JPH02190846A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To progress the desilvering of the color photosensitive material and to shorten the processing time thereof by forming the silver iodobromide or silver iodochlorobromide contg. a specific ratio of silver iodide in the chemically sensitized silver halide particles forming at least one emulsion layer of the photosensitive material into a phase structure and incorporating a specific ratio of the silver iodide into the outermost layer of the silver halide particles. CONSTITUTION:At least one emulsion layer of the silver halide color photographic sensitive material is formed of the chemically sensitized silver halide particles and the silver iodobromide or silver iodochlorobromide contg. 30 to 45mol% silver iodide is made to exist in the silver halide particles by having the distinct phase structure; in addition, the outermost layer of the silver halide particles is formed of the silver halide contg. <=8mol% silver iodide. The rapid bleach-fix processing of the silver halide color photographic sensitive material which has high sensitivity and high image quality and is subjected to high iodization for influence is possible in this way without degrading the fixing.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for processing exposed silver halide color photographic materials (hereinafter referred to as color photographic materials), and in particular, relates to methods for processing exposed silver halide color photographic materials (hereinafter referred to as color photographic materials). The present invention relates to a simple and rapid processing method for colored photosensitive materials.

(Prior art) - The basic steps in processing color photosensitive materials for IC are a color development step and a desilvering step. In the color development step, silver halide exposed to light is reduced by a color developing agent to produce silver, and The oxidized color developing agent reacts with the color former (coupler) to provide a dye image. In the next desilvering step, the silver produced in the color development step is oxidized by the action of an oxidizing agent (bleaching agent), and further transformed into a soluble silver complex by a silver ion complexing agent (fixing agent). It is removed by melting.

By going through this desilvering step, only a dye image is created on the color photosensitive material.

In addition to the basic steps mentioned above, the actual development process includes various auxiliary steps to maintain the photographic and physical quality of the image or to improve the preservation of the image. bath, stop bath, image stabilization bath, washing bath, etc.

In recent years, there has been a strong demand in this industry to speed up processing, that is, to shorten and simplify the processing time, and in particular, shortening the desilvering process, which accounts for nearly half of the processing time, has become a major issue. There is.

Conventionally, as a means of simplifying and speeding up the desilvering process, a bleach-fixing solution containing a ferric aminopolycarboxylic acid complex salt and a thiosulfate in one solution, which is described in German Patent No. 866.605, has been used. It has been known. By making this desilvering process a one-bath bleach-fixing process, simplification is achieved; Since the bleaching blade is made to coexist with the liquid, the bleaching blade is significantly weakened, and sufficient desilvering is extremely difficult for color photographic materials with high sensitivity and high silver content, making it unsuitable for practical use. In particular, in order to improve the sensitivity and image quality of color light-sensitive materials for photographing, the use of silver halide emulsions with higher iodine content has been promoted and is becoming essential. On the other hand, methods of adding various bleach accelerators to bleach-fixing baths or their pre-baths have been proposed as a method of increasing the bleaching edge.

Such bleach accelerators are described, for example, in U.S. Pat.
3.858 specification, British Patent No. 138842, JP-A-53-141623 and JP-A-61-20945; disulfide bonds as described in JP-A-53-95630; thiazolidine derivatives as described in Japanese Patent Publication No. 5.39854; isothiourea derivatives as described in Japanese Patent Publication No. 53-94927;
Thiourea derivatives as described in JP-A No. 8506 and JP-A No. 49-26586; Thioamide compounds as described in JP-A No. 49-42349;
Examples include dithiocarbamates such as those described in Japanese Patent No. 42349. Among them, mercaptothiadiazole, which is described in JP-A-61-20945, is particularly excellent because it has a high bleaching accelerating ability and is stable in bleach-fix solutions, but photosensitive materials containing high iodine emulsions There was a problem in that fixing deteriorated when bleach-fixing was performed.

(Problems to be Solved by the Invention) Accordingly, a first object of the present invention is to provide a method that facilitates desilvering of color light-sensitive materials, shortens processing time, and facilitates processing.

The second object of the present invention is to shorten the processing time of color photosensitive materials with improved desilvering properties, photographic properties, especially sensitivity and graininess, and
The purpose is to provide a method that can be easily processed.

A third object of the present invention is to provide an image forming method that can obtain high WiH images through rapid processing by combining a specific color photosensitive material and a specific processing method.

(Means for Solving the Problems) It has been found that various aspects of the present invention can be achieved by the following method. That is, after the color photosensitive material is subjected to color development processing,
In the method of processing with a bleach-fix solution, at least one emulsion layer of the color light-sensitive material is composed of chemically sensitized silver halide grains, and the silver halide grains contain 30 to 45 mol% of silver iodide. Silver iodobromide or silver iodochlorobromide exists with a clear phase structure, and the outermost layer of the silver halide grains is composed of silver halide containing 8 mol% or less of silver iodide. This was achieved using a characteristic processing method for color photosensitive materials.

The silver halide grains of the present invention will be explained in detail below.

In the silver halide grains of the present invention, silver iodobromide or silver iodochlorobromide containing 30 to 45 mol % of silver iodide exists with a distinct phase structure.

The distinct phase structure of the present invention and the presence of silver iodobromide or silver iodochlorobromide containing 30 to 45 mol % of silver iodide can be determined, for example, by the method of X-ray diffraction. An example of applying the X-ray diffraction method to silver halide grains is H.

This is described in Hirsch's Journal of Photographic Science, Vol. 10 (1962), pages 129 onwards. When the lattice constant is determined by the halogen composition, a diffraction peak occurs at a diffraction angle that satisfies Black's condition (2dsinθ=nλ).

Regarding the measurement method of xg diffraction, refer to Basic Analytical Chemistry Course 24 “X
It is described in detail in books such as ``X-Ray Analysis'' (Imori Publishing) and ``X-ray Diffraction Guide'' (Rigaku Denki Co., Ltd.). The standard measurement method is to use Cu as a target and obtain the diffraction curve of the (220) plane of silver halide using β rays as a radiation source (tube voltage 40 kV, tube current 60 mA).

In order to increase the resolution of the measuring device, the width of the slit (divergent slit, light receiving slit, etc.), the time constant of the device, the scanning speed of the goniometer, and the recording speed are selected appropriately and the measurement accuracy is confirmed using a standard sample such as silicon. There is a need to.

In the present invention, a clear phase structure is one in which the diffraction angle (2θ) is in the range of 386 to 426 and is 7? When a curve of diffraction intensity versus diffraction angle of the (220) plane of silver halide is obtained using a line, there are diffraction peaks corresponding to a high iodine layer containing 30 to 45 mol% silver iodide and 8 mol% or less of silver iodide. At least two diffraction maxima of the diffraction peaks corresponding to a low iodine layer containing silver iodide of This refers to a case where the diffraction intensity is 1/10 to 3/1 of the diffraction intensity. More preferably, the diffraction intensity ratio is 115 to 3/1.
, especially in the case of I/3 to 3/1.

In the emulsion having substantially two distinct phase structures in the present invention, it is more preferable that the minimum peak between the two peaks has a weaker diffraction intensity among two or more diffraction maxima (peaks). It is preferable that the amount is 90% or less.

More preferably 80% or less, particularly preferably 6
It is 0% or less. The method of decomposing a diffraction curve made up of two diffraction components is well known, and is explained in, for example, Experimental Physics Course 11 Lattice Defects (Imori Publishing).

It is also useful to assume that the curve is a function such as a Gaussian function or a Lorentzian function and to analyze it using a curve analyzer manufactured by DU ['ont.

Even in the case of an emulsion in which two types of grains having different halogen compositions that do not have a distinct phase structure coexist, two peaks appear in the X-ray diffraction.

Such emulsions cannot exhibit the excellent photographic performance obtained with the present invention.

In order to judge whether a silver halide emulsion is an emulsion according to the present invention or an emulsion in which two types of silver halide grains coexist as described above, in addition to the X-ray diffraction method, the EPMA method (E
Electron-Probe Micro.

This is possible by using the ^nalyzer method).

In this method, a well-dispersed sample is prepared so that the emulsion grains do not come into contact with each other, and then an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis using electron beam excitation.

By this method, the halogen composition of each particle can be determined by determining the characteristic X-ray intensities of silver and iodine emitted from each particle.

By confirming the halogen composition of at least 50 grains by the EPMA method, it can be determined whether the emulsion is an emulsion according to the present invention.

In the emulsion of the present invention, it is preferable that the iodine content between the grains is more uniform.

When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is preferably 50% or less, more preferably 35% or less.

Another preferred interparticle iodine distribution is one in which the logarithm of particle size and iodine content exhibit a positive correlation. In other words, this is the case where the iodine content of the large size particles is high and the iodine content (2) of the small size particles is low. Emulsions exhibiting such a correlation give favorable results in terms of graininess. This correlation coefficient is preferably 40% or more, more preferably 50% or more.

In the core part, the silver halide other than silver iodide may be either silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high. The silver iodide content may be 30 to 45 mol%, preferably 35 to 43 mol%. More preferred silver halide in the core is silver iodobromide containing 35 to 43 mol % of silver iodide.

The silver halide composition of the outermost layer is silver halide containing 8 mol% or less of silver iodide, and the silver halide includes silver iodobromide, silver iodochlorobromide, silver bromide, and silver chlorobromide. Can be mentioned. Silver halide containing 0.5 to 6 mol % of silver iodide is preferred.

The silver iodide content of the outermost layer of silver halide grains is XPS
(X-ray Photoelectron 5p
It can be measured by a surface analysis method (electroscopy). Regarding this method, see Atsushi Aihara et al.'s ``Spectroscopy of Electrons'' (Kyodo Library 16, Imori Publishing, 1930).
3rd year) etc. can be referred to.

The standard XPS measurement method uses M g −
This method uses Ka to observe the intensity of photoelectrons (usually I 3dsy□, Ag5ds/z) of iodine (N) and limit (Ag) released from silver halide grains in an appropriate sample form.

To determine the iodine content, a calibration curve of the photoelectron intensity ratio (intensity (I) 7 intensity (Ag)) of iodine H) and silver (Ag) is calculated using several types of standard samples with known iodine contents. It can be determined from this calibration curve. In the case of a silver halide emulsion, XPS measurement must be performed after gelatin adsorbed on the surface of silver halide grains is decomposed and removed using a protease or the like.

As for the average halogen composition of the entire grain, it is preferable that the silver iodide content exceeds 8 mol%, more preferably 1
It is 0 to 24 mol%, more preferably 12 to 20 mol%.

The average grain size of the silver halide grains of the present invention is 0.1
0 to 3.0 μm is preferable, more preferably 0.30 μm.
~2.0μm, more preferably 0°40~1. 5μ
It is m.

The average grain size of silver halide grains in the present invention is
T.H. James (T.H.

``The Theory of the Photographic Process'' by James et al.
of thePhotographic Processes
s) is the geometric mean value of particle size well known in the art as described in 3rd Edition, p. 39, published by Macmillan (1966). In addition, the particle size can be determined from "Introduction to Particle Size Measurement" by Masafumi Marukaku (Powder Engineering Society Journal, Vol. 17, 299-313).
(1980), for example, Coulter counter method, single particle light scattering method,
It can be measured by a method such as a laser light scattering method.

The type of silver halide grains having a clear phase structure of the present invention may have regular crystal shapes (normal crystal grains) such as hexahedron, octahedron, dodecahedron, and dodecahedron. It may also have an irregular crystal shape such as spherical, potato-shaped, or tabular, especially with an aspect ratio of 1.0 to 10, especially 1.
Two to five tabular twin grains are preferred.

In the case of normal crystal grains, grains having 50% or more (111) planes are particularly preferred. Even in the case of irregular crystal forms (111)
Particularly preferred are particles having 50% or more faces, (111)
The surface area ratio can be determined by the Kubelka-Munk dye adsorption method. This is because dyes are preferentially adsorbed to either the (111) plane or the (100) plane, and the association state of the dye on the (111) plane and the association state of the dye on the (100) plane are spectrally different. select. The surface ratio of the (111) plane can be determined by adding such a dye to an emulsion and carefully examining the spectra with respect to the amount of dye added.

Although it is possible for the emulsions of the present invention to have a wide grain size distribution, it is preferable to have an emulsion with a narrow grain size distribution.Especially in the case of normal crystal grains, the total weight or number of silver halide grains in each emulsion is It is also possible to use a monodispersed emulsion in which the size of grains accounting for 90% of the average grain size is within ±40%, or even within ±30% of the average grain size.

The effect of the present invention can be best seen in twin grains. It is preferable to contain tabular grains having two or more parallel twin planes in a projected area of 30% or more, preferably 50% or more, more preferably 70% or more.

The emulsion of the present invention having a defined phase structure can be prepared by selecting and combining various methods known in the field of silver halide photographic materials.

First, to prepare the core particles, methods such as the acidic method, neutral method, and ammonia method can be selected, and methods for reacting the soluble root salt and soluble halogen salt can be selected from the one-sided mixing method, simultaneous mixing method, and combinations thereof. .

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a controlled double jet method can also be used. As another form of the simultaneous mixing method, a triple die-cyto method (for example, a soluble root salt, a soluble bromine salt, and a soluble iodine salt) in which soluble halogen salts of different compositions are added independently can also be used.

Silver halide solvents such as ammonia, rhodan salts, thioureas, thioethers, and amines may be selected and used during core preparation. It is desirable that the emulsion has a narrow grain size distribution of core grains. In particular, the above-mentioned monodisperse core emulsion is preferred. It is desirable to have an emulsion in which the halogen composition, particularly the iodine content, of the individual grains is more uniform at the core stage.

Whether the halogen composition of each particle is uniform can be determined by the aforementioned X-ray diffraction method and EPMA method. When the halogen composition of the core particles is more uniform, the diffraction width of X-ray diffraction becomes narrower and sharper peaks are obtained.

After creating a silver iodobromide seed crystal containing a high concentration of silver iodide,
Iridescent odor can be reduced by the method of accelerating the addition rate over time as disclosed by Irie and lead powder in Japanese Patent Publication No. 48-36890, or the method of increasing the addition concentration over time as disclosed by Saito in U.S. Pat. No. 4,242.445. Uniform silver iodobromide can also be obtained by the method of growing silver iodobromide grains.

These methods give particularly favorable results. Irie et al.'s method involves the production of poorly soluble inorganic crystals for photography by a double decomposition reaction in which two or more inorganic salt aqueous solutions are simultaneously added in approximately equal amounts in the presence of a protective colloid. , addition at a constant temperature acceleration or higher and at an addition rate Q that is less than or equal to the addition rate proportional to the total surface area of the growing poorly soluble inorganic salt crystal, that is, addition at Q = 7 or more and Q = αt2 + βt + γ or less. It is.

On the other hand, Saito's method is a silver halide crystal manufacturing method in which two or more inorganic salt aqueous solutions are simultaneously added in the presence of a protective colloid, and the concentration of the inorganic salt aqueous solution to be reacted is adjusted so that almost no new crystal nuclei are produced during the crystal growth period. 6. Silver halide grains with a clear phase structure according to the present invention that increase the number of grains to such an extent that they do not occur! J! ! ! In J, shelling may be carried out directly after the formation of core particles, but it is preferable to wash the fur emulsion with water for desalination and then apply shelling.

Shelling can also be prepared by various methods known in the field of silver halide photographic materials, but a simultaneous mixing method is preferred. Irie et al.'s method and Saito's method mentioned above are clearly compatible.
This is preferable as a method for producing a structured emulsion.

In the case of fine-grain emulsions, conventional tools are useful for preparing grains with a well-defined phase structure, but they alone are not sufficient to improve the degree of perfection of the phase structure. First, it is necessary to carefully determine the halogen composition of the high iodine layer. Silver iodide and silver bromide each have different thermodynamically stable crystal structures, and it is known that they do not form mixed crystals at any composition ratio. The mixed crystal composition ratio depends on the temperature during particle preparation, but is 15~
It is important to select the optimum one from within the range of 45 mol%. Although the stable mixed crystal composition ratio depends on the atmosphere, 30
It is estimated that it exists in ~45 mol%.

temperature when growing a low iodine layer outside the high iodine layer,
Of course, it is important to select pf, pAg, stirring conditions, etc., but it is also important to select four protective colloids when growing a low iodine layer, and halogens such as spectral sensitizing dyes, antifoggants, and stabilizers. It is preferable to take measures such as growing a low iodine layer in the presence of a compound adsorbed on the surface of silver oxide. It is also effective to add fine grain silver halide instead of adding water-soluble root salt and water-soluble alkali metal halide when growing a low iodine layer.

As mentioned above, in the present invention, silver halide grains having a clear phase structure mean that there are two different halogen compositions within the grains.
It has been explained that there are essentially three or more regions, and the center side of the particle is the core part, and the surface side is the shell part.

Substantially, the two are the core part and the third region (other than the shell part).
For example, this means that there may be a layer between the central core portion and the outermost shell portion.

However, even if such a third region exists, when an X-ray diffraction pattern is obtained as described above, two peaks (two peaks corresponding to a high iodine portion and a low iodine portion) are obtained.
This means that it may exist within a range that does not substantially affect the shape of the .

The same applies when the third region exists inside the core portion.

It is essential that the color light-sensitive material of the present invention has at least one emulsion layer containing the silver halide grains of the present invention. It is present in an amount of preferably 50% or more, more preferably 70% or more, particularly preferably 90% or more of the sum of the projected areas of all silver halide grains present.

Dyes used when growing the low iodine layer include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei, and nuclei in which aromatic hydrocarbon rings are fused to these nuclei; namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, hendithiazole nucleus, naphthothiazole nucleus, benzylselenazole I, penzimidazole nucleus, quinoline nucleus, etc. can be used. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include pyrazolin-5-one, thiohydantoin, and 2-thioxazolidine-2 as nuclei having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

For example, Re5search Disclosure +
The compounds described in Itew 17643, page 23, section (■) (December 1978) or the compounds described in the cited literature can be used.

Typical examples include the compounds described in Japanese Patent Application No. 62-47225.

Antifoggants and stabilizers are also useful compounds when growing low iodine layers. Re5search D described above
It is possible to select and use the compounds shown in the isclosure. However, there are some compounds, such as the tetrazaindene compounds shown in Examples, that do not exhibit desirable effects. Preference is given to the invention to add mercapto compounds.

The mercapto compound preferably used in the present invention is a compound represented by the following general formula.

In the general formula, Ml represents a hydrogen atom, a cation, or a protecting group for a mercapto group that is cleavable with an alkali, and Z represents an atomic group necessary to form a 5- to 6-membered hemopenic ring. This heterocycle may have a substituent or be fused. To explain in more detail, Ml is a hydrogen atom,
Cations (e.g. sodium ions, potassium ions,
ammonium ion, etc.) or alkali-cleavable mercapto group protecting groups (e.g. -〇OR'-COOR'
-C1h GHz COR' etc. However, R' represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, etc.

Z represents an atomic group necessary to form a 5- or 6-membered heterocycle. This heterocycle contains sulfur atoms, selenium atoms, nitrogen atoms, oxygen atoms, etc. as heteroatoms, and or may have a substituent on the heterocycle or condensed ring.

Examples of Z include tetrazole, triazole, imidazole, oxazole, thiadiazole, pyridine, pyrimidine, triazine, azabenzimidazole, purine, tetraazaindene, triazaindene, pentaazaindene, penztriazole, benzimidazole, benzoxazole , benzthiazole, benzselenazole, and naphthimidazole. Substituents for these rings include alkyl groups (e.g. methyl group, ethyl group, n-hexyl group, hydroxyethyl group, carboquinethyl group, etc.), alkenyl groups (e.g. allyl group, etc.), aralkyl groups (e.g. benzyl group, etc.). group, phenethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, p-acetamidophenyl group, p-carboquinethyl group, m-hydroxyethyl group, p-sulfamoylphenyl group, p-acetylphenyl group, 0-methoxyphenyl group, 2.4-diethylaminophenyl L 2,
4-dichlorophenyl group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, n-butylthio group, etc.), ruthio group (e.g., phenylthio group, naphthylthio group, etc.), aralkylthio group (e.g., hensylthio group, etc.), mercapto group. It may be UtQ'd with a group or the like. Furthermore, in addition to the above-mentioned 71 substituents, a nitro group, an amino group, a halogen atom, a carboxyl group, a sulfo group, etc. may be substituted on the condensed ring.

The amount of these mercapto-containing compounds used is halogenated fli! It is preferably 10-2 mol or less per mol.

Specific examples of preferred nitrogen-containing heterocyclic compounds having a mercapto group are described in Japanese Patent Application No. 62-47255.

Silver halides of different compositions may be bonded to the emulsion of the present invention by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical sensitization and spectral enhancement. During the physical ripening process, various polyvalent metal ion impurities (cadmium, zinc,
It is also possible to introduce salts or complex salts of lead, copper, chlorine, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.). Compounds used for chemical sensitization include those described in the specification of JP-A-62-215272, from the lower right column on page 18 to the upper right column on page 22. Further, additives used in such a process are described in RDlt17643 and Kaimagnetic Report 18716, and the two corresponding parts are summarized in the table in IB. Known photographic additives that can be used in the present invention also include the above two R
D, and the relevant notes a are shown in the table below.

Hirakata FI class chemical sensitizer Sensitivity enhancer Spectral sensitizer, Super sensitizer Brightener Antifoggant and stabilizer Light absorber, Filter dye, RD17643 RD187] 6 Page 23 Page 648 Right column Same as above 23~ Page 24 Page 648 Right Column - Page 649 Right Column Page 24 Pages 24-25 Page 649 Right Column - Pages 25-26 Page 649 Right Column - Page 650 Left Column Ultraviolet Absorber 7 Stain Inhibitor Dye Image Stabilizer Hardener Binder Plasticizer, lubricant coating aid, surface active agent 13 Static prevention page 25 right column 25 pages 26 pages 26 pages 27 true 26-27 pages 65050 pages right column 651 pages left column Same as above 650 pages right column 650 pages right column top book The emulsion of the invention may be contained in any layer as long as it is contained in the light-sensitive emulsion layer of a silver halide color photographic window optical material, but emulsion layer groups having substantially the same color sensitivity have the same sensitivity. 21 different? It is preferable to use it when it is divided into J or more, and when it is divided into 2N, it is used as a high-sensitivity layer, and when it is divided into 3N or more, it is used as a high-sensitivity layer.
Alternatively, it is preferable to use it for an intermediate sensitivity layer.

By using the emulsion of the present invention, not only the desilvering property is improved even if the following bleach-fixing process is performed, but also the emulsion has excellent photographic properties, particularly sensitivity and graininess.

Next, the bleach-fix solution of the present invention will be explained.

In the present invention, all known bleaching agents can be used in the bleach-fix solution, but aminopolycarboxylic acid ferric complex salts are particularly preferred. Representative examples of the aminopolycarboxylic acids of the ferric aminopolycarboxylic acid complex salts include: A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 1,3-Diaminopropanetetraacetic acid A-41,2-
Diaminopropanetetraacetic acid A-5 ethylenediamine-N-
(β-oxyethyl)-N,N',N'-triacetic acid A-6 Nitrilotriacetic acid A-7 Cyclohexanediaminetetraacetic acid A-8 Iminodiacetic acid A-9 Dihydroxydiethylglycine A-10 Ethyl etherdiaminetetraacetic acid A -11 glycol ether diamine tetraacetic acid, A-12 ethylene diamine tetrapropion tetraacetic acid, etc., but are not limited to these exemplified compounds. Among these compounds, A1 to A-3,
Aminopolycarboxylic acid ferric complex salts, preferably A-10, may be used in the form of complex salts, or may be used in the form of ferric salts, such as ferric sulfate, ferric chloride, ferric nitrate, ferric sulfate. A ferric ion complex salt may be formed in a solution using diiron ammonium, ferric phosphate, etc., and an aminopolycarboxylic acid.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred from the viewpoint of solubility. When used in the form of a complex salt, one type of complex salt or two or more types of complex salts may be used. On the other hand, when forming a ferric ion complex salt in a solution using a ferric complex salt and an aminopolycarboxylic acid, one type or 21! of ferric complex salts are used. You may use more than that. Furthermore, one or more aminopolycarboxylic acids may be used.

In either case, the aminopolycarboxylic acid is a ferric ion! It is preferable to use the compound in excess to form the 11 salt, and it is preferable to use it in an excess of 1 to 15% of the aminopolycarboxylic acid ferric complex salt.

In addition, the bleach-fix solution containing the above-mentioned ferric ion complex contains
Metal ion complex salts other than iron such as cobalt and copper may also be contained.

In the present invention, the amount of bleach used per bleach-fix solution 1e is 0.05 to 0.5 mol, preferably O11 to
It is 0.4 mol.

Examples of fixing agents include thiosulfates (e.g., sodium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate), thiocyanates (e.g., sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate), thioether compounds, thioureas, A large amount of iodide salts can be used, but thiosulfate is commonly used, and ammonium thiosulfate is particularly preferred from the viewpoint of solubility and fixing speed, and it is also good to use it in combination with other fixing agents.
The amount of these fixing agents ranges from 0.3 to 11 parts of the bleach-fixing solution.
3 mol, preferably 0. It is 5 to 2 moles.

Furthermore, bleach accelerators can be added to the bleach-fixing baths or their pre-baths. Such bleach accelerators are described, for example, in U.S. Pat. No. 3,893,858, German Patent No. 1,
290,812, British Patent No. 138842, JP-A-53-95630, Research Disclosure No. 17129 (July 1978) Compounds having a mercapto group or disulfide group; JP-A-50-1
Thiazolidine derivatives described in US Pat. No. 40129; thiourea derivatives described in U.S. Pat. No. 3,706,561; iodides described in JP-A-58-16235;
Polyethylene oxide compounds described in Japanese Patent Publication No. 748,430; polyamine compounds described in Japanese Patent Publication No. 45-8836 can be used. In particular, the following general formula (1
) or a salt thereof is preferred because it has a high bleaching accelerating ability, exists stably in a bleach-fixing solution, and continuously exhibits its bleaching accelerating ability.

General formula (1) In the formula, R1 and R2 represent a hydrogen atom, a hydroxyl group, an amino group (e.g., amine, dimethylamino, diethylamino, methylamino, etc.), a carboxyl group, a sulfo group, or an alkyl group, and R3 and R4 represent hydrogen. It represents an atom, an alkyl group, or an acyl group, and R3 and R4 may be connected to form a ring. M represents a hydrogen atom, an alkali metal atom (eg, sodium, potassium, etc.) or an ammonium group, n represents an integer from 2 to 5, and 0 is preferably 2 or 3.

The alkyl groups represented by R1, RZ, R3 and R' are
It is preferable that the alkyl group has 1 to 5 carbon atoms (
For example, methyl, ethyl, propyl, etc.) may have a substituent. Examples of substituents include carboxyl group, hydroxyl group, sulfo group, amino group (e.g., amino, dimethylamino, etc.), alkoxy group (e.g., methoxy, ethoxy, etc.), sulfonyl M (e.g., methanesulfonyl,
ethanesulfonyl, etc.), carbamoyl groups (e.g., carbamoyl, methylcarbamoyl, etc.), sulfamoyl groups (sulfamoyl, methylsulfamoyl, etc.),
Amide groups (e.g., acetylamino, etc.), sulfonamido groups (e.g., methanesulfonylamino, etc.), alkoxycarbonyl groups (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), cyano groups or halogen atoms (
For example, chlorine, bromine, etc.).

The acyl group represented by R1 and R4 preferably has 3 or less carbon atoms (for example, acetyl).The ring formed by connecting R3 and R4 includes a pyrrole ring, a pyrrolidine ring, a pyrazole ring, and an imidazole ring. , triazole ring, morpholine ring, piperidine ring, pyridine ring, pyrimidine ring, pyrazine ring and the like.

-C In the compound (1), preferably used in the present invention, n is 1 or 2, and R3 or R4
is a hydrogen atom, an alkyl group having 1 or 2 carbon atoms, or R
1 and R4 are connected to form an imidazole ring, a triazole ring,
It is a compound that forms a pyridine ring.

Specific examples of the compound represented by general formula (1) are shown below,
It is not limited to these.

/ The compound represented by the general formula (1) used in the present invention is
Advanced in Heterocyclic°chemistry
hemistry, 9.165-209 (196
8), 2,5-dimercapto-1,3,4
It can be easily synthesized by alkylation of thiadiazole. A specific synthesis example is given in JP-A No. 61-20945.
It is stated in the No.

The compound represented by the general formula (1), which is the bleach accelerator used in the present invention, may be contained only in the bleach-fixing bath or its pre-bath, or in both the bleach-fixing bath and its pre-bath. It may also be included.

Addition when incorporating the compound of the present invention into these liquids■
Although it varies depending on the type of processing solution, the type of photographic material to be processed, the processing temperature, the time required for the intended processing, etc., it is appropriate that the , preferably lXl0-' to lX10-
'It's a mole.

The bleach-fix solution of the present invention contains preservatives such as sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.), hydroxylamine, hydrazine, bisulfites of aldehyde compounds (e.g., acetaldehyde sodium bisulfite, etc.), or Carbonyl bisulfite adducts and sulfinic acid compounds are preferred, and in the fixer, aminopolycarbon MI! is used to improve the stability of the fixer.
or an organic phosphonic acid chelating agent (preferably 1-hydroxyethylidene-1,1-diphosphonic acid and NN, N
', N''-ethylenediaminetetraphosphonic acid).

The bleach-fix solution of the present invention may contain rehalogenating agents such as bromides (e.g., potassium bromide, sodium bromide, ammonium bromide, etc.) and chlorides (e.g., potassium chloride, sodium chloride, ammonium chloride, etc.) and silver nitrate (e.g., pIrH buffers such as boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, Known additives such as metal corrosion inhibitors such as ammonium sulfate, various fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol, etc. can be added.

The bleach-fix solution has a pl+ of 4.0 to 9.0, preferably
5.0 to 8.0, more preferably 6.0 to 7.5.

Further, the temperature of the bleach-fixing solution can be treated at 10 to 60'C, preferably 30 to 50C, more preferably 35 to 45C.

As a replenisher for the bleach-fix solution, photosensitive materials 1. (Win,
100~3000mi! is preferable, and more preferably 300 to 10,100O.

Examples of the desilvering step in the present invention include, but are not limited to, the following.

Part 1: Bleach-bleach-fixing Kan 2 Bleaching - Bleach fixing constant -3 fixing - bleach fixing 11k14 Bleach fixing As the desilvering step, the above-mentioned No. 4 is most preferable.

It is preferable that the stirring of each treatment solution in the desilvering process of the present invention be as strong as possible from the viewpoint of shortening the desilvering process time. Examples include the method described above, and in the case of a means of colliding jets, it is preferable to carry out the collision within 15 seconds after the photosensitive material is introduced into the processing liquid.

In the present invention, the crossover time (time in the air from when the photosensitive material leaves the processing solution to when it enters the next processing solution) is 10
It is preferably within seconds, more preferably within 5 seconds.

In addition, the desilvering process is usually performed after the development process, but
A bath for washing with water, rinsing, bleaching acceleration, etc. may be provided between these.

Furthermore, the bleach-fixing process or each step of bleaching and fixing may be carried out in a forward current or countercurrent multi-stage process.

A bleaching bath can be provided between the color developing bath and the bleach-fixing bath of the present invention. For the bleaching solution used in the bleaching bath, the bleaching agents that can be used in the bleach-fixing solution of the present invention can be similarly used. Further, as for bleach accelerators and other additives, all compounds that can be used in bleach-fix solutions can be used in the same manner.

A fixing bath can be provided before or after the bleach-fixing bath of the present invention. In the fixing solution used in the fixing bath, fixing agents and preservatives that can be used in the bleach-fixing solution of the present invention can be similarly used, as well as fixing agents and preservatives that are known to be used in fixing solutions such as fixing accelerators. (Additives can be added.

The color developing solution of the present invention will be explained below.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene 2-amino-5-(N-ethyl-N-laurylamino)
Toluene 4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline 2-methyl-4-[N-ethyl-N- [β-hydroxyethyl)aminocoaniline 4-amino-3-methyl-N -Ethyl-N-(β-(methanesulfonamide)ethyltwoaniline N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide N,N-:,'Methyl-p-phenylenediamine 4-amino-3 ~Methyl-N=ethyl-N-methoxyethylaniline 4-amino-3-methyl-N-ethyl N-β-ethoxyethylaniline 4-amino-3-methyl-N-ethyl-N-β-butoxyethylaniline above Among the p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-)luenesulfonates. The amount of the aromatic-grade amine developing agent used is preferably about 0.1 g to about 20 g per developer solution 11.
More preferably about 0.

The concentration is between 5g and Log.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

A preferable addition amount is 0 per 11 color developing solutions.

The amount is 5 g to 10 g, more preferably 1 g to 5 g.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Hydroxamic acids described in No. 9, hydrazines and hydrazides described in No. 61-170756, and hydrazides described in No. 61-188
Phenols described in No. 742 and No. 61203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-180
Various tJs listed in issue 616! It is preferable to add tit. In addition, in combination with the above compounds, patent application No. 1478/1986
No. 23, No. 61-166674, No. 61-16562
No. 1, No. 61-164515, No. 61-170789
and monoamines described in No. 61-168159, etc., diamines described in No. 61-173595, No. 61-164515, No. 61-186560, etc., No. 61-168159, etc.
No. 1-165621 and polyamines described in No. 61-169789, polyamisos described in No. 61-188619, nitroxy radicals described in No. 61-197760, No. 61-186561, and No. 61-197.
It is preferable to use the alcohols described in No. 419, the oximes described in No. 61-198987, and the tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in US Pat. No. 349, US Pat.
The aromatic polyhydroxy compound described in No. 746.544 may be included if necessary, and addition of an aromatic polyhydroxy compound is particularly preferred.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, 0-
Sodium hydroxybenzoate (sodium salicylate), potassium O-hydroxybenzoate, 5-sulfo-2
Examples include sodium hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferable that it is more than 0. 1 mol/l~0
．． 4 moles/7! It is preferable that

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferable, such as aminopolycarboxylic acids described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347,
Special Publication No. 56-39359 and West German Patent No. 2,227,
Organic phosphonic acids described in No. 639, JP-A-52-102
No. 726, No. 53-42730, No. 54-12112
No. 7, No. 55-126241 and No. 55-65950
Phosphonocarboxylic acids described in No. 6, etc., and other JP-A No. 1973
Examples thereof include compounds described in Japanese Patent Publication No. 8-195845, No. 58-203440, and Japanese Patent Publication No. 53-40900. Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-1 rimethylenephosphonic acid, ethylenediamine-N,N,N'N°-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1.2- diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,1-)
Licarponic acid, l-hydroxyethylidene-1,1 diphosphonic acid, N,N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, two or more of these chelating agents may be used in combination as necessary. It's okay.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means that it is contained in an amount of 2 ml or less per developer IE, preferably not at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent No. 3,
813,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho 44-30074, JP-A-56-156826 and JP-A No. 52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2,
No. 494.903, No. 3,128゜182, No. 4,2
No. 30,796, No. 3,253.919, Special Publication No. 1977
-11431, amine compounds described in U.S. Patent No. 2,482.546, U.S. Pat. No. 3,128,183
Polyalkylene oxides disclosed in Japanese Patent Publications No. 11431/1983, 23883/1983, and U.S. Patent No. 3,532,501, as well as 1-phenyl-3-pyrazolidones, imidazoles, etc. Can be added.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl- Representative examples include nitrogen-containing heterocyclic compounds such as benzimidazole, 2-thiazolylmethyl-benzimidazole, imidazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain an optical brightener. As the fluorescent brightener, 44'-diamino-2,2'-disulfostilbene compounds are preferred.

The amount added is 0 to 5 g/l, preferably 0.1 g to 4 g/l.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. The amount of replenishment is preferably small, but 100 to 1500 ml is preferably 100 to 80 ml (1 m 1 ) per 1 rrr of photosensitive material.

More preferably 100mff to 400mj! It is.

Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. In the present invention, the black-and-white developer used at this time may be a so-called black-and-white first developer used in the reversal processing of color photographic light-sensitive materials, which is commonly known, or a developer used in the processing of black-and-white light-sensitive materials. In addition, various well-known additives that are generally added to black and white developers can be included.

Typical additives include developing agents such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Examples include inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, and methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. be able to.

The processing method of the present invention comprises processing steps such as color development, bleach-fixing, and fixing as described above. Here, after the treatment step with fixing ability, processing steps such as washing with water and stabilization are generally performed, but after the bath with fixing ability, stabilization treatment is performed without substantially washing with water. It is also possible to use convenient treatment methods that perform the following steps.

The rinsing water used in the rinsing process may contain known additives as necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic sulfuric acid, and various bacteria. A bactericide/antifungal agent (for example, isothiazolone, an organic chlorine bactericide, benzotriazole, etc.) to prevent the growth of algae, a surfactant to prevent drying load and unevenness, etc. can be used. Or L, E
.

West l”Water Quality Cr1
teria'' + Photo, Sci.

and Eng,, vol, 9.11k16. Pa
Compounds described in GE 344-359 (1965) and the like can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used. The stabilizing liquid may contain ammonium compounds, metal compounds such as Bi and Aji, optical brighteners, chelating agents (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides, fungicides, A hardening agent, a surfactant, etc. can be used. Here, formalin can also be removed from the solution. In this case, reduction of environmental pollution (reduction of pollution load)
, which is preferable in terms of improving the working environment.

Further, the water washing step and the stabilization step are preferably carried out by a multistage countercurrent method, and the number of stages is preferably 2 to 4 stages. The amount of replenishment is 1 to 50 times, preferably 2 to 30 (a, more preferably 2 to 15 times) the amount brought in from the previous bath per unit area.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
, Mg concentration is 5mg/j! Deionized water,
It is preferable to use water that has been sterilized with halogen, ultraviolet germicidal lamps, etc.

In each of the above processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. becomes. In order to correct such concentration of the processing liquid, it is preferable to replenish an appropriate amount of water or correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid from the water washing step or the stabilization step is allowed to flow into a bath having a fixing ability, which is a pre-bath.

The present invention can be applied to color photographic materials such as color negative films and color reversal films.

In addition to the silver halide emulsion used in the present invention, conventionally known silver halide emulsions can be used in combination. This silver halide photographic emulsion can be used, for example, in Research Disclosure (RD), 17643 (December 1978), pp. 22-23, "1.
sion preparation and types
)”, and 1t18716 (November 1979)
Month), page 64B, “Physics and Chemistry of Photography” by Grafkide,
Published by Paul Montell (p. 1.1fkides).

Chemic et Ph1sique PhoLo
graphique Paul Montel, l
967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin + Photo
graphic E+mulsion Chemist
ry (Focal Press.

1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L.

ZelikIIIan et al, Making a
nd Coatin'g PhotographicE
mulsion, Focal Press, l
964), etc., can be used to produce A.

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Gatz, Photographic Science and Engineering CCutoff, PhotographicSci.
ence and Engineering), 1st
4, pp. 248-257 (1970); U.S. Patent No. 4
, No. 434.226, No. 4,414,310, No. 433.048, No. 4,439,520, and British Patent No. 2,112,157. Can be done.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435,503.

Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned RDN117643, ■-C-G
It is described in the patent described in .

As a yellow coupler, for example, U.S. Patent Tube 3.93
No. 3,501, No. 4,022,620, No. 4,326
, No. 024, No. 4,401,752, No. 4,248,
No. 961, Special Publication No. 58-10739, British Patent No. 1,
No. 425,020, US Pat. No. 1.476.760, US Pat. No. 3,973.968, US Pat. No. 4,314,023, US Pat. Preferably.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0,619, No. 4,351,897, European Patent No. 7
No. 3,636, U.S. Patent No. 3.061,432, No. 3
, No. 725,064, RD Block 24220 (June 1984), JP-A-60-33552, RD Floor 24230
(June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 551
No. 18034, No. 60-185951, U.S. Patent No. 4
, No. 500, 630, 4. 540. No. 654, No. 4,556,630, WO (PCT) 8810479
Particularly preferred are those described in No. 5 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052,212.
No. 4,146.396, No. 4.228,233, No. 4,296,200, No. 2,369.929,
No. 2,801,171, No. 2,772.162, No. 2,895,826, No. 3,772,002, No. 3
, 758°308, 4,334,011, 4,
No. 327.173, West German Patent Publication No. 3,329,729
European Patent No. 121,365A, European Patent No. 249°453
A, U.S. Patent No. 3,446.622, U.S. Patent No. 4,333
, No. 999, No. 4,753,871, No. 4,451,
No. 559, 4. 427. No. 767, 4,690
, No. 889, No. 4,254゜212, No. 4,296,
Preferably, those described in No. 199, JP-A-6142658, etc.

Colored couplers for correcting unnecessary absorption of color-forming dyes are described in Section 1-G of RD Floor 17643, U.S. Patent No. 4,1.
63.670, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4,004,929, U.S. Pat. A coupler that corrects unnecessary absorption of a coloring dye using a fluorescent dye released during coupling as described in U.S. Patent No. 4,774,181, and U.S. Patent No. 4,777゜1.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 20.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
, 570, European Patent No. 96.570, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
It is described in 4,367.282, 4,409.320, 4,576.910, British Patent 2,102,173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the ftl image suppressor is the previously described RD1764.
3. Patents listed in sections ■ to F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, U.S. Patent No. 4,248,9
No. 62 and No. 4°782.012 are preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2.097.140;
Those described in JP-A No. 2,131.188, JP-A-59-157638, and JP-A-59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. 4.310,618, etc. DIR redox compound releasing couplers, DIR couplers releasing couplers, DIR described in JP-A-60-185950, JP-A-62-24252, etc.
Coupler-releasing redox compound or DIR redox-releasing redox compound, European Patent No. 173.302A
R
D Arashi 11449, 24241, JP-A-61-2012
Bleach accelerator-releasing couplers described in US Pat. No. 47, etc., ligand-releasing couplers described in US Pat. , 774, 181, etc., which emit a fluorescent dye.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-ice dispersion method are described in US Pat. No. 2,322.027 and the like.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are described in U.S. Pat.
1.230 etc.

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution.

There is also a method of using a polymer as a coupler dispersion medium, as described in Japanese Patent Publication No. 4B-30494, Japanese Patent Publication No. 5139835, US Pat. No. 3,619,195, West German Patent No. 1,957.
There are various descriptions in No. 467.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W○88100723 are used. In particular, the use of acrylamide-based polymers is preferred from the viewpoint of color image stabilization.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D,, page 28 of l1h17643, and same side 1871
It is described from the right column on page 647 to the left column on page 648 of G.

The present invention will be further explained below with reference to Examples.

Example-1 (Preparation of emulsion) 20 g of inert gelatin 1 2.4 g of potassium bromide.

An aqueous solution of 2.05 g of distilled potassium iodide dissolved in 800 ml of distilled water was stirred at 75°C, and nitric acid was added to it. 5.0
Instantly add 150 ccfc of an aqueous solution containing g
After adding excess potassium bromide, the mixture was physically aged for 20 minutes. Further, according to the method described in U.S. Pat. No. 4,242,445,
mol/1 silver nitrate and potassium halide aqueous solution (15 mol% potassium iodide to 85 mol% potassium bromide)
15 mol % of silver iodobromide grains were grown. The emulsion was washed with water for desalination to prepare emulsion a. The finished amount of emulsion a was 900 g. The grain size of emulsion a is 0.93 μm. According to emulsion a, 0.76 μm・25 mol%, 0.66, crm・
40 mol%, 0.71 μm・39 mol%, 0.72 μm
・42 mol%, 0゜70μm・50 mol% and 0.75
Adjust silver iodobromide grains of μm・60 mol%, emulsion b-g
And so.

Take 900g of Emulsion A, add 21g of distilled water, 9Qcc of lO% potassium bromide, and 5cm of the following compound (1), heat to 60°C, and stir to form an aqueous solution 15 in which 17g of silver nitrate is dissolved.
0cc and 150c of an aqueous solution containing 13g of potassium bromide
c was added at the same time over 20 minutes, and 400 cc of an aqueous solution containing 50 g of silver nitrate and 400 cc of an aqueous solution containing 38 g of potassium bromide were simultaneously added for 60 minutes to form an iodine odor with a silver iodide content of 10 mol% and 1.07 μm. Silver Fide Emulsion 1 was prepared.

Compound (1) Emulsions 2 to 7 as shown in Table 1-1 were prepared by shelling emulsions b to g with silver bromide in accordance with the method used to prepare emulsion 1 from emulsion a.

The structures of emulsions 1 to 7 are summarized in Table 1-1. A clear phase structure is one in which maximum absorption at a high silver iodide content and maximum absorption at a low silver iodide content are observed by X-ray diffraction measurement, and there is at least one minimum between them.

Potassium thiocyanate was used instead of compound (1) that was present when preparing emulsion 5 by adding an emulsion e-shell.
Emulsions 8 and 9 were prepared in the same manner except that X 10-'' mol/2 and lXl 0-'' mol/1 were present.

on a subbed cellulose triacetate film support.
Sample 101, which is a multilayer color brightening material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The number corresponding to each component indicates the coating type expressed in g/cd, and for silver halide, indicates the coating type in terms of silver. However, regarding the sensitizing dye, the coating amount per mole of silver halide of the same 11 is shown in mole units.

(Sample 101) 1st layer (antihalation layer) Black colloid silver 0.18 Gelatin 0.40 2nd layer (intermediate layer) Emulsion I] Silver 0.092.5
-di-t-pentadecylhydroquinone 0.18EX-1
0.07 EX-30,05 -2 Gelatin 0, OO2 0,06 0,08 0,10 0,10 0,02 1,04 Silver 0.10 1 0,15 6.9X10-'1.8X10-' 3, lX10-' 0, 335 0.020 0.030 0.015 0.030 0,060 0,90 4th layer (second red-glare emulsion layer) Emulsion F Sensitizing dye ■ Sensitizing dye ■ Enhancing dye ■ EX-2 EX-3 EX -10 II B S -2 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion F Enhanced dye■ Sensitizing dye■ Enhanced dye■ EX-3 EX-4 i艮0, 90 5゜lXl0-' 1.4X10 -'2.3X10-' 0.400 0,050 0, O15 0,080 0,040 0,080 0,060 1,50 Silver 1.50 5.4X10-'1.4XIO-'2.4XIO-' o,oi.

O, O83 EX-2 B5-1 B5-2 Gelatin 6th layer (intermediate layer) EX-5 B5-1 Gelatin 7th WJ (first green emulsion layer) Emulsion A Emulsion B Enhanced dye V Enhanced dye ■ Sensitizing dye ■ EX-6 EX-1 EX-7 EX-8 B5-1 B5-3 0.097 0,22 0.10 1,50 0,080 0.020 0,80 Silver 0.15! IO,15 3,0X10-5 1.0X10-'3.8XIO-' 0,26 0 0.040 0, O65 0,025 0,100 0,010 Gelatin 8th layer (7th green-sensitive emulsion layer) Emulsion C Enhanced dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 EX-7 )I B S -1 HB S -3 Gelatin 9th layer (3rd green emulsion WJ) Emulsion sensitizing dye ■ Exacerbating dye ■ Exacerbating dye ■ EX-13 EX-11 EX-1 0, 66 Silver 0.45 2, lX1O-'7.0X10-'2.6X10-' 0, 1 0 5 0.029 0.029 0, 1 60 o, oos 0, 60 i艮 1, 60 3.5XIO-'8.0X10-'3.0X10-' 0.015 0, 1 00 0, 025 HBS-10,25) 1Bs-20,10 Gelatin 1.50 1st O layer (yellow filter layer) Yellow colloidal silver Silver 0.05EX-5
0,15 8BS-10,08 Gelatin 0.50 11th layer (first blue emulsion layer) Emulsion A 0.08 Emulsion B
Silver 0.07 emulsion E
Silver 0.07 Concentrating dye■
3.5X10-'EX-90,721 EX-80,042 HBS-10,28 Gelatin 1.10 No. 127
i2i (second blue emulsion rri>emulsion F
Silver 0.45 sensitizing dye ■ 2
．． lX10-'EX-9 EX-10 H13S -1 Gelatin 13th layer (third blue emulsion layer) Emulsion G Sensitizing dye EX-9 HB S -1 Gelatin 14th layer (first protective layer) Emulsion H H133 -1 Gelatin No. 15N (second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0, 154 0,007 0, 05 0, 78 i艮 0, 77 2.2X10-' 0, 20 0, 07 0, 69 Silver 0, 54 0, 20 Gelatin 1, 20 In addition to the above components, a gelatin hardening agent H-1 and a surfactant were added to each layer.

EX-3 X X X X H C, Hl(n) Ch　I(+5(n) H CH□ X (J X-8 HI C1(.

1’EX Ill5 C, Tl.

C,11,O20,' H (t)C4Jlq H Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ (CH2)4SO3days (C1(Js SO3II・N (Cz Hs)sCH
l 1■ cHt -CH OI Ht CONH-CH.

Cl1ff TomiCH-3ow -CL -CONI(-
C1hNext, the 5th N of the emulsion used in test f4101
Samples prepared by replacing Emulsion 1 with Emulsions 2 to 9 shown in 21-1 were designated as Samples 102 to 109, respectively. The sample prepared above was cut to 35 m/m, imagewise exposed, and then the following processing steps and processing solution were used until the cumulative replenishment of the developer became twice the mother solution tank capacity. ,
Continuous processing (running processing) was performed for each separately.

Table 1-3 Processing method Step Processing time Processing temperature Refill gl? Capacity color development 3 minutes 15 seconds 38℃ 45mj!
5j! Bleach constant 27 4 minutes 00 seconds 38℃ 5
0m1 51Wash fl) 20 seconds 35
℃ (2) to 11+ 27! Countercurrent piping method.

Water washing +21 20 seconds 35℃ 30m1
24! Stable 25 seconds 35℃ 2
0me 21 drying 50 seconds 6
The replenishment amount at 5° C. was 35 mm per length of 91 m. Next, the composition of the treatment solution is described.

(Color developer) Diethylenetriaminepentaacetic acid l-hydroxyethylidene 1,l-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β hydroxyethylamino) 2-Methylaniline Add sulfate water and pH (Bleach-fix solution) Mother solution, replenisher common Ethylenediaminetetraacetic acid ferric ammonium hydrate Ethylenediaminetetraacetic acid disodium mother solution (g) Replenisher (g) 2.0 2.2 3.0 3.2 4.0 30.0 1.4 1.5 ■ 2.4 4.5 4.4 37.0 0.7], Qffi 1.07! 10.05 10.10 Unit (g) 90.0 5.0 Lithium salt Sodium sulfite ammonium thiosulfate aqueous solution (70%) Acetic acid (98%) Add water and p) I (Stable solution) Mother liquor and replenisher common 12. 0 300.0m 1 5.0m1 1, Oj! 6.0 units (g) Formalin (37%) 2. Qea1
Polyoxyethylene-p-monono 0.30 nylphenyl ether (average type synthetic leather 10) Ethylenediaminetetraacetic acid disodium 0.05 um Add salt water 1. OJp ■,
1 5.0 to 8.0 (Washing water) Mother liquor and replenisher common Tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). Water was passed through a mixed bed column packed with IR-400) to reduce calcium and magnesium ion C degrees to 3/1. The following treatment was followed by 20 μl/l of sodium isocyanurate dichloride and 0.0 μl/l of sodium sulfate. 15g/7! was added. pH of this solution
is in the range of 6.5 to 7°5.

The desilvering performance of each sample was compared based on the amount of silver remaining in the highest concentration part of the sample at the end of the run. The amount of residual silver was determined by fluorescent X-ray analysis. The sensitivity is R concentration of sample 101 0.2
The sensitivity is expressed as relative sensitivity with the sensitivity of 100 as 100.

The RMS value representing graininess was expressed as a value 1000 times the standard deviation of the variation in density value that occurs when a temperature with a cyan density of 0.5 is scanned with a microdensitometer having an aperture of 4871 m in diameter. The results are shown in Table 1-4.

Table 1 Compound T311 S■ was added, heated to 70°C, stirred, and 300 cc of an aqueous solution in which 33 g of silver nitrate was dissolved and 320 cc of an aqueous solution in which 25 g of potassium bromide were dissolved were simultaneously added over 30 minutes. 800 cc of an aqueous solution in which 100 g of potassium bromide was dissolved and 8 of an aqueous solution in which 75 g of potassium bromide was dissolved.
By simultaneously adding 60 cc for 60 minutes, silver iodobromide emulsion 1 containing silver iodide ff114 mol% 1.03 μm
1 was adjusted.

Compound (2) Compound (3) As is clear from Table 1-4, the samples containing the silver halide grains of the present invention had significantly improved desilvering properties even in bleach-fixing treatment, and also showed improvements in sensitivity and graininess. Good results were also obtained.

Example-2 Take 300 g of emulsion e, add 850 cc of distilled water and 30 cc of 10% potassium bromide, and prepare the following compound! l! 71(2)2rN
Emulsions 12 to 14 were prepared in the same manner as emulsion 11, except that the ratio of potassium bromide was changed as shown in Table 2-1.

Next, emulsion 1 of the fifth layer of sample 101 prepared in Example 17
Sample 2 was obtained by replacing emulsions 11 to 14 shown in Table 2-1.
01-204 were created. Samples 201 to 204 were compared in the same manner as in Example 1 in terms of desilvering properties, sensitivity, and graininess. The results are shown in Table 2-2.

In Table 2-2, the light-sensitive materials containing the silver halide grains of the present invention have good desilvering properties, sensitivity, and
It can be seen that the graininess is excellent.

Example 3 Samples 102, 104, and 105 prepared in Example 1 were subjected to a running treatment with a bleach-fix solution to which a bleach accelerator was added. The treatment solution was the same as in Example 1, but the bleach accelerator shown in Table 3-2 was added to the bleach-fix solution, and the treatment was carried out according to the method shown in Table 3-1.

The amount of residual silver in the maximum density area and the unexposed area after bleach-fixing was measured in the same manner as in Example 1, and the bleaching performance and fixing performance were compared.

The smaller the amount of residual silver in the highest density area and the unexposed area, the better the bleaching and fixing properties, respectively. The results are shown in Table 3-2.

Table 3-1 Processing method Step Processing time Processing temperature Replenishment Q 't Sink amount Color development 2 minutes 30 seconds 40℃ 45mj!
51 Bleach fixing 2 minutes OO seconds 40℃ 5Q
mj! 5j! Water washing (1, 1 20 seconds water washing +21 20 seconds constant 20 seconds drying 50 seconds Replenishment amount is 35ml width, safe drying at 35℃ 21 Countercurrent piping system from (2) to (1).

35°C 30m1 35°C 20m1 65°C Per 1m length In Table 3-2, the photosensitive material containing the silver halide grains of the present invention can improve bleaching without deteriorating fixing even in bleach-fixing processing. Ta.

Example-4 The sample prepared in Example 1 was treated in the same manner as in Example 1 at night using the treatment method shown below, and the remaining 2DI in the highest concentration area was
The desilvering properties were compared. The results are shown in Table 4-2.

Table 4-1 Processing method Step Processing time Processing temperature Replenishment rJ't tank volume M color development 3 minutes 15 seconds 38℃ 45me
IO! 1 Bleach 2 minutes 00 seconds 38
℃ 20mj! 41 bleach fixing 1/3
5 seconds 38°C 39m4 3f water washing (2) 1 minute 00 seconds 35°C Stability 40 seconds 38°C Drying 1 minute 15 seconds 55°C The replenishment amount is per 1 m length of 35 mm Next, the composition of the treatment solution is shown.

Qmf 0ml (Color developer) Same as Example 1 (Bleach solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium chloride Ammonium bromide Ammonium nitrate Add aqueous ammonia (27%) if (Bleach-fix solution) Common to mother liquor and replenisher Ethylenediaminetetraacetic acid ferric ammonium dihydrate Ethylenediaminetetraacetic acid disodium salt Sodium sulfite unit (g> 120.0 10.0 100.0 10.0 150.0ta7! 1 .0 1 6.3 Unit <g) 50.0 5.0 12.0 Ammonium thiosulfate aqueous solution Add aqueous ammonia (27%) to H (washing water) Same as Example) (Stable solution) Same table as Example 1 4-2 240.0 tal1 6.0 m1 1.01 7.2 Even when the desilvering process is a bleach-bleach-fix treatment, the sample containing the silver halide grains of the present invention has excellent desilvering properties.

(Effects of the Invention) By carrying out the present invention, highly iodinated silver halide color photographic light-sensitive materials for high sensitivity and high image quality can be rapidly bleach-fixed without deteriorating fixing. Ta.

Claims (2)

[Claims] (1) In a method in which a silver halide color photographic light-sensitive material is processed with a bleach-fix solution after color development processing, at least one emulsion layer of the silver halide color photographic light-sensitive material is made of chemically sensitized silver halide grains. In the silver halide grains, silver iodobromide or silver iodochlorobromide containing 30 to 45 mol% of silver iodide exists with a clear phase structure, and the silver halide grains have a clear phase structure. 1. A method for processing a silver halide color photographic light-sensitive material, wherein the outermost layer is made of silver halide containing 8 mol % or less of silver iodide. (2) The bleach-fix solution or its prebath has the following general formula (
Claim No. (1) characterized in that it contains at least one compound represented by I) or a salt thereof.
A method for processing a silver halide color photographic light-sensitive material as described in . General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 and R^2 represent a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group, a sulfo group, or an alkyl group, and R
^3 and R^4 represent a hydrogen atom, an alkyl group, or an acyl group, and R^3 and R^4 may be connected to form a ring. M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n represents an integer from 2 to 5.