 2.

First layer (emulsion layer) EM-1 0.30 Gelatin 2.00 Cyan coupler 1 0.40 Cyan coupler 2 0.20 Anti-fading agent 1 0.10 Anti-fading agent 2 0.10 Anti-fading agent 3 0.10 Dispersion medium (for coupler) 0.06 Di (2-ethylhexyl) phthalate (solvent for coupler) 0.066 Trinonyl phosphate (solvent for coupler) 0.066 Di (3-methylhexyl) phthalate (solvent for coupler) ) 0.066 development accelerator 0.10

Second layer (protective layer) Gelatin 0.90 1,2-bis (vinylsulfonylacetamide) ethane (gelatin hardener) 0.085 4,6-dichloro-2-hydroxy 1,3,5-triazine Sodium salt (gelatin hardener) 0.085 Modified Poval 0.05

Further, in each layer, alkanol XC (manufactured by Du Pont) and sodium alkylbenzene sulfonate as an emulsifying dispersant, succinic acid ester and Magfac F-120 (Dainippon Ink and Chemicals, Inc.) as coating aids were used.
Manufactured) was used as preservatives 1, 2, and 3, respectively. Stabilizers 1 and 2 were used in the layer containing silver halide or colloidal silver. The photographic material thus prepared was designated as sample number S-11. Next, EM of sample S-11
In the same manner as in the preparation of Sample S-11, except that EM-2 to 6 were used instead of -1, Sample S-12 to Sample S-12
16 was created.

With respect to the sample (photographic material) obtained as described above, 0.5 seconds (100 CM
S), and the development process and development process (P-
1) was performed. A characteristic curve was obtained from the reflection density of the obtained cyan image. The sensitivity was obtained as the reciprocal of the exposure amount that gives a density of half the maximum color density, and the sensitivity when the sample S-11 was processed by the development processing P-1 was displayed as 100.

──────────────────────────────────── Treatment process time Temperature Mother liquor tank capacity Replenishment amount ── ────────────────────────────────── Black and white development 75 seconds 38 ℃ 8 liters 330ml / m ² First water washing ( 1st bath) 45 seconds 33 ° C 5 liters None 1st water washing (2nd bath) 45 seconds 33 ° C 5 liters 5000 ml / m ² Reverse exposure 15 seconds (100 lux) Color development 135 seconds 38 ° C 15 liters 330 ml / m ² 2 water washing 45 seconds 33 ℃ 5 liter 1000ml / m ² bleach-fixing (1st bath) 60 seconds 38 ℃ 7 liter none bleach-fixing (2nd bath) 60 seconds 38 ℃ 7 liter 150ml / m ² 3rd water washing (1st bath) ) 45 seconds 33 ° C 5 liters None 3rd water washing (2nd bath) 45 seconds 33 ° C 5 liters None 3rd Washing (Third bath) 45 sec 33 ° C. 5 liters 5000 ml / m ² Drying 45 sec 75 ℃ ───────────────────────────── ───────

The first and third washing steps are
Countercurrent washing method was adopted for each. That is, in the first rinsing step, rinsing water was caused to flow in the second bath, and the overflow liquid was led to the first bath. In the third washing step, washing water was poured into the third bath, the overflow solution was introduced into the second bath, and the overflow solution in the second bath was introduced into the first bath. The composition of each treatment liquid is shown below.

──────────────────────────────────── Black and White Developer (FD-1) Mother Liquid Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylenephosphonic acid ・ 5 Sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid / 5 sodium salt 3.0 g 3.0 g Potassium sulfite 30.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Hydroquinone monosulfonic acid Potassium 25.0g 25.0g 1-Phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0g 2.0g Potassium chloride 0.2g None Potassium bromide 0.5g None ──── ─────── ──────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 ──── ────────────────────────────────

──────────────────────────────────── Color developer (CD-1) Mother liquor replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12.0 ml 14. 0 ml 3,6-dithia-1,8-octane-diol 0.20 g 0.25 g nitrilo-N, N, N-trimethylenephosphonic acid.5 sodium salt 0.5 g 0.5 g diethylenetriamine 5 acetic acid.5 sodium salt 2 0.0 g 2.0 g sodium sulfite 2.0 g 2.5 g hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 8 0.0 g optical brightener ( Aminostilbene type) 1.0 g 1.2 g Potassium bromide 0.5 g None Potassium iodide 1.0 mg None ────────────────────────── ────────── Add water 1000ml 1000ml pH (adjust with hydrochloric acid or potassium hydroxide) 10.25 10.40 ────────────────── ──────────────────

──────────────────────────────────── bleach-fixing solution mother liquor replenisher ───── ──────────────────────────────── ethylenediaminetetraacetic acid ・ 2 sodium ・ dihydrate 5.0g 5.0g ethylenediaminetetraacetic acid Fe (III) ammonium monohydrate 80.0 g 80.0 g sodium sulfite 15.0 g 15.0 g ammonium thiosulfate aqueous solution (700 ml / l) 160 ml 160 ml 2-mercapto-1,3,4-triazole 0.5 g 5g ──────────────────────────────────── Add water 1000ml 1000ml pH (with acetic acid or aqueous ammonia) Adjustment) 6.50 6.50 ────────────────── ──────────────────

Next, the development processing P-1 is performed in P-21 to P-2.
An experiment similar to the above was performed except that the number was changed to 6. In the development processings P-21 to P-26, the black and white development processing liquid (FD-1) in the development processing P-1 was replaced with FD-21 to FD-26 shown in Tables 2 to 7 below. Processing. Each of the treatment liquids FD-22, 23, 25 and 26 described below has a bromine ion concentration of 1 × 10 ⁻³ mol / l or less and a sulfite ion concentration of 1 × 10 ⁻¹ mol / l or less. Table 8 shows the experimental results
It is shown in Table 13.

[0073]

[Table 2] Table 2 ──────────────────────────────────── Black and White Developer (FD-21 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 30.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.2 g None potassium bromide 0.05 g None ──────── ─────────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Supplement Volume (ml / m ² ) 110 ─────────────────────────────────────

[0074]

[Table 3] Table 3 ──────────────────────────────────── Black and White Developer (FD-22 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.2 g None potassium bromide 0.05 g None ───────── ────────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Supplement amount (Ml / m ² ) 110 ─────────────────────────────────────

[0075]

[Table 4] Table 4 ──────────────────────────────────── Black and White Developer (FD-23 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 0.5 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.2 g None potassium bromide 0.05 g None ───────── ────────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Supplement amount (Ml / m ² ) 110 ─────────────────────────────────────

[0076]

[Table 5] Table 5 ──────────────────────────────────── Black and White Developer (FD-24 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.2 g None potassium bromide 0.5 g 0 .5g ───────── ─────────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Supplement Volume (ml / m ² ) 110 ─────────────────────────────────────

[0077]

[Table 6] Table 6 ──────────────────────────────────── Black and White Developer (FD-25 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Hydroquinone potassium monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.2 g None potassium bromide None None ── ────────── ─────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Supplement amount (ml / m ² ) 110 ────────────────────────────────────

[0078]

[Table 7] Table 7 ──────────────────────────────────── Black and White Developer (FD-26 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 0.5 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Hydroquinone potassium monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.2 g None potassium bromide None None ── ────────── ─────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Supplement amount (ml / m ² ) 110 ────────────────────────────────────

[0079]

[Table 8] Table 8 ──────────────────────────────────── Experiment number Sample number Development processing sensitivity Maximum color density ──────────────────────────────────── 101 (Comparative example) S-11 P-1 100 0.48 102 (Comparative example) S-11 P-21 102 0.59 103 (Comparative example) S-11 P-22 102 0.80 104 (Comparative example) S-11 P-23 104 104 0.82 105 (Comparative example) S-11 P-24 100 0.52 106 (Comparative example) S-11 P-25 105 0.85 107 (Comparative example) S-11 P-26 106 106 0.87 ────── ──────────────────────────────

[0080]

[Table 9] Table 9 ──────────────────────────────────── Experiment number Sample number Development process Sensitivity Maximum color density ──────────────────────────────────── 108 (Comparative example) S-12 P-1 105 0.42 109 (Comparative example) S-12 P-21 108 0.50 110 (Comparative example) S-12 P-22 107 0.71 111 (Comparative example) S-12 P-23 109 0.72 112 (Comparative Example) S-12 P-24 106 0.43 113 (Comparative Example) S-12 P-25 109 0.74 114 (Comparative Example) S-12 P-26 110 110 0.77 ────── ──────────────────────────────

[0081]

[Table 10] Table 10 ───────────────────────────────────── Experiment number Sample number Development process Sensitivity Maximum coloring density ──────────────────────────────────── 115 (Example) S-13 P-1 110 0.71 116 (Example) S-13 P-21 111 0.80 117 (Example) S-13 P-22 112 1.20 118 (Example) S-13 P-23 115 1.23 119 (Example) S-13 P-24 109 0.73 120 (Example) S-13 P-25 115 1.25 121 (Example) S-13 P-26 117 1.28 ────── ──────────────────────────────

[0082]

[Table 11] Table 11 ──────────────────────────────────── Experiment number Sample number Development processing sensitivity Maximum color density ──────────────────────────────────── 122 (Example) S-14 P-1 142 0.72 123 (Example) S-14 P-21 145 0.83 124 (Example) S-14 P-22 147 1.34 125 (Example) S-14 P-23 150 1.37 126 (Example) S-14 P-24 143 0.75 127 (Example) S-14 P-25 151 151.40 128 (Example) S-14 P-26 153 1.45 ─────── ──────────────────────────────

[0083]

[Table 12] Table 12 ──────────────────────────────────── Experiment number Sample number Development process Sensitivity Maximum color density ──────────────────────────────────── 129 (Example) S-15 P-1 163 0.73 130 (Example) S-15 P-21 168 0.84 131 (Example) S-15 P-22 169 1.39 132 (Example) S-15 P-23 173 1.40 133 (Example) S-15 P-24 162 0.77 134 (Example) S-15 P-25 174 1.43 135 (Example) S-15 P-26 176 1.48 ─────── ──────────────────────────────

[0084]

[Table 13] Table 13 ──────────────────────────────────── Experiment number Sample number Development processing sensitivity Maximum Color Density ──────────────────────────────────── 136 (Example) S-16 P-1 173 0.75 137 (Example) S-16 P-21 179 0.87 138 (Example) S-16 P-22 180 1.45 139 (Example) S-16 P-23 184 1.47 140 (Example) S-16 P-24 174 0.80 141 (Example) S-16 P-25 186 1.55 142 (Example) S-16 P-26 205 1.58 ─────── ──────────────────────────────

From the results shown in Tables 8 to 13, Samples S-13 to 16 using the silver chloride-based silver halide emulsion having a silver bromide localized phase were found to have bromine ions substantially in the black and white developer. Development processing P-22, 23, 2 containing no sulfite ion
It can be seen that when processed with Nos. 5 and 26, the sensitivity is high and the maximum color density is high. In particular, sample S using Emulsion EM-3 in which the formation position of the silver bromide localized phase is inside the cubic grain
Sample S-14 using Emulsions EM-4 to 6 in which the formation position of the silver bromide localized phase is at the corner of the cubic grain rather than -13.
More preferable results were obtained in the range of -16. The most preferable result was obtained with Sample S-16 using the emulsion EM-6 in which the silver bromide localized phase was formed at the corner of the cubic grain by mixing and ripening the silver chloride grain and the silver bromide ultrafine grain.

Example 2 Emulsion EM prepared in Example 1
-2 means that the grain size is 0.3 μm and 0.5 μm, respectively, by changing the temperature at the time of silver halide grain formation and the time required to add the silver nitrate aqueous solution and the alkali halide aqueous solution.
And 0.8 μm emulsions EM-21, EM-22, EM
-23 was prepared. The grain size distribution of the obtained emulsion is
It was 0.07, 0.08 and 0.09, respectively.
Next, 60 mg of green sensitizing dye-1 was added in place of the red sensitizing dyes-1, 2 and 3 added to EM-2, the particle size was 0.3 μm (size distribution 0.07), and the particle size was 0.
45 μm (size distribution 0.08) and particle size 0.
Emulsions of 8 μm (size distribution 0.09) were prepared and designated as EM-24, EM-25 and EM-26, respectively. Also,
Instead of the red sensitizing dyes-1, 2 and 3 added to EM-2, 160 mg of blue sensitizing dye-1 was added, and the particle size was 0.4 μm (size distribution 0.06) and the particle size was 0.5.
5 μm (size distribution 0.07) and particle size 1.1
Emulsions of μm (size distribution 0.11) were prepared and designated as EM-27, EM-28, and EM-29, respectively.

[0087]

[Chemical 4]

[0088]

[Chemical 5]

Thickness 2 laminated on both sides with polyethylene
A 20 μm paper support was multilayer-coated with the following first to twelfth layers to prepare a color photographic material. To the polyethylene coated on the first layer, 15% by weight of anatase type titanium dioxide white was added as a white pigment and a slight amount of ultramarine blue was added as a bluing dye. The chromaticity of the surface of the support is (L *,
a *, b *) color system, 89.0, -0.1, respectively.
It was 8 and -0.73.

(Composition of Each Layer) The components of each layer and the coating amount (g / m ² ) are shown below. However, for silver halide, the coating amount in terms of silver is shown. First layer (gelatin layer) gelatin 0.30 Second layer (antihalation layer) black colloidal silver 0.07 gelatin 0.50

Third Layer (Low Sensitivity Red Sensitive Layer) EM-21 0.06 EM-22 0.07 Gelatin 1.00 Cyan Coupler 1 0.14 Cyan Coupler 2 0.07 Antifading Agent 1 0.03 Antifading Agent 2 0.03 Anti-fading agent 3 0.03 Dispersion medium (for coupler) 0.03 Di (2-ethylhexyl) phthalate (solvent for coupler) 0.02 Trinonyl phosphate (solvent for coupler) 0.02 Di (3 -Methylhexyl) phthalate (solvent for coupler) 0.02 Development accelerator 0.05 Fourth layer (high-sensitivity red-sensitive layer) EM-23 0.15 Gelatin 1.00 Cyan coupler 1 0.20 Cyan coupler 20. 10 Anti-fading agent 1 0.05 Anti-fading agent 2 0.05 Anti-fading agent 3 0.05 Dispersion medium (for coupler) 0.03 Di (2-ethylhexyl) phthalate ( Solvent for coupler) 0.033 Trinonyl phosphate (solvent for coupler) 0.033 Di (3-methylhexyl) phthalate (solvent for coupler) 0.033 Development accelerator 0.05 Fifth layer (intermediate layer) Magenta colloidal silver 0.02 Gelatin 1.00 Color mixing inhibitor 1 0.08 Tricresyl phosphate (solvent for color mixing inhibitor) 0.08 Dibutyl phthalate (solvent for color mixing inhibitor) 0.08 Polyethyl acrylate latex (Molecular weight 10,000 to 100,000) ) 0.10

6th layer (low-sensitivity green-sensitive layer) EM-24 0.03 EM-25 0.05 Gelatin 0.80 Magenta coupler 1 0.05 Magenta coupler 2 0.05 Anti-fading agent 4 0.10 Stain prevention Agent 1 0.05 Anti-staining agent 2 0.05 Anti-staining agent 3 0.001 Anti-staining agent 4 0.01 Dispersion medium (for coupler) 0.05 Tricresyl phosphate (solvent for coupler) 0.075 Trioctyl phosphate (Coupler solvent) 0.075 7th layer (high-sensitivity green-sensitive layer) EM-26 0.10 Gelatin 0.80 Magenta coupler 1 0.05 Magenta coupler 2 0.05 Anti-fading agent 4 0.10 Anti-stain agent 3 0.001 Anti-staining agent 4 0.01 Dispersion medium (for coupler) 0.05 Tricresyl phosphate (solvent for coupler) 0.075 Trioctyl phosphate (solvent for coupler) 0.075

Eighth layer (yellow filter layer) Yellow colloidal silver 0.03 Gelatin 1.00 Color mixing inhibitor 1 0.06 Tricresyl phosphate (solvent for color mixing inhibitor) 0.075 Dibutyl phthalate (solvent for color mixing inhibitor) ) 0.075 polyethyl acrylate latex (molecular weight 10,000 to 100,000) 0.10 ninth layer (low sensitivity blue sensitive layer) EM-27 0.07 EM-28 0.10 gelatin 0.50 yellow coupler 1 0.10. Yellow coupler 2 0.10 Anti-fading agent 5 0.10 Anti-staining agent 3 0.001 Dispersion medium (for coupler) 0.05 Trinonyl phosphate (solvent for coupler) 0.05 10th layer (high sensitivity blue sensitive layer) EM-29 0.25 Gelatin 1.00 Yellow coupler 1 0.20 Yellow coupler 2 0.2 Anti-fading agent 5 0.10 Stain inhibitor 3 0.002 dispersant (couplers for) 0.15 trinonyl phosphate (coupler solvent) 0.10

Eleventh layer (UV absorbing layer) Gelatin 1.50 UV absorbing agent 1 0.50 UV absorbing agent 2 0.50 Color mixing inhibitor 2 0.04 Dispersion medium (for UV absorbing agent) 0.15 di (2 -Ethylhexyl) phthalate (solvent for UV absorber) 0.075 Trinonyl phosphate (solvent for UV absorber) 0.075 Dye 1 (for prevention of irradiation) 0.01 Dye 2 (for prevention of irradiation) 0.01 Dye 3 (for prevention of irradiation) 0.01 Dye 4 (for prevention of irradiation) 0.01 12th layer (protective layer) Gelatin 0.90 1,2-bis (vinylsulfonylacetamide) ethane (gelatin hardener) 0. 085 4,6-dichloro-2-hydroxy 1,3,5-triazine sodium salt (gelatin hardener) 0.085 non-photosensitive The silver halide (silver chlorobromide, silver bromide 3 mol%, average particle size 0.2 [mu] m) 0.02 modified Poval 0.05

Further, in each layer, Alkanol XC (manufactured by Du Pont) and sodium alkylbenzene sulfonate as an emulsifying dispersant, succinic acid ester and Magfac F-120 (Dainippon Ink and Chemicals, Inc.) as coating aids were used.
Manufactured) was used as preservatives 1, 2, and 3, respectively. The following stabilizers 1 and 2 were used in the layer containing silver halide or colloidal silver. The photographic material thus prepared was designated as Sample No. S-21. The compounds used to prepare the photographic material are shown below.

[0096]

[Chemical 6]

[0097]

[Chemical 7]

[0098]

[Chemical 8]

[0099]

[Chemical 9]

[0100]

[Chemical 10]

[0101]

[Chemical 11]

[0102]

[Chemical formula 12]

[0103]

[Chemical 13]

[0104]

[Chemical 14]

Next, from the emulsion EM-3 prepared in Example 1, emulsions EM-31, EM-32 and EM-21, EM-22 and EM-23 having the same grain size and the same grain size distribution as EM-21, EM-22 and EM-23 were prepared.
EM-33 was prepared. Similarly, from the emulsion EM-3, the emulsions EM-34 to 39 corresponding to the emulsions EM-24 to 29 were prepared. Then, the emulsions EM-21 to 29 of Sample S-21
A photographic material using Emulsions EM-31 to 39 instead of was prepared as Sample No. S-22. Hereinafter, similarly, emulsions EM-61 to EM-61 prepared based on the emulsion EM-6 of Example 1 were similarly prepared.
69 was used to prepare sample S-23.

For the sample (photographic material) obtained as described above, 0.5 seconds (200 CM
S) was given and the development processing shown in Table 14 was performed. A characteristic curve was obtained from the reflection density of the obtained image, and the sensitivity and maximum color density of cyan (C), magenta (M) and yellow (Y) images were determined.

The photographic materials were then exposed to red light through an optical wedge and developed as shown in Table 4.
Furthermore, the light of three colors (red light, green light, and blue light) is adjusted so that the sample that is exposed to white light and developed is gray, and each photographic material is exposed through an optical wedge, and similarly developed. did. In addition, the exposure amount of red light at the time of red exposure and the exposure amount of red light contained in white light were the same. The densities of the samples obtained as described above were measured, and the difference in the exposure amount when the cyan density was 0.6 during red light exposure and white light exposure, Δlog
E (R) was determined as the interimage effect on the red-sensitive silver halide emulsion layer. Similarly, the inter-image effect on other silver halide emulsion layers, ΔlogE (G) and ΔlogE (B) were determined. The results are shown in Table 14.

[0108]

[Table 14] Table 14 ──────────────────────────────────── Experimental sample Development sensitivity Maximum color density Inter-image effect Δ logE number Number processing C MY C MY C M Y ──────────────────────────────── ────── 201 (Comparative example) S-21 P-1 100 100 100 1.70 1.68 1.45 0.09 0.10 0.08 202 (Invention) S-22 P-1 145 150 153 1.72 1.70 1.47 0.10 0.11 0.09 203 (Invention) ) S-23 P-1 170 173 178 1.73 1.71 1.49 0.10 0.12 0.10 204 (Comparative example) S-21 P-21 101 100 102 1.74 1.72 1.49 0.10 0.11 0.09 205 (Invention) S-22 P-21 147 150 154 1.74 1.74 1.52 0.12 0.12 0.10 206 (invention) S-23 P-21 172 173 179 1.76 1.75 1.54 0.12 0.13 0.12 207 (comparative example) S-21 P-22 103 105 104 1.85 1.83 1.59 0.13 0.14 0.12 208 (invention) ) S-22 P-22 168 172 175 2.05 2.07 2.00 0.20 0.23 0.20 209 (invention) S-23 P-22 192 195 198 2.08 2.09 2.03 0.21 0.24 0.22 210 (comparative example) S-2 1 P-23 104 107 104 1.86 1.85 1.60 0.13 0.14 0.13 211 (Invention) S-22 P-23 170 173 177 2.12 2.15 2.10 0.21 0.24 0.21 212 (Invention) S-23 P-23 192 198 200 2.20 2.24 2.18 0.22 0.25 0.22 213 (Comparative example) S-21 P-24 100 101 101 1.73 1.71 1.48 0.09 0.11 0.09 214 (Invention) S-22 P-24 145 149 152 1.73 1.72 1.50 0.10 0.11 0.10 215 (Invention) S- 23 P-24 170 169 179 1.84 1.85 1.70 0.11 0.13 0.11 216 (Comparative example) S-21 P-25 105 119 110 1.98 1.98 1.90 0.13 0.15 0.13 217 (Invention) S-22 P-25 188 190 197 2.24 2.26 2.20 0.22 0.24 0.22 218 (invention) S-23 P-25 202 208 205 2.40 2.44 2.35 0.23 0.25 0.23 219 (comparative example) S-21 P-26 105 112 110 1.98 1.97 1.92 0.13 0.15 0.13 220 (invention) S- 22 P-26 190 200 205 2.30 2.32 2.30 0.23 0.24 0.23 221 (Invention) S-23 P-26 210 215 218 2.52 2.62 2.50 0.24 0.26 0.25 ───────────────── ───────────────────

From the results shown in Table 14, Sample S-2 using a silver chloride-based silver halide emulsion having a silver bromide localized phase
Nos. 2 and 23 are the development treatments P-21, 22, 24 and 25 in which the black and white developing solution contains substantially no bromine ion and sulfite ion.
It can be seen that in the case of the treatment (1), the sensitivity and the maximum color density are high, the inter-image effect is large, and preferable results are obtained in terms of color reproducibility.

[Embodiment 3] Embodiment 2 Regarding the sample S-23, the development processing P-22 of Embodiment 2 was carried out by the following P-31 to P-31.
An experiment similar to that in Example 2 was performed, except that the experiment was changed to −35. The development processes P-31 to P-35 are the development process P-1.
In the black and white development processing solution (FD-22),
It is the process replaced with FD-31 to FD-35 shown in Table 5 to Table 19. The chloride ion concentration of each of the following treatment liquids FD-32 to 35 is 5 × 10 ⁻³ mol / l or more and 1 × 10 ⁻¹ mol / l or less. The experimental results are shown in Table 20.

[0111]

[Table 15] Table 15 ──────────────────────────────────── Black and White Developer (FD-31 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.1 g None potassium bromide 0.05 g None ─────── ──────────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Replenishment amount (ml / m ² ) 110 ─────────────────────────────────────

[0112]

[Table 16] Table 16 ──────────────────────────────────── Black and white developer (FD-32 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.4 g None potassium bromide 0.05 g None ─────── ──────────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Replenishment amount (ml / m ² ) 110 ─────────────────────────────────────

[0113]

[Table 17] Table 17 ──────────────────────────────────── Black and white developer (FD-33 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.8 g None potassium bromide 0.05 g None ─────── ──────────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Replenishment amount (ml / m ² ) 110 ─────────────────────────────────────

[0114]

[Table 18] Table 18 ──────────────────────────────────── Black and White Developer (FD-34 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Hydroquinone potassium monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.8 g None potassium bromide None None-- ──────── ───────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Replenishment amount ( ml / m ² ) 110 ────────────────────────────────────

[0115]

[Table 19] Table 19 ──────────────────────────────────── Black and white developer (FD-35 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 0.5 g 30.0 g Potassium thiocyanate 1.2 g 1.2 g Potassium carbonate 35.0 g 35.0 g Hydroquinone potassium monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.8 g None potassium bromide None None-- ──────── ───────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Replenishment amount ( ml / m ² ) 110 ────────────────────────────────────

[0116]

[Table 20] Table 20 ──────────────────────────────────── Sensitivity Maximum color density Experimental number Sample No. Development Processing CMY CMY ───────────────────────────────────── 301 S-23 P -22 192 195 198 2.08 2.09 2.03 302 S-23 P-31 192 193 197 2.05 2.07 2.00 303 S-23 P-32 193 194 198 2.15 2.18 2.11 304 S-23 P-33 193 194 197 2.26 2.27 2.20 305 S- 23 P-34 202 209 205 2.45 2.49 2.40 306 S-23 P-35 210 215 218 2.59 2.65 2.53 ──────────────────────────── ─────────

As is clear from the results shown in Table 20, the chloride ion concentration is 5 × 10 ^-3 mol / l or more and 1 × 10 ^-1 mol / l.
More preferable results were obtained in Experiment Nos. 303 to 306 using the treatment liquid of 1 or less.

[Embodiment 4] With respect to the sample S-23 of the embodiment 2, the development processing P-22 of the embodiment 2 is changed to the following P-41.
An experiment similar to that of Example 2 was performed except that P-45 was used. The development processes P-41 to P-45 are the development process P-22.
Black-and-white development processing solution (FD-22) in
This is a process in which FD-41 to FD-45 shown in Tables 1 to 25 are replaced. The rhodane ion concentration of each of the following processing liquids FD-42 to 45 is 1 × 10 ^-2 mol / l or less. The experimental results are shown in Table 26.

[0119]

[Table 21] Table 21 ──────────────────────────────────── Black and white developer (FD-41 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate 2.0 g 2.0 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.2 g None potassium bromide 0.05 g None ─────── ──────────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Replenishment amount (ml / m ² ) 110 ─────────────────────────────────────

[0120]

[Table 22] Table 22 ──────────────────────────────────── Black and white developer (FD-42 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate 0.1 g 0.1 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g potassium chloride 0.2 g None potassium bromide 0.05 g None ─────── ──────────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Replenishment amount (ml / m ² ) 110 ─────────────────────────────────────

[0121]

[Table 23] Table 23 ──────────────────────────────────── Black and white developer (FD-43 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 0.5 g 30.0 g Potassium thiocyanate None None Potassium carbonate 35.0 g 35.0 g Hydroquinone monosulfonic acid Potassium 25.0 g 25.0 g 1-Phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0 g 2.0 g Potassium chloride 0.2 g None Potassium bromide 0.05 g None ──── ─────── ──────────────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 Supplement amount (ml / M ² ) 110 ────────────────────────────────────

[0122]

[Table 24] Table 24 ──────────────────────────────────── Black and white developer (FD-44 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 2.0 g 30.0 g Potassium thiocyanate None None Potassium carbonate 35.0 g 35.0 g Hydroquinone monosulfonic acid Potassium 25.0g 25.0g 1-Phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0g 2.0g Potassium chloride 0.2g None Potassium bromide None None ────── ──────── ───────────────────── Water was added 1000 ml 1000 ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 replenishment rate (ml / m ² ) 110 ─────────────────────────────────────

[0123]

[Table 25] Table 25 ──────────────────────────────────── Black and white developer (FD-45 ) Mother liquor Replenisher ──────────────────────────────────── Nitrilo-N, N, N-trimethylene Phosphonic acid-5 sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid-5 sodium salt 3.0 g 3.0 g Potassium sulfite 0.5 g 30.0 g Potassium thiocyanate None None Potassium carbonate 35.0 g 35.0 g Hydroquinone monosulfonic acid Potassium 25.0g 25.0g 1-Phenyl-4-hydroxymethyl-4-methyl-4-methyl-3-pyrazolidone 2.0g 2.0g Potassium chloride 0.2g None Potassium bromide None None ────── ──────── ───────────────────── Water was added 1000 ml 1000 ml pH (adjusted with hydrochloric acid or potassium hydroxide) 9.60 9.70 replenishment rate (ml / m ² ) 110 ─────────────────────────────────────

[0124]

[Table 26] Table 26 ──────────────────────────────────── Sensitivity Maximum color density Experiment number Sample No. Development Process C M Y C M Y ──────────────────────────────────── 401 S-23 P -22 192 195 198 2.08 2.09 2.03 402 S-23 P-41 180 182 183 1.90 1.92 1.88 403 S-23 P-42 192 195 195 199 2.25 2.27 2.20 404 S-23 P-43 193 195 199 2.31 2.33 2.30 405 S- 23 P-44 203 209 206 2.48 2.53 2.51 406 S-23 P-45 211 215 217 2.60 2.64 2.60 ──────────────────────────── ─────────

As is clear from the results shown in Table 26, more preferable results were obtained in Experiment Nos. 403 to 406 using the treatment liquid having a rhodanate ion concentration of 1 × 10 ^-2 mol / l or less.

[Embodiment 5] With respect to the sample S-23 of the embodiment 2, the development processing P-22 of the embodiment 2 is changed to the following P-51.
An experiment similar to that in Example 2 was performed, except that P-58 was used. The development processing P-51 to P-58 are the development processing P-
In No. 22, the color developing treatment liquid (CD-1) was replaced with CD-51 to CD-58 shown in Tables 27 to 34 below. The following treatment liquids CD-52 to 53, 57
The bromine ion concentration of each of ˜58 is 1 × 10 ⁻³ mol / l or less, and the sulfite ion concentration is 1 × 10 ⁻² mol / l or less. The experimental results are shown in Table 35.

[0127]

[Table 27] Table 27 ──────────────────────────────────── Color developer (CD-51 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.05 g 0.05 g nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 0.5 g 0.5 g diethylenetriamine 5 acetic acid 5 Sodium salt 2.0 g 2.0 g Sodium sulfite 0.2 g 0.2 g Hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0g 8.0g Fluorescent Whitening agent (diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.2 g None Potassium bromide 0.5 g None ─────────────────────── ────────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.40 Replenishment rate (ml / m ² ) 110 ──────────────────────────────

[0128]

[Table 28] Table 28 ──────────────────────────────────── Color developer (CD-52 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.05 g 0.05 g nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 0.5 g 0.5 g diethylenetriamine 5 acetic acid 5 Sodium salt 2.0 g 2.0 g Sodium sulfite 0.2 g 0.2 g Hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0g 8.0g Fluorescent Whitening agent (diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.2 g None Potassium bromide 0.1 g None ─────────────────────── ───────────── Add water 1000 ml 1000 ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ──────────────────────────────

[0129]

[Table 29] Table 29 ──────────────────────────────────── Color developer (CD-53 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.05 g 0.05 g nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 0.5 g 0.5 g diethylenetriamine 5 acetic acid 5 Sodium salt 2.0 g 2.0 g Sodium sulfite 0.2 g 0.2 g Hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0g 8.0g Fluorescent Whitening agent (diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.2 g None Potassium bromide None None ───────────────────────── ─────────── Add water 1000 ml 1000 ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ──────── ────────────────────────────

[0130]

[Table 30] Table 30 ──────────────────────────────────── Color developer (CD-54 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.05 g 0.05 g nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 0.5 g 0.5 g diethylenetriamine 5 acetic acid 5 Sodium salt 2.0 g 2.0 g Sodium sulfite 2.0 g 2.5 g Hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0g 8.0g Fluorescent Whitening agent (diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.2 g None Potassium bromide 0.1 g None ─────────────────────── ───────────── Add water 1000 ml 1000 ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ──────────────────────────────

[0131]

[Table 31] Table 31 ──────────────────────────────────── Color developer (CD-55 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.05 g 0.05 g nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 0.5 g 0.5 g diethylenetriamine 5 acetic acid 5 Sodium salt 2.0 g 2.0 g Sodium sulfite 2.0 g 2.5 g Hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0g 8.0g Fluorescent Whitening agent (diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.2 g None Potassium bromide None None ───────────────────────── ─────────── Add water 1000 ml 1000 ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ──────── ────────────────────────────

[0132]

[Table 32] Table 32 ──────────────────────────────────── Color developer (CD-56 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.05 g 0.05 g nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 0.5 g 0.5 g diethylenetriamine 5 acetic acid 5 Sodium salt 2.0 g 2.0 g Sodium sulfite None None Hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 8 0.0 g optical brightener ( Diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.2 g None potassium bromide 0.5 g None ───────────────────────────── ────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ─────────── ───────────────────────────

[0133]

[Table 33] Table 33 ──────────────────────────────────── Color developer (CD-57 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.05 g 0.05 g nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 0.5 g 0.5 g diethylenetriamine 5 acetic acid 5 Sodium salt 2.0 g 2.0 g Sodium sulfite None None Hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 8 0.0 g optical brightener ( Diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.2 g None Potassium bromide 0.1 g None ───────────────────────────── ────────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ─────────── ───────────────────────────

[0134]

[Table 34] Table 34 ──────────────────────────────────── Color developer (CD-58) ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml 3,6-dithia-1,8-octane-diol 0.05 g 0.05 g nitrilo-N, N, N-trimethylenephosphonic acid 5 sodium salt 0.5 g 0.5 g diethylenetriamine 5 acetic acid 5 Sodium salt 2.0 g 2.0 g Sodium sulfite None None Hydroxylamine sulfate 3.0 g 3.6 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 8 0.0 g optical brightener ( Diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.2 g None Potassium bromide None None ───────────────────────────── ─────── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ───────────── ────────────────────────

[0135]

[Table 35] Table 35 ──────────────────────────────────── Experiment No. Sample No. Development Treatment Mottle X 1000RMS (G) ──────────────────────────────────── 701 S-24 P-51 2.53 702 S-27 P-51 2.58 703 S-34 P-51 2.42 704 S-38 P-51 2.45 705 S-24 P-52 1.90 706 S-27 P-52 1.90 707 S-34 P-52 1.81 708 S-38 P-52 1.87 709 S-24 P-53 1.82 710 S-27 P-53 1.87 711 S-34 P-53 1.79 712 S-38 P-53 1.78 713 S-24 P-54 2.53 714 S-27 P-54 2.57 71 S-34 P-54 2.40 716 S-38 P-54 2.44 717 S-24 P-55 2.51 718 S-27 P-55 2.59 719 S-34 P-55 2.41 720 S-38 P-55 2.42 721 S-24 P-56 2.50 722 S-27 P-56 2.59 723 S-34 P-56 2.41 724 S-38 P-56 2.42 725 S-24 P-57 1.83 726 S-27 P-57 1.88 727 S-34 P-57 1.71 728 S-38 P-57 1.78 729 S-24 P-58 1.74 730 S-27 P-58 1.75 731 S-34 P-58 1.66 732 S-38 P-58 1.63 ───────────────────── ───────────────

As is clear from the results shown in Table 35, the experiment number using a treatment solution having a bromine ion concentration of 1 × 10 ⁻³ mol / l or less and a sulfite ion concentration of 1 × 10 ⁻² mol / l or less Further favorable results were obtained with 503, 504, 508, and 509.

[Embodiment 6] With respect to the sample S-23 of the embodiment 2, the development processing P-22 of the embodiment 2 is the same as the following P-61.
An experiment similar to that of Example 2 was performed except that P-64 was used. The development processing P-61 to P-64 are the development processing P-
No. 22 is a process in which the color developing treatment liquid (CD-1) is replaced with CD-61 to CD-64 shown in Tables 36 to 39 below. The chloride ion concentration of each of the following treatment liquids CD-63 to 64 is 5 × 10 ^-3 mol / l or more and 1 × 10 ^-1
Mol / l or less. The experimental results are shown in Table 40.

[0138]

[Table 36] Table 36 ──────────────────────────────────── Color developer (CD-61 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 0.5 g 0.5 g diethylenetriamine pentaacetic acid-5 sodium salt 2.0 g 2.0 g sodium sulfite 0.5 g 0.7 g N- Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 8.0 g Optical brightener (diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.1 g None Brominated Potassium 0.05g None ── ────────────────────────────────── Add water 1000ml 1000ml pH (adjust with hydrochloric acid or potassium hydroxide) 10.25 10.40 Replenishment rate (ml / m ² ) 110 ──────────────────────────────────── ─

[0139]

[Table 37] Table 37 ──────────────────────────────────── Color developer (CD-62 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 0.5 g 0.5 g diethylenetriamine pentaacetic acid-5 sodium salt 2.0 g 2.0 g sodium sulfite 0.5 g 0.7 g N- Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 8.0 g Optical brightener (diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.2 g None Brominated Potassium 0.05g None ── ────────────────────────────────── Add water 1000ml 1000ml pH (adjust with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ──────────────────────────────────── ─

[0140]

[Table 38] Table 38 ──────────────────────────────────── Color developer (CD-63 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 0.5 g 0.5 g diethylenetriamine pentaacetic acid-5 sodium salt 2.0 g 2.0 g sodium sulfite 0.5 g 0.7 g N- Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 8.0 g Optical brightener (diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.5 g None Brominated Potassium 0.05g None ── ────────────────────────────────── Add water 1000ml 1000ml pH (adjust with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ──────────────────────────────────── ─

[0141]

[Table 39] Table 39 ──────────────────────────────────── Color developer (CD-64 ) Mother liquor Replenisher ──────────────────────────────────── Benzyl alcohol 15.0 ml 16.5 ml Diethylene glycol 12 0.0 ml 14.0 ml Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 0.5 g 0.5 g diethylenetriamine pentaacetic acid-5 sodium salt 2.0 g 2.0 g sodium sulfite 0.5 g 0.7 g N- Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 8.0 g Optical brightener (diaminostilbene type) 1.0 g 1.2 g Potassium chloride 0.8 g None Brominated Potassium 0.05g None ── ────────────────────────────────── Add water 1000ml 1000ml pH (adjust with hydrochloric acid or potassium hydroxide) 10.25 10.45 Replenishment rate (ml / m ² ) 110 ──────────────────────────────────── ─

[0142]

[Table 40] Table 40 ──────────────────────────────────── Experiment No. Sample No. Development Treatment Mottle X 1000RMS (G) ──────────────────────────────────── 801 S-24 P-61 2.32 802 S-27 P-61 2.30 803 S-34 P-61 2.20 804 S-38 P-61 2.15 805 S-24 P-62 1.31 806 S-27 P-62 1.37 807 S-34 P-62 1.29 808 S-38 P-62 1.21 809 S-24 P-63 1.35 810 S-27 P-63 1.33 811 S-34 P-63 1.27 812 S-38 P-63 1.28 813 S-24 P-64 2.36 814 S-27 P-64 2.38 81 S-34 P-64 2.23 816 S-38 P-64 2.25 ──────────────────────────────── ─────

As is clear from the results shown in Table 40, the chloride ion concentration is 5 × 10 ^-3 mol / l or more and 1 × 10 ^-1 mol / l.
Experiment Nos. 604 and 60 using treatment liquids of 1 or less
In No. 5, more preferable results were obtained.

[Example 7] The same experiment as in Example 2 was carried out on Sample S-23 of Example 2 except that the developing treatment P-1 of Example 2 was changed to P-71 shown below. The development processing step and processing solution composition of development processing P-71 are shown below. The black and white development processing solution of the development processing P-71 is a processing solution which does not substantially contain sulfite ion, bromine ion and rhodanate ion. Further, the color developing treatment liquid of the development treatment P-71 is a treatment liquid which does not substantially contain sulfite ion and bromine ion. The experimental results are shown in Table 41.

──────────────────────────────────── Treatment process (P-71) Time Temperature Mother liquor tank Capacity Replenishment amount ──────────────────────────────────── Black and white development 20 seconds 38 ℃ 8 liters 75ml / m ² First water washing (first bath) 20 seconds 33 ° C 5 liters None First water washing (second bath) 20 seconds 33 ° C 5 liters 1000 ml / m ² Reverse exposure 15 seconds (100 lux) Color development 40 seconds 38 ° C 15 liters 75 ml / m ² Second water wash 20 seconds 33 ° C 5 liters 500 ml / m ² Bleach fixing (first bath) 20 seconds 38 ° C 7 liters No bleach fixing (second bath) 20 seconds 38 ° C 7 liters 75 ml / m ² 3rd Washing with water (1st bath) 20 seconds 33 ° C 5 liters No 3rd washing with water (2nd bath) 20 seconds 33 ° C 5 liters No 3rd water (Third bath) 20 sec 33 ° C. 5 liters 1000 ml / m ² Drying 30 sec 75 ℃ ────────────────────────────── ──────

The first and third washing steps are
Countercurrent washing method was adopted for each. That is, in the first rinsing step, rinsing water was caused to flow in the second bath, and the overflow liquid was led to the first bath. In the third washing step, washing water was poured into the third bath, the overflow solution was introduced into the second bath, and the overflow solution in the second bath was introduced into the first bath.

The composition of each processing liquid is shown below.

──────────────────────────────────── Black and White Developer Mother Solution Replenisher ───── ─────────────────────────────── Nitrilo-N, N, N-trimethylenephosphonic acid-5-sodium salt 1.0 g 1.0 g Diethylenetriamine pentaacetic acid / 5 sodium salt 3.0 g 3.0 g Potassium carbonate 35.0 g 35.0 g Potassium hydroquinone monosulfonate 25.0 g 25.0 g 1-phenyl-4-hydroxymethyl-4-methyl-4- Methyl-3-pyrazolidone 2.0 g 2.0 g Potassium chloride 0.5 g None ────────────────────────────────── ─── Add water 1000ml 1000ml pH (hydrochloric acid or potassium hydroxide Adjustment) 9.60 9.70 ────────────────────────────────────

──────────────────────────────────── Color developer Mother solution replenisher ───── ─────────────────────────────── Nitrilo-N, N, N-trimethylenephosphonic acid-5-sodium salt 0.5g 0.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g 2.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-aminoaniline sulfate 5.0 g 11.0 g Optical brightener ( (Diaminostilbene type) 1.0 g 1.4 g Potassium chloride 0.2 g None ─────────────────────────────────── ── Add water 1000ml 1000ml pH (adjusted with hydrochloric acid or potassium hydroxide) 10.25 10.5 0 ────────────────────────────────────

[0150]

[Table 41] Table 41 ──────────────────────────────────── Experiment Sample Development Processing Mottle (G ) Sensitivity difference (ΔS _0.5 (G)) No. No. X100 RMS 35/5 ℃ ────────────────────────────── ─ ─ ─ ─ ─ 801 S-24 P-7 1.12 -0.01 802 S-27 P-7 1.23 -0.02 803 S-34 P-7 0.98 -0.00 804 S -38 P-7 1.09 -0.01 205 S-24 P-1 2.54 -0.04 208 S-27 P-1 2.62-0.05 305 S-34 P-1 2.43 -0.03 309 S-38 P-1 2.47 -0.04 ───────────────────────────────── ────

From the results shown in Table 41, it is understood that the developing process P-71 using the black-and-white developing solution and the color developing solution containing neither sulfite ion nor bromine ion can significantly reduce the replenishment amount.

Claims (8)

[Claims] 1. A layer containing a silver halide emulsion comprising silver halide having chlorine, bromine, and iodine contents of 90 mol% or more, 10 mol% or less, and 0 mol%, respectively, or chlorine, bromine, or The content of iodine is 88 mol%
At least one layer containing a silver halide emulsion of 10 mol% or less and 0.1 to 2 mol% is included, and the silver halide grains contained in the silver halide emulsion have a bromide content of 20 mol% or more. Using a color photographic light-sensitive material having a silver bromide localized phase with a silver content, a color reversal image is formed on the photographic light-sensitive material by image exposure processing, black and white development processing, reversal processing, color development processing and desilvering processing. Color reversal image forming method. 2. The silver halide grain is a cube or 1.
It has a tetrahedral shape, and the silver bromide localized phase is at least one of the vertices of the edges of a cube or a tetrahedron or in the vicinity thereof.
The image forming method according to claim 1, wherein the image forming method is present in a place. 3. The silver halide grains are formed by mixing and ripening host grains and grains having a grain size smaller than the host grains and having a silver bromide content of 20 mol% or more. The image forming method according to claim 1. 4. The image forming method according to claim 1, wherein the processing solution for the black and white development processing contains substantially no bromine ion and sulfite ion. 5. The image forming method according to claim 1, wherein the processing solution for black and white development processing contains chlorine ions in an amount of 5 × 10 ⁻³ mol to 1 × 10 ⁻¹ mol / liter. 6. The image forming method according to claim 1, wherein the processing solution for the black and white development processing contains substantially no thiocyanate ion. 7. The image forming method according to claim 1, wherein the processing solution for color development processing contains substantially no bromine ion and sulfite ion. 8. The image forming method according to claim 1, wherein the processing solution for color developing treatment contains chlorine ions in an amount of 5 × 10 ⁻³ mol to 1 × 10 ⁻¹ mol / liter.