JPH02190855A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To form color photographic images having good image quality with rapid bleaching and fixing processing by specifying the average silver iodide content of the silver halide in all the emulsion layers of the photosensitive material in the case of processing the photosensitive material with a bleaching agent contg. the ferric complex salt of 1, 3-diaminopropanetetraacetic acid. CONSTITUTION:The average silver iodide content of the silver halide in all the emulsion layers of the photosensitive material is specified to >=10mol% in the method for processing the photosensitive material with the bleaching agent contg. the ferric complex salt of 1, 3-diaminopropanetetraacetic acid, then processing the material with the processing liquid having fixability. At least one emulsion layer has preferably >=12mol%, further preferably >=14mol% average silver iodide content. The photosensitive material preferably contains the emulsion particles in which the silver iodobromide contg. 15 to 45mol% silver iodide exists by having the distinct phase structure and in which the silver iodide content over the entire particle exceeds 10mol% in at least >=2 layers. The color photographic images having the good image quality are formed with the rapid bleaching and fixing processing in this way.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for rapid desilvering of silver halide color photographic materials (hereinafter referred to as color photographic materials), and in particular, to a rapid bleaching and desilvering method. The present invention relates to an improved development processing method capable of forming color photographic images of good image quality through fixing processing.

(Prior Art) Generally, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. That is, the exposed silver halide color photographic material is subjected to a color development process. Here, silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former to provide a dye image. Afterwards, the color photographic material is subjected to a desilvering process. Here, the silver produced in the previous step is oxidized by the action of an oxidizing agent (commonly called a bleaching agent), and then dissolved and removed by a silver ion complexing agent, commonly called a fixing agent. Therefore, only dye images are produced in photographic materials that have undergone these steps. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary steps to maintain the photographic and physical quality of the image, or to improve the storage stability of the image. Contains. For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing, a stopping bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a stripping bath to remove the backing layer of the support. Examples include membrane baths.

In addition, the desilvering process mentioned above is carried out in two steps, with the bleaching bath and fixing bath being separate baths, and in other cases, the processing process is simplified for the purpose of speeding up processing and labor saving, and bleaching agent and fixing agent are used together. Sometimes it is carried out in one step using a bleach-fixing bath.

In recent years, in color photographic materials, from the viewpoint of quick and simple processing and prevention of environmental pollution, ferric ion complex salts (e.g., ferric aminopolycarboxylic acid ion complex salts, etc.), especially iron ethylenediaminetetraacetate ( [[I)
Bleaching treatment methods based on complex salts are mainly used.

However, ferric ion complex salts have a relatively small oxidizing power and do not have an adequate bleaching edge, so products using this as a bleaching agent are, for example, low-sensitivity silver halide color photographs based on silver chlorobromide emulsions. If the material is bleached or bleach-fixed, it is possible to achieve the desired purpose, but if the material is bleached or bleach-fixed, it is possible to achieve the desired purpose. When processing silver color photographic materials, especially color reversal photographic materials and color negative photographic materials that use high silver emulsions,
The disadvantages are that the bleaching effect is insufficient, resulting in poor desilvering, and that bleaching takes a long time. On the other hand, with the aim of achieving even higher sensitivity and higher image quality in color photosensitive materials for photography, the use of silver halide emulsions with higher iodine content is progressing, and there is an even stronger need for technology to improve the above-mentioned problems. was.

Persulfates are known as bleaching agents other than ferric ion complex salts, and persulfates are usually mixed with chloride to act as a bleaching solution. However, a disadvantage of bleaching solutions using persulfates is that they have a weaker bleaching edge than ferric ion complexes and take a significantly longer time to bleach.

In general, bleaching agents that are not polluting or corrosive to equipment are associated with weak bleaching blades, and therefore bleaching agents with weak bleaching blades, especially bleach solutions or bleach-fix solutions using ferric ion complexes or persulfates. It was desired to increase the bleaching capacity of.

Under these circumstances, a bleaching solution containing a ferric complex salt of 1,3-diaminopropanetetraacetic acid (hereinafter abbreviated as !, 3-DPTA・Fe) as described in JP-A No. 62-222252 has been developed. Because of its high oxidizing power, rapid bleaching is possible, and it is particularly effective in processing color negative films and color reversal films that contain silver iodide and have a high silver content.

(Problems to be Solved by the Invention) However, if fixing treatment is performed immediately after treatment with the bleaching solution containing 1,3-DPTA/Fe, the conventional ferric complex salt of ethylenediaminetetraacetic acid (hereinafter referred to as EDTA-
It was found that the fixing speed was significantly lower than that when treated with Fe (abbreviated as Fe) or the like.

Therefore, a first object of the present invention is to provide a processing method for rapidly desilvering color light-sensitive materials.

A second object of the present invention is to provide a processing method that allows rapid bleaching with a bleaching solution containing 1,3-DPTA-Fe and then rapid fixing.

A third object of the present invention is to provide a processing method that allows quick bleaching with a bleaching solution containing 1,3-DPTA and Fe, and then quick fixing, and that has improved photographic properties. There is a particular thing.

(Means for Solving the Problems) The above aspects of the present invention provide one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support. A method of processing a color light-sensitive material with a bleaching solution containing a ferric complex salt of 1,3-diaminopropanetetraacetic acid, and then processing it with a processing solution having a fixing ability, wherein all emulsion layers in the light-sensitive material are halogenated. This was achieved by a method for processing color light-sensitive materials characterized in that the average silver iodide content of silver is 10 mol % or more.

In the present invention, the average silver iodide content of silver halides in all emulsion layers is 1! of all silver halides (not including metallic silver) present in a light-sensitive material. fi (AgX) and total iodine f (
1) and multiplied by 100. In the present invention, it is necessary that the average silver iodide content is 10 mol% or more, preferably 10.5 to 20.0 mol%, more preferably 11.0 to 15.0 mol%. be.

In the present invention, it is necessary that the red, green, and blue-sensitive silver halide emulsion layers each have an IN or more, but it is preferable that they have different sensitivities of 21 or more. More preferably, it consists of three layers with different sensitivities.

In the present invention, it is preferable that at least one emulsion layer has an average silver iodide content of 12 mol% or more, and 14
More preferably, it is mol% or more.

In the present invention, emulsion grains in which silver iodobromide containing 15 to 45 mol% of silver iodide exist with a clear silk-like structure and the silver iodide content in the entire grain exceeds 10 mol% are used. It is preferable to include at least two layers.

The clear silk-like structure mentioned here can be determined by the method of X-ray diffraction. An example of applying the X-ray diffraction method to silver halide grains can be found in H. Hirsch, Journal of Photographic Science, No. 1 os (1962), 129.
It is stated on the following pages. When the lattice constant is determined by the halogen composition, the blank condition (2dsinθ=nλ
) The diffraction peak resides at the diffraction angle that satisfies the following.

Regarding the measurement method of X-ray diffraction, please refer to Basic Analytical Chemistry Course 24rX
! Analysis'' (Kyoritsu Shuppan) and ``X-ray Diffraction Guide'' (Rigaku Denki Co., Ltd.), etc., describe this in detail. 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 5 QmA).

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 distinct silk-like structure is defined by the diffraction intensity versus diffraction angle of the (220) plane of silver halide using β rays for Cu with a diffraction angle (2θ) in the range of 38° to 42″. When a curve is obtained, at least two diffraction peaks are found, one corresponding to a high iodine layer containing 15 to 45 mol% silver iodide, and the other diffraction peak corresponding to a low iodine layer containing 8 mol% or less silver iodide. When there is a diffraction maximum and one minimum between them, and the diffraction intensity corresponding to the high iodine layer is 1/10 to 3/1 of the diffraction intensity of the peak corresponding to the low iodine layer. More preferably, the diffraction intensity ratio is 115 to 3/1,
This is especially the case when the ratio is 1/3 to 3/1.

In the present invention, the emulsion consisting of silver halide grains having a distinct silk-like structure preferably has a diffraction maximum (peak) in which the minimum value of diffraction intensity between two peaks is at least two peaks.
Of these, it is preferable that the strength is 90% or less of the weaker one.

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 (Kyoritsu 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 Pant.

Even in the case of an emulsion in which two types of silver halide grains with different halogen compositions coexist, which do not have a distinct silk-like structure, two peaks appear in the X-ray diffraction. Although such emulsion grains may be used, emulsion grains having a distinct silk-like structure as described above are preferred. Whether the silver halide emulsion is an emulsion consisting of silver halide grains having a distinct silk-like structure or as described above.
In addition to the XwA diffraction method, EPMA method (Elec.
Tron-Probe Micro Analyzer
This is possible by using the following 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 particle beam excitation.

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

By confirming the halogen composition of at least 50 grains by the EPM A method, it can be determined whether the emulsion is composed of silver halide grains having a clear phase structure.

In the emulsion of the present invention, it is preferable that the iodine content among 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, the iodine content of large size particles is high and the iodine content of 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 15 to 45 mol%, preferably 25 to 45 mol%, more preferably 3
It is 0 to 45 mol%. The most preferred silver halide for the core portion is silver iodobromide containing 30 to 45% silver iodide.

The composition of the outermost layer is preferably a silver halide containing 8 mol% or less of silver iodide, more preferably a silver halide containing 6 mol% or less of silver iodide.

The silver halide other than silver iodide in the outermost layer may be silver chloride, silver chlorobromide or silver bromide, but it is preferable that the proportion of silver bromide is high. Particularly preferred for the outermost layer is silver iodobromide or silver bromide containing 0.1 to 6 mol % of silver iodide.

The average halogen composition of the entire grain preferably has a silver iodide content of more than 10 mol%, more preferably 11 to 2
It is 0 mol%, more preferably 14 to 17 mol%.

The size of the silver halide grains of the present invention is 0.10 to 3.0
μm, preferably 0.20 to 2.00 μm, more preferably 0.30 to 1.1 pm.

More preferably, it is 0.40 to 1.4 μm.

The average grain size of silver halide grains in the present invention is
T.H. James (T, II, Ja
``The Theory of the Photographic Ink Process J'' by Mes et al.
the PhctographProcess)
The particle size geometric mean value is well known in the art as described in 3rd Edition, p. 39, published by Macmillan (1966). In addition, the average size is determined from "Introduction to Particle Size Measurement," Washing Text (Journal of Powder Engineering Society, pp. 171299-313 (19
80), and can be measured by methods such as the Coulter counter method, single particle light scattering method, and laser light scattering method.

The silver halide grains of the present invention may have regular crystal shapes (normal crystal grains) such as hexahedron, octahedron, dodecahedron, or dodecahedron, or may have a spherical, potato-like, or tabular shape. It may also have an irregular crystal shape such as a shape. In particular, twin grains with an aspect ratio of 1.0 to 10, especially 1.5 to 8, 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 circularity rate of the surface can be determined by the Kubelka-Munk dye adsorption method. This is because the dye preferentially adsorbs to either the (111) plane or the (100) plane, and the association state of the dye on the (11L) plane and the association state of the dye on the (100) plane differ spectrally. select. By adding such a dye to an emulsion and examining the spectra in detail with respect to the amount of dye added, the circularity rate of the (111) plane can be determined.

The emulsions preferred for use in the present invention can have a broad grain size distribution, but emulsions with a narrow grain size distribution are preferred. In particular, in the case of normal crystal grains, 90% of the total weight or number of silver halide grains in each emulsion
The particle size that accounts for % is ±4096 of the average particle size.
A monodispersed emulsion within ±30% can also be used.

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 consisting of silver halide grains having a distinct silk-like structure and preferably used in the present invention can be prepared by selecting and combining various methods known in the field of silver halide photographic materials. can.

First, to prepare the core particles, methods such as the acidic method, neutral method, and ammonia method can be selected, and methods for reacting soluble silver salt and soluble halogen salt can be selected from 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 type of simultaneous mixing method, a triple jet method in which soluble halogen salts of different compositions are added independently (for example, a soluble root salt, a soluble bromine salt, and a soluble iodide salt) can also be used.

During core preparation, halogenated solvents such as ammonia, rhodan salts, thioureas, thioethers, and amines may be selected and used. 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,
A method of accelerating the addition rate over time as disclosed in Japanese Patent Publication No. 4B-36890 by Irie and lead powder, or a method of increasing the addition concentration over time as disclosed by Tifuji 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. , at a constant temperature acceleration or higher and at an addition rate Q that is lower than the addition rate proportional to the total surface area of the growing poorly soluble inorganic salt crystal, that is, at Q-1 or higher and at Q=α(!+βt+y or lower). It is added.

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. This is to increase the amount to such an extent that it does not occur. In preparing the preferred silver halide grains of the present invention having a distinct silk-like structure, shelling may be carried out directly after core grain formation, but it is preferable to carry out shelling after washing the core emulsion with water for desalting. .

Shelling can also be prepared by various methods known in the field of silver halide photographic materials, but a simultaneous mixing method is preferred. The aforementioned methods of Irie et al. and Saito's method are preferred as methods for producing emulsions having a distinct silk-like structure.

In the case of fine-grain emulsions, conventional tools are useful for preparing grains with a well-defined phase-shifting structure, but they alone are not sufficient to improve the degree of perfection of the silk-like 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%.

When growing a low iodine layer outside the high iodine layer, the temperature
Of course, it is important to select pI, pAg, stirring conditions, etc., but it is also important to select the amount of protective colloid when growing a low iodine layer, and to select the amount of 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 that adsorbs on the surface of silver oxide, and instead of adding water-soluble root salts and water-soluble alkali metal halides when growing the low-iodine layer. A method of adding fine grain silver halide is also effective.

As mentioned above, in the present invention, the term "silver halide grains having a clear phase structure" means that there are two different halogen compositions in 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 .

That is, there is a core region with high iodine content, a middle region, and a shell region with low iodine content, and the X-ray diffraction pattern has two peaks and two peaks.
There is one minimum part between the two peaks, and the diffraction intensity corresponding to the high iodine part is 1/10 to 1/10 of that of the low iodine part.
3/1, preferably 115 to 3/1, especially 1/3 to 3/1
1, and the minimum portion is less than 90%, preferably less than 80%, especially less than 70% of the smaller of the two peaks, then such silver halide grains have substantially two distinct layered structures. They are particles with a structure.

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

The color light-sensitive material of the present invention preferably has at least two emulsion layers containing the silver halide grains of the present invention, and in the emulsion layer, the grains of the present invention are present in the core layer. 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.

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, pyridine nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei; i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxane nucleus, etc. Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on the phosphorus atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heteroartic ring nucleus such as a 4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, a diobarbituric acid nucleus, etc. can be applied.

For example, Re5earch Disclosure, I
tem 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.

The emulsion of the present invention may be further bonded with silver halide having a different composition by epitaxial bonding, or may be bonded with a compound other than silver halide, such as rotane silver or lead oxide.

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 ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Note 17.
643 and the same number 18716, and the corresponding part is 1! are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the two Research Disclosures mentioned above, and the relevant notes are shown in the table below.

Additive type RD17643 17018716
1 Chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity increasing agent
Same as above 4 Brightener Page 24 The total amount of coated silver (including metallic silver) in the photosensitive material of the present invention is 3.0 to 8.
．． 0 g/rtr is preferable, 4.0 to 7.5 g/n (more preferable, and 4.5 to 7.0 g/rtr is even more preferable. If the amount of silver is larger than this, there will be problems in desilvering property and radiation resistance. Yes, if there is less, graininess will worsen.

The film thickness of the photosensitive material of the present invention is preferably 13 to 25 μm, more preferably 15 to 23 μm, and 17 to 22 μm.
is even more preferable. The desilvering property of thicker layers is not bad, but if the layer is thinner, there will be problems such as insufficient color density and weak film strength.

Dye image stabilizer Hardener Binder Plasticizer, lubricant Page 25, page 26, page 26, page 27, page 651, left column Same as above, page 650, right column In the present invention, the photosensitive material to be processed is expressed by the following formula (1
It is preferable to contain a mercapto compound represented by ). By containing this compound, the effect of the present invention becomes more pronounced and fixing can be further accelerated.

Next, the compound of general formula (1) will be explained.

-Formula CI) Q-SM' where Q represents a heterocyclic residue directly or indirectly bonded to at least one member selected from the group consisting of -COOM'-OH and -NR'R'; M
1 and Mt independently represent a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium, and R' and R'' represent a hydrogen atom or a substituted or unsubstituted alkyl group.

- It is thought that the compound of formula (1) is imparted with water solubility or has improved water solubility in the pH atmosphere of the developing solution, and flows out from the photosensitive material into the developing solution. In other words, if the compound of general formula (1) is contained in a photosensitive material, it will dissolve in the developer and contaminate the developer.

Despite this, it is truly surprising that the change in development finish characteristics is small and the fog is low. This unexpected effect is thought to be due to the fact that the effect of the compound represented by formula (1) is significantly different when it is contained in a photosensitive material and when it flows out into a developer. , its details are unknown, and the current research will clarify its behavior.

As a photosensitive material containing the compound of general formula (1) used in the present invention, Japanese Patent Publication No. 58-9939 describes -
A silver halide color photosensitive material containing a heterocyclic mercapto compound having at least one group selected from 3O3H5-COOHl-○H1NH There is no mention of whether or not the above-mentioned problems can be solved when the above-mentioned development process is carried out.

Specific examples of the heterocyclic residue represented by Q in General 2CU) include oxazole ring, thiazole ring, imidazole ring, selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, bentazole ring, and pyrimidine ring. , thiasia ring, triazine ring,
a thiadiazine ring, or a ring fused with another carbocycle or heterocycle, such as a benzothiazole ring, benzotriazole ring, benzimidazole ring, benzoxazole ring,
Examples include a benzoselenazole ring, a naphthoxazole ring, a triazaindolizine ring, a diazaindolizine ring, and a tetraazaindolizine ring.

Among the mercapto heterocyclic compounds represented by the general formula C11), those represented by the formulas ([ff) and (rV) are particularly preferred.

General formula (III) (L'), -R' General formula (rV) In general formula (III), Y and Z are independently a nitrogen atom or CR'(R' is a hydrogen atom, W-substituted or unsubstituted represents an alkyl group, or a substituted or unsubstituted aryl group), and R3 is SO3M" -COO
An organic residue substituted with at least one selected from the group consisting of group, hexyl group, dodecyl group, octadecyl group, etc.), an aryl group having 6 to 20 carbon atoms (e.g. phenyl group, naphthyl group, etc.), and Ll is -
It represents a linking group selected from the group consisting of 3--0--N--CO-8O- and -3O□-, where n is 0 or 1.

In addition to these alkyl groups and aryl groups, halogen atoms (F, C1, Br, etc.), alkoxy groups (methoxy group, methoxyethoxy group, etc.), aryloxy groups (phenoxy group, etc.), alkyl M (R” is aryl), group), an aryl group (when R2 is an alkyl group),
Amide group (acetamido group, benzoylamino group, etc.)
, carbamoyl group (unsubstituted carbamoyl group, phenylcarbamoyl group, methylcarbamoyl group, etc.), sulfonamide group (methanesulfonamide group, phenylsulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group, phenyl sulfamoyl group, etc.), sulfonyl group (methylsulfonyl group, phenylsulfonyl group, etc.), sulfinyl group (methylsulfinyl group, phenylsulfinyl group, etc.), cyano group, alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (such as a phenoxycarbonyl group), and other substituents such as a nitro group.

Here, the substituent of R3 is -3O3M, COOM"O
When there are two or more H and -NR'R'', they may be the same or different.

M2 means the same as that represented by general formula (n).

Next, in formula (IV), X represents a sulfur atom, an oxygen atom or -N-, and R5 represents a hydrogen atom, an S substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

R2 is 100NR'-NR'CO 3Ot N R6-NR' S O□--〇C〇-C
OO--3--NR'--C0 -3O--0COO--NR"C0NR'--NR'C
OO--〇C0NR'- or N RhS Oz N
Represents R'-, R6, R? each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

R3, M! means the same as those represented by general formulas (II) and (III), and n represents 0 or 1.

Furthermore, Ra, Rs, R6 and R? The substituents for the alkyl group and aryl group represented by are the same as those listed as the substituent for R3.

In the general formula, R3 is -OxM2 and -COOM
” is particularly preferred.

Specific examples of preferred compounds represented by general formula (n) used in the present invention are shown below.

fi+ COOII CHzC[ItCllzSOJa Q(11 CfhCHzOH COOI+ SO,Na 0OH Ct+iCIlzSOJa CH2CH2C00I+ coon CH2COOI+ The compound represented by the general formula (II) is known, and It can be synthesized by the method described in the following literature.

U.S. Patent No. 2,585,388, U.S. Patent No. 2,541.92
No. 4, Special Publication No. 42-21,842, Japanese Patent Publication No. 53-50
, No. 169, British Patent No. 1,275.701, D. A. Virginis et al., ``Journal of Heterocyclic Chemistry'' (D. A. Be
rgeset,al,,”Journal of He
Terocyclic Chemistry') No. 15
Volume 981 (1978), 'The Chemistry Op.
Heterocyclic Chemistry” Imidazole and Derivatives, Part! (The Chemi
try of 1terocyclic Che
mistryImidazole and Deriv
atives part I), pp. 336-9, Chemical Abs.
tract), ■, No. 7921 (1963), p. 394, E.

Hogarth, 'Journal of the Chemical Society
Chemical 5ociety”) 1160~7
(1949), and S. R. Saladra, W. Kawa,
'Organic Functional Group Prevaluation', Academic Press (S, R, 5a
udler, W. aro%'OrganicFan
ctional Group Preparation
'Academic Press) pages 312-5,
(1968) M, ChaIIldon+eL, a
l, +)
de France (Bulletin de Ia 5oc)
France)
, 723 (1954), Shirley, D.W., Alley, Journal of the American Chemical Society (D.A.
5hirley+ D, W, AIIey, J, Ame
r,Chem,Soc,), 79.4922 (195
4) A, Paul, W, Marchwald, Belisochite (^, Wo
hl+j1. Marchwald+Ber, ) (Journal of the German Chemical Society), Journal of the American Chemical Society (J, A+mer, Chem, Soc,
), ■Sat, pp. 1502-10, U.S. Patent No. 3,017,270, British Patent No. 940.
No. 169, Japanese Patent Publication No. 8,334, 1983, Japanese Patent Publication No. 55-5
No. 9.463, Advanced in Heterocyclic Chemistry
c Chemistry), 9.165-209
(1968) West German Patent No. 2,716,707, The Chemistry of Heterocyclic Compounds Imidazole and Derivatives (The
Chemistry of 1reterocycle
ic Compoundsliidazole and
Derivatives), Vol, 384 pages, Organic Synthesis (Org, 5ynth,) I
V.

Berichte (Ber,), 9.465 (1976
), Journal of the American Chemical Society (J, Amer, Chem, Soc, ), 45
-12390 Japanese Patent Publication No. 50-89.034, 53-2
No. 8゜426, No. 55-21,007, Special Publication No. 402
No. 8.496.

The compound represented by the general formula (1) is contained in the silver halide emulsion layer and the hydrophilic colloid layer (intermediate layer, surface protection layer, yellow filter layer, undishalation layer, etc.).

It is preferable to contain it in a silver halide emulsion layer or a layer adjacent thereto.

Also, the amount added is IXIO-? 〜1×10 mol/rrr, preferably 5×10−′〜LX
10-'mol/rd, more preferably I X 1
0-6~3X IO-'mol/rd.

In addition, the following compounds can be contained in the photosensitive material used in the present invention.

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

Various color couplers can be used in the present invention, and specific examples thereof include the aforementioned RDTh17643, ■-C to G
It is described in the patent described in .

Yellow couplers include, for example, U.S. Patent Section 3.93.
3.501, 4,022,620, 4,326
, No. 024, No. 4,401,752, No. 4,248.
No. 961, Special Publication No. 5B-10739, British Patent No. 1,
No. 425.020, US Pat. No. 1.476.760, US Pat. No. 3,973.968, US Pat. Preferably.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent Section 4,31
No. 0,619, No. 4,351,897, European Patent No. 7
No. 3,636, U.S. Pat.
, No. 725,064, RD Seki 24220 (June 1984), JP-A-60-33552, RD Magneto 24230
(June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 55-
118034, 60-185951, U.S. Patent Sections 4,500,630, 4,540.654, 4
, No. 556,630, WO (PCT) 8 B10479
Particularly preferred are those described in No. 5 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent Section 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. No. 826, No. 3,772,002,
No. 3,758゜308, No. 4,334,011, No. 4,327.173, West German Patent Publication No. 3,329.7
No. 29, European Patent No. 121,365A, 249°4
No. 53A, U.S. Patent Section 3,446,622, 4,3
No. 33,999, No. 4,753,871, No. 4,45
No. 1,559, No. 4,427.767, No. 4,690
, No. 889, No. 4.254212, No. 4,296,1
99, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unwanted absorption of chromogenic dyes are described in Section 1-G of RD No. 17643, U.S. Patent Section 4. ．．
No. 163.670, Japanese Patent Publication No. 57-39413, U.S. Pat.
British patent cylinder 1. Preferably, those described in U.S. Pat. .77
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. 7120.

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. DIR couplers releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
No. 57-154234, No. 60-184248, No. 63-37346, U.S. Patent No. 4,248,962
No. 4°782.012 is 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 the competitive couplers described in U.S. Patent 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
Dnu11449, D24241, 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-water 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 disclosed in U.S. Pat.
41,230, etc.

Additionally, these couplers can be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble, organic solvent-soluble polymer.

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, U.S. Patent 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. W08810 O723 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, 1k17643, page 28, and the same page 18716, page 647 right column to page 648 left column.

Next, the processing used in the present invention will be described.

In the present invention, as a desilvering step, after bleaching with a bleaching solution containing 1,3-DPTA-Fe, processing is performed with a processing solution having fixing ability.

], a bleaching solution containing 3-DPTA-Fe is described, for example, in JP-A-62-222252;
It is known to have high oxidizing power and high bleaching speed.

However, if a conventional photosensitive material is processed with a bleaching solution containing 1.3-DPTA-Fe and then treated with a processing solution that has fixing ability, the bleaching that does not contain 1.3-DPTA-Fe will result. When treated with a liquid (e.g. ED as a bleaching agent)
However, when processing a light-sensitive material containing an emulsion with a high silver iodide ratio, such as in the present invention, there is almost no decrease in the fixing speed. Or rather, they discovered that it could be made faster.

Decrease in fixing speed due to 1.3-DPTA-Fe occurs markedly in photosensitive materials containing iodine-containing emulsions (for example, silver iodobromide emulsions with a low silver iodide ratio). , 3-DPTA-Fe coexist, some kind of fixation inhibition state occurs, and this fixation inhibition state occurs significantly only in a certain range of iodine concentration on the emulsion surface. In light-sensitive materials, as fixing progresses, the iodide ion concentration on the emulsion surface becomes extremely high and deviates from this range, so it is presumed that the fixing inhibiting state is reduced.

Furthermore, the mercapto compound of general formula (T) is considered to have the effect of promoting the reduction of this fixation inhibiting state.

The bleaching agent contained in the bleaching solution is 1,3DPTA.
-Fe, EDTA -Fe, diethylenetriaminetetraacetic acid ferric complex salt (1) PPA-Fe) or 1
．． 2-Cyclohexanediaminetetraacetic acid ferric complex salt (Cy
DPTA-Fs) etc. may be used in combination, among others,
Most preferably, it is used in combination with EDTA/Fe. When used together,
The ratio of 1.3-DPTA.Fe to the total bleaching agent is preferably 10 to 80%, particularly preferably 20 to 50%.

The above aminopolycarboxylic acid ferric complex salt (1゜3-DP
TA-Fe, EDTA-Fe, etc.) are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred since they have excellent solubility and bleaching properties.

1.3-DPTA-Fe and the combined aminopolycarboxylic acid ferric complex salt are preferably added in a total amount of 0.01 mol to
1.0 mol/1, more preferably 0.1 to 0.7 mol/1
! It is.

Further, the bleach solution or bleach-fix solution containing the above-mentioned ferric ion complex salt may contain a metal ion complex salt other than iron, such as cobalt or copper.

Further, in addition to the above-mentioned ferric aminopolycarboxylic acid complex salt, it is preferable to add an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, or an alkali metal salt or ammonium salt thereof to the bleaching solution of the present invention. In particular, it is preferable to add the same type of aminopolycarboxylic acid as the compound used as the bleaching agent. The preferable addition amount of these aminopolycarboxylic acids is 0.0001 mol to 0.1 mol/
l, more preferably 0.003 to 0.05 mol/l.

Various bleaching accelerators can be added to the bleaching solution of the present invention.

Such bleach accelerators are described, for example, in U.S. Pat. No. 3,893,858 and German Patent No. 1,290.
, 812, British Patent No. 1 138.842, JP-A-53-95630, and Research Disclosure No. 17129 (July 1978 issue). Compounds, thiazolidine derivatives described in JP-A No. 50-140129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German patents Polyethylene oxides described in specification No. 2,748.430, Japanese Patent Publication No. 1974-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferred is British Patent No. 1.138.
Mercapto compounds such as those described in '842 are preferred.

The bleaching solution of the present invention preferably contains bromide ions as a rehalogenating agent. The preferred amount of bromide ions added is 1.2 mol/1 or more, particularly 1.5 to 2.0 mol/1.
l is preferred.

Furthermore, the bleaching solution may contain chloride ions and iodide ions in addition to the above-mentioned bromine ions.These halogen ions can be added as alkali metal salts or ammonium salts, but it is particularly preferable to add them as ammonium salts. .

In addition, the pH buffering capacity of nitrates such as ammonium nitrate, sodium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and tartaric acid. Known additives commonly used in bleaching solutions can be added, such as one or more existing inorganic acids, organic acids and salts thereof, metal corrosion inhibitors such as ammonium sulfate, and the like.

The pH of the bleaching solution of the present invention is generally 6 to 3, preferably 5.8 to 3.5, most preferably 5.3 to 4,
It is 0. In the preferred pH range of 5ff, there is little bleaching blade blemish and the desilvering performance is also excellent.

The bleaching solution is preferably aerated in order to oxidize the ferrous complex produced by the bleaching process or reaction with the color developing solution brought in by the photosensitive material. Aeration may be performed only during processing, only during temperature adjustment of the automatic processor, or throughout the day, but it is preferable to perform it as thoroughly as possible.

In the present invention, after processing with a bleaching solution, processing is performed with a processing bath having fixing ability. Immediately after treatment with a bleaching solution, treatment with a treatment bath having a fixing ability is preferred because the effects of the present invention can be brought out significantly. After processing with a bleaching solution, washing with water, etc., and then processing with a processing bath that has fixing ability increases the number of steps by one, and it is not preferable from the viewpoint of processing speed and compactness of the processing machine. However, this may be done in order to assist the effects of the present invention.

The processing bath having fixing ability according to the present invention refers to a bleach-fixing bath and a fixing bath.

As fixing agents for processing solutions used in processing baths having these fixing abilities, thiosulfates (e.g., sodium thiosulfate, ammonium ammonium thiosulfate, potassium thiosulfate), thiocyanates (e.g., sodium thionanate, thiocyanate) are used as fixing agents. ammonium, potassium thiocyanate)
, thioether compounds, thioureas, large amounts of iodide salts, etc., but it is preferable to use thiosulfate because it provides a high fixing speed and exhibits the effects of the present invention most markedly. In particular, ammonium thiosulfate is preferred from the viewpoint of solubility and fixing speed. It may also be used in combination with other fixing agents.

The amount of these fixing agents is preferably 1.1 mol/E or more, particularly preferably 1.3 to 1.7 mol/E. Within the preferred range, the effects of the present invention are significant.

When the bath having fixing ability of the present invention is a bleach-fixing bath, it may contain a known bleaching agent in addition to the above-mentioned bleaching agent.

The fixing bath 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.). ), carbonyl bisulfite adducts, sulfinic acid compounds, etc.). Furthermore, organic solvents such as various fluorescent brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, and methanol can be used. In particular, as a preservative, a sulfinic acid compound described in Japanese Patent Application No. 60-283831 can be used.

The bath having fixing ability of the present invention contains 1,3-DPTAFe by bringing in the bleaching solution of the pre-bath with the photosensitive material, but in this case, the stability of the processing solution having fixing ability tends to decrease slightly. There is. In order to improve the stability of a processing liquid having fixing ability, it is preferable to add an aminopolycarboxylic acid-based chelating agent or an organic phosphonic acid-based chelating agent. As the organic phosphonic acid chelating agent, the following general formula fl), (2)
Or a compound represented by (3) can be mentioned.

General formula (1) General formula (2) General formula (3) In the formula, M represents a hydrogen atom, lithium, sodium, potassium, or ammonium, and is preferably a hydrogen atom. Further, R1 represents an alkyl group or alkenyl group having 1 to G carbon atoms, and R□ represents an alkylene group having 2 to 8 carbon atoms. These substituents may be linear or branched.

The preferred carbon numbers of Ro and R2 are 1-3 and 2-6, respectively. a, b,, C% d,, e%
f and g are each integers of 1 to 3, preferably 1.

As a specific example, l-hydroxyethyl'/thea-1
, 1-diphosphonic acid, 1-hydroxypropylidene-1
, 1-diphosphonic acid, N, N, N', N'-ethylenediaminetetraphosphonic acid, N, N, N''N'-propylenediaminetetraphosphonic acid, N.

N,N',N'-hexylenediaminetetraphosphonic acid, N,N,N',N'~butylenediaminetetraphosphonic acid, N,N,N-nitriatrimethylenephosphonic acid and N,N,N -Nitrilotripropylenephosphonic acid or salts thereof (e.g. ammonium or sodium salts)
can be mentioned.

Addition of the chelating agent to the processing solution having fixing ability (3) is 0.
01 mol/1 or more, particularly preferably 0.02 to 1
It is preferable to include 0.1 mol/i because the stability of the processing liquid having fixing ability can be improved in terms of flight ff/J.

In particular, the effect is great when processing with a fixing solution immediately after processing with a bleaching solution containing 1.3-DPTA/Fe.

Particularly preferred chelating agents include organic phosphonic acid chelating agents. Among these, 1-hydroxyethylidene-1,1-diphosphonic acid or a salt thereof (eg, ammonium or sodium salt) is most preferred.

p)l of the processing liquid having fixing ability of the present invention is 3 to 9,
Preferably it is 5-8.

The shorter the total time of the desilvering step of the present invention, the more significant the effects of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes.

Furthermore, the treatment temperature is 25°C to 50°C, preferably 35°C to 4°C.
The temperature is 5°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after treatment is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is disclosed in JP-A-62-18346.
No. 0, 62-. 183461, a method of impinging a jet of processing liquid on the emulsion surface of a light-sensitive material, and JP-A-183461-1.
No. 183461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material without bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. and a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. Improving stirring is achieved by adding bleach into the emulsion film,
It is believed that this speeds up the supply of fixing agent and, as a result, increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The cross-over time from each processing solution to the next processing solution (the time in the air from when the photosensitive material leaves the processing solution to when it enters the next processing solution) of the present invention is preferably within 10 seconds, more preferably 5 seconds. Within

The automatic developing machine used in the present invention is disclosed in Japanese Patent Application Laid-Open No. 601912.
It is preferable to have the photosensitive material conveying means described in No. 57, No. 191258, and No. 191259. As described in JP-A No. 60-191257, such a conveying means can significantly reduce the amount of processing liquid brought into the post bath from the front bath, and is highly effective in preventing the performance price of the processing liquid from increasing. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

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 include 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 D-32-amino-5-(N-ethyl-N-laurylamino) Toluene D-44-(N-ethyl= N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-(N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N to ethyl-N −(β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N-ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl N-β-
Ethoxyethylaniline D-114-amino-3-methyl-N=ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Furthermore, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. Preferably about 0.1 g to about 20 g,
More preferred is a concentration of about 0.5g to 10g.

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.

However, in order to improve the color development properties of the color developer, it is preferable that sulfite ions are not substantially contained, and the effects of the present invention are particularly remarkable in such systems. Here, "substantially not containing" means 0.5 g/j in terms of sodium sulfite per 11 color developing solutions! , preferably 0.2 g/11, more preferably no content at all.

The preferred amount of preservative added is Color Developer II! Hit 0
．． 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. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61188741, and/or No. 61-180
It is preferable to add various sugars described in No. 616, and
In combination with the above compounds, Japanese Patent Application No. 61-147823,
Monoamines described in No. 61-166674, No. 61-165621, No. 61-16451.5, No. 61-170789, and No. 61-168159, No. 61-173595, No. 6]-164515 No. 6
Diamines described in No. 1-186560, etc., No. 61-1
65621 and polyamines described in 61-169789, polyamines described in 61-188619, nitroxy radicals described in 61-197760, alcohols described in 61-186561 and 61-197419. It is preferable to use the oximes described in Japanese Patent No. 61-198987, and the tertiary amines described in Japanese Patent 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
No. 349, the polyethyleneimines described in U.S. Patent No. 3.
The aromatic polyhydroxy compound described in No. 746,544 and the like may be contained as necessary. Particularly preferred is the addition of an aromatic polyhydroxy compound.

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,
Sodium 0-hydroxybenzoate (sodium salicylate), potassium 〇-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) Examples include potassium salicylate). 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/1~0
．． Particularly preferred is 4 mol/i.

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 aminopolycarbonic acid compounds described in Japanese Patent Publication No. 48-30496 and Japanese Patent Publication No. 44-30232, Japanese Patent Publication No. 56-97347,
Special Publication No. 66-39359 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
The phosphonocarbon fI1 described in No. 6 and the like. and other compounds described in JP-A No. 58-195845, JP-A No. 58-203440, and JP-B 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-)rimethylenephosphonic acid, ethylenediamine-N,N.

N',N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid , 1-hydroxyethylidene-11-diphosphonic acid, N,N'-bis(2
-Hydroxybenzyl)ethylenediamine-N,N'-
Diacetic acid and two or more of these chelating agents may be used in combination, if necessary.

The amount of these chelating agents added may be sufficient as long as the amount is 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, 1i1 liquid properties, and prevention of color staining.

Here, "substantially" means that the developer contains 2 or less, preferably not at all, per 11 parts of the developer.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 3B-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, U.S. Patent No. 2,482,546, 2. 596. 926 and 3,582,346, etc., Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, U.S. Patent No. 3,128,18
No. 3, Special Publication No. 41-11431, No. 42-23883
and U.S. Pat. No. 3,532,501, etc., and other 1-phenyl-3-
Pyrazolidones, imidazoles, etc. can be added as necessary.

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-benzimidazole, Typical examples include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain an optical brightener. As the optical brightener, a 4°4'-diamino-2,2°-disulfostilbene compound is preferred6.The amount added is O~5g/! Preferably 0.1g to 4g
/R.

Further, various surfactants such as alkylsulfonic acid, ary-phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid 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 3 minutes. The amount of replenishment is preferably small, but is 100 to 1500 - preferably 100 to 800 - per rrf of photosensitive material. More preferably 100-
~400d.

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 can 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 methylhentthiazole, 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.9 For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
Disinfectants and anti-fungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or L, E,
West.

Water Quality Cr1teria”, P
hot, Sci, and Eng, +Vo1.9. &6
, pages 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, Bi, metal compounds such as Affi, optical brighteners, chelating agents (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides,
Antifungal agents, hardeners, surfactants, etc. can be used. Here, formalin can also be removed from the solution. This case is preferable in terms of reducing environmental pollution (reducing pollution load) and 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 times, and 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
, Mgta degree 5q/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 may occur due to one shot of evaporation, especially when the processing amount is small or the opening area of the processing solution is large. becomes noticeable. 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 flows into a pre-bath having a fixing ability.

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

Example 1 (Preparation of emulsion) An aqueous solution of 20 g of inert gelatin, 2.4 g of potassium bromide, and 2.05 g of potassium iodide dissolved in 800 g of distilled water was stirred at 58°C, and nitric acid ff15 was added to -9. ．． Ogt
- 150 cc of the dissolved aqueous solution was added instantaneously, and then an excess of potassium bromide was added, followed by physical aging for 20 minutes. Furthermore, 0.2 mol/1.0.67 mol/1.2 mol/
1 of silver nitrate and a potassium halide aqueous solution (mixed with 58 mol% of potassium bromide and 42 mol% of potassium iodide) were each added at a flow rate of 10 cc/min to grow 42 mol% of silver iodobromide grains. I let it happen. 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 0.69 μm.

Take 200 g of Emulsion A, add 850 eC of distilled water and 39 cc of 10% potassium bromide, heat to 70°C and stir, then add 320 cc of an aqueous solution containing 300 cc of an aqueous solution of 33 g of silver nitrate and 25 g of potassium bromide. 30 at the same time
Add nitric acid i! By simultaneously adding 800 cc of an aqueous solution containing 100 g of potassium bromide and 860 ee of an aqueous solution containing 75 g of potassium bromide for 60 minutes, 1.09 μm silver iodobromide particles containing 10 mol% of silver iodide gold were obtained. . Emulsion 1 had twin crystals with an aspect ratio of 2.3, and its (111) content ratio was 85%. Emulsions A to G listed in Table 1 were prepared according to this method.

Sample 101, which is a multilayer color light-sensitive material, was prepared by coating each layer having the composition shown below in a multilayer manner on a cellulose triacetate support produced by the production method described in JP-A-62-115035.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rd units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(Sample 101) 1st layer: Antihalation layer Black coid 8!1 0.18 Gelatin 1,40 2nd layer: Intermediate layer 2.5-di-t-bank decylhydroquinone 0,18EX71
0.07EX-30,05 U-10,06 0-20,08 0-30,10 HBS-10,10 HBS-20,02 Gelatin 1.04 Third layer (first red-sensitive emulsion N) Emulsion A Silver 0.20 emulsion B
Silver 0.20 Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-2 EX-3 EX-10 EX-15 Gelatin 4th layer (second red-sensitizing emulsion) 'W) Emulsion C Sensitizing dye ■ Sensitizing Dye ■ Exacerbating dye ■ EX-2 EX-3 EX-14 EX-10 Gelatin 5th layer (third red-sensitive emulsion N) Emulsion D 6.9X10-'1.8X10-' 3, lX10-' 0.335 0 .025 0.020 Q,0L5 0,87 Silver l,00 5,lX10-'1.4X10'''2.3X10-' 0.4QQ O,025 0,030 0,015 1,30 Silver1,40 Increase Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-3 EX-4 EX-2 SB-1 B5-2 Gelatin 6th layer (intermediate layer) EX-5 B5-1 Gelatin 7th layer (first green emulsion Layer) Emulsion A Emulsion B Enhanced dye ■ Enhanced dye ■ Enhanced dye ■ EX-6 5,4X10-'1.4X10-'2.4X10-' 0.007 o, os.

O,095 0,22 0,10 1,63 0,060 0,040 0,70 Silver 0.15 S 0, l 5 3.0X10-'1.0X10-'3.8X10-' 0.260 EX -1 EX-7 EX-8 EX-15 B5-1 B5-4 Gelatin 8th layer (second green-sensitive emulsion layer) Emulsion C Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ EX-6 EX-8 EX -7 1-IBs-1 B5-4 9th layer of gelatin (3rd emulsion N) Emulsion D i , 00 2, lXl0-' ? , 0X10-'2.6X10-' 0.094 0.018 0.026 0.160 0.008 0,50 Silver 1° sensitizing dye V 3.5XIO-' Sensitizing dye Vl B, 0X10-' Sensitizing Pigment■
3.0X10-'EX-130,01
S EX-110,,100 EX-10,025 HBS-10,25 HBS-20,10 Gelatin 1,54 10th layer (
Yellow filter layer) Yellow colloidal silver Silver 0.05EX-5
0,08 8BS-10,03 Gelatin 0.95 No. 11N (
First blue-sensitive emulsion Ji) Emulsion A t! 0.08 emulsion B
Silver 0.07 Emulsion C Silver 0.1
5 Sensitizing dye ■ 3.5X10-'EX-9
0,721 EX-8 HBS-1 Gelatin 12th layer (second blue emulsion layer) Emulsion C Sensitizing dye ■ EX-9 Ex-i.

HB S -1 Gelatin 13th layer (3rd blue emulsion [) Emulsion sensitizing dye ■ EX-9 HB S -1 Gelatin 14th layer (1st protective 8i layer) I-4 B5-1 0.042 0 , 28 1.10 Silver 0,70 2, lX10-' 0.154 0.007 0,05 0,78 Silver 0,80 2.2X10-' 0,20 0,07 0,69 0,11 0,17 0,05 Gelatin 1.00 No. 15N (
2nd protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) 0.54 emulsion G
O,10H-10,38
O 3-10,2 O 3-20,05 Gelatin 1,20 In addition to the above components, a surfactant was added to each layer.

(Samples 102-104) Samples 102-104 were prepared by changing the emulsion of Sample 101 as shown in Table 2.

(Samples 105 to 108) A specific example of the compound of general formula (1) 0η was added to each of the 5th layer, 9th layer, and 13th layer of Samples 101 to 104 at 2
IO-'1aol/n (added to samples 105-10
8 was produced.

Tank loading formula of the compound used in Example 1 EX-1 C11゜ I EX EX-3 H EX-4 0 ■ EX 0■ EX-6 CI+.

EX-1 EX EX-11 l Ca11. Ko (n) EX-8 EX-9 EX-12 EX X H 已X-15 C11゜ CI+! -(-CIl□-〇±1 (-CI+, -C-)-F Co-0-CI+3 Cl-5 If BS-1 tricresyl phosphate H[3S dibutyl phthalate 11.C -CHff Cl+.

C CI+.

C.I.

H,C-C CH3 L BS Hz L Sensitizing dye■ S03'□ 03Na Sensitizing dye■ (CHz+zSoff- CCHt+ssOxNa Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ C11゜03Na CHl Sensitizing dye■ Proceed as above The sample lot prepared was 3511/11.
After imagewise exposure under standard exposure conditions of 150400, continuous processing (running processing) was performed using an automatic processor using the processing steps and processing solution described below. In addition,
Running treatment consists of 50 35-/- width 101 per day.
The test was carried out for 20 consecutive days.

The crossover time between each processing solution in the automatic processor was 5 seconds.

In addition, an aeration device was attached to the bleach solution tank of the automatic processor, and fine air was bubbled for 10 hours a day, including in the processing solution.

The processing steps are described below.

Process Processing time Processing temperature Refill FJ'! Ink capacity color development 3 minutes 15 seconds 38℃ 38d 10
1! Bleach 40 seconds 38℃
4-51 fixed at 1 minute 38
30d 5J stable +11 20 seconds 38℃
-3i stable +21 20 seconds 38℃ -31 stable +31 20 seconds 38℃ 35m1' 31 drying
1 minute 15 seconds 50 to 70℃ Replenishment amount is 35 per meter of length *Stabilizing solution is stable (3) → stable (2) → stable fil 3
A tank countercurrent system was adopted.

Next, the composition of the treatment liquid will be described.

(Color developer) Dry diethylenetriamine pentaacetic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-β-hydroxyethylamino)-2= Methylaniline sulfate mother liquor (g) Replenishment Solution (g) 5.0 6.0 4.0 4.4 30.0 37.0 1.3 0.9 1.2■ 2.0 2.8 4.7 5.3 Add water and adjust the pH ( Bleach solution) 1.3-Diaminopropane tetraacetic acid ferric ammonium dihydrate 1.3-Diaminopropane tetraacetic acid Ammonium bromide Ammonium nitrate Acetic acid (98%) Add water and H (Fixer) 1-Hydroxyethythene -1,1-diphosphonic acid ammonium sulfite 1.01 10.00 Mother liquor (g) 160.0 4.3 200.0 30.0 60#1 1.01 4.2 Mother liquor (g) 5.0 14.0 1.01 10.05 Replenisher (g) 290.0 6.5 300.0 50.0 0jIf 1.01 3.3 Replenisher (g) 6.0 16.0 Ammonia water (28%) Ammonium thiosulfate aqueous solution (70%-/V) Add water and pH (Stable solution) Mother solution and replenisher common 3, 〇- 5, 〇- 330.0d 360.0d 1, Oj! 1. OJ 6.7 7.4 Units (g) Formalin (37%) 1.2-triethanolamine 2.05-chloro-2
-Methyl-4-isothiazolin-3-one
6. O■L 2-benzisothiazolino-3-one 3.0LIf surfactant 0. 4(C+oHt+
-〇(CH! CHz O) lo H) Ethylene glycol 1,0 Add water
1.0 l pH 5,0~7.0 Using the treatment solution after the above running treatment, sample 10
After each of 1 to 108 was processed without exposure to light, it was determined by fluorescent X-ray analysis that it remained! I was determined and the fixing speed was evaluated. (Processing A) In addition, the sensitivity of the cyan layer of each window material was determined by processing the sample subjected to wedge exposure. The sensitivity was expressed as a relative sensitivity, with the sensitivity at a concentration of sample 101 plus 0.2 being the lowest concentration as 100.

In addition, the RMS value of each sample was determined in the same manner.

The RMS value representing graininess is at a cyan density of 0. The concentration of No. 5 is expressed as a value 1000 times the standard deviation of the variation in density value that occurs when scanning with a microdensitometer having an aperture of 48 μm in diameter.

In addition, in the above running process, the 1,3-diaminopropanetetraacetic acid ferric complex salt and the 1,3-diaminopropanetetraacetic acid ferric complex salt used in the bleach solution mother liquor and replenisher solution were added in equal moles of ethylenediaminetetraacetic acid ferric complex salt, respectively. Sample 101 was prepared using the treatment solution after performing the same running treatment except that it was replaced with ethylenediaminetetraacetic acid.
-109 were processed without exposure and the amount of residual silver was measured.

(Treatment B: Comparison) Furthermore, after each sample was exposed to 1OCMS at a color temperature of 4800°, treatments A and B were applied to each sample, and when the bleaching properties were examined, it was found that all treatments A had completed bleaching. However, processing B
For each sample, residual ff of 30 μg/aJ or more
fl, and bleaching was not completed.

Table 3 shows the results without exposure.

As is clear from Table 3, samples 10 to 10 containing silver halide grains of the present invention were treated with treatment A (1°3'-DPT
Treatment B (treatment with bleach solution using A-Fe) and treatment B (EDT
For samples 101.102.106 to 109, which had a higher fixing speed than the treatment with bleach solution using A-Pet,
This result is surprising considering that Process A has much worse fixation than Process B. At the same time, sensitivity and graininess are also improved, which is an unexpected effect. These results indicate that bleaching and fixing can be achieved satisfactorily in the light-sensitive materials containing the emulsions of the present invention subjected to the processing of the present invention.

Furthermore, in the present invention, when r17, which is a compound of general formula [1] that can be preferably used, is used (10
It can be seen that the fixing speed of cases 6 to 108) is even higher than that of cases 102 to 104).

Example-2 In Example-1, sample 108 was used instead of sample 01.
A running process similar to Process A of Example-1 was performed using the following.

In addition, 1,1-hydroxyethylidene-1,
The same running treatment as above was carried out, except that 1-diphosphonic acid was removed or replaced with the chelating agent shown in Table 3.

The amount of residual silver in the unexposed area and the exposed area (color temperature 4800'K, 10 CMSR light) of sample 104 at the end of each run was measured.

Furthermore, after each run, put 11 pieces of each fixer into beakers of the same size (opening area 10-) and add 3
The number of days until precipitation occurred (sulfidation) was determined by aging at 8°C.

The results are shown in Table 4.

As can be seen from Table 4, by incorporating a chelating agent into the fixing solution, the stability of the fixing solution can be greatly improved without reducing the rapid desilvering properties. In particular, it can be seen that organic phosphonic acid-based chelating agents are excellent in preventing sulfurization without reducing desilvering properties.

(Effect of the invention) By carrying out the present invention, 1.3-DPTA-Fe
Desilvering properties, sensitivity, and graininess were improved even after treatment with a bleaching solution containing .

Claims (1)

[Claims] A silver halide color photographic material having one or more red-sensitive silver halide emulsion layers, one or more green-sensitive silver halide emulsion layers, and one or more blue-sensitive silver halide emulsion layers on a support,
In the method of processing with a bleaching solution containing ferric 1,3-diaminopropanetetraacetic acid complex salt and then processing with a processing solution having fixing ability, the average silver iodide of silver halide in all emulsion layers in the light-sensitive material is A method for processing a silver halide color photographic material, characterized in that the content is 10 mol% or more.