JPH01221747A - Processing of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To perform desilvering of a highly sensitive color negative sensitive material having high picture quality rapidly by incorporating a ferric complex salt of a specified compd. and a ferric complex salt of 1,3-diaminopropane tetraacetic acid into a treating soln. having bleaching effect as a bleaching agent. CONSTITUTION:At least one kind of ferric complex salt of (A-1) ethylenediamine tetraacetic acid, (A-2) diethylenetriamine pentaacetic acid, (A-3) cyclo- hexanediamine tetraacetic acid, and (A-4) 1,2-propylenediamine tetraacetic acid, is incorporated as a bleaching agent together with a ferric complex salt of 1,3-diaminopropane tetraacetic acid into a treating soln. having bleaching effect in <=3:1 proportion of the former to the latter, by molar ratio. Thus, a highly sensitive color negative photographic sensitive material is processed rapidly.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for processing color photosensitive materials, and particularly to a method for rapidly processing color negative photosensitive materials for high-sensitivity photography.

(Prior Art) In recent years, with advances in the technology of photographic photosensitive materials, highly sensitive photosensitive materials have been released one after another. Shooting areas using high-sensitivity photosensitive materials, such as high-speed photography using a strobe in a dark room, high-speed shutter photography using a telephoto lens for sports photography, and photography that requires long exposures such as astronomical photography. The expansion of technology is an eternal theme for this industry.

Many efforts have been made to increase the sensitivity of photosensitive materials. Numerous studies have been conducted on formation methods such as the shape and composition of silver halide grains, chemical sensitization, spectral sensitization, additives, coupler structures, etc., and several Yoshihiko inventions have been made. However, the demands for highly sensitive photosensitive materials are greater than the advances in technology, and unfortunately these methods alone have not been sufficient. Therefore, it has become common practice in the industry to increase the size of silver halide emulsion grains in combination with other techniques to produce high-sensitivity light-sensitive materials in order to increase sensitivity.

Increasing the size of the silver halide emulsion grains increases the sensitivity to a certain extent, but as long as the silver halide content is kept constant, the number of silver halide emulsion grains inevitably decreases, and therefore the development starting point increases. The major disadvantage is that the number is reduced and the graininess is greatly impaired. In order to compensate for this drawback, British Patent No. P, 2J, 0μj, Special Publication Akihiroter/! A photographic material having two or more emulsion layers having the same color sensitivity and different sensitivities, that is, different silver halide grain sizes, as described in Geta J Publication, JP-A-Sho! j-1
2μ! A method using a fast-reacting coupler as described in US Pat. No. 3, λ27. ! ! μ, U.S. Patent No. 3. t32゜Hiroshi 3! So-called DIR couplers, methods using DIR compounds, as described in British Patent No. 2, or 3. A method using a coupler that produces a mobile dye as described in No. a≠O, JP-A No. 6
A method using silver halide having a high average silver iodide content is known, as described in Japanese Patent No. 0-12111143.

Although each of these methods is an excellent invention with great effects, they are not sufficient technologies to meet the great demand for high sensitivity and high image quality. Therefore, in order to increase the grain size of silver halide emulsion grains and at the same time increase the number of development initiation points even slightly, high-sensitivity color negative light-sensitive materials are required to have various performances such as desilvering properties during bleach-fixing processing. Designs have been made in which the content of silver halide emulsion grains is increased within a range.

On the other hand, it has been known to change the positions of the layers of a multilayer color negative photosensitive material in order to achieve high sensitivity or to achieve both high sensitivity and high image quality. For example, US Patent No. 41. /III,t
Number 7, number 4! , 7.2F.

No. 11, No. ≠, /It, No. 0/, British Patent No. 1,! 1
,0. RI Aj No., U.S. Patent No. 3, IT B.

oii, 1I, 267, Ko6da, No. 1, /7j,
lA7ri issue, No. 1, /! 7. ri No. 17, No. ≠.

its, Ko3 No. 2, British Patent No. 2, i3t, No. 26λ, JP-A-Sho! Tar/77.112, British Patent No. 2. /J
No. 7,372, Japanese Patent Application Publication No. 7,372.

No. 351, Tokukai Sho! ter/rO, jjt issue, jter 20
It is described in μ, oJr issue, etc.

These technologies were developed by the aforementioned Tokkai Sho! As described in Patent No. 77, No. 112, the emulsion layer closer to the support is affected by the emulsion layer farther away, resulting in loss of exposure and delay in development, resulting in low sensitivity, Since it is known that the tone becomes soft, it is usually preferable to move the most sensitive emulsion layer of each of the red-sensitive emulsion layer and/or green-sensitive emulsion layer, which are located on the side closer to the support, as far away from the support as possible. The aim is to achieve high sensitivity by positioning the

On the other hand, high-sensitivity photographic materials such as those described above are often used in the news field, and there is a particular need for speedy processing. In conventional processing processes, desilvering and fixing processes account for a large proportion;
In order to speed up processing, it was necessary to shorten the bleaching and fixing steps. For this reason, the development of bleaching agents with large bleaching blades has continued.

Conventionally, bleaching methods using ferric ion complex salts (for example, aminopolycarboxylic acid ferric ion complex salts, etc., especially ethylenediaminetetraacetic acid iron (III) complex salts) as the main bleaching agent have been mainly used.

However, since ferric ion complex salts have a relatively small oxidizing power and a bleaching blade is insufficient, 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 bleaching effect may be insufficient and desilvering may be insufficient. It has the disadvantage of requiring a long time.

In color light-sensitive materials, sensitizing dyes are generally used for the purpose of color sensitization. In particular, when using tabular grains with high silver or high ast ratio to achieve high sensitivity, the sensitizing dye adsorbed on the silver halide surface inhibits the bleaching of the silver produced during development of the silver halide. A problem arises.

Persulfates are known as bleaching agents other than ferric ion complex salts, and persulfates are usually used as a bleach solution by adding chloride. 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 is desired to increase the bleaching capacity of.

In contrast, Research Disclosure 1t02
J (/?1rll-year μ month), JP-A-Sho-JjO
3! No. 3, etc., describe processing methods that use two or more of various ferric aminopolycarboxylic acid complex salts in combination, but these methods have not yet achieved a sufficient bleaching promotion effect. .

(Problems to be Solved by the Invention) By the way, it has been found that when the positions of the layers of a multilayer color negative light-sensitive material are changed in order to increase the sensitivity, the following disadvantages occur. By locating the most sensitive emulsion layer far from the support, the lower sensitivity emulsion layer located closer to the support will experience greater exposure loss and development delays. However, if the grain size and content of silver halide grains in a low-sensitivity emulsion layer are increased, it becomes impossible to maintain the gradation and maximum density required of a light-sensitive material. Also, by changing the position of the layers, there is an increase in the number of interlayers that weaken the emulsion layers with different color sensitivities, and the film thickness increases, causing desilvering and deterioration of fixing properties. Rapid processing aptitude is being attacked there.

The present inventors found that among many ferric aminopolycarboxylic acid complex salts, using a bleaching solution containing a ferric complex salt of l,3-diaminoprono-tetraacetic acid rapidly desilvered silver halide photographic light-sensitive materials. I found out that it can be done. However, when processing with the above-mentioned bleaching solution, there has been a problem in that significant staining occurs and photographic properties are significantly impaired.

Therefore, the first object of the present invention is to provide a processing method for quickly desilvering a high-quality, high-sensitivity color negative light-sensitive material. A second object of the present invention is to provide a desilvering method that hardly causes staining and does not adversely affect photographic properties in the processing of high-quality, high-sensitivity color negative light-sensitive materials.

(Means for Solving the Problems) The object of the present invention is to have blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, and at least seven of these layers have λ or more layers having different sensitivities from each other. The two or more layers are arranged in order from the low-sensitivity layer to the high-sensitivity layer when viewed from the support side, and there is at least a silver halide emulsion layer having different color sensitivity between the low-sensitivity layer and the high-sensitivity layer. In a method in which a color photosensitive material is color-developed and then treated with a processing solution having bleaching ability, the processing solution having bleaching ability is a ferrous iron compound selected from the following compound group (A) as a bleaching agent. A silver halide color photographic light-sensitive material comprising at least one complex salt and a ferric complex salt of l,3-diaminopronotetraacetic acid in a molar ratio of 3 or less to the latter. Achieved through processing methods.

Compound Group (A) A-/Ethylenediamineacetic acid A-J Diethylenetriaminepentaacetic acid A-j Cyclohexanediaminetetraacetic acid A-9.2-Propylenediaminetetraacetic acid The present invention will be described in detail below.

The photosensitive material of the present invention is a color photosensitive material for photographing with high image quality and high sensitivity, and has a specific photographic sensitivity of 3-0 or more, and the total amount of silver contained in the photosensitive material is J,0-/3. .0
g7m2 is preferred. When the specific photographic sensitivity is 320 or less, it is not necessary to adopt the layer structure as in the present invention. Also, the amount of silver is /j
g/m2 or more, it is difficult to shorten the desilvering process even if the bleaching agent of the present invention is used.

For the definition and measurement method of specific photographic sensitivity, please refer to the patent application 6/-2 Hiroshi! ! 7! It is described on page I7 from issue No.

Several methods are known for analyzing the silver content of photosensitive materials,9 and any method may be used. For example, elemental analysis using fluorescent X-rays is convenient.

The specific photographic sensitivity of the color negative light-sensitive material of the present invention is 320
In the case of relatively low sensitivity, the combination of the arrangement order of the layers of the multilayer color negative light-sensitive material of the present invention and the amount of silver contained is very effective. The Fi value is preferably 00 or higher, more preferably 0 or higher.

The color negative light-sensitive material of the present invention is composed of two or more emulsion layers, each having a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer, each having a different sensitivity. At least one emulsion layer having a different color sensitivity from the highest sensitivity layer closest to the support is located between the sensitive emulsion layer, the layer closest to the support among the most sensitive blue-sensitive emulsion layers, and the support. There is a need to.

Further, in order to further improve the graininess, it is more preferable to configure each color-sensitive calendar with a three-layer structure, and this technique is described in Japanese Patent Publication No. 15,495/1983.

There may be a non-light sensitive layer between each light sensitive emulsion layer,
This non-light-sensitive layer may exist between two or more emulsion layers having the same color sensitivity, or if there are adjacent light-sensitive emulsion layers with different color sensitivities, there may be a non-light-sensitive layer between them. Scavenger substances may also be included in such non-photosensitive interlayers, which are preferably provided. Also, JP-A-59
It is also preferable to provide a non-light-sensitive reflective layer under the light-sensitive emulsion layer to improve sensitivity, as described in Japanese Patent No. 160,135. No, but usually contains a yellow filter layer.

Specific examples of the arrangement order of the light-sensitive emulsion layers in the color negative light-sensitive material of the present invention are listed below, but are not limited to these. Note that the non-light-sensitive layers are omitted here, but are similar to those described above. It may exist in various positions.

(1) Support, low sensitivity red sensitive emulsion layer (hereinafter RL), low sensitivity green sensitive emulsion M (hereinafter referred to as GL), low sensitivity blue sensitive emulsion layer (hereinafter BL), high sensitivity red sensitive pore layer (RH) , high-sensitivity green-sensitive emulsion M (GH), high-sensitivity blue-sensitive emulsion ff (BH
).

(2) Support, RL, GL, BL, GH, RH,
BH (3) Support, RL, GL, BL, RH1 intermediate green-sensitive emulsion layer (GM), GH, BH (4) Support, RL, GL, GM, BL, R
H, GM, BH (5) support, RL, medium-opening red-sensitive emulsion layer (hereinafter referred to as RM).

GL, GM, BL, medium-opening blue-sensitive emulsion M (hereinafter referred to as BN)
, R.H.

GH, BH (6) Support, RL, GL, BL, RM, RH,
GM, GH, BM.

(7) Support, RL, GL, RH, G)1. BL
, BH (8) support, GL, RL, RH, GH,
BL, BH (9) support, RL, GL%RH1G
M, G) I, BL, B) l (10) support, R
L, GL, GH, RH, BL, BH The photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention contains silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver halide. Any silver chloride may be used, but the preferred silver halide is 3
It is silver iodobromide containing 0 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing from 2 mol % to 20 mol % silver iodide. In addition, in order to achieve both high sensitivity and high image quality, the average silver iodide content of silver halide in all emulsion layers must be 8 mol% or more, as described in JP-A-60-128,443. It is known that graininess is significantly improved by increasing the average silver iodide content of silver halide, but if the silver iodide content exceeds a certain level, the development speed will be delayed, There are drawbacks such as desilvering and slow fixing speed. However, in the present invention, although this is probably due to the small amount of silver contained, even if the silver iodide content is increased, these drawbacks are unlikely to become a problem, which is very preferable.

The silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention have a core consisting essentially of silver iodobromide containing 5 mol % or more of silver iodide.

It is preferable to have a double structure consisting of a shell covering the core and consisting essentially of silver iodobromide or silver bromide, the silver iodide content of which is lower than the silver iodide content of the core.
The silver iodide content of the core is more preferably 10 mol% or more, most preferably 20 mol% or more and 44 mol% or less, and the shell silver iodide content is 5 mol% or less. preferable.

The core may contain silver iodide uniformly, or may consist of multiple phases with different silver iodide contents. ! In the latter case, the silver iodide content of the phase with the highest silver iodide content is 5 mol% or more, more preferably 1
0 mol% or more, and the silver iodide content of the shell is lower than that of the highest silver iodide content phase of the core, and "consisting essentially of silver iodobromide" means It mainly consists of silver iodobromide, but it means that it may also contain up to about 1 mol % of other components.

In a further preferred embodiment of the silver halide grains used in the photographic emulsion layer of the silver halide photographic light-sensitive material of the present invention, silver halide grains having a diffraction angle (2θ) in the range of 38 to 42@ When we obtain the diffraction intensity vs. diffraction angle curve for the (220) plane, we find that there are two diffraction maxima, a diffraction peak corresponding to the core part and a peak corresponding to the shell part, and one minimum between them. In addition, the particles have a structure such that the diffraction intensity corresponding to the core portion is 1710 to 3/1 of that of the seal portion. Particularly preferably, the diffraction intensity ratio is 115 to 311, more preferably 1/3 to 3/1.

Two like this! ! The structuring makes it possible to use a high-iodine silver iodobromide emulsion without causing a delay in development speed, and it is possible to achieve a light-sensitive material with excellent graininess even with a small amount of coated silver.

The average grain size of the silver halide grains in a photographic emulsion (grain diameter for spherical or near-spherical grains).

In the case of cubic particles, the principal is the particle size, and the projected area is expressed as an average.) is not particularly important, but 0.05
The average size of silver halide grains in each emulsion layer having the highest sensitivity is preferably 0.5 μm or more and 10 μm or less.
The range is preferably 0.6 μm or more, 2.
More preferably, it is 5 μm or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have a regular crystalline structure such as a cube or a hexagonal, or may have a spherical or hexagonal shape.
They may have irregular crystal bodies, such as plate-like particles, or may be composites of these crystal forms.

Further, it is preferable to use tabular grains having a high color sensitization efficiency using a sensitizing dye and having an aspect ratio of 5 or more.

Tabular grains are produced by Cutoff, Photographic Science and Engineering.

Photograp)+ic 5science and
Engineering), Volume 14, 248-2
57 pages (1970); U.S. Patent No. 4,434,226
No. 4,414,310, No. 4,433,048, No. 4,439,520 and British Patent No. 2,112
, No. 157, etc., it can be easily prepared by olfaction.

The photographic emulsion used in the present invention is P, Glafkide.
Chigis at Physique Photo
ographique (published by Paul Monte1,
(1967), Photo by G. F. Duffin.
graphic emulsion chemist
ry (The Focal Press, 1966
), V, L, Zelik++ an at al.
AuthorMaking and Coating Photo
Graphic Emulsion (The Foca
1 Press, 1964). That is, any of the acid method, neutral method, ammonia method, etc. may be used.

Further, as a method of reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). PA in the liquid phase in which silver halide is produced as a form of simultaneous mixing method
A method of keeping & constant, that is, the so-called chondral
A double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion used in the present invention has crystals defined by the Miller index (n n 1) (n≧2, n is a natural number) on the outer surface as described in Kokai Technical Report No. 86-9598. Silver halide grains having faces are preferably used.

Also preferably used is a silver halide emulsion having a hollow conductive portion from the surface toward the inside, as described in JP-A-61-75337. Such a silver halide emulsion having a large specific surface area is more effective when combined with the present invention because it is easier to achieve sensitivity than an emulsion having the same volume, especially when color sensitized.

Also, JP-A-57-133540, JP-A No. 5B-1085
Composite particles prepared by epitaxially growing a silver salt having a specific composition on a host particle as described in No. 26 or No. 59-162540 can be preferably used in the present invention. Since such particles exhibit photographic properties with high sensitivity and high contrast, they are preferably used in combination with the present invention.

Also, JP-A-61-14630 and JP-A-60-122
The silver halide emulsion grown in the presence of tetrazaindene as described in No. 935 has a high silver iodide content and excellent monodispersity, so it exhibits high sensitivity and excellent graininess. It is preferably used as a silver halide emulsion.

Also, as shown in Japanese Patent Application Laid-Open No. 58-126526,
Silver halide emulsions that have been subjected to total sulfur sensitization or gold selenium sensitization in the presence of a nitrogen-containing heterocyclic compound are preferred as silver halide emulsions used in the present invention because they exhibit low fog and high sensitivity. I can stay on the moon.

Also, JP-A-59-149345 or JP-A No. 59-1
It was described in No. 49344. Slightly rounded cubic or tetradecahedral crystals are preferred as silver halide emulsions used in the present invention because they provide high sensitivity performance.

In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt.

Iridium salt or its complex salt, rhodium salt or its complex salt,
Iron salts or complex salts thereof may also be present.

Among these, silver halide emulsions in which grains are formed in the presence of iridium have high sensitivity (Japanese Patent Publication No. 43-49
No. 35, Japanese Patent Publication No. 45-32738) is particularly preferred as the silver halide emulsion used in the present invention.

After the emulsion is precipitated or physically ripened, soluble salts are usually removed (1).As a means for this purpose (2), the long-known Tardel water washing method, which is carried out by gelatinizing gelatin, may be used. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (e.g. polystyrene sulfonic acid), or gelatin derivatives (e.g. aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) A sedimentation method (flocculation) may also be used.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, 1 e.g. H, Fr1eser9"D
ieGrundlagendar PhotoHrap
hischen Prozessa witSilbe
r-halogenidan'' (Akademisch
eVerlagsgessllchaft, 196g
) The method described on pages 675 to 734 can be used.

Namely, sulfur sensitization using sulfur-containing compounds that react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, Reduction sensitization using noble metal compounds (e.g., total complex salts, P
(complex salts of metals in group II of the periodic table, such as t, Ir, and Pd)
A noble metal sensitization method using a sensitizer can be used alone or in combination.

Furthermore, it is preferable to use a selenium sensitization method using a selenium-containing compound that can react with active gelatin or silver in combination with other sensitization methods because a highly sensitive emulsion can be obtained.This technique is described in U.S. Pat. 574, No. 944, No. 1,60
No. 2,592, No. 1,623,499, Special Publication No. 1972-
No. 38408, Japanese Patent Publication No. 5-22090, Japanese Patent Publication No. 59-1983
-180536, U.S. Patent No. 4,565,778,
JP-A-59-185329, JP-A-60-15004
It is described in issue 6 etc.

The photographic emulsion used in the present invention is spectrally sensitized with methine dyes and others as necessary6. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine pigment.

Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes 1w1-cyanine dyes and dyes belonging to complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. i.e. vilorin nucleus.

Oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and aromatic in these nuclei A nucleus of fused hydrocarbon rings.

Namely, indolenine nucleus, benzindolenine nucleus.

Indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolindine-
2,4-dione nucleus, thiazolidine-2゜4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus or a thiobarbic acid nucleus can be applied.

Useful sensitizing dyes include, for example, German Patent No. 929.0
No. 80, U.S. Patent No. 2,231,658, U.S. Patent No. 2,493
, No. 748.

No. 2,503,776, No. 2,519,001, No. 2,912,329, No. 3,656,959, No. 3
, No. 672,897, No. 3,694,217.

No. 4,025,349, No. 4,046,572, British Patent No. 1.242,588, Japanese Patent Publication No. 44-14030
No. 52-24844.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of one-strong color sensitization.

Typical examples are U.S. Pat. Nos. 2,688,545 and 2,9
No. 77.229, No. 3,397,060, No. 3,52
No. 2,052.

No. 3,527,641, No. 3,617,293, No. 3,628,964.

No. 3,666.480, No. 3,672,898, No. 3,679,428.

No. 3,703,377, No. 3,769,301, No. 3,814,609, No. 3,837,862, No. 4
, No. 026,707, British Patent No. 1.344,281,
It is described in Japanese Patent Publications No. 1,507,803, Japanese Patent Publication No. 43-4936, Japanese Patent Publication No. 53-12375, and Japanese Patent Application Publication No. 110618/1982 and Japanese Patent Publication No. 52-109925.

Along with sensitizing dyes, dyes that do not themselves have spectral sensitizing effects or substances that do not substantially absorb visible light, 1
For example, the emulsion may contain a substance exhibiting supersensitization.
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups) For example, U.S. Pat.
No. 21), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), cadmium salts.

US Pat. No. 3, which may contain azaindene compounds, etc.
No. 615,613, No. 3,615,641, No. 3,6
The combinations described in Nos. 17,295 and 3,635,721 are particularly useful.

A color coupler is added to the photographic emulsion layer used in the present invention as a dye image-forming substance.

Generally, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. For example, an infrared-sensitive layer may be combined for use in pseudo-color photography or semiconductor laser exposure.

Also, U.S. Patent No. 3,497,350 or Japanese Patent Application Publication No. 5
As described in No. 9-214853, it is also possible to use a method in which the color sensitivity of the emulsion layer and a color image-forming coupler are appropriately combined and this layer is provided at the farthest position from the support.

For example, magenta couplers include 5-pyrazolone couplers and pyrazolobenzimidazole couplers.

There are cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc.
As a cyan coupler.

These include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible ones that have a hydrophobic group called a ballast group in the molecule, or are polymerized. Couplers may have either 4-equivalent or 2-equivalent to silver ions, but In order to reduce the silver content contained in the photosensitive material, it is preferable to use a two-equivalent coupler that has higher silver utilization efficiency.
In particular, it is preferable that the most sensitive emulsion layer of each of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer M contains a 2-equivalent coupler. It is more preferable that all of the most sensitive emulsion layers contain a two-equivalent coupler.

Further, as the coupler used in the present invention, a so-called fast reaction coupler having high coupling reactivity can be used.

The coupling reactivity of couplers is determined by the color image obtained by mixing two types of couplers M and N, which give different dyes that can be clearly separated from each other, and adding the mixture to an emulsion for color development. It can be determined as a relative value by measuring the amount of pigment.

The maximum concentration of coupler M (DH)wax, .In the middle stage, the color development of concentration ON is expressed, and that of coupler N is expressed as (DN)+iax, respectively.If the color development of DN is expressed as the ratio of the reaction activity of the double force puller. R/RN is expressed by the following formula.

That is, the coupling activity ratio RM/RN is determined from the slope of a straight line obtained by plotting several plots obtained by subjecting an emulsion containing a mixed coupler to light exposure at various stages and developing one color.

Here, by using a fixed coupler N and determining the value of RM/RN for various couplers as described above, the relative coupling reactivity can be determined.

For example, the following coupler may be used as the above coupler N to find it.

The RM/RN value determined using the above-mentioned coupler N is used as the magenta coupler for the cyan coupler and the fast reaction coupler used in the present invention for the yellow coupler.

It is preferable that the cyan coupler has a value of 7.1 or more, the magenta coupler has a value of 2.5 or more, and the yellow coupler has a value of more than 1.

In the present invention, the red-sensitive emulsion layer contains at least one naphthol coupler. Naphthol couplers are conventionally known couplers, but in short-time processing as in the present invention, it has been found that they have high color density and little staining, as shown in the Examples.

The naphthol coupler of the present invention has the following general formula (1), where % is an aliphatic group having 1 to 30 carbon atoms, t-JO
aromatic groups, and heterocyclic groups having a carbon number of J-J O. R3 and R4 may each be a hydrogen atom.

R2 represents a group (including an atom, the same applies hereinafter) that can be substituted on the naphthol ring, and typical examples include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyan group, an aliphatic group, an aromatic group, Heterocyclic group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, etc., and the number of carbon atoms contained in R2 is 0-JO,
The group having a hydrogen atom may be further substituted with these substituents. An example of a bicyclic 82 in which m = J is a dioxymethylene group. n is O or /.

X represents )0, >S or R,N, and R6 represents a hydrogen atom or a heptavalent organic group.The heptavalent organic group is preferably R7 (Ya) represented by the following general formula (III). l-(
m) Here, Ya represents -NH,':;co or -S02, l represents zero or /, R7 is a hydrogen atom, carbon number/-J (7 aliphatic group, carbon number 6- 30 aromatic groups, C2-C30 heterocyclic groups, -0R3, R3 and R4 represent the groups defined above and may be present.

In Rxt or R7, -NR3R, R3 and R
4 may be bonded to each other to form a nitrogen-containing heterocycle (morpholine ring, biyridine ring, pyrrolidine ring, etc.).

Yl represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Typical examples of coupling-off groups include halogen atom, -0R8, -8R8, -QC
R8, -NHCOR8, -NHCOS R8, 6-30
aromatic azo group, a heterocyclic group having carbon number/-30 and connected to the coupling active position of the coupler with a nitrogen atom (succinimide group, phthalimide group, l-hydantoinyl group,
l-pyrazolyl group, cobenzotriazolyl group, etc.). Here R8 is carbon number/-30
aliphatic group, aromatic group having 4 to 30 carbon atoms, or 2 carbon atoms
- Indicates a heterocyclic group of JO.

In the present invention, the aliphatic group may be saturated or unsubstituted, substituted or unsubstituted, linear, branched, or cyclic,
Typical examples include methyl group, ethyl group, butyl group, cyclohexyl group, allyl group, pronoergyl group, methoxyethyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl group, Heptafluoropropyl group, dodecyloxypropyl group, λ, ≠-di-t
ert-amylphenoxyprobyl group, co,≠-dit
e, r t-amylphenoxydityl group, etc. are included.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples include phenyl group, tolyl group, -1-tetradecyloxyphenyl group, -tafluorophenyl group,
Kokuro-! -)'decyloxycarbonylphenyl group, ≠-chlorophenyl group, ≠-cyanophenyl group, ≠
-Hydroxyphenyl group, etc.

In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples include copyridyl group, derpyridyl group,
It includes a caufuryl group, a μm thienyl group, a quinolinyl group, and a quinolinyl group.

When the aliphatic/aromatic or heterocyclic group has seven or more substituents, the substituents may further have one or more substituents.

Preferred examples of substituents in the present invention will be explained below. R
1 is preferably -CONR3R, and particularly preferably one of R3 and R4 is a hydrogen atom.

Specific examples include carbamoyl group, ethylcarbamoyl group,
Morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, tecyloxypropylcarpamoyl group, dodecyloxypropylcarbamoyl group,
Ko, Hiro-G tart-amylphenoxypropylcarbamoyl group, 2°1! -di-tert-amylphenoxybutylcarpamoyl group and the like.

Regarding R2 and m, it is most preferable that m=θ, that is, unsubstituted, and relatively preferable substituents for R2 include a halogen atom, an aliphatic group, a carbonamide group, and a sulfonamide group.

Preferred is XFiR6N'4, where R6 is -
COR7 (formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, -</tafluorobenzoyl group, p-chlorobenzoyl group, etc.)
, -COOR3 (methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group), -8O2R7 (methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group, hexadecanesulfonyl group) group, benzenesulfonyl group, toluenesulfonyl group, p-chlorobenzenesulfonyl group)
, -CONR3R, (N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-dibutylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, dacyanophenylcarpamoyl group, 3
．． ≠-dichlorophenylcarbamoyl group, goomethanesulfonylphenylcarbamoyl group, etc.), -8O2NR
3R4 (N, N-dimethylsulfamoyl group, N, N-
diethylsulfamoyl group, N,N-dipropylsulfamoyl group, etc.). Particularly preferable X is〉N
COR and ;NSO2R7. Here 83,
It has the same meaning as before R4Fi.

Preferred examples of Yl include a hydrogen atom, a halogen atom (for example, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, etc.),
Aliphatic oxy groups (e.g. λ-hydroxyethoxy group, λ
-chloroethoxy group, carboxymethyloxy group, l-
Carboxyethoxy group, λ-methanesulfonylethoxy group, 3-carboxypropyloxy group, comethoxyethoxycarpamoylmethyloxy group, l-carmexytridecyloxy group 2.2-(/-carboxytridecylthio)ethyloxy group, -monocarboxymethylthioethyloxy group, co-methanesulfonamide ethyloxy group, etc.), aromatic oxy groups (e.g. ≠-acetamidophenoxy group, co-acetamidophenoxy group, ≠-(3-carboxypronocarboxamide) phenoxy group, ≠-mesylphenoxy group, etc.), and heterocyclic thio groups (e.g. l-phenyltetrazol-!-ylthio group, l-ethyltetrazol-!-ylthio group, l-phenylimidazole-coylthio group, goupyridylthio group, etc.) It is.

The coupler represented by general formula (1) has substituents R1, R2
, X or Yl may form a dimer or a multimer of more than 1, which is bonded to each other via a divalent or covalent or higher valent group. In this case, the carbon number range shown in each of the above-mentioned substituents may be outside the specified range.

General formula [! When the coupler represented by ] forms a multimer, a typical example is a single or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue. In this case, the multimer contains the repeating unit of the general formula [■], and the cyan coloring repeating unit represented by the formula [■] may be contained in the multimer with /m or more, and as a copolymer component. It may also be a copolymer containing one or more non-color-forming ethylene polymers.

In the formula, R9 represents a hydrogen atom, an alkyl group having l-μ carbon atoms, or a chlorine atom, A represents -CONH-1-COO- or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene group. group, phenylene group or aralkylene group, Z is 100NH-1-NHCON
H-1-NHCOO-1-NHCO-1-0CONH-
1-NH-1-COO-1-OCO-1-CO-1-O
-2-SO2-1-NH8O2- or -802NH-
represents. a, b, c represent O or /. Q represents a cyan coupler residue from which a hydrogen atom other than the hydrogen atom of the hydroxyl group at position 97 has been removed from the compound represented by the general formula (1),
Preferably the general formula [! ] In the compound, the substituent R1,
Indicates a cyan coupler residue in which one hydrogen atom has been removed from R2, X or Yl.

As the multimer, a copolymer of a cyan color-forming monomer that provides a coupler unit of the general formula [■] and a non-color-forming ethylene-like monomer shown below is preferred.

Examples of non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid,
α-chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-
butylacrylamide, diacetone acrylamide, methylene bisacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butylacrylate, t-butylacrylate), 1ao-butylacrylate, coethylhexyl acrylate,
n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic vinyls Compounds (e.g. styrene and its derivatives such as vinyltoluene, cyhinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic esters, N
-vinyl-copyrrolidone, N-vinylpyridine, and co-vinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. The non-color-forming ethylene-like monomers used here may be used in combination. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to formula [■] above depends on the physical properties and/or chemical properties of the copolymer to be formed. properties, such as solubility, compatibility with the binder of the photographic colloid composition, such as gelatin, its flexibility,
It can be selected so that thermal stability etc. are favorably influenced.

A cyan polymer coupler used in the present invention (a lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the formula [■] above) is dissolved in an organic solvent and added to an aqueous gelatin solution. It may be made by emulsifying and dispersing it in the form of latex, or it may be made directly by emulsion polymerization.

A method of emulsifying and dispersing a lipophilic polymer coupler in an aqueous gelatin solution in the form of latex is described in US Patent No. 3. μ
si, rJO, U.S. Patent No. ≠ for emulsion polymerization,
The method described in Oro, No. 277, No. 3, No. 370, No. 52 can be used.

Examples of cyan couplers according to the present invention are shown below (C
-i) Shown below.

(C-/) (C-2) (C-j) (C-da) (C-z) (C-4) (C-7) (cr) (C-ta) (C-10) (C-/l) (C-tko) 12H25 (C-/3) (C-ip) i C4Mg (JUNki Rishi M2LJi25
L;n2u(Jun(C-/1) (C-t6) (C-/7) C12H25 (C-/I) (C-/ri) C12H25 (C-JO) (C-co/) (C- λko) (C-23) (C-2g) (C-2j) (C-kot) (C-27) H2 (=C-kot) (C-2ri) (C-3o) (C-3/) (C-32) x:y=70:30 (molar ratio) (C-33) x:y=jO:jl (molar ratio) (C-3μ) (C-Jj) Present invention The naphthol coupler can be used in combination with other known cyan couplers, but the λO of all cyan couplers
Must contain more than molch. The effect of the present invention is not exhibited below -0 molti.

As the magenta coupler, pyrazoloazole type magenta couplers are preferred from the viewpoint of hue.

In particular, since there is little sub-absorption in the blue light absorption band, colored couplers can be reduced, which is particularly advantageous in the high-sensitivity photosensitive material of the present invention. Pyrazoloazole type couplers are
It may be the entire amount of magenta pigment-forming component or other!
- May be used in combination with pyrazolone type couplers.

(M-/) (M-'L) (M-3) .

(M-堡) (M-total) (M-6) (Satsu-7) (M-t) (M-7) (M-tρ) /′ ,-・／ ／′＞′ /-′ / (kl-//) (M-73) (kL-7q) z/y-50150 (weight (M-1da) x/y Tsu 5015G (weight) (M-/4) (5,9) (8,2) difference.

(2-19) Example of yellow coupler (Part 3) In the present invention, such a fast-reacting coupler is preferably added at least to the unit emulsion layer with the highest sensitivity among each color-sensitive layer. There is no particular restriction on the amount of dicyanide fast-reacting coupler o, oor per mole of silver.
~0.11 magenta fast reaction coupler o, oot-o,
i, yellow fast-reacting coupler o,ooz to o,i are preferred.

In addition, the present invention utilizes paragraphs 1 and 3 through 3 of U.S. Pat.
It is preferable to use a diffusion-resistant coupler in which the generated dye has an appropriate diffusivity, as specified in No. IO3, etc., to improve sensitivity and graininess by improving covering power. These couplers are contained in at least seven of the highly sensitive blue, green and red sensitive layers, and preferably in two or more of the highly sensitive layers. Among the couplers used in the high-speed layer, 10 to 100% of the couplers can be couplers in which the resulting dye has moderate diffusivity, and the others can be couplers that form substantially non-diffusible dyes. These suitably diffusible dye-forming couplers can be used not only in high speed layers but also in medium speed emulsion layers. These couplers are disclosed in the above-mentioned patents and in Japanese Patent Application Publication No. 2003-120002.
No. 7-3234, same! ! According to the method described in U.S. Pat.
Can be easily synthesized.

In addition to the couplers described above, colored couplers having a color correction effect or couplers that release a development inhibitor during development (so-called DIR couplers) may be used in the present invention.

In addition to DIR couplers, there are also colorless DIR couplers in which the coupling reaction product is colorless and releases a development inhibitor.
It may also contain a coupling compound.

In the present invention, it is preferable to achieve high sensitivity by using a compound (hereinafter referred to as FR compound) that can form a development accelerator or fogging agent during silver development. These PR compounds are described in U.S. Pat.
ir, a, rx, dohiro.

j26. rtJ issue, same! , 44F, 2,4J5i',
Japanese Patent Publication No. 39-137631, jt9-/70141
No. 0, tO-/rj9! No. 60-107022
It can be easily synthesized by the method described in No.

Two or more FR compounds may be used in combination. The amount of the FR compound added is 0.2 mol or less and 70-10 mol or more, preferably 0.02 mol or more and 10-7 mol or more, per 1 mol of silver in the same layer or an adjacent layer.

The FR compound can be used alone or together with a color image forming coupler to achieve the desired purpose by introducing it into the silver halide emulsion layer by an oil-in-water dispersion method known as the oil protection method. .

In order to satisfy the characteristics required of a photosensitive material, two or more types of couplers etc. can be used together in the same layer, or the same compound can be added to different co-layers or more.
Of course it doesn't matter.

Couplers can be introduced into silver halide emulsion layers by known methods, such as in the US Pat. The method described in No. 22.027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.),
Phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyldutylphosphate), citric acid esters (
(e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. trimesic acid or organic solvents with a boiling point of 3o0c to 1zo0c, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isodityl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc. After being dissolved in a hydrophilic colloid, it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

Also, Tokko Akira! /-32163, Tokukai Shoj/-! Tata≠
The dispersion method using polymers described in No. 3 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The photographic color formers used are conveniently selected to provide intermediate scale images. The maximum absorption band of the cyan dye formed from the cyan color former is about 600 to 7 J.
Onrn, and the maximum absorption band of the magenta dye formed from the magenta color former is from about zoo to j I Onrn.
Preferably, the maximum absorption band of the yellow dye formed from the yellow color former is between about aOO and μr o nm0.

The photosensitive material of the present invention may contain a dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.

Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patent RRTTT, TO2, 1,77.4
', No. 22, JP-A-Sho≠♂-1j130, and Tar-22
1.20, same data//Hiroshi 4120, same jλ-to
riiz, US Patent 2.2. T! .

No. 077, λ, 27≠, 7t2, λ, 320.7
No. 07, same, Da 23, 7≠ No. 7, same.

jjj, 4t7.2, samej, 1113, 4jf
J issue, same u, 9! t, No. 179, J, /III
, No. 117, 3. /77.071 issue, same! ,,2!
t7. /No.27, same J,! lAO, No. 117, J.
171, 70≠ issue, same 3. Le 33. Or No. 3
,71♂.

μ72, same≠, 07/,, 112, same≠, 070
．． No. 312, same da 1μm0, jj,! This is what was written in No. r.

In the photographic material of the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be mordanted with a cationic polymer or the like. For example, U.S. Patent tri, 1471, U.S. Patent U, 67j
, j/& issue, same a, r35Pl≠O7 issue, same co, rr co, izt issue, same 3゜our, ttry issue, same! ,/I
t, No. 302, No. 3, ≠≠Jr, No. 23/, West German Patent Application (OLS) 1, Rilhiro, No. 3t2, JP-A-10-17
Polymers described in No. 4.2, No. 10-71332, etc. can be used.

In the light-sensitive material of the present invention, various additives that are generally used in silver halogenide light-sensitive materials can be used. Such materials are disclosed, for example, in U.S. Pat.
It is described in the specification of No. 30/. To give a representative example,
Surfactants (column 33), water-insoluble or sparingly soluble polymers (j
j-j4! column), ultraviolet absorbers (columns 37-31), color anti-capri agents (column 37), color cast inhibitors (column 31), hydroquinones (column jj), and the like.

The photosensitive material of the present invention can be used, for example, in the above-mentioned US patent application.

J Tata, 30/issue statement 34! It can be developed according to the methods described in columns 3j to 3j.

In the present invention, it is preferable to use a derivative of naphthalenesulfonic acid as the surfactant used in the photosensitive material.

If the water washing step after color development is omitted or shortened as in the processing steps of the present invention, a portion of the developer will be carried into the subsequent processing steps, causing various troubles. For example, they may be carried into bleaching solutions, reducing bleaching performance or causing an increase in concentration. The amount of developer carried into the bleach bath normally depends on the film thickness and degree of swelling of the photosensitive material, but it is also known that even with the same film thickness and amount of hardener, it depends on the type of surfactant. The inventors have discovered.

Among the surfactants, naphthalene sulfonic acid derivatives are particularly preferred. The reason for this is thought to be related to the amount of developing agent incorporated into the surfactant micelles and slight differences in the swelling of the membrane containing the surfactant in the developer, but it has not been clarified.

Furthermore, naphthalene sulfonic acid derivatives cause less generation of bubbles in the treatment liquid, and are particularly preferred when stirring is intensified for short-time treatment as in the case of the present invention. Taking sodium dodecylbenzenesulfonate as an example of a surfactant used in photosensitive materials, it foams significantly in color developing baths and bleaching baths, and the foam that is generated is difficult to disappear. On the other hand, the naphthalene sulfonic acid derivative of the present invention is characterized by less generation of foam and easy defoaming.

In the present invention, the surfactant used in the photosensitive material is 0.
It is preferable that the naphthalene sulfonic acid derivative accounts for 5 g or less and toqb or more of the total amount of surfactant.

The total number of carbon atoms in the substituents of naphthalene sulfonic acid is preferably /r or less, and the following preferred examples are given, but the present invention is not limited thereto.

-i Cyanamid Aerosol O8Dupont
Alkanol B W-Hiro-s -r W-/ / W-1,2 03Na Wi ≠ Hereinafter, the treatment bath having bleaching ability of the present invention will be described.

In the present invention, immediately after color development, processing is carried out in a processing bath having bleaching ability.

A processing bath having bleaching ability generally refers to a bleaching solution and a bleach-fixing solution, but in the present invention, a bleaching solution is preferred since it has an excellent bleaching blade. Further, the desilvering step of the present invention includes, for example, the following steps, but is not limited thereto.

■ Bleach-fixing ■ Bleach-bleach-fixing ■ Bleach-fixing ■ Bleach-fixing-bleach-fixing ■ Bleaching-Washing constant fixing Particularly, steps (1) and (2) are preferred in order to exert the effects of the present invention.

The bleaching agent of the present invention contains at least one ferric complex salt of a compound selected from the compound (A) group;

A ferric complex salt of 3-diaminopropanetetraacetic acid is used in combination at a molar ratio of the former to the latter of 3 or less (including O). A preferred molar ratio is 1.t to 0.2.

When the molar ratio exceeds 3, the bleaching strength decreases, resulting in poor desilvering. Furthermore, if the ratio of ferric 1,3-diaminopropanetetraacetic acid salt is extremely high, slight bleaching may occur.

The amount of the bleaching agent of the present invention to be added is as follows:
) o, oz mol to 1 mol, preferably 0.1 mol to Q,!
It is a mole.

In addition to the above-mentioned aminopolycarboxylic acid iron (III) complex, an aminopolycarboxylic acid salt can be added to the treatment solution having bleaching ability according to the invention. Especially compound group (A)
It is preferred to add a compound of

The preferred amount added is 0.0001 mol to 0.1 mol/l
More preferably, it is 0.003 mol to 0.0 j mol/l.

Aminopolycarboxylic acids and their ferric complex salts are usually preferably used in the form of alkali metal salts or ammonium salts, and ammonium salts are particularly preferred because they have excellent solubility and bleaching properties.

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

Various bleach accelerators can be added to the bath having bleaching ability of the present invention.

Such bleach accelerators are described, for example, in U.S. Pat. try specification, German patent cylinder 12.2
Rio, Rico specification, British patent cylinder 1°/31. t≠λ
No. specification, Japanese Patent Application Laid-open No. Sho J3-ta JA30, Research
Compounds having a mercapto group or disulfide group described in Disclosure No. 17/2 (July issue/7R), thiazolidine derivatives described in JP-A No. 17/01/2, U.S. Thiourea derivatives described in Patent No. 3,704,141, JP-A-Sho! r-7123
Iodide described in Publication No. J, German patent cylinder 2.7≠I? ,
Polyethylene oxides described in No. 1730,
Polyamine compounds described in Japanese Patent Publication No. Sho≠t-rrJa can be used. Particularly preferred are mercapto compounds as described in British Patent No. I, ISR, RUJ.

Particularly preferred are the following.

The amount of bleaching accelerator added is o, o per 1 liquid i having bleaching ability.
Ig~koOg is preferably 0.5g A-10g.

In addition to the bleaching agent and the above-mentioned compounds, the bleaching solution constituting the present invention includes bromides such as potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included.

The concentration of the rehalogenating agent is 0.00% per liter of bleach solution. /~! mol, preferably 0.1 to 3 mol. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, metaboric acid, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. pH of
Additives known to be commonly used in bleaching solutions, such as one or more inorganic acids, organic acids, and salts thereof, having a buffering capacity can be added.

The pH of the bath having bleaching ability of the present invention is generally 6 to 1, but preferably! , 1-1,j, most preferably! ,
It is 3~ko. In a preferred pH range, there is little bleaching and the desilvering performance is excellent.

The replenishment amount of the bath having bleaching ability of the present invention is preferably 100 ml to 1) poml to xooooml per m2 of photosensitive material.
It is 0100O.

In the present invention, after treatment with a bath having bleaching ability, treatment is generally performed with a bath having fixing ability.

However, this does not apply when the bath having bleaching ability is a bleach-fixing solution.

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

Fixing agents for baths having these fixing abilities include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate; urea,
Thioether etc. can be used. The amount of these fixing agents ranges from 0.3 mol to 3 mol per liter of processing solution, preferably <t
rio.

The amount is 5 mol to 2 mol.

The bath having fixing ability contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, such as acetaldehyde sodium bisulfite. It can be included.

Furthermore, various optical brighteners, antifoaming agents, surfactants,
Organic solvents such as polyvinylpyrrolidone and methanol can be contained, but in particular as preservatives,
It is preferable to use the sulfinic acid compound described in the specification of No.-213113/.

The amount of replenishment of the bath having fixing ability is preferably JOOml to JOOOOml per m2 of photosensitive material, more preferably 300ml to iooml.

Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the bath having fixing ability of the present invention for the purpose of stabilizing the solution.

The total time of the desilvering process of the present invention is short, and the effect of the basic invention can be significantly obtained. The preferred time is /min to μmin, more preferably 1 minute and 30 seconds to 3 minutes.

Also, the treatment temperature is 250 to 50°C, preferably 3j0C.
-≠r'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 be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is JP-A-Sho JJ-/13≠1.
The stirring effect can be achieved by using the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material as described in No. 0, No. 1.2-/IJIItI, or using the rotating means of JP-A No. 1, R3-Hiroj/No. In addition, a method of moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade installed in the liquid to create turbulent flow on the emulsion surface improves the stirring effect, increasing the circulation flow rate of the entire processing liquid. Here are some ways to do it. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improving 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 automatic developing machine used in the present invention is
It is preferable to have a photosensitive material conveying means described in No. 237, No. 1dsr, and No. P/2j. As described in the above-mentioned Japanese Patent Application Laid-Open No. 12-12-7, such a conveying means can significantly reduce the carry-over of processing liquid from the front bath to the rear 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 developer 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-/N, N-diethyl-p-phenylenediamine D-,2-co-amino-1-diethylaminotoluene D-3-co-amino-5-(N-ethyl-N-laurylamino)toluene D-≠ ≠-[N-ethyl-N -(β-hydroxyethyl)aminocoaniline D-z,2-methyl-Hiroshi-[N-ethyl-N-(β-hydroxyethyl)aminecoaniline D-64t-amino-3-methyl-N-ethyl- N-[
β-(methanesulfonamido)ethyl]-aniline D-7N-(,2-amino-!-diethylaminophenylethyl)methanesulfonamide D-IN, N-dimethyl-p-phenylenediamine D-y ≠-amino-3 -methyl-N-ethyl-N
-methoxyethylaniline D-to guamino-3-methyl-N-ethyl-N
-β-ethoxyethylaniline D-// Hiro-amino-3-methyl-N-ethyl-N-
Among the above-mentioned -phenylenediamine derivatives on β-cutoxyethylaniline, exemplified compound D-z is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites, and p-toluenesulfonates. The amount of the aromatic-grade amine developing agent used is preferably about 0.0.0. /g ~ approx. 20g1
More preferably, the concentration is from about 0.5 g to about iog.

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.

The preferred addition amount is O1 per liter of color developer. g~i
og, more preferably /g-jg.

In addition, as compounds for directly collecting the color developing agent, various hydroxylamines, patent application Sho t/-/161j
Hydroxamic acids described in No. A/-/707! Hydrazines and hydrazides listed in the same issue A/-/l#
Phenols described in No. 7≠2 and J/-co 03233, α-hydroxyketones and α-7 minoketones described in No. 6/-/♂r7μ/, and/or No. 7/-/r
It is preferable to add various saccharides described in No. 01.16.

In addition, in combination with the above compounds, patent application Sho A/-/'7712
No. 3, 4/-/ AA No. 474j, t/-/l
, j1.2/ issue, A/-/4 μsit issue, A/-/
Monoamines described in No. 7071 and J/-/61/j, etc., j/-/737 No. 1, t/-/l
11. ! Diamines described in rIj No., A/-1, rtjto No., etc., A/-/4j62/, and ≦/-
Polyamines described in /Ari No. 7t, same j/-/1r6
Polyamines described in No. /R, nitroxy radicals described in No. A/-/16j6/, No. A/-/16j6/,
and alcohols listed in No. 6/-/ri7hiro/ri, the same J/
-/91917 oximes and the same A/-λl
,j/! It is preferable to use the tertiary amines described in No. I.

Other stool collection agents include JP-A-57-14C/≠ and the same! 7-! Each rice metal listed in J7'l issue, Tokukai Sho!
Salicylic acids described in No. trozrr, Japanese Patent Application Publication No. Sho 1μm
Alkanolamines described in No. 3332, JP-A-Sho! B-
Polyethyleneimines described in No. 3≠R, aromatics described in No. 3.7 μt of the US patent, aromatics described in No. j≠μ, 1-lyhydroxy compounds, etc. 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 ~1.0, more preferably 2~1.0, and contains other known developer component compounds. can be set.

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

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

The amount of the buffer added to the color developer is 0o1 mol/1
It is preferable that it is more than 0.1 mol/l-0.
Particularly preferred is hmol/l.

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 preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarminic acids.

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, cordiaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, cophosphonobutane-l, λ, ≠- Tricarmenic acid, /-hydroxyethylidene-1,/-diphosphonic acid, N,N/-bis(cohydroxybenzyl)ethylenediamine-N,N/-diacetic acid Two or more of these chelating agents may be used in combination as necessary. You may do so.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example /l
It is about 0.5g 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 indyl alcohol from the viewpoints of pollution, formulation properties, and prevention of color staining. Here, "substantially" means that it is contained in an amount of 2 ml or less per liter of developer solution, preferably not at all.

Other development accelerators include: Japanese Patent Publication No. 37-/70111
No., J7-1917, No. 31-7126, Doumu μ
m12sro issue, same≠j-ta oi issue and US patent cylinder J
,! 1, 3, -≠7, etc., JP-A Showa Jλ-Hori Rari No. 10-/! j
! 'p-phenylenediamine compound represented by No. I, JP-A-Sho! O-/j77.27, special public showμ≠-JOO
No. 7, Japanese Patent Application Publication No. JA-/J412J and J2-IJ
4CJ No., etc., U.S. Patent No. 2. Hiro≠, No. 203, same J, / Kot.

No. 112, same a, x3o, yyA, same 3. ．． 2 to 3,
ri/ri issue, special public Akihiro/-//da 31, US patent cylinder 2.
≠ra, z≠ issue, same co, jrit, 9-6 and same J,
Amine-based compounds with 3≠ in the number etc., Tokko Shoj
7-ItOt No. 1, same≠2-szaoi, US Patent No. 3. i@2r, irJ issue, special public Shoda/-7/≠37 issue,
≠--23rrJ and U.S. Patent No. 3. ! 3, zo
Polyalkylene oxides represented by No. i etc., other l-phenyl-3-pyrazolidones, imidazoles,
etc. can be added as necessary.

In the present invention, any anti-capri agent can be added as required. As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. Examples of organic anti-capri agents include benzotriazole, t-nitroimidazole, and! - Nitroinindazole! -Methyl is nzotriazole, j-nitrobenzotriazole,! Typical examples include nitrogen-containing heterocyclic compounds such as -chlorobenzotriazole, corchiazolyl-benzimidazole, λ-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The color developer used in the present invention may contain an optical brightener. As an optical brightener, ≠.

G'-diamino-2,2'-disulfostilbene type compounds are preferred. The amount added is o-jg/l, preferably 0.5
g-da g/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 20-100C, preferably 30-μr'C. Processing time is 10 seconds~j
Preferably 30 seconds to 3 minutes.

It is preferable that the replenishment amount is small, but the replenishment amount is
00~/s Ooml preferably 1oo-room
It is l. More preferably, it is Filooml-100ml.

Further, the color developing bath may be divided into co-baths or more 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 /-phenyl-3-pyrazolidone, developing agents such as 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, comethylbenzimidazole, and methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. be able to.

The processing method of the present invention comprises the above-mentioned processing steps of color development, bleaching, bleach-fixing, and fixing.

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can 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,
It is possible to use disinfectants and fungicides to prevent the growth of various types of ζcutilia and algae (e.g., isothiazolone, organochlorine disinfectants, benzotriazole, etc.), surfactants to prevent drying load and unevenness, etc. can. Or L, E
.

West, “Water Quality Cr1te
ria'.

Phot, Set, and Eng,, vol.
R, AA.

Compounds described in page j≠Hiro~3jri (/ri+j) 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 liquid having a buffering capacity of pH J to B, a liquid containing an aldehyde (for example, formalin), etc. can be used. The stabilizing solution may contain ammonium compounds, Bi, Al-based metal compounds, optical brighteners, chelating agents (for example, l-hydroxyethylidene-1,/-diphosphonic acid), bactericides, fungicides, A hardening agent, a surfactant, etc. can be used.

Further, the water washing step and the stabilization step are preferably carried out by a multistage countercurrent system, and the number of stages is preferably λ to μ stages. The amount of replenishment is 7 to 50 times, preferably 2 to 30 times, and more preferably 2 to 75 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
, water that has been deionized to a Mg concentration of less than 100 mg/l,
It is preferable to use water that has been sterilized with halogen, ultraviolet germicidal lamps, etc.

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

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

〔Example〕

The present invention will be specifically explained below using examples.

Example 1 On a subbed cellulose triacetate film support,
A sample of a multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

(Composition of photosensitive layer) No. LIII (haleshine prevention M) Black colloidal silver 0.3 Gelatin 1.0 Ultraviolet absorber UV-10.1.

Same as above υV-20,1 Same as above UV-30,1 Dispersion oil 0il-10,2 Same as above 0i1-2 0.1 2nd MC intermediate layer) Gelatin 1.0 Colored coupler〇-20,02 Dispersion oil 0il-10,01 No. 3-layer (low-speed blue-sensitive emulsion) Monodispersed silver iodobromide emulsion (silver iodide 3 mol%, average a<a, O
μ) Sensitizing dye I 1.4
Xlo″″4 Sensitizing Dye II
7 Xl0-'Cabra-C-L
O,5 coupler C-20,05 Dispersion oil 0il-30,03 Dispersion oil 0il-40,03 4th layer (middle M) Gelatin 1. Ol Compound AO01 5th layer (low-sensitivity green-sensitive emulsion N) East-dispersed silver iodobromide emulsion (silver iodide 3 mol%, average grain size 1.0
μ) 1.4 (Silver iodide 3 mol%, average grain 7i0.3μ) 0.3 Gelatin 0.8 Sensitizing dye m 3 X 1
0-' Sensitizing dye IV I
X 10-'sensitizing dye V
I Low-speed blue-sensitive emulsion NJ) 6-drop dispersed silver iodobromide emulsion (silver iodide 3 mol%, average a.
0μ) 0.7° (Silver iodide 3 mol%, average grain '(10,3μ) 0.2 Gelatin 1.0 Sensitizing dye VI 2 X 1
0-' Sensitizing dye ■ 2XIO
-'Coupler C-60,6 Coupler C-100,6 Dispersion oil 0il-10,1 8th. V (intermediate layer) Gelatin 1.0 Compound A O,1 9th N (white-sensitive red-sensitive emulsion, 1) Polydispersed silver iodobromide emulsion (silver iodide 6 mol%, average grain size 2.0
μ) 2.3 Gelatin 1.2 Sensitizing dye I 7X10-
'Sensitizing dye II 2XI
O-'Coupler C-8Q, 1 Coupler C-L O, 2 Dispersed Oy/L/0il-40,2.

10th layer (intermediate layer) Gelatin 1.0 Coupler C-50,2 Compound A 0.1 11th layer (highly sensitive green-sensitive emulsion layer) Polydispersed silver iodobromide emulsion (fi5 mol% iodide, average grain 4i2
．． Oμ) 2.0 Coupler C-90,2 Dispersion oil 0il-10,4 12th layer (middle M) Fine grain silver bromide emulsion (average grain size 0.07μ) 2.0 Gelatin 1.2 Compound A O,1 13th M (high sensitivity blue-sensitive emulsion Hi) Exposure-dispersed silver iodobromide emulsion (silver iodide 3 mol%, average grain size 2.1
μ) 1.8 drops 1 dispersed silver iodobromide emulsion (silver iodide 3 mol%, average grain concentration 1.
2μ) 0.5 Monodisperse silver iodobromide emulsion (silver iodide 3 mol%, average grain size 0,
3μ) 0.2 Fine grain silver iodobromide emulsion (average afi 0.09μ) 0.2 Gelatin 1.2 Sensitizing dye VI 3X10-
'Sensitizing dye ■ l X 10
-'Coupler C-60,3 Dispersion oil 0il-10,06 14th layer (first protective layer) Coupler C-70,1 Ultraviolet absorber UV-10,05 Same as above υV-20,05 Same as above UV-30,05 Same as above UV-40,05 Same as above uv-so o, os Gelatin 0.6 Dispersion oil 0il-40,1 15M (second protection calendar) Gelatin 0.5 Polymethyl methacrylate particles (diameter 1.5μ) Each layer has In addition to the above components, surfactant W-1 was added as a coating aid. Additionally, formalin scavenger was added.

The amount added to the light-sensitive material is shown in grams per 1, silver halide emulsion and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in molar ratio with silver halide. Ta.

Compounds used in examples \ t C5H1, (t) (s, l 0CH, CONHCH, CH, OCH.

Sensitizing dye! Same as above ■ Same as above ■ Same as above ■ Same as above ■ Same as above ■ Same as above ■ JV-1 V-2 V-3 V-4 V-5 Shitnz Compound A W-1 This photosensitive material is referred to as Sample 10/. The specific photographic sensitivity of sample 00/ was determined to be i, zoo.

Next, after imagewise exposure, sample 10/ was subjected to continuous processing (running test) in the following processing steps until twice the tank capacity of the color developer was replenished. However, the composition of the bleaching solution was changed as shown in Table 1, and the test was conducted for each of them.

The automatic developing machine used was JP-A-1.0-/R123.
The belt conveyance method described in No. 7 was used, and each treatment bath used the jet stirring method described in JP-A No. 31140.

The processing steps are shown below.

Color development 3 minutes! Seconds Jr 0CJrmlj
white 7 minutes jr 0c
11m1 fixed 7 minutes JI 0C
JOml Stable / 20 seconds 310C- Stable 20 seconds JJ"C- Stable! 20 seconds 3♂'CJ!ml*Drying/min is seconds jO ~ 711) 0C-* Stable solution is stable 3 → stable 2 → stable l A three-tank countercurrent system was used.

The composition of each treatment liquid used is shown below.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid j, OA, 0 Sodium sulfite μ, 0 ≠, ILL Potassium carbonate 30.0 37.0 Potassium bromide 1,3 0.2 Potassium iodide
1,2mg -Hydroxylamine sulfate 2.0 2. r≠−[N−
Ethyl-N-β-hydroxyethylamino] monomethylaniline sulfate 7j, J Add water i, oLi, oLpH1
0,0010,0! (Bleach solution) Mother solution Replenisher 1,3-diaminopropane tetraacetic acid rR≠, Og j, 0g ammonium bromide 100. Og /lO, 0g ammonium nitrate 30.0g jO, 0g aqueous ammonia (J7%) 20. Oml lJ, 0ml acetic acid <yrs>, 0ml lj /j, add 0ml water i, oL 1, (7L pH see Table 1) HCl (fixer) mother solution replenisher l-hydroxyl tylide 7-1, / - Diphosphonic acid j, Og A, 0g Sodium sulfite 7.0g r, 0g Sodium bisulfite j, Og j, !g Ammotau thiosulfate aqueous solution (70%) / 70.Oml Add 200.0ml water t, oL t,oLp H4
, 7A, t (Stable solution) Mother solution, replenisher common formalin (37 t) 1, λml yo-chlorocomethyl-μm inthiazolin-3-one A, Omg-monomethyl-guinthiazolin-3-one j, Omg surfactant o, p (CIoH21-0
+CH2CH2O%H, 1 ethylene glycol
Add 1,0 water
t, oL pH 7.0-7.0 After exposing the sample to tcMs, it was treated with each running equilibrium solution, and the amount of residual silver was determined by fluorescent X-ray method. The amount of residual silver is recorded in the right column of Table 1.

From the above, it has been shown that desilvering can be accelerated by using the bleaching bath of the present invention.

Example 2 Sample 20/ was prepared in the same manner as in Example 1 except that the coupler C-/ in the third layer of Example/ was changed to coupler (a) having the following structure and used in an equimolar amount with C-/. Had made.

Further, Sample 202 was prepared in exactly the same manner as in Example 1, except that the coupler C-r in the second layer was changed to a coupler having the following structure and used in an equimolar amount with C-r.

Samples 101 and 20/SλOλ were subjected to the same treatment as in Example/. However, using bleach baths A and E, and exposure to j
imagewise with cMs, and the amount of residual silver was uniformly jc in another sample.
It was determined by exposure using Ms. The cyan density was determined based on the exposure amount that gave the densities i and s for sample #02. The stain was expressed as the increase in yellow density in bleaching baths A and E, based on the yellow density when using bleaching solution J below.

<Bleach bath J> Ethylenediaminetetraacetic acid ferric ammonium salt common to mother liquor and replenisher /20. Og ethylenediaminetetraacetic acid disodium salt io, og ammonium nitrate io, og ammonium bromide ioo, og bleach accelerator
Add j x 10-3 mol ammonia water
pHj, J Add water 1,O
Coupler (jL) Coupler (b) From the above, it has been found that the combination of the naphthol coupler of the present invention and the bleach bath of the present invention gives the best results.

Example 3 Sample 3oi, which is a multilayer color light-sensitive material consisting of each layer having the composition shown below, was prepared on an undercoated cellulose 93-acetate film support.

1st layer (antihalation layer) Black colloidal silver 0.3 Gelatin 1.0 Ultraviolet absorber U
V-1o, i Same as above UV-10, / Same as above UV-Jo, / Dispersion oil 04l-t o, 2 Same as above 0
il-ro, second layer (intermediate layer) gelatin i,.

Colored coupler C-to, o-dispersed oil 0il-/0.0/Third layer (low-sensitivity red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide t morch, average grain size i, o
μ) 1, dagelatin 1,/sensitizing dye 1 1.4txto-4 sensitizing dye [7
×10-5 Coupler C-J o, z Coupler C-jO, Oj Coupler C-≠ 0.02 Dispersion oil 0il-J O, OJ Dispersion oil 0i
l-≠ 0. OJ third layer (middle layer) Gelatin 1.0 Dispersion oil 01l-/0.0! t coupler C
-zo, tj 3rd layer (low-sensitivity green-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 1 mole, average grain size 1.0
μ) 1. ! Monodisperse silver iodobromide emulsion (3 moles of silver iodide, average grain size 0.3μ) 0.3 gelatin Oo sensitizing dye ms x 10-4 sensitizing dye PI
txio-4 sensitizing dye V
/X10-4 sensitizing dye Mtxto-4 coupler C-IQ, Hiro coupler C-10, / dispersion, tyl 01l-j O, /th layer (intermediate layer) gelatin i,.

Dispersion oil 0il-i o, or coupler C-to, /z 7th layer (low sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide t morch, average grain size i, o
μ) o, tazelatin
1,0 sensitizing dye■
Co×10-4 sensitizing dye■ Co×
10-4 coupler C-7o, dispersion oil 0il-IO, / rth layer (
Intermediate layer) Gelatin 1,0 coupler C-to, iz 2nd layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 3.1 mol, average grain size λ, θμ)
/Silver iodobromide emulsion (2 moles of silver iodide, average grain size 1.2μ)
o,r Silver iodobromide emulsion (#co,!mol iodide, average grain size 0.2μ) 0.3 Gelatin 1.2 Sensitizing dye 1 7X10-5 Sensitizing dye■ CoX10-5 Coupler C-10
, / Coupler C-see 0.2 Dispersion oil Ot, 1-≠ 0.2 10th layer (intermediate layer) Gelatin 1,0 Coupler C-to, l 11th layer (high-sensitivity green-sensitive emulsion layer) Iodobromide Silver emulsion (iodide @S, Z morch, average grain size, Oμ
) 1. λ silver iodobromide emulsion (silver iodide r mol% 1.0μ) O, ? Gelatin /・0 sensitizing dye ill 1,! ×1O-4JIIV
jX10'# V
jXlo 51Vi
j x 10SI rICl x 10-5 Coupler C-I Q-2 Coupler C-1o, or Dispersion oil 0il-10, da 12th layer (intermediate layer) Fine grain silver bromide emulsion (average grain size 0.07μ), O Gelatin 10.2 Dispersion oil 01l-/0.0! Coupler C-
j O01 73rd layer (high sensitivity blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide t morch, average grain size ko, l
μ) i, r Monodisperse silver iodobromide emulsion (1 molt of silver iodide, average grain size 1,-μ)
O0! Monodisperse silver iodobromide emulsion (3 mol of silver iodide, average grain size 0.3μ) O, Co Fine grain silver iodobromide emulsion (average grain size 0.02μ) Ql, 2 Gelatin 1, Co Sensitizing dye■ JXlo -4 sensitizing dye■
/×10-4 coupler C-70,7 Dispersion oil oil-/o,ol 1st layer (first protective layer) Ultraviolet absorber UV-10,or Same as above UV-,20,Oj Same as above UV-JO,OJ Same as above UV-≠ 0.0! Same as above UV-to, oj gelatin o, dispersion oil 0il-hiro 0. /1st layer (second protective layer) Gelatin 0.j polymethyl methacrylate particles (diameter 1.3μ) In addition to the above ingredients, each layer contains a total of 0 surfactant WA-/
．． 00g of Kojgs hardener H-t was used. Additionally, formalin scavenger was added.

The amount added to the light-sensitive material is shown in grams per 7 m2, silver halide emulsion and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in molar ratio with silver halide. .

Compounds used in the examples UV-j UV-z C-/C-coC-3 C-Hiro-r ShisMtt(su-g Sensitizing dye■ Same as above■ Same as above■ Same as above■ Same as above■ Same as above■ Same as above■ CH3 1l -1 0il-ko1l-3 0il-da2H5 -t CH2=CH-8o 2-CH2 CH2=CH-8o2-CH2 WA-/ Change coupler C-2 in the third layer of sample 30/ to C-r Thirty samples were made using equimolar amounts.

Furthermore, the coupler C-r in the second layer of sample 30/ was changed to C-2, and the coupler C-u in the second and third layers was changed to (in the coupler in Example C), and the same as in sample 30 was obtained. Sample 303 (for comparison) was made using molar amounts.

When these samples 30/-303 were subjected to the same treatment as in Example λ, the same results as in Example 1 were obtained.

Example ≠ By changing the type and amount of surfactant in sample JO/ of Example 3 as follows, sample Hiro 0/-≠O! made.

Using this sample No. 0/~1701, it was passed through the treatment process of Example 1 (with the bleaching bath FiE). This process is referred to as process α. A running test was carried out using the above-mentioned light-sensitive material, and the process in which the color developer was continuously processed until it was refilled by μ times the tank capacity and then subjected to the steps in Example 1 was defined as β.

In treatments α and β, the continuous throughput was twice as high, and it is thought that the bleaching solution in β was more exhausted. sample aoi-po
After applying imagewise exposure of jcMs at t, processing α and β were performed. Cyan density l in processing α.

The cyan density of processed β was read at the exposure amount giving j and is shown in the table below. In addition, the sample after treatment β is taken at 0c70%RH.
The sample was stored for one week under the conditions below, and the increase in yellow density was measured and recorded in the table below.

By comparing sample 1101, pot and sample≠02~≠θ≠, sample≠01,170! It can be seen that it is excellent.

Patent applicant: Fuji Photo Film Co., Ltd.

Claims (3)

[Claims] (1) It has blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, at least one of which consists of two or more layers with mutually different sensitivities, and these two or more layers are on the side of the support. A color photosensitive material in which at least one silver halide emulsion layer having different color sensitivities is arranged in order from a low-sensitivity layer to a high-sensitivity layer and having a different color sensitivity between the low-sensitivity layer and the high-sensitivity layer is color-developed. After that, in the method of treating with a treatment liquid having bleaching ability, the treatment liquid having bleaching ability contains the following compound group (A) as a bleaching agent.
) at least one type of ferric complex salt of a compound selected from
1. A method for processing a silver halide color photographic light-sensitive material, which comprises containing a ferric complex salt of 1,3-diaminopropanetetraacetic acid in a molar ratio of 3 or less to the latter. Compound Group (A) A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 Cyclohexanediaminetetraacetic acid A-41,2-Propylenediaminetetraacetic acid (2) It has blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, at least one of which is composed of two or more layers with different sensitivities, and these two or more layers are on the support side. When viewed from above, at least one silver halide emulsion layer having different color sensitivities is arranged in order from a low-sensitivity layer to a high-sensitivity layer, and between the low-sensitivity layer and the high-sensitivity layer, and the red-sensitivity emulsion A method for processing a silver halide color light-sensitive material, which comprises subjecting a light-sensitive material whose layer contains 20 mol % or more of at least one naphthol coupler to the processing according to claim 1. (3) It has blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layers, at least one of which is composed of two or more layers having mutually different sensitivities, and these two or more layers are on the side of the support. When viewed from above, at least one silver halide emulsion layer having different color sensitivities is arranged in order from a low-sensitivity layer to a high-sensitivity layer, and between the low-sensitivity layer and the high-sensitivity layer, and the red-sensitivity emulsion A photosensitive material in which the layer contains at least 20 mol % of at least one naphthol coupler and the total amount of surfactant in the photosensitive material is 0.5 g or less is subjected to the treatment described in claim 1. Processing method for silver halide color light-sensitive materials.