JPH02190853A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To speed up desilvering and fixing by forming one of emulsion layers of the photosensitive material of chemically sensitized specific silver halide particles and forming the outermost layer of the silver halide particles of silver halide contg. a specific ratio of silver iodide. CONSTITUTION:At least one emulsion layer of the photosensitive material consists of the chemically sensitized silver halide particles and the silver iodobromide or silver iodochlorobromide contg. 30 to 45mol% silver iodide exists in the silver halide particles by having a distinct phase structure; in addition, the outermost layer of the silver halide particles consist of the silver halide contg. <=8mol% silver iodide. The phase structure refers to the case in which at least two diffraction max. of the diffraction peak corresponding to the high iodine layer contg. 30 to 45mol% silver iodide and the diffraction peak corresponding to the low iodine layer contg. <=8mol% silver iodide and one min. therebetween appear and the diffraction intensity corresponding to the high iodine layer is 1/10 to 3/1 the diffraction intensity of the peak corresponding to the low iodine layer. The desilvering and fixing are rapidly executed 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) -g. The basic steps of 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 is melted and removed by a silver ion ljing 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. For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing, a stop bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a backing layer of the support. For example, a membrane removal bath is used to remove water.

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 ( m) 1M
Bleaching treatment methods based mainly on salt (salt) 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. I was being bullied.

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, the 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 1,3-DPTA-Fe) as described in JP-A-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, conventional ethylenediaminetetraacetic acid ferric complex salt (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 in which fixing can be carried out quickly after rapid bleaching with a bleaching solution containing 1,3-DPTA/Fe, and the photographic properties are improved. There is a particular thing.

(Means for Solving the Problems) It has been found that the above aspects of the present invention can be achieved by the following method. That is, in a method in which a color light-sensitive material is treated with a bleaching solution containing a ferric complex salt of 1,3-diaminopropanetetraacetic acid, and then treated with a processing solution having a fixing ability,
At least one emulsion layer of the light-sensitive material is composed of chemically sensitized silver halide grains, and the silver halide grains contain 3
Silver iodobromide or silver iodochlorobromide containing 0 to 45 mol% of silver iodide exists with a clear phase structure, and the outermost layer of the silver halide grain contains 8 mol% or less of iodine. This was achieved by a method for processing a silver decagenide color photographic light-sensitive material, which is characterized by being made of silver halide containing silver oxide.

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 silk-like structure.

The distinct silk-like 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 X-ray diffraction, please refer to Basic Analytical Chemistry Course 24rX
It is described in detail in books such as ``Radio Analysis'' (Kyoritsu Shuppan) and ``X-ray Diffraction Guide'' (Rigaku Denki Co., Ltd.). The standard measurement method uses Cu as the target and the l? line as &iI source (tube voltage 40kV, tube current 60mA)
This is a method for determining the diffraction curve of the (220) plane of silver halide. 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 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 the curve was obtained, a diffraction peak corresponding to a high iodine layer containing 30 to 45 mol% silver iodide, and a low diffraction peak corresponding to a low iodine layer containing 8 mol% or less silver iodide (both 2 There is a wood 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 having substantially two distinct silk-like structures is more preferably one in which the minimum diffraction intensity between the two peaks is the weakest of 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 (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 DOPont.

Even in the case of an emulsion in which two types of grains with different halogen compositions that do not have a distinct silk-like structure coexist, the above-mentioned X! 'i
Two peaks appear in one diffraction.

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

The silver halide emulsion is an emulsion according to the invention or a 2f! emulsion as described above! In order to determine whether the emulsion contains silver halide grains of J, in addition to the XvA diffraction method, EPMA
method (Electron-Probe Micro.

This is possible by using the Analyzer 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. 1! Elemental analysis of extremely small parts can be performed by XvA analysis using particle 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.

If the halogen composition of 50 grains (T11!) is confirmed by the EPMA method, it can be determined whether the emulsion is an emulsion according to the present invention or not.

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.

In other words, the iodine content of the large size particles is high and the iodine content of the small size particles is low.

Emulsions exhibiting such a correlation give favorable results in terms of graininess. This correlation coefficient is over 40% and even 50%
It is preferable that it is above.

In the core part, the silver halide other than silver iodide may be either silver chlorobromide or silver bromide, but a higher proportion of silver bromide is preferable, and the silver iodide content is 30 to 45 mol%. Any amount is acceptable, but 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 rate of silver iodide in the outermost layer of silver halide grains is XP S
(X-ray Photoelectron 5pec
(Loscopy) It can be measured by Q-plane analysis method. Regarding this method, see Atsushi Aihara et al.'s ``Electron Spectroscopy'' (Shared Library 16, Imori Publishing, 1972).
2014) etc. can be used as a reference.

The standard measurement method for XPS is α for Mg- as the excited
Using an appropriate fL test [form 9], photoelectrons of iodine (11) and Cu (Ag) released from silver halide grains (usually I-JdS/2, Ag-j d 5/2)
It is determined by the method of observing the intensity of .

K to determine the iodine content is the iodine content; iodine (1) and Ag
It is possible to create a test line for the intensity ratio of photoelectrons (strong mass (■) 7 intensity (person g)) and find this rod amount string force . /
- After removing the gelatin adsorbed on the surface of the silver particles by protein silicolysis (7 minutes, etc.), it is necessary to carry out KXPS 1 lill determination.

It is preferable that (1) exceeds 8 mol%, more preferably 10 to 24 mol%, still more preferably 12 to 20 mol%.

The average grain size of uninvented silver halide grains is o,
io to 3.0 μm is preferable, more preferably 0.3
0 to 2.0 μm, more preferably 0.40 to 1.5 μm
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 J” by JB＊es et al.
y of the Photographic Pro
c@ss) 3rd edition, 39 pages, published by Macmillan (1966)
It is a geometric mean value of particle size well known in the art, as described in 2010). In addition, the particle size can be determined from "Introduction to Particle Size Measurement" by Masafumi Arayo (Journal of Powder Engineering Society, Vol. 17, 299).
It is expressed in equivalent sphere diameter as described in 1980, p. 313, and can be measured by methods such as the Coulter counter method, sheep particle light scattering method, and laser light scattering method.

The silver halide grains of the present invention having a definite set structure may have regular crystal shapes (normal crystal grains) such as hexahedrons, octahedrons, dodecahedrons, and dodecahedrons. , or may have an irregular crystal shape such as spherical, potato-like, or tabular, especially with an aspect ratio of 1.0 to 10, especially 1.
Tabular twin grains of Z to 5 are preferred.

In the case of normal crystal grains, particles having 50% or more (111) planes are particularly preferred; even in the case of irregular crystal shapes, (111)
) Particles having 50% or more of surfaces are particularly preferred, N11)
The surface pressure 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 pressure ratio of the (111) plane can be determined by adding such a dye to an emulsion and examining the spectra in detail with respect to the amount of the dye added.

Although the emulsions of the present invention can have a wide grain size distribution, emulsions with a narrow grain size distribution are preferred. In particular, in the case of regular grains, monodisperse grains in which the weight or number of silver halide grains are such that the size of the grains that account for 0% of the total weight of each emulsion are within ±4 tO% of the average grain size, and further within 1304 Emulsions can also be used.

The effect of the present invention can be best seen in twin grains. It is preferred that tabular grains having two or more parallel twin planes be contained in a projected area of 30% or more, preferably 00% or more, and 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 soluble silver salt and soluble halogen salt can be selected from one-sided mixing method, simultaneous mixing method, and combinations thereof. .

As one form of the simultaneous mixing method, a method of keeping pAg'r constant in the liquid phase in which silver halogenide is produced, such as a Wachi control 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 (eg, soluble silver salt, soluble bromine salt, and soluble iodine salt) can also be used.

Silver chloride 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, especially the iodine content, of individual grains is more uniform at the fur stage.

Whether the halogen composition of each particle is uniform can be determined by the aforementioned X-ray diffraction method and EPMA method. X if the fur particle composition is more uniform
Gives sharp peaks with a narrow diffraction width in line diffraction.

After creating silver iodobromide crystals containing high concentrations of silver iodide,
A method of accelerating the addition rate over time as disclosed in Japanese Patent Publication Akihiro r-J x r 0 by Irie and lead powder, or US Patent No. G by Saito.

2≠2. Gu Hong! Uniform silver iodobromide can also be obtained by the method of growing silver iodobromide grains by increasing the additive concentration over time, as disclosed in the above publication.

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. , to be added at a rate of addition 1fQ at a constant temperature acceleration or higher and at a rate less than or equal to the addition rate proportional to the total surface area of the growing poorly soluble inorganic salt crystal, that is, to add at a rate of Q = γ or more and Q = αt2 + βt + r or less. It is.

On the other hand, Saito's method is a method for producing silver halogenide crystals in which two or more types of 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 new crystal nuclei are almost completely removed during the crystal growth period. This increases the workload to the extent that it does not occur often. In producing V4 silver halide grains having a clear coarse structure according to the present invention, shelling may be performed directly after core grain formation, but it is preferable to perform 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 clear coarse structure, but they alone are not sufficient to perfect the coarse structure. First, it is necessary to carefully determine the halogen composition of the high iodine layer. It is known that silver iodide and silver bromide have different thermodynamically stable crystal structures and do not form mixed crystals depending on the composition ratio of P1. The mixed crystal composition ratio depends on the temperature during particle preparation, but 15
~G! It is important to choose the most suitable one from the range of mulch. Although the stable mixed crystal composition ratio depends on the atmosphere, 3
It is estimated that it exists in θ~pr morchi. When growing low iodine/if on the outside of the high iodine layer, it is of course important to select the temperature, p-type, pAg1 stirring conditions, etc., but the amount of colloid extracted when growing low iodine/1Ft is of course important. It is preferable to take measures such as growing a low iodine layer in the presence of compounds that adsorb to the surface of silver halide, such as spectral sensitizing dyes, antifoggants, and stabilizers. It is also effective to add vK fine grain silver halide to a water-soluble silver salt and a water-soluble alkali metal halide when growing a low iodine layer.

As mentioned above, in the present invention, the /% silver halide grains having a clear coarse structure means that there are substantially two or more regions with different halogen compositions within the grains, and the inner grains have a distinct coarse structure. Is the center side the core part and the surface side? Just in case I explained it as a shell.

Substantially λ means a third region (in addition to the core and shell).
For example, there may be a layer between the central core and the outermost shell.

However, even if such a third region exists, when the X-ray diffraction pattern is obtained as described above, λ peaks (two peaks corresponding to the high iodine portion and the low iodine portion)
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. The sum of the projected areas of all the silver halide grains present is preferably at least jO, more preferably at least 70, particularly preferably at least O.

Dyes often used when growing low iodine layers 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, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus,
Pyridine nuclei, etc.; nuclei in which these nuclei are fused with alicyclic hydrocarbon rings; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei; i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, induoxa Dole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzonazole nucleus, (zuimidazole nucleus, quinoline nucleus, etc.) can be applied. These nuclei may be substituted on the diagonal atom.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline as a core with a ketomethylene structure! -on nucleus, thiohydantoin nucleus, 2-thioxazolidine-1,
S -X member heteroartic ring nuclei such as Hiro-dione nucleus, thiazolidine-1, goudion nucleus, rhodanine nucleus, and thiono-9 rubituric acid nucleus can be applied.

For example, Re5search Disclosure,
Item/7t≠3, page 23, item ■ (/7? year 1.2
It is possible to use the compounds described in Japanese Patent Application No. 2-IA722 as representative examples.

Antifoggants and stabilizers are also useful compounds when the low iodine layer is fully grown. 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 formula, Ml represents a hydrogen atom, a cation or a protective group of a mercapto group that is cleaved with an alkali, and Z represents an atomic group required to form a j-negative to t-membered heterocycle. 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 groups (e.g., (bar COR', -COOR
', -CH2CH2COR,/etc. However, R' represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, etc.).

Z! Represents a group of atoms necessary to form a negative to t-membered heterocycle. This heterocycle contains a sulfur atom, selenium atom, nitrogen atom, oxygen atom, etc. as a heteroatom, and may be fused, or may have a substituent on the heterocycle or the fused ring. good.

Examples of Z include tetrazole, triazole, imidazole, oxazole, thiadiazole, pyridine, pyrimidine, triazine, azabenzimidazole, purine, tetraazaindene, doriazaindene, hantaazaindene, benztriazole, benzimidazole, benzoxazole, benzthiazole , benzselenazole, and naphthoimidazole. Substituents for these rings include alkyl groups (e.g., methyl group, ethyl L n-hexyl group, hydroxyethyl group, carboxyethyl group, etc.), alkenyl groups (e.g., allyl group, etc.), aralkyl groups (e.g., benzyl group, phenethyl group, etc.), aryl group (e.g. phenyl group, naphthyl group, p-acetamidophenyl group, p-carboxyphenyl group, m-hydroxyphenyl group, p-sulfamoylphenyl group, p-acetylphenyl group, 0-methoxy Phenyl group, 2.≠-diethylaminophenyl &-
21≠-dichlorophenyl group, etc.), alkylthio group (
For example, it may be substituted with a methylthio group, an etherthio group, an n-butylthio group, etc.), an arylthio group (eg, a phenylthio group, a naphthylthio group, etc.), an aralkylthio group (eg, a benzylthio group, etc.), a mercapto group, etc. Furthermore, in addition to the above-mentioned substituents, a nitro group, an amine 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 preferably lo-3 mol or less per mol of silver halide.

Specific examples of preferred nitrogen-containing heterocyclic compounds containing a mercapto group are described in Japanese Patent Application No. 47255/1983.

Silver halides of different compositions may be further bonded to the emulsion of the present invention by eviaxial 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 sensitization. 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, thallium, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum, etc.). Compounds used for chemical sensitization include those described in the lower right column of page 18 to the upper right column of page 22 of the specification of JP-A-62-215272. In addition, the additives used in such a process are described in RD k 17643 and Nα1B716, and the relevant parts are summarized in the table below. 0 Known photographic additives that can be used in the present invention The above two R
D, and the relevant descriptions are shown in the table below.

Search for Rui! 1 Chemical sensitizer 2 Sensitivity enhancer 3 Spectral enhancer, super sensitizer 4 Brightener 5 Anti-fogging agent and stabilizer 6 Light absorber, filter dye, ultraviolet absorber 7 Anti-stinting agent Page 25 closes 650 pages left to right (
Between 8 Dye image stabilizer page 25 9 Hardener page 26] 0 Binder 26 page 24 page 651 left column Same as above page 25-26 649 page right side 650 page left column 24-25 page 649 right side page 15 Shi Other Tsukikyuru page 23 Page 648 right column Same as above pages 23-24 Page 648 right side 1 Page 649 right column 11 Plasticizer, lubricant Page 27 Page 650 right column 1
2 Coating aid, pages 26-27 Page 650 Right column Surface active agent 13 Static, page 27 Same as above Patch agent The emulsion of the present invention can be incorporated into the light-sensitive emulsion layer of a silver halide color photographic light-sensitive material. Although it may be contained in any layer, it is preferably used when an emulsion layer group having substantially the same color sensitivity is divided into two or more layers with different sensitivities; , for the high-sensitivity layer,
When the layer is divided into three or more layers, it is preferable to use it for the high-sensitivity layer and/or the intermediate-sensitivity layer.

By using the emulsion of the present invention, not only the bleaching and fixing speeds are improved even if the following bleaching processing is performed, but also the processing that has fixing ability is performed, and the photographic properties, especially sensitivity and graininess, are also improved. Has performance.

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

In the present invention, the desilvering step is performed by bleaching with a bleaching solution containing J-DPTA-Fet and then processing with a processing solution having a fixing ability.

A bleaching solution containing J-DPTA-Fe'i is described, for example, in JP-A No. 22221λ, and is known to have high oxidizing power and rapid bleaching reaction.

However, when a conventional photosensitive material is used, if it is treated with a white liquor containing i,j-DPTA-FevI and then treated with a processing solution having a constant flow rate,
(For example, when processing with a bleaching solution that does not contain EDTA-Fe, the fixing speed is lower than when using only EDTA-Fe as a bleaching agent. However, when processing a photosensitive material containing the emulsion of the present invention, the fixing speed is lower. They found that the decline occurs little or even faster.

/, J-DPTA-Fe causes a noticeable decrease in fixing speed in light-sensitive materials containing iodine-containing emulsions (for example, silver iodobromide emulsions).
It is thought that the coexistence of J-DPTA-Fe causes a state of inhibition of fixation.

It is presumed that an emulsion with a low iodine concentration on the surface and a high internal silver iodide ratio like the one used in the present invention would not suffer from fixation inhibition on the emulsion surface as in the case of upper-grain piping, but surprisingly, the fixing speed It has also been found that there are cases in which the ratio becomes large (for example, in the processing of light-sensitive materials containing a high proportion of the emulsion of the present invention).

The bleaching agent contained in the bleaching solution is 1,3-DPTA.
-Fe, EDTA-Fe, diethylenetriaminetetraacetic acid ferric complex salt (DPPA-Fe) or 1.2-
Cyclohexanediaminetetraacetic acid ferric complex salt (CyDPT)
A-Fe), among others, EDTA
The combination with -Fe is most preferred. When used together, 1.3-
The ratio of DPTA-Fe to the total bleach is 10
~80% is preferred, particularly 20-50%.

The above aminopolycarboxylic acid ferric complex salt (13-DPT
A-Fe, EDTA-Fe, etc.) is usually preferably used in the form of an alkali metal salt or an ammonium salt, and ammonium salts are particularly preferred since they have excellent solubility and bleaching properties.

1. The preferable total addition amount of 3-DPTA-Fe and the aminopolycarboxylic acid ferric complex salt used in combination is 0, O1 mol ~
1.0 mol/l, more preferably 0.1-0.7 mol/l
Scarce.

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 tB 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 a bleaching agent. For moles, it is 0.1 mol, 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, German Pat.
, 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 oquinides described in Tsutsu No. 2,748.430, Japanese Patent Publication No. 1974-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferably British patent tube 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/I! , especially 1.5 to 2.0 mol/! 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.

-th, ammonium nitrate, sodium nitrate, etc. Nitrates, 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, one or more inorganic acids and organic acids and salts thereof, metal corrosion inhibitors such as ammonium sulfate, etc., which can be used in ordinary bleaching solutions. Additives can be added.

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 a preferred pH range, there is little bleaching fog and the desilvering performance is excellent.

It is preferable to aerate the bleaching solution in order to oxidize the ferrous complex produced by the bleaching process or the reaction with the color developing solution brought in by the photosensitive material. Aeration may be carried out only during processing, or Also, it may be carried out only during the temperature adjustment of the automatic processor, or throughout the day, but it is better to carry out 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. It is preferable to immediately perform treatment with a treatment bath having a fixing ability after treatment with a bleaching solution because the effects of the present invention are significantly exhibited. Although processing in a bath increases the number of steps by one and is not preferable from the viewpoint of processing speed and compactness of the processing machine, it may be carried out 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.

The fixing agents for processing solutions used in processing baths having these fixing abilities include thiosulfates (e.g., sodium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate), thiocyanates (e.g., sodium thiocyanate, thiocyanate), ammonium, potassium thiocyanate)
, thioether compounds, thioureas, large amounts of iodide salts, etc., but the use of thiosulfate is preferable because it has a high fixing speed and exhibits the effects of the present invention most markedly. Ammonium sulfate is preferred from the viewpoint of solubility and fixing speed, and may be used in combination with other fixing agents.

These fixatives contain 1.1 mol/! The above is preferable, particularly preferably 1.3 to 1.7 mol/l. 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, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained. 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 I,3-DPTA/Fe 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 is tends to decrease slightly. In order to improve the stability of the processing solution that has 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-based chelating agent, the following general formula (1), (
Examples include compounds represented by 2) or (3).

- 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, R5 represents an alkyl group or alkenyl group having 1 to 6 carbon atoms, and R8 represents an alkylene group having 2 to 8 carbon atoms. These substituents may be linear or branched.
The preferred carbon numbers of R5 and R2 are 1-3 and 2-6, respectively. a, b, c, d, e
, f and g are each an integer of 1 to 3, preferably 1.

Specific examples include 1-hydroxyethylidene-1,1-diphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, N, N, N', N''-ethylenediaminetetraphosphonic acid, N, N, N' , N'-propylenediaminetetraphosphonic acid 1, N, N, N', N"-hexylenediaminetetraphosphonic acid, N, N, N", N'-
Examples include butylene diamine tetraphosphonic acid, N,N,N-nitrilotrimethylenephosphonic acid, and i,N,N-nitrilotripropylenephosphonic acid, or salts thereof (eg, ammonium and sodium salts).

The amount of the chelating agent added to the processing liquid having fixing ability is 0.
01 mol/I! or more, particularly preferably 0.02
It is preferable to contain up to 0.1 mol/1 because the stability of the processing liquid having fixing ability can be dramatically improved.

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

The pH of the processing liquid having fixing ability of the present invention is 3 to 9, preferably 5 to 8.

The shorter the total time g1 of the desilvering step of the present invention, the more remarkable the effect 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.

Further, the treatment temperature is 25°C to 50°C, preferably 35°C to
It is 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring for one night 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, No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183-1.
No. 83461 uses a rotating means to increase the stirring effect, and furthermore, the one-per-period effect is achieved by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples of methods include increasing the circulating flow rate of the entire processing liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that stirring for one night speeds up the supply of bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Also, the above-mentioned stirring 11! The improvement means is more effective when a bleach accelerator is used, and the accelerating effect can be significantly increased and the fixing inhibiting effect caused by the bleach accelerator can be eliminated.

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 JP-A-6O-19T.
It is preferable to have the photosensitive material conveying means described in JP-A-60-191257, which preferably has the photosensitive material conveying means described in JP-A-60-191257. 6) It is possible to significantly reduce the amount of processing liquid brought into the post-bath, and it is highly effective in preventing the performance price of the processing liquid from increasing.11. 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 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 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-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-mentioned p-phenylenediamine KR'4 compounds, Exemplified Compound D-5 is particularly preferred.

Furthermore, these p-phenylenediamine derivatives may be salts such as silicate, hydrochloride, sulfite, and P-)luenesulfonate. Preferably about 0.1 g to about 20 g per 11,
More preferred is a concentration of about 0.5 g to 10 g.

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/l, more preferably not at all.

The preferable amount of preservative added is 0.000000000000000000000000000000000000000000000000000 that
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, vF Application No. 61-1865
Hydroxamic acids described in No. 59, No. 61-170756
Hydrazines and hydrazides described in No. 61-18
Phenols described in No. 8742 and No. 61203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-18
It is preferable to add various saccharides described in No. 0616, and in combination with the above compounds, Japanese Patent Application No. 61-147823, No. 61-166674, No. 61-165621-, No. 61-164515, No. 61-164515, No. 61-170789,
and monoamines described in No. 61-168159, etc.
Diamines described in No. 61-173595, No. 61-164515, No. 62-186560, etc., No. 61-186560, etc.
165621 and polyamines described in 61-169789, polyamines described in 61-188619, nitroxy radicals described in 61-197760, 61-186561, and 61-197419
It is preferable to use the alcohols described in No. 61-198987, the oximes described in No. 61-198987, and the tertiary amines described in No. 61-265149.

In addition, as a preservative, the various degrees described in JP-A-57-44148 and JP-A-57-53749, JP-A-59
- Salicylic acids described in No. 180588, JP-A-54-3
Alkanolamines described in No. 532, JP-A-56-9
Polyethyleneimines described in No. 4349, U.S. Patent No. 3
, 746,544, etc., may be included if necessary, and addition of aromatic polyhydroxy compounds 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, O-
Sodium hydroxybenzoate (sodium salicylate), potassium 0-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/!
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
4 mol/I! , is particularly preferable.

Various chelating agents can be used in color developing solutions as calcium and magnesium precipitation inhibitors or for improving the stability of color developing solutions.

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-trimethylenephosphonic acid, ethylenediamine-N,N,N"No-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropane Tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N,N'-bis(2-hydroxy benzyl)ethylenediamine-N,N'-diacetic acid, and two or more of these chelating agents may be used in combination as necessary.

The amount of these chelating agents added may be sufficient as long as it is sufficient to sequester all the ions in the color developer. For example, tp
It is about 0.1 g to 10 g 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 the developer contains 2 or less, preferably not at all, per developer If.

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-phinidine diamine 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-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 Nos. 2,482,546, 2,596,926, and 3,582,346, etc.;
No. 42-25201, U.S. Patent No. 3.128,183
Polyalkylene oxides disclosed in Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3,532,501, and other I-phenyl-3-
Pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any anti-capri agent can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic anti-capri agents 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 fluorescent brightener, 44'-diamino-2,2'-disulfostilbene compounds are preferred.

Addition ヱ is O~5g/7! Preferably 0.1 g to 4 g/
It is l.

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. It is preferable that the amount of replenishment is small, but it is 100 to 1500 Il per 1 nf of photosensitive material.
11 is preferably 100 to 800 d. More preferably, it is 100 Id, ~400 ml.

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 water filled.

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 is commonly known as the black and white first developer used for the reversal processing of color photographic light-sensitive materials, or Those used for processing black and white photosensitive materials can be used. 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. ,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. I can give it to you.

The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above. Here, after the treatment step that has fixing ability, it is common practice to perform treatment steps such as water washing and stabilization, but after the bath that has fixing ability, stabilization treatment is performed without substantially washing with water. Preliminary treatment methods may also be used.

The rinsing water used in the rinsing step can contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, 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,
WesL” Hatar Quality Cr1ter
ia”+ Phol Sc4. and Eng.

vol 9. No, 6. Pages 344-359
(1965) and the like can also be used.

As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used.8For example, a solution having a buffering capacity of pH 3 to 6, a solution containing aldehyde (for example, formalin), etc. can be used. Can be done. The stabilizing liquid may contain ammonium compounds, metal compounds such as Bi and Al1, optical brighteners, chelating agents (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides,
A fungicide, a hardening agent, a surfactant, 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.

In addition, the water washing step and the stabilization step are preferably performed using a multi-stage countercurrent method, and the number of stages is preferably 2 to 4. The replenishment amount is 1 to 50 times the amount brought in from the previous bath per unit area, preferably 2 to 30 times. times, more preferably 2 to 15 times.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
, MgfJ degree 5 mg/I! It is preferable to use deionized water, water sterilized by halogen, ultraviolet germicidal lamp, etc. below.

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 pre-bath having a stabilizing ability.

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 is described, for example, in Research Disclosure (RD), Nα17643 (December 1978), pp. 22-23, (2).

Emulsion preparation
and types)”.

and Dobei 18716 (November 1979), 648
Page, Graphic "Physics and Chemistry of Photography", Published by Beaumontel (P, Glafkides, Chemic e
L PhysiquePhoLographique
Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F,
Duffin, PhotoI! rapic Em
ulsion Chesistry (Focal Pr.
ess, 1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L.

Zeljk+san et al. Making a
nd Coating Photographic Em
ulsion, Focal Press+ 1964
), etc.).

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 Gutoff, Photographic Science and Engineering.
ence and Engineering), No. 14
@, pp. 248-257 (1970); U.S. Patent No. 4,
No. 434,226, No. 414,310, No. 4.4
33 048, 4,439,520, and British Patent No. 2.112.157.

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 RD No. 17643, ■
It is described in the patent listed in -〇-G.

As a yellow coupler, for example, U.S. Patent No. 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 Section 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 the Mazenk coupler, 5-pyrazolone and pyrazoloazole compounds are preferred; US Patent Box 4. '3
10.619, 4,351,897, European Patent Box 73.636, US Patent Box 3,061,432, 3,725.064, RD k 24220 (19
June 1984), JP-A-60-33552, RDNα2
4230 (June 1984), JP-A-60-4365
No. 9, No. 6i-72238, No. 60,35730,
No. 55-118034, No. 60-185951, U.S. Patent Box No. 4,500,630, No. 4,540,654
No. 4,556,630, WO (PCT) 881
Particularly preferred are those described in No. 04795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent Box 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, No. 4,334,011, No. 4
, 327, 173, West German patent publication tube 3,329.72
No. 9, European Patent No. 121,365A, European Patent No. 249.45
3A, U.S. Patent Box 3.446.622, U.S. Patent Box 4,33
No. 3.999, No. 4,753,871, No. 4,451
．． No. 559, No. 4,427,767, No. 4,690,
No. 889, 4,254. No. 212, 4,296,
199, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in RD k17643, Section ■-G, US Patent Box 4.
, No. 163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. In addition, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling, as described in U.S. Patent Box 4,774.181, and U.S. Patent Box 4,777.
．． 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. 120.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent Box 4,366.237 and British Patent Section 2,125.
．． Preferred are those described in No. 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533.

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 that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
No. 63-37346, U.S. Patent No. 4,248,96
No. 2, 4°782, (the one described in No. 12 is preferred).

Couplers that imagewise release a nucleating agent or a development accelerator during development include British Patent Section 2,097,140;
Those described in JP-A No. 2.131.188, JP-A No. 59-157638, and JP-A No. 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, DIR redox compound releasing couplers, DIR coupler releasing couplers, DI couplers described in JP-A-60-185950, JP-A-62-24252, etc.
R coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173°302
A coupler that releases a dye that after-releases after separation as described in item A;
RD 11449, 24241, JP-A-61-20
Bleach accelerator-releasing couplers described in US Pat. No. 1247, Gantt-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 oil-in-water dispersion methods are described in U.S. Patent No. 2,322.027 and others.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. No. 4,199,363 and OLS No. 2. ．． No. 541,274 and No. 2,
It is described in No. 541゜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 high-boiling organic solvents as 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. 1B-30494, No. 51-39835, U.S. Patent No. 3,619.195, and West German Patent No. 1,95.
There are various descriptions in No. 7,467.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO38100723 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 17643, and 6 of 18716
It is described from the right column on page 47 to the left column on page 648.

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

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

An aqueous solution of 2.05 g of potassium iodide dissolved in 800 rr+j of N running water was stirred at 75° C., and 5.0 g of silver nitrate was added thereto. 15 Qcc of an aqueous solution containing Olg was added instantaneously, and after adding excess potassium bromide, the mixture was physically aged for 20 minutes. Furthermore, 0.00% was prepared according to the method described in U.S. Pat. No. 4,242,445. 2 moles/1.0.67 moles/! , 2 mol/l of mineral acid i+￥ and a potassium halide aqueous solution (mixed with 85 mol% of potassium bromide and 15 mol% of potassium iodide) at 1o/min, respectively.
The silver iodobromide grains were added at a rate of c c@ to grow 15 mol % silver iodobromide grains. 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
It is μm. 0.76μm・25mol% according to emulsion a
, 0.66 μm・40 mol%, 0.71 μm・39 mol%, 0.7'Z μm・4Z mol%, 0.70 μm-50
Silver iodobromide grains of mol % and 0.75 μm/60 mol % were adjusted to form emulsions b-g.

Take 900 g of emulsion a, add 21 g of distilled water, 90 cc of 10% potassium bromide, and 5 mg of the following compound (1), and heat at 60'C.
150 cc of an aqueous solution in which 17 g of silver nitrate was dissolved and 150 cc of an aqueous solution in which 13 g of potassium bromide were dissolved.
By simultaneously adding 0 cc over 20 minutes and then simultaneously adding 400 cc of an aqueous solution containing 50 g of nitric acid and 400 cc of an aqueous solution containing 38 g of potassium bromide for 60 minutes, a silver iodide content of 10 mol% and 1.07 μm was obtained. Silver iodobromide emulsion 1 was prepared.

Emulsions 2 to 7 shown in Table 1-1 were prepared by shelling emulsions b-H 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 finger-like structure is one in which a maximum absorption at a high silver iodide content and a maximum absorption at a low silver iodide content are observed by chi-ray diffraction measurement, and there is at least one minimum between them.

Potassium thiocyanate was added instead of compound (1) that was present when preparing emulsion 5 by adding an emulsion e-shell.
Xl0-ff mol/j! Emulsions 8 and 9 were prepared in the same manner except that 1X10-''mol/!

Compound (1) was applied on a cellulose triacetate film support coated with LJIJ primer,
Sample F4101, which is a multilayer color brightening material, was prepared by applying layers having the compositions shown below.

(Photosensitive NH4 composition) The numbers corresponding to each component indicate the coating amount expressed in g/%, and for silver halide, the coating amount is calculated by silver IA. However, for aggravating dyes, The amount of coating per mole of silver halide is shown in moles.

(Sample 101) 1st F! (Hareshi town prevention layer) Black colloidal silver Silver 0.18 Gelatin 0.40 Second layer (middle N) Emulsion H silver 0.09 2.5-Di-L-pencudecylhydroquinone 0.18EX-1
0,07 E B5-2 Gelatin 0.002 0.06 0.08 0.10 α, 10 0.02 1.04 Silver 0.10 Primate 0.15 6.9X10-'1.8X10-' 3, lX10"' 0. 335 0.020 0.030 0.015 0.030 0.060 0.90 4th F! (Second red-glare emulsion layer) Emulsion F Enhanced dye I Sensitizing dye ■ Enhanced dye ■ X-2 X-3 X- 10 J-1 B5-2 Gelatin No. 511 (Third red-glare emulsion layer) Emulsion 1 Enhanced dye I Sensitizing dye ■ Sensitizing dye ■ X-3 10-'2.3X10-' 0.400 o, os.

o,ots O,080 0,040 o,os.

O,060 1,50 Silver 1.50 5.4X10-' 1.4XIO-5 2,4X10-' 0.010 0.080 X-2 B5-1 1 (BS-2 gelatin No. 61ii (intermediate N) X-5 B5-1 gelatin 7th layer (first green emulsion layer) Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Eχ-・6 X-1 X-7 X-8 BS-1 B5-3 0.097 0.22 0.10 1.50 0.080 0.020 0.80 Resentment 0,15 Silver 0.15 3.0X10-' 1.0X10-' 3.8X10-' 0.260 0.040 0.065 0.025 0.100 o, at.

Gelatin 8th layer (second green emulsion layer) Emulsion C Enhancing dye ■ Sensitizing dye ■ Sensitizing dye ■ ) Emulsion sensitizing dye ■ Sensitizing dye ■ Enhanced dye ■ X-13 X-11 029 0.029 0.160 0,008 0.60 i艮 1.60 3.5X10-'8.0XIO-'3.0X10-' 0.015 0.100 0.025 B5-1 B5-2 Gelatin No. 1ON (yellow filter N) Yellow colloidal silver Eχ-5 B5-1 Gelatin 11th layer (first blue emulsion N) Emulsion A Emulsion B Emulsion E 2 blue emulsion layer) Emulsion F Enhancing dye ■ 0.25 0.10 1.50 1 0.05 0.15 0.08 0.50 Primate 0.08 Primate 0.07 Line 0.07 3.5X10- ' 0.721 0.042 0.28 1.10 Root 0.45 2.1X10-' EX-9 EX-10 B5-1 Gelatin 13th layer (3rd blue emulsion N) Emulsion G Sensitizing dye ■ EX -9 B5-1 Gelatin 14th layer (first protective layer) Emulsion H B5-1 Gelatin 15th layer (second protective layer) Polymethyl acrylate particles (diameter approximately t, S μm) 0,154 0,00? 0. 05 0.7 days Gelatin 1.20 In addition to the above ingredients, gelatin hardening agent H-1 and a surfactant were added to each layer.

tM 0.7? 2.2X10-' 0.20 0.07 0.69 ! ! 0.50 0.11 0.17 0.05 1.00 0.54 0.20 EX-1 EX-2 H I EX-3 H EX-4 0■ EX-5 EX-6 EX-10 1;1 EX-12 zlls C1ll.

C, H, OSOρ EX-7 Shil EX-8 EX-9 EX-13 I (L) Shi411? U-4 UV-5 B5-1 Tricresyl phosphate B5-2 Di-n-butyl phthalate aggravating dye V Aggravating dye■ Sensitizing dye■ Sensitizing dye I Aggravating dye■ Aggravating dye■ Aggravating dye■ Proceed as above The prepared sample 101 was cut to 35 m/m, imagewise exposed under standard exposure conditions of rsO400, and then subjected to continuous processing (running processing) using an automatic developing machine using the processing steps and processing solution described below. The running treatment was carried out for 20 consecutive days in 101 strips with a width of 35 m/- for 50 m each day.

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

In addition, an air lacing device was attached to the bleach solution tank of the automatic processor, and fine air was blown into the processing solution for 10 hours a day.

The processing steps are described below.

Process Processing time Processing temperature Replenishment amount Tank capacity Color development 3 minutes 15 seconds 38°C 3 days ml 104
2 Bleach 40 seconds 38°C 4ml
5N fixation 1 minute 38°
C30m1siV.

Stable (1) 20 seconds 38'C37! stable (2)
20 seconds 38°C 3N stable (3) 20 seconds 38°C 35m1 umbrella 31 drying 1 minute 15 seconds 50-70'C The amount of replenishment is stable (3) → stable (2 ) → Stable (1) Tank same flow system was adopted.

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

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriamine 5.0 6.0 Sodium sulfite pentaacetate 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.9 Iodide potassium
1.2m 11 hydroxylamine sulfur 2.
0 2. Add 8-acid 4-(N-ethyl-N4゜75.3 β-hydroxyethylamino)-2-methylaniline sulfate aqueous solution 1.0ffi 1.
Oj! p F (10,0010,05 (bleaching solution) 13-diaminopropanetetraacetic acid ferric ammonium dihydrate 1.3-diaminopropanetetraacetic acid ammonium bromide ammonium nitrate acetic acid (98χ) Add water and H (fixing solution) 1-Hydroxyethythelene-1,1-diphosphonic acid ammonium sulfite ammonia water (28χ) Ammonium thiosulfate mother liquor (g) Replenishment solution (g) 160.0 4.3 200.0 30.0 0 d 1.01 4.2 290.0 6.5 300.0 50.0 0 d 1.0 /! 3.3 Mother liquor (g) Replenisher solution (g) 5.0 6.0 14.0 16.0 3.0 d 330.0m 5,〇- 360,0ai! Aqueous solution (70%-/V) Add water 1.0i p)l 6.7 (stable solution) Mother solution and replenisher common 1, ON 7.4 Formalin (37%) Tri Ethanolamine 5-Chloro-2-methyl-4-isothiapurin-3-one 1.2-pendiisothiazolin-3-one Surfactant IC+Jt+-0 (CHaC11□0) 16III Add ethylene glycol water and H unit (g) 1.2m 2.0 6.0mg 3.0+ag 0.4 1.0 1, ON 5.0~7.0 Next, emulsion l of the first layer among the emulsions used in sample 10/
10 to 10 samples were prepared by replacing the emulsion colors shown in Table 1 to 10, respectively.

Sample 10 was prepared using the treatment solution after the above running treatment.
/ ~ 10 W'f After each treatment without exposure, the amount of residual silver was determined by fluorescent X-ray analysis, and the fixing speed was evaluated. (The processor) also increases the sensitivity of the cyan layer of each photosensitive material by giving wedge exposure and processing nine samples. Incidentally, the sensitivity was expressed as a relative sensitivity as the lowest concentration of sample 10/plus the sensitivity at a concentration of O, 2ioo.

In addition, the RMSll of each sample was determined in the same manner. RMS representing graininess [is cyan #degrees θ,! The concentration of diameter 1
The values were added at 1000 times the standard deviation of the fluctuation in the concentration plate that occurs when scanning with a microdensitometer having a scanning aperture of μm.

In addition, in the above running process, 9/, J-diaminopro, R-tetraacetic acid ferric complex salt and/, 3-diaminoprono-tetraacetic acid t used in the mother liquor and replenisher of the bleaching solution.
Sample 1 was replaced with equimolar amounts of ferric complex salt of ethylenediaminetetraacetic acid and ethylenethiaquintetraacetic acid.
The samples were processed without exposure from 0/10 to 10, and the amount of remaining silver was measured.

(Process @B: Comparison) Furthermore, each sample was exposed to 1OCMS at a color temperature≠roo 0, and then treated with A and Bt, respectively, and the bleaching property t
- According to research, the bleaching process has been completed on all of the workers.
Regarding treatment B, the amount of residual silver of 30 μt/12 or more was 69 for each sample, and the bleaching was not completed.

The results without exposure are shown in 't-Table/-J.

As is clear from the table, samples io3 to io10 containing the silver halide grains of the present invention are
Even in treatment a) with a bleach solution using j-DPTA-Fei, the fixing speed is higher than in treatment B (treatment with a bleach solution using EDT/Fei). Sample 10/, 10 pieces, 104, 10
Considering that the fixation of BiA is much worse in P than BiBK, this result is remarkable, and the fact that the sensitivity and graininess have also been improved at the same time may be an unexpected effect. It is.

From the above, bleaching and fixing? It can be seen that the processing of the photographic material containing the emulsion of the present invention was carried out satisfactorily.

Example-2 Take 300 g of emulsion e, add 850 cc of distilled water, 30 cc of 10% potassium bromide, 2 mg of the following compound (2), and 15 mg of the following compound (3,), heat to 70°C, and stir. 300cc of an aqueous solution of 33g of Ti nitric acid dissolved in
By simultaneously adding 320 cc of an aqueous solution containing 100 g of silver nitrate and 860 cc of an aqueous solution containing 75 g of potassium bromide for 60 minutes, silver gold iodide was dissolved. Silver iodobromide emulsion 11 with ff114 mol % and 1.03 μm was prepared.

Compound 'l''J (2) Ishiharamono (3) Emulsion 12 was prepared in the same manner as when Emulsion 11 was prepared by changing the ratio of potassium bromide for adding a shell to Emulsion e as shown in Table 2-1. ~14 were adjusted.

Next, 5M emulsion 1 of sample 101 prepared in Example 1
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 photosensitive material containing the silver halide grains of the present invention has no desilvering property even after being treated with a bleaching solution containing 1,3-DPTA-Fe and then subjected to a treatment with fixing ability. It can be seen that the film is excellent in sensitivity and graininess.

Example-3 In Example-1, instead of sample 10/, sample 10≠
A coating treatment similar to treatment A of Example 7 was carried out using gold.

In addition, /, /-hydroxyethylidene-/l in the fixer
/-Diphosphone eR was completely removed, or the chelating agent shown in Table 3 was replaced, and the same running treatment as above was carried out.

At the end of each coating/coating, the amount of residual silver in the unformed portion and g-primed portion (1tocMs exposure at color temperature aroo°) of Sample 10 was measured.

Furthermore, after each run, each fixer solution was placed in a beaker of the same size (opening area/Ocws 2) and aged in JI'C for the number of days until precipitation occurs (sulfurization).

The results are shown in Table JiC.

As can be seen from Table 3, by including a chelating agent in the fixing solution, a constant N
The stability of the t-liquid can be greatly improved. In particular, it can be seen that chelating agents such as organic phosphonic acids are excellent in preventing sulfurization without reducing desilvering properties.

(Effect of the invention) By implementing the present invention, /, J-DPTA-Fe
Desilvering properties, sensitivity, and graininess were improved even after treatment with a bleaching solution containing 'T-containing bleaching solution and a treatment with fixing ability r.

Claims (1)

[Claims] A method in which a silver halide color photographic light-sensitive material is processed with a bleaching solution containing a ferric complex salt of 1,3-diaminopropanetetraacetic acid, and then processed with a processing solution having a fixing ability, in which at least one emulsion of the light-sensitive material is processed. The layer consists of chemically sensitized silver halide grains, and the silver halide grains contain 30 to
Silver iodobromide or silver iodochlorobromide containing 45 mol% of silver iodide exists with a clear phase structure, and the outermost layer of the silver halide grains contains 8 mol% or less of silver iodide. 1. A method for processing a silver halide color photographic light-sensitive material, comprising a silver halide containing.