JPH07120004B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for processing a color light-sensitive material, and more particularly to a method for rapidly processing a color negative light-sensitive material for photographing having high sensitivity.

(Prior Art) In recent years, with the progress of the technology of the photosensitive material for photographing, high-sensitivity photosensitive materials have been released one after another. Expanding the shooting area by increasing the sensitivity of the photosensitive material, such as shooting without a strobe in a dark room, shooting with a high-speed shutter using a telephoto lens for sports photography, and shooting that requires long exposure such as astronomical photography Is an eternal theme imposed on the industry.

Many efforts have been made so far for increasing the sensitivity of photosensitive materials. Numerous studies have been conducted on the method of forming the shape and composition of silver halide grains, chemical sensitization, spectral sensitization, additives, coupler structures, etc., and some useful inventions have been made. However, the demand for high-sensitivity light-sensitive materials is greater than the technological progress, and unfortunately these methods alone have not been sufficient. Therefore, it is a common practice in the art to produce a high-sensitivity light-sensitive material by using a method of increasing the size of silver halide emulsion grains for higher sensitivity in combination with other techniques. Increasing the size of silver halide emulsion grains increases the sensitivity to some extent, but as long as the content of silver halide is kept constant, the number of silver halide emulsion grains inevitably decreases, and thus development begins. The major drawback is that the number of dots is reduced and the graininess is greatly impaired. In order to compensate for this drawback, two or more emulsions having the same color sensitivity and sensitivity, that is, different silver halide grain sizes, as described in British Patent No. 923,045 and Japanese Patent Publication No. 49-15495. A light-sensitive material having a layer, a method using a fast-reacting coupler as described in JP-A-55-62454, U.S. Pat.
554, so-called DIR couplers such as those described in U.S. Pat.No. 3,632,435, methods using DIR compounds, methods using couplers to produce mobile dyes described in British Patent 2,083,640, JP A method using silver halide having a high average silver iodide content described in JP-A-60-128443 is known. Each of these methods is an excellent invention having a great effect, but it is not a sufficient technique for 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 start points, various properties such as desilvering property during bleach-fix processing are allowed for high-sensitivity color negative photosensitive materials. Designs have been made with a high content of silver halide emulsion grains in the range.

On the other hand, it has been known to change the positions of layers of a color negative photosensitive material composed of multiple layers in order to realize high sensitivity in a high sensitivity color negative photosensitive material or to achieve both high sensitivity and high image quality. For example, U.S. Pat.Nos. 4,184,876 and 4,1
29,446, 4,186,016, British Patent 1,560,965, U.S. Patent 4,186,011, 4,267,264, 4,173,479.
No. 4,157,917, 4,165,236, British Patent No. 2,138,
962, JP-A-59-177,552, British Patent No. 2,137,372
No. 59-180,555, 59-180,556, 59-
No. 204,038, etc.

In these techniques, as described in the above-mentioned JP-A-59-177,552, the emulsion layer closer to the support causes a loss of exposure amount and delay of development due to the influence of the emulsion layer on the faster side. It is known that the sensitivity and softness tend to be low. Therefore, the most sensitive emulsion layer of each of the red-sensitive emulsion layer and / or the green-sensitive emulsion layer, which is located closer to the support than usual, should be as far as possible from the support. It is intended to achieve high sensitivity by locating it far away.

On the other hand, the above-mentioned high-sensitivity photographic materials are often used in the field of news reporting, and in particular, it is required to speed up processing. In the conventional processing process, the desilvering and fixing processes occupy a large proportion,
In order to speed up the processing, it was necessary to shorten the bleaching and fixing steps. For this reason, the development of bleaching agents with high bleaching power has been continued.

Heretofore, as a bleaching agent, a bleaching method mainly comprising a ferric ion complex salt (for example, ferric ion complex salt of aminopolycarboxylic acid, especially ethylenediaminetetraacetic acid iron (III) complex salt) has been mainly used.

However, the ferric ion complex salt has a relatively small oxidizing power and an insufficient bleaching power. Therefore, a compound using this as a bleaching agent is a low-sensitivity silver halide color photographic light-sensitive material mainly composed of a silver chlorobromide emulsion. When the material is subjected to a bleaching treatment or a bleach-fixing treatment, the desired purpose can be achieved for a while, but the main component is a silver chlorobromoiodide or silver iodobromide emulsion, and a color-sensitized, highly sensitive halogenated When processing a silver color photographic light-sensitive material, especially a color reversal light-sensitive material for photography and a color negative light-sensitive material for photography using a high silver content emulsion, the bleaching action is insufficient and desilvering failure occurs, and it takes a long time to bleach. It has the drawback of being time consuming.

Further, in color light-sensitive materials, sensitizing dyes are generally used for the purpose of color sensitization. Especially when using tabular grains with high silver or high aspect ratio for the purpose of high sensitization, there is a problem that the sensitizing dye adsorbed on the surface of the silver halide inhibits bleaching of silver produced in the development of silver halide. Occurs.

Persulfate is known as a bleaching agent other than ferric ion complex salt, and it is usually used as a bleaching solution containing persulfate containing chloride. However, a drawback of the bleaching solution using persulfate is that it has a weaker bleaching power than the ferric ion complex salt and has a remarkably long time for bleaching.

Generally, bleaching agents that are not pollutant or corrosive to equipment have weak bleaching power, and therefore bleaching agents having weak bleaching power, especially bleaching solutions or bleach-fixing solutions using ferric ion complex salts or persulfates. There is a desire to increase the bleaching capacity of.

In contrast, Research Disclosure 24023 (198
(April 4), JP-A-60-230653 and the like describe treatment methods in which two or more kinds of ferric aminopolycarboxylic acid complex salts are used in combination. However, these methods also provide sufficient bleaching. It has not yet reached the 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 color negative photosensitive material composed of multiple layers are changed in order to increase the sensitivity, the following disadvantages are unfavorable. By arranging the emulsion layer with the highest sensitivity on the side farther from the support, the loss of exposure and the delay in development received by the emulsion layer with the lower sensitivity located on the side closer to the support are increased, and Unless the grain size of silver halide grains in the emulsion layer of sensitivity is increased and the content thereof is increased, the gradation and maximum density required for the light-sensitive material cannot be maintained. Also, by changing the position of the layers, there is an increase in the film thickness due to an increase in the number of intermediate layers that direct emulsion layers with different color sensitivity,
It causes desilvering and deterioration of fixability, and the appropriateness of swift treatment is impaired.

The present inventors rapidly desilver silver halide photographic light-sensitive materials by using a bleaching solution containing a ferric complex of ferric tetraacetate with 1,3-diaminoprohane among many ferric complexes of aminopolycarboxylic acid. I found that I can. However, processing with the above-mentioned bleaching solution has caused a problem that remarkable stain is caused and photographic characteristics are remarkably impaired.

Accordingly, it is an object of the present invention to firstly provide a processing method for rapidly desilvering a high-quality, high-speed color negative photosensitive material. A second object is to provide a desilvering method which is less likely to cause stains and has no adverse effect on photographic properties in the processing of a color negative photosensitive material having high image quality and high sensitivity.

(Means for Solving the Problems) An object of the present invention is to have blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, and at least one of them has two or more layers having different sensitivities. 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 at least a silver halide emulsion layer having different color sensitivity is provided between the low-sensitivity layer and the high-sensitivity layer. One red-sensitive emulsion layer is provided with a bleaching ability after color development of a color light-sensitive material containing at least one naphthol cyan coupler in an amount of 20 mol% or more based on all cyan couplers in the same layer. In the method of treating with a liquid, the treatment liquid having the bleaching ability is a bleaching agent containing at least one ferric complex salt of a compound selected from the following compound group (A), and a ferric complex complex of 1,3-diaminopropanetetraacetic acid. And the molar ratio of the former to the latter is 3 or more. I connexion was achieved method for processing a silver halide color photographic light-sensitive material characterized in that it contains a proportion of.

Compound group (A) A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 Cyclohexanediaminetetraacetic acid A-4 1,2-Propylenediaminetetraacetic acid The present invention will be described in detail below.

The light-sensitive material of the present invention is a high-quality, high-sensitivity color light-sensitive material for photographing, having a specific photographic sensitivity of 320 or more, and the total amount of silver contained in the light-sensitive material is 3.0 to 13.0 g / m ^2. preferable. When the specific photographic sensitivity is 320 or less, it is not necessary to take the layer constitution as in the present invention. Further, when the amount of silver is 13 g / m ² or more, it is difficult to shorten the desilvering process even with the bleaching agent of the present invention.

For the definition and measurement method of specific photographic sensitivity, refer to
No. 61-245575, pages 7 to 17.

Several methods are known to analyze the silver content of the light-sensitive material, and any method may be used. For example, elemental analysis using fluorescent X-rays is easy.

When the specific photographic sensitivity of the color negative light-sensitive material of the present invention is lower than 320, the effect of the combination of the arrangement of layers of the multilayer color negative light-sensitive material of the present invention with the amount of silver contained is not sufficiently exerted. Of. It is preferably 400 or more, more preferably 800 or more.

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

Further, it is more preferable that each color-sensitive layer has a three-layer structure in order to further improve the graininess. This technique is described in Japanese Examined Patent Publication No. 49-15495.

A non-photosensitive layer may be present between each photosensitive emulsion layer. This non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. When light-sensitive emulsion layers having different color sensitivities are adjacent to each other, it is preferable to provide a non-light-sensitive layer between them. Such a non-photosensitive intermediate layer may contain a scavenger substance. In addition, JP-A-59-160,
It is also preferred to provide a non-light sensitive reflective layer under the light sensitive emulsion layer to improve sensitivity as described in JP-A-135.
The color negative light-sensitive material of the present invention usually contains a yellow filter layer, though it is not always necessary.

Specific examples of the order of arranging the light-sensitive emulsion layers in the color negative light-sensitive material of the present invention are shown below, but the order is not limited thereto. Although the non-photosensitive layer is omitted here, it may be present at the position as described above.

(1) Support, low-sensitivity red-sensitive emulsion layer (hereinafter RL), low-sensitivity green-sensitive emulsion layer (hereinafter GL), low-sensitivity blue-sensitive emulsion layer (hereinafter B)
L), high-sensitivity red-sensitive emulsion layer (RH), high-sensitivity green-sensitive emulsion layer (GH), high-sensitivity blue-sensitive emulsion layer (BH).

(2) Support, RL, GL, BL, GH, RH, BH (3) Support, RL, GL, BL, RH, intermediate green sensitive emulsion layer (hereinafter GM), GH, BH (4) Support , RL, GL, GM, BL, RH, GH, BH (5) Support, RL, intermediate red-sensitive emulsion layer (hereinafter RM), G
L, GM, BL, intermediate blue sensitive emulsion layer (hereinafter BM), RH, GH, B
H (6) Support, RL, GL, BL, RM, RH, GM, GH, BM, BH (7) Support, RL, GL, RH, GH, BL, BH (8) Support, RL, RL , RH, GH, BL, BH (9) Support, RL, GL, RH, GM, GH, BL, BH (10) Support, RL, GL, GH, RH, BL, BH Silver halide of the present invention Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material. A preferred silver halide is silver iodobromide containing 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing 2 to 20 mol% of silver iodide. In order to achieve both high sensitivity and high image quality, the average silver iodide content of silver halide in all emulsion layers should be 8 mol% or more as described in JP-A-60-128,443. Is preferred. It is known that if the average silver iodide content of silver halide is increased, the graininess is remarkably improved. However, when the silver iodide content exceeds a certain level, the developing speed is delayed and the desilvering and fixing speeds are increased. Defects such as delay come out. However, in the present invention, it is probably because the content of silver contained is small, but even if the silver iodide content is increased, these drawbacks are less likely to cause a problem and are very preferable.

The silver halide grain used in the photographic emulsion layer of the silver halide photographic material of the present invention comprises a core consisting essentially of silver iodobromide containing 5 mol% or more of silver iodide and an iodide coating the core. It is preferable to have a double structure constituted by silver iodobromide or a shell consisting essentially of silver bromide having a silver content lower than the silver iodide content of the core. The silver iodide content of the core is 10
More preferably, it is 20 mol% or more 44
Most preferably, it is at most mol%. The silver iodide content of the shell is preferably 5 mol%.

The core may contain silver iodide uniformly, or may have a multiple structure composed of phases having different silver iodide contents. In the latter case, the silver iodide content of the phase having the highest silver iodide content is 5 mol% or more, more preferably 10 mol% or more, and the silver iodide content of the shell is the core. It is better if it is lower than that of the highest silver iodide content phase. or,
The phrase "consisting essentially of silver iodobromide" means that it is mainly composed of silver iodobromide, but other components may be contained up to about 1 mol%.

As a more 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, a silver halide grain having a diffraction angle (2θ) of 38 to 42 ° and using Cu Kβ rays is used. When the curve of the diffraction intensity vs. diffraction angle of the (220) plane is obtained, two diffraction maxima, a diffraction peak corresponding to the core part and a peak corresponding to the shell part, and one minimum appears between them, and the core It is a particle having a structure in which the diffraction intensity corresponding to the portion is 1/10 to 3/1 of that of the shell portion. Particularly preferably, the diffraction intensity ratio is 1/5 to 3 /
1 and 1/3 to 3/1.

With such a double structure, it is possible to use a high iodine silver iodobromide emulsion without delaying the development speed, and to achieve a light-sensitive material having excellent graininess even with a small amount of coated silver. You can

The average grain size of silver halide grains in a photographic emulsion (the grain diameter in the case of spherical grains or grains close to spheres, the edge length in the case of cubic grains is the grain size, and is represented by the average based on the projected area). Although not particularly limited, it is preferably 0.05 μm or more and 10 μm or less. The average size of silver halide grains in each emulsion layer having the highest sensitivity is preferably 0.5 μm or more and 4 μm or less, more preferably 0.6 μm or more and 2.5 μm or less.

The particle size may be narrow or wide.

The silver halide grains in the photographic emulsion may have regular crystal bodies such as cubes and octahedra, and spherical,
Those having an irregular crystal body such as a plate shape, or a composite form of these crystal forms may be used. It may consist of a mixture of particles of various crystal forms.

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

Tabular grains are described by Gatov, Photographic Science and Engineering (Gutoff, Photographic
Science and Engineering), Volume 14, pp. 248-257 (197
0 years); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,4
It can be easily prepared by the method described in 33,048, 4,439,520 and British Patent 2,112,157.

The photographic emulsion used in the present invention is described by P. Glafkides, Chimie et.
Physique Photographique (published by Paul Montel, 1967
), GF Duffin Photographic Emulsion Chemistry
(The Focal Press, 1966), VLZelikman et al
By Making and Coating Photographic Emulsion (The Fo
Cal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Good.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
Can also be used, that is, a so-called controlled double jet method can be used.

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

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

The silver halide emulsion used in the present invention has a crystal plane defined by the Miller index (nn1) (n ≧ 2, n is a natural number) on the outer surface as described in JP-A-86-9598. A silver halide grain having is preferably used.

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

Further, JP-A-57-133540, JP-A-58-108526 or JP-A-57-133540
Composite particles in which silver salts having different compositions are epitaxially grown on host particles as described in 59-162540 can be preferably used in the present invention. Such particles are preferable in combination with the present invention because they exhibit high hardness and high photographic properties.

Further, silver halide emulsions grown in the presence of tetrazaindene as described in JP-A-61-146030 and JP-A-60-122935 have high silver iodide content and excellent monodispersity. Therefore, since it exhibits high sensitivity and excellent graininess, it is preferably used as a silver halide emulsion used in the present invention.

Further, as disclosed in JP-A-58-126526, a silver halide emulsion sensitized by gold sulfur or gold selenium in the presence of a nitrogen-containing heterocyclic compound exhibits high fog sensitivity and high sensitivity. Therefore, it is preferably used as a silver halide emulsion used in the present invention.

The slightly rounded cubic or tetradecahedral crystals described in JP-A-59-149345 or 59-149344 are silver halide emulsions used in the present invention because they have high sensitivity. Is preferred as

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together.

Of these, silver halide emulsions formed in the presence of iridium have high sensitivity (Japanese Patent Publication No.
And JP-B-45-32738), and particularly preferred as the silver halide emulsion used in the present invention.

Emulsions are usually freed from soluble salts after precipitation or physical ripening. As a means therefor, the Nudel water washing method, which is a known method of gelling gelatin, may be used. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulphonic acid), or gelatin derivatives (eg aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin) The sedimentation method (flocculation) described above may be used.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, “Die Crundlagender P” edited by H. Frieser.
hotographischen Prozesse mit Silber−halogeniden "
(Akademische Verlagsgesellchaft, 1968) Pages 675 to 734 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, first tin salt, Reduction sensitization using amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds; noble metal compounds (eg, gold complex salts, etc.)
A noble metal sensitization method using a complex salt of a metal of Group VIII of the Periodic Table such as Pt, Ir, Pd and the like can be used alone or in combination.

Further, it is preferable to use a selenium sensitizing method using a compound containing selenium capable of reacting with active gelatin or silver in combination with another sensitizing method because a high sensitivity emulsion can be obtained. This technology is disclosed in U.S. Pat.Nos. 1,574,944, 1,602,592, 1,623,
Japanese Patent Publication No. 499, Japanese Patent Publication No. 52-38408, Japanese Patent Publication No. 57-22090, Japanese Patent Publication No. 59-180536, U.S. Patent No. 4,565,778, Japanese Patent Publication No. 59-1.
85329, JP-A-60-150046 and the like.

The photographic emulsion used in the present invention is spectrally sensitized with a methine dye or the like, if necessary. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes complex merocyanine dyes, holopolar cyanine dyes,
Hemicyanine dyes, styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine nuclei, indole nuclei, benzoxadol nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benz Imidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thiooxazoline gin-
A 5- or 6-membered heterocyclic nucleus such as 2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, or thiobarbituric acid nucleus can be applied.

Examples of useful sensitizing dyes include German Patent 929,080.
U.S. Patents 2,231,658, 2,493,748, 2,503,77
No. 6, No. 2,519,001, No. 2,912,329, No. 3,656,959,
No. 3,672,897, No. 3,694,217, No. 4,025,349, No. 4,0
46,572, British Patent 1,242,588, Japanese Patent Publication No. 44-14030,
The one described in No. 52-24844 can be mentioned.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. A typical example is a US patent
2,688,545, 2,977,229, 3,397,060, 3,52
2,052, 3,527,641, 3,617,293, 3,628,964
No., No. 3,666,480, No. 3,672,898, No. 3,679,428,
3,703,377, 3,769,301, 3,814,609, 3,8
37,862, 4,026,707, British Patent 1,344,281, 1,
No. 507,803, Japanese Patent Publication No. 43-4936, No. 53-12375, Japanese Patent Laid-Open No.
Nos. 52-110618 and 52-109925.

A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For example,
Aminostil compounds substituted with nitrogen-containing heterocyclic groups) such as those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), and cadmium salts ,
An azaindene compound or the like may be included. US Patent 3,61
5,613, 3,615,641, 3,617,295, 3,635,721
The combinations described in item No. are particularly useful.

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

It is common to include a cyan-forming coupler in the red-sensitive emulsion layer, a magenta-forming coupler in the green-sensitive emulsion layer, and a yellow-forming coupler in the blue-sensitive emulsion layer, but different combinations can be used in some cases. For example, a combination of infrared-sensitive layers may be used for pseudo color photography or semiconductor laser exposure.

Also, U.S. Pat.No. 3,497,350 or JP-A-59-214853.
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 as described in JP-A No. 1994-242, and this layer is provided at a position farthest from the support.

For example, magenta couplers include 5-pyrazolone couplers, pyrazolone imidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), and the like. There are naphthol couplers, phenol couplers, and the like as cyan couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule, or polymerized ones. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions, but in order to reduce the content of silver contained in the light-sensitive material, a 2-equivalent coupler having higher silver utilization efficiency should be used. It is preferable to use. In particular, it is preferable to incorporate a 2-equivalent coupler in each of the most sensitive emulsion layers of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer. Further, it is more preferable to incorporate a 2-equivalent coupler in each of the most sensitive emulsion layers of the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer.

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 the coupler is determined by mixing two types of couplers M and N which give different dyes which can be clearly separated from each other, and adding them to the emulsion to develop a color image. It can be determined as a relative value by measuring the dye amount.

Maximum density (DM) max. Of coupler M, density DM in the middle stage
Of the coupler N and that of the coupler N respectively represent the color development of (DM) max., DM, the ratio RM / RN of the reaction activities of both couplers is represented by the following formula.

In other words, several emulsions containing mixed couplers are exposed to light at various stages, and several DM and DN pairs obtained by color development are made into two orthogonal axes. The coupling activity ratio RM / RN is obtained from the slope of the straight line obtained by plotting.

If the value of RM / RN is obtained as described above for various couplers using a fixed coupler N, the coupling reactivity is relatively obtained. The coupler N may be obtained by using, for example, the following coupler.

For cyan coupler For magenta coupler and yellow coupler As the fast-reacting coupler used in the present invention, the value of RM / RN obtained using the above-mentioned coupler N has a value of 1.5 or more in the case of a cyan coupler, 2.5 or more in the case of a magenta coupler, and 1 in the case of a yellow coupler. Each is preferred.

In the present invention, the red-sensitive emulsion layer contains at least one naphthol coupler. The naphthol coupler is a conventionally known coupler, but it has been found that, in the short-time treatment as in the present invention, high color density and low stain are obtained as shown in Examples.

The naphthol coupler of the present invention is represented by the following general formula (I).

(I) R ₁ is _{-CONR 3 R 4, -NHCOR 3,} -NHCOOR 5, -NHSO 2 R 5, -N
Indicates HCONR ₃ R ₄ or -NHSO ₂ NR ₃ R ₄ . As R ₃ , R ₄ and R ₅ , an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, and 2 carbon atoms
The heterocyclic group of -30 is mentioned. R ₃ and R ₄ may each be a hydrogen atom.

R ₂ represents a group capable of substituting on a naphthol ring (including atoms, the same applies hereinafter), and representative examples thereof include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aliphatic group, and an aromatic group. , Heterocyclic group, carbonamido 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 Examples thereof include a sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, and an imide group. The number of carbon atoms contained in R ₂ is 0-30, and a group having a hydrogen atom is further included in these groups. It may be substituted with a substituent. An example of cyclic R ₂ when m = 2 is a dioxymethylene group. n is 0 or 1. However, when n = 0, XH represents H.

X represents O, S or R ₆ N, and R ₆ represents a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably R ₇ (Y ₃ ) l- (III) represented by the following general formula (III), wherein Y ₃ represents NH, CO or SO ₂ , and l represents zero or 1. R ₇ is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, —OR ₃ , —COR ₃ , and —SO ₂ R ₃ , Where R ₃ and R ₄ represent a group as previously defined, In, R ₃ and R ₄ may be the same or different.

In R ₁ or R ₇ , R ₃ and R ₄ of —NR ₃ R ₄ are bonded to each other to form a nitrogen-containing heterocycle (morpholine ring, piperidine ring,
(Eg, a pyrrolidine ring) may be formed.

Y ₁ represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). Representative examples of a coupling split-off group, a halogen atom, -OR _8, -SR _8, -NHCOR ₈ , -NHCOSR ₈ , -NHSO ₂ R ₈ , Aromatic azo group having 6 to 30 carbon atoms, heterocyclic group having 1 to 30 carbon atoms and linked to the coupling active position of the coupler in the nitrogen element (succinimide group, phthalimido group, 1-hydantoinyl group, 1-pyrazolyl group , 2-benzotriazolyl group) and the like. Here, R ₈ represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms.

In the present invention, the aliphatic group may be saturated / unsaturated, substituted / unsubstituted, linear / branched / cyclic,
Typical examples are methyl group, ethyl group, butyl group, cyclohexyl group, allyl group, propargyl group, methoxyethyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl group, heptafluoro. Propyl group, dodecyloxypropyl group, 2,4-di-tert-
Examples include an amylphenoxypropyl group and a 2,4-di-tert-amylphenoxybutyl group.

Further, the aromatic group may be substituted or unsubstituted,
Typical examples are a phenyl group, a tolyl group, a 2-tetradecyloxyphenyl group, a pentafluorophenyl group,
2-chloro-5-dodecyloxycarbonylphenyl group, 4-chlorophenyl group, 4-cyanophenyl group, 4
-Hydroxyphenyl group and the like are included.

Further, the heterocyclic group may be substituted or unsubstituted,
Typical examples are a 2-pyridyl group, a 4-pyridyl group,
A 2-furyl group, a 4-thienyl group, a quinolinyl group, and the like are included.

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

Preferred examples of the substituent in the present invention will be described below. R ₁
Is preferably —CONR ₃ R ₄ , particularly preferably one of R ₃ and R ₄ is a hydrogen atom. As a specific example, a carbamoyl group,
Ethylcarbamoyl group, morpholinocarbonyl group, dodecylcarbamoyl group, hexadecylcarbamoyl group, decyloxypropylcarbamoyl group, dodecyloxypropylcarbamoyl group, 2,4-di-tert-amylphenoxypropylcarbamoyl group, 2,4-di Examples include -tert-amylphenoxybutylcarbamoyl group.

With respect to R ₂ and m, m = 0, that is, an unsubstituted one is most preferable, and then a halogen atom, an aliphatic group, a carbonamido group, a sulfonamide group and the like are relatively preferable substituents for R ₂ .

Preferred X is R ₆ N, wherein R ₆ is —COR ₇ (formyl group, acetyl group, trifluoroacetyl group, chloroacetyl group, benzoyl group, pentafluorobenzoyl group, p-chlorobenzoyl group, etc.), COOR ₃ (methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group, etc.),
--SO ₂ R ₇ (methanesulfonyl group, ethanesulfonyl group,
Butanesulfonyl group, hexadecane sulfonyl group, benzenesulfonyl group, toluenesulfonyl group, etc. p- chlorobenzenesulfonyl _{group), - CONR 3 R 4 (} N, N- dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N
-Dibutylcarbamoyl group, morpholinocarbonyl group,
Piperidinocarbonyl group, 4-cyanophenylcarbamoyl group, 3,4-dichlorophenylcarbamoyl group, 4-
Methanesulfonyl phenylcarbamoyl group, etc.), -SO
₂ NR ₃ R ₄ (N, N-dimethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-dipropylsulfamoyl group, etc.) can be mentioned. Particularly preferred X are NCOR ₇ and NSO ₂ R ₇ . Here, R ₃ and R ₄ have the same meanings as before.

Preferred Y ₁ is a hydrogen atom, a halogen atom (eg, chlorine atom, fluorine atom, bromine atom, iodine atom, etc.),
Aliphatic oxy group (for example, 2-hydroxyethoxy group, 2
-Chloroethoxy group, carboxymethyloxy group, 1-
Carboxyethoxy group, 2-methanesulfonylethoxy group, 3-carboxypropyloxy group, 2-methoxyethoxycarbamoylmethyloxy group, 1-carboxytridecyloxy group, 2- (1-carboxytridecylthio) ethyloxy group, 2- Carboxymethylthioethyloxy group, 2-methanesulfonamidoethyloxy group, etc.), aromatic oxy group (for example, 4-acetamidophenoxy group, 2-acetamidophenoxy group, 4- (3-carboxypropanamide) phenoxy group) , 4-mesylphenoxy group, etc.), and a heterocyclic thio group (for example, 1-phenyltetrazol-5-ylthio group, 1-ethyltetrazol-5-ylthio group, 1-phenylimidazole-group).
2-ylthio group, 4-pyridylthio group, etc.).

The coupler represented by the general formula [I] has substituents R ₁ , R ₂ and X.
Alternatively, Y ₁ may form a dimer or a multimer which is bonded to each other via a divalent or divalent or higher valent group. In this case, the carbon number range shown in each of the above substituents may be out of the range.

When the coupler represented by the general formula [I] forms a multimer, a homopolymer or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming monomer) having a cyan dye-forming coupler residue is a typical example. . In this case, the multimer contains a repeating unit represented by the general formula [IV], and one or more cyan color-forming repeating units represented by the general formula [IV] may be contained in the multimer. It may be a copolymer containing one kind or two or more kinds of color forming ethylene-like monomers.

In the formula, R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a chlorine atom, A represents —CONH—, —COO— or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted group. An alkylene group, a phenylene group or an aralkylene group is shown, and Z is -CONH-, -NHCONH-, -NHCOO-,
-NHCO-, -OCONH-, -NH-, -COO-, -OCO-, -C
O -, - O -, - SO 2 -, - NHSO 2 - or represents a -SO ₂ NH-. a, b, and c represent 0 or 1. Q represents a cyan coupler residue in which a hydrogen atom other than the hydrogen atom of the hydroxyl group at the 1-position is eliminated from the compound represented by the general formula (I),
Preferably in the compound of general formula [I], the substituent R ₁ ,
It represents a cyan coupler residue in which one hydrogen atom has been removed from R ₂ , X or Y ₁ .

As the multimer, a copolymer of a cyan color-forming monomer giving a coupler unit of the general formula [IV] and the following non-color-forming ethylene-like monomer is preferable.

As the non-color-forming, ethylene-like monomer that does not couple with the oxidation product of the aromatic primary amine developing agent, acrylic acid,
α-Chloroacrylic acid, α-alkylacrylic acid (eg methacrylic acid) Esters or amides derived from these acrylic acids (eg acrylamide, methacrylamide, n-butylacrylamide, t)
-Butyl acrylamide, diacetone acrylamide,
Methylene bis acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate,
n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic Vinyl compounds (eg styrene and its derivatives such as vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ethers (eg vinyl ethyl ether), maleic acid esters , N-vinyl-2-pyrrolidone, N-vinyl pyridine and 2- and 4-vinyl pyridine.

Acrylic acid ester, methacrylic acid ester, and maleic acid ester are particularly preferable. Two or more kinds of non-color-forming ethylenic monomers used here can be used together. 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 well known in the field of polymer couplers, the ethylenically unsaturated monomer for copolymerization with the vinyl monomer corresponding to the above-mentioned general formula [IV] has physical and / or chemical properties of the copolymer formed. Properties such as solubility, compatibility with photographic colloid composition binders such as gelatin, its flexibility,
It can be chosen such that the thermal stability etc. is positively affected.

A cyan polymer coupler used in the present invention (a lipophilic polymer coupler obtained by polymerization of a vinyl-type monomer giving a coupler unit represented by the above general formula [IV]) dissolved in an organic solvent is added to an aqueous gelatin solution. It may be emulsified and dispersed in the form of a latex, or may be directly emulsified.

U.S. Pat.No. 3,451, for a method of emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution.
820, U.S. Pat.No. 4,080,211 for emulsion polymerization,
The method described in No. 3,370,952 can be used.

Hereinafter, examples of cyan couplers according to the present invention (C
-1) Shown below.

The naphthol coupler of the present invention can be used in combination with other known cyan couplers, but it is necessary to contain 20 mol% or more of all cyan couplers. If it is 20 mol% or less, the curing of the present invention is not exhibited.

As the magenta coupler, a pyrazoloazole type magenta coupler is preferable from the viewpoint of hue. In particular, since the secondary absorption in the blue light absorption band is small, it is possible to reduce the number of colored couplers, which is particularly advantageous in the high-sensitivity light-sensitive material of the present invention. The pyrazoloazole type coupler may be the total amount of the magenta dye-forming component, or may be used in combination with another 5-pyrazolone type coupler.

Yellow coupler example In the present invention, such a fast-reacting coupler is preferably added to at least the most sensitive unit emulsion layer of each color-sensitive layer. There is no particular limitation on the amount used, but a cyan fast reaction coupler 0.005 to 0.1 per mol of silver,
A range of 0.005 to 0.1 for the magenta high speed reaction coupler and 0.005 to 0.1 for the yellow high speed reaction coupler is preferable.

Further, in the present invention, a non-diffusive coupler in which the formed dye defined in US Pat. No. 4,420,556 (1) and (3) to (8) and JP-A-59-191036 has a suitable diffusivity. It is preferable to improve the sensitivity by improving the covering power and improve the graininess. These couplers are contained in at least one of a high-sensitivity blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, preferably 2 of the high-sensitive layers.
Included in the above. 10-100 of couplers used for high sensitivity layer
Mol% is a coupler in which the resulting dye has an appropriate diffusivity,
Others can be couplers that form dyes that are substantially non-diffusible. These couplers which form dyes having an appropriate diffusibility can be used not only in the high sensitivity layer but also in the medium sensitivity emulsion layer. These couplers are disclosed in the above patents and JP-A-56-1938, 57-3934, 53-105226,
According to the method described in U.S. Pat.
Can be easily synthesized.

In the present invention, in addition to the above-mentioned coupler, a colored coupler having a color correction effect, or a coupler which releases a development inhibitor upon development (so-called DIR coupler) may be used.

In addition to the DIR coupler, a non-colored DIR coupling compound which is colorless as a product of the coupling reaction and releases a development inhibitor may be contained.

In the present invention, it is preferable to use a compound capable of forming a development accelerator or a fogging agent (hereinafter referred to as FR compound) with silver development to achieve high sensitivity. These FR compounds are described in U.S. Patent Nos. 4,390,618, 4,518,682 and 4,526,
No. 863, No. 4,482,629, JP-A Nos. 59-157638 and 59-17.
It can be easily synthesized by the methods described in 0840, 60-185950, 60-1007029 and the like.

Two or more FR compounds may be used in combination. The amount of FR compound added is 0.2 mol or less per 1 mol of silver in the same layer or adjacent layers 1
It is 0 ^-10 mol or more, preferably 0.02 mol or less and 10 ^-7 or more. The FR compound can be used alone or in combination with the coupler for forming a color image by introducing it into the silver halide emulsion layer by an oil-in-water dispersion method known as an oil protect method, to achieve the intended purpose. .

The couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound to two or more different layers.

To introduce the coupler into the silver halide emulsion layer, known methods such as the method described in US Pat. No. 2,322,027 are used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphonate, triphenyl phosphonate, tricresyl phosphonate, dioctyl butyl phosphonate), citric acid ester (eg acetyl) Tributyl citrate), benzoic acid esters (eg octyl benzoate), alkylamides (eg diethyllaurylamide), fatty acid esters (eg dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg tributyl trimesate)
, Or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After being dissolved in methyl cellosolve acetate or the like, it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

Further, the dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 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 developer used is conveniently carried to provide the intermediate scale image. The maximum absorption band of the cyan dye formed from the cyan color former is between about 600 and 720 nm, the maximum absorption band of the magenta dye formed from the magenta colorant is between about 500 and 580 nm, and the maximum absorption band of the yellow color former. The maximum absorption band of the yellow dye formed is preferably between about 400 and 480 nm.

The light-sensitive material of the present invention may contain a dye in the hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. Specific examples of dyes that can be used include British Patents 584,609 and 1,77,429.
No. 48-85130, No. 49-99620, No. 49-114420
No. 52-108115, U.S. Patents 2,255,077, 2,274,7.
No. 82, No. 2,390,707, No. 2,493,747, No. 2,533,472
No. 2, No. 2,843,486, No. 2,956,879, No. 3,148,187,
3,177,078, 3,247,127, 3,540,887, 3,5
75,704, 3,653,905, 3,718,427, 4,071,31
No. 2, No. 4,070,352, No. 4,420,555.

In the light-sensitive material of the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like. For example, U.S. Pat.Nos. 685,475, U.S. Pat.
9,401, 2,882,156, 3,048,487, 3,184,309
No. 3,445,231, West German patent application (OLS) 1,914,362
The polymers described in JP-A Nos. 50-47624 and 50-71332 can be used.

Various additives generally used in silver halide light-sensitive materials can be used in the light-sensitive material of the present invention.
Such materials are described, for example, in US Pat. No. 4,599,301. A typical example is column 33 of the same specification.
From line 12 to column 38, line 45: Surfactant (column 33), water-insoluble or sparingly soluble polymer (column 33-34), UV absorber (column 37-38), antifoggant (column 37) , Anti-foggants (column 38), hydroquinones (column 38) and the like.

The light-sensitive material of the present invention is, for example, the above-mentioned US Pat. No. 4,599,301.
It can be developed according to the method described in columns 34 to 35 of the specification.

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

If the water washing step after color development as in the processing step of the present invention is omitted or shortened, a part of the developer is brought into the subsequent processing step, causing various troubles. For example, it may be brought into a bleaching solution to reduce the bleaching ability or cause an increase in concentration. Such bringing of the developing solution into the bleaching bath usually depends on the film thickness and the degree of swelling of the light-sensitive material, but even if the film thickness and the amount of the hardener are the same, it depends on the kind of the surfactant. The inventors have found out. Among the surfactants, a derivative of naphthalene sulfonic acid is particularly preferable. The reason for this is thought to be related to the amount of the developing agent incorporated into the surfactant micelles and a slight difference in the swelling of the film containing the surfactant in the developer, but it has not been clarified. Further, the naphthalenesulfonic acid derivative is particularly preferable in the case where the generation of bubbles in the treatment liquid is small and the stirring is intensified for a short time treatment as in the present invention. Taking sodium dodecylbenzene sulfonate as an example of the surfactant used in the light-sensitive material, the foaming in the color developing bath and the bleaching bath is remarkable, and the foam once generated is hard to disappear. On the other hand, the naphthalenesulfonic acid derivative of the present invention is characterized in that bubbles are less likely to occur and defoaming is easy.

In the present invention, the surfactant used for the light-sensitive material is 0.5 g
In the following, it is preferable that 60% or more of the total amount of the surfactant is a naphthalenesulfonic acid derivative.

The total carbon number of the substituents of naphthalene sulfonic acid is preferably 18 or less, and the following preferred examples are given, but the present invention is not limited thereto.

W-2 Cyanamid Aerosol OS W-3 Dupont Alkanol B Hereinafter, the processing bath having the 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 a bleaching ability.

The processing bath having a bleaching ability generally refers to a bleaching solution and a bleach-fixing solution, but a bleaching solution is preferred in the present invention because of its excellent bleaching power. The desilvering process of the present invention includes, for example, the following processes, but is not limited to these.

Bleaching-fixing Bleaching-bleaching fixing Bleaching fixing Bleaching fixing-bleaching fixing Bleaching-washing-fixing In particular, the steps and are preferable in order to exert the effect of the present invention.

The bleaching agent of the present invention comprises at least one ferric complex salt of a compound selected from the above-mentioned compound (A) and 1,3-diaminopropanetetraacetic acid ferric complex salt in a molar ratio of the former to the latter of 3
The following ratios (including 0) are used together. The preferable molar ratio is 1.8 to 0.5. If the molar ratio exceeds 3, the bleaching power will decrease, resulting in poor desilvering. Further, when the ratio of ferric iron salt of 1,3-diaminopropanetetraacetic acid becomes extremely high, slight bleaching fog may occur.

The addition amount of the bleaching agent of the present invention is 1 per bath having a bleaching ability.
0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol.

In addition to the aminopolycarboxylic acid iron (III) complex described above, an aminopolycarboxylic acid salt can be added to the processing solution having bleaching ability of the present invention. Particularly, it is preferable to add the compound of the compound group (A). The preferred addition amount is 0.0001
Mol to 0.1 mol / l, more preferably 0.003 to 0.05 mol
/ l.

The aminopolycarboxylic acid and its ferric iron complex salt are usually preferably used in the form of an alkali metal salt or an ammonium salt, and an ammonium salt is particularly preferable in view of its excellent solubility and bleaching power.

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

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

Such bleaching accelerators are described, for example, in US Pat.
3,893,858 specification, German Patent 1,290,812 specification,
Compounds having a mercapto group or a disulfide group described in British Patent No. 1,138,842, JP-A No. 53-95630 and Research Disclosure No. 17129 (July 1978), JP-A No. 50-140129. Thiazolidine derivatives described in the publication, U.S. Patent No. 3,706,561 thiourea derivatives described in the specification, iodide described in JP-A-58-16235, German Patent 2,748,430 polyethylene oxides described, The polyamine compounds described in JP-B-45-8836 can be used. Particularly preferred are mercapto compounds as described in British Patent 1,138,842. Especially preferred are:

The amount of bleaching accelerator added is 0.01 g per 1 liquor with bleaching ability.
-20 g, preferably 0.1-10 g.

The bleaching solution constituting the present invention, in addition to the bleaching agent and the above compounds, bromide, 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 rehalogenating agent is bleach 1
The amount is 0.1 to 5 mol, preferably 0.5 to 3 mol.
In addition, nitrates such as sodium sulfate and ammonium nitrate,
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, etc. One or more inorganic acids having pH buffering ability, organic Additives known to be used in ordinary bleaching solutions such as acids and salts thereof can be added.

The pH of the bleaching bath of the present invention is generally 6 to 1, but preferably 5.8 to 1.5, most preferably 5.3 to 2. In the preferred pH range, there is little bleaching fog, and
Excellent desilvering performance.

The replenishing amount of the bleaching bath of the present invention is 5 per 1 m ² of the light-sensitive material.
It is 0 ml to 2000 ml, preferably 100 ml to 1000 ml.

In the present invention, after the treatment with a bath having a bleaching ability, the treatment is generally performed with a bath having a fixing ability. However, this does not apply when the bath having a bleaching ability is a bleach-fixing solution.

The bath having fixing ability of the present invention means a bleach-fixing bath or a fixing bath.

Examples of the fixing agent for the bath having these fixing ability include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, and thiosulfates. urea,
Thioether or the like can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.5 mol to 2 mol, per treatment liquid.

The bath having fixing ability contains sulfite as a preservative, for example, sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adduct of hydroxylamine, hydrazine, and aldehyde compound, such as acetaldehyde sodium bisulfite. be able to. Further, various fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol can be contained, and especially as a preservative, Japanese Patent Application No. 60-28
It is preferable to use the sulfinic acid compound described in 3831.

The replenishing amount of the fixing bath is 3 per 1 m ² of the light-sensitive material.
It is preferably from 00 ml to 3000 ml, more preferably from 300 ml to 1000 ml.

Further, 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 liquid.

The shorter the total time of the desilvering process 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. Also, the processing temperature is 25 ° ~
The temperature is 50 ° C, preferably 35 ° C to 45 ° C. In the preferable temperature range, the desilvering rate is improved and the stain generation after the processing is effectively prevented.

In the desilvering process of the present invention, it is preferable that stirring is strengthened as much as possible in order to more effectively exhibit the effects of the present invention.

As a concrete method for strengthening stirring, JP-A-62-183460,
No. 62-183461, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material, a method of increasing the stirring effect by using the rotating means of JP-A No. 62-183461, and a wiper provided in the solution. Examples include a method of moving the light-sensitive material while bringing the blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate.

Further, the agitation improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic processor used in the present invention is disclosed in JP-A-60-191257.
No. 191258, No. 191259, it is preferable to have the photosensitive material conveying means. As described in JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath and has a high effect of preventing the performance price of the treatment liquid. 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 used in the present invention contains a known aromatic primary amine color developing agent. A preferred example is a p-phenylenediamine derivative, and typical examples thereof are shown below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3 -Methyl-N-ethyl-N-
[Β- (Methanesulfonamide) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Of the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferable.

Further, these p-phenylenediamine derivatives may be salts such as sulfates, hydrochlorides, sulfites and p-toluenesulfonates. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g, more preferably about 0.5 g to about 10 g per developer.

Further, as a preservative, a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, or a carbonyl sulfite adduct is added to the color developer as needed. be able to.

The preferable addition amount is 0.5 g to 10 g, and more preferably 1 g to 5 g, per color developing solution.

Further, as a compound for directly preserving the color developing agent, various hydroxylamines, hydroxamic acids described in Japanese Patent Application No. 61-186559, hydrazines described in 61-170756, and hydrazides, 61-188742. No. and No. 61-2032
No. 53 phenols, α-hydroxyketones and α-aminoketones described in 61-188741, and / or
It is preferable to add various sugars described in JP-A No. 61-180616. Further, in combination with the above compound, Japanese Patent Application No. 61-147823,
61-166674, 61-165621, 61-164515,
61-170789, and 61-168159 and the like monoamines, 61-173595, 61-164515, 61-186560.
Diamines described in No. 61-165621, and No. 61-165621
Polyamines described in No. 169789, polyamines described in No. 61-1888619, nitroxy radicals described in No. 61-197760, No. 61-186561, and alcohols described in No. 61-197419, No. 61-198987. The described oximes, and 61-26
It is preferable to use the tertiary amines described in 5149.

Other preservatives are disclosed in JP-A-57-44148 and 57-537.
Various metals described in JP-A-49-58, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, polyethyleneimines described in JP-A-56-94349, U.S. Pat. The aromatic polyhydroxy compound described in 3,746,544 may be contained as necessary. It is particularly preferable to add an aromatic polyhydroxy compound.

The color developer used in the present invention preferably has a pH of 9 to 1.
2, more preferably from 9 to 11.0, and the color developing solution may contain other known developing solution component compounds.

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

Specific examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax) potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-
Examples thereof include sodium 2-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 developing solution is preferably 0.1 mol / l or more, and particularly preferably 0.1 mol / l to 0.4 mol / l.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution.

The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids and phosphonocarboxylic acids. Specific examples are shown below, but the present invention is not limited thereto.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid,
Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2
-Diaminopropane tetraacetic acid, hydroxyethyliminodiacetic 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-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid These chelating agents may be used in combination of two or more kinds, if necessary.

The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. Eg 1
It is about 0.1g to 10g.

If necessary, any development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution of the present invention does not substantially contain benzyl alcohol from the viewpoints of pollution, solution preparation and color contamination prevention. Here, "substantially" means that the amount of the developer is not more than 2 ml, preferably not contained at all.

Other development accelerators include JP-B-37-16088 and 37
-5987, 38-7826, 44-12380, 45-9019
No. 3,813,247 and the like, thioether compounds, JP-A-52-49829 and JP-A-50-15554, p-phenylenediamine compounds, JP-A-50
-137726, Japanese Patent Publication No. 44-30074, Japanese Unexamined Patent Publication Nos. 56-156826 and 52-43429, and the like, quaternary ammonium salts, U.S. Patent Nos. 2,494,903, 3,128,182, and 4,23.
0,796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent Nos. 2,482,546, 2,596,926 and 3,582,346, etc., amine compounds described in Japanese Patent Publication Nos. 37-16088, 42-2.
5201, U.S. Pat.No. 3,128,183, Japanese Patent Publication No. 41-11431,
Polyalkylene oxides represented by U.S. Pat. No. 4,242,883 and U.S. Pat. No. 3,532,501, and others 1-phenyl-3
-Pyrazolidones, imidazoles, etc. can be added as required.

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

The color developer used in the present invention may contain a fluorescent whitening agent. As the fluorescent whitening agent, 4,4'-diamino-2,2'-disulfostilbene compound is preferable. The addition amount is 0 to 5 g / l, preferably 0.1 g to 4 g / l.

If necessary, various surfactants such as alkylsulfonic acid, arylphosphonic acid, aliphatic carboxylic acid and aromatic carboxylic acid may be added.

The processing temperature of the color developer of the present invention is preferably 20 to 50 ° C.
30 to 45 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The replenishment amount is preferably small, but it is 100 to 1500 ml, preferably 100 to 800 ml, per 1 m ^{2 of} the light-sensitive material. More preferably, it is 100 ml to 400 ml.

If necessary, the color developing bath may be divided into two or more baths, and the color developing replenisher may be replenished from the frontmost bath or the last bath to shorten the developing time or the replenishing amount.

The processing method of the present invention can also be used for color reversal processing. In the present invention, as the black and white developing solution used at this time, what is commonly known as a black and white first developing solution used for reversal processing of a color photographic light-sensitive material or one used for processing a black-and-white light-sensitive material can be used. Further, various well-known additives which are generally added to the black and white developer can be contained.

Typical additives include a developing agent such as 1-phenyl-3-pyrazolidone, metol and hydroquinone, a preservative such as sulfite, and an accelerator composed of an alkali such as sodium hydroxide, sodium carbonate or potassium carbonate. , Potassium bromide, 2-methylbenzimidazole,
Inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as polyphosphates, trace amounts of iodides, and development inhibitors composed of mercapto compounds can be mentioned.

The processing method of the present invention comprises the processing steps such as color development, bleaching, bleach-fixing and fixing described above. Here, after the bleach-fixing or fixing step, treatment steps such as washing and stabilizing are generally carried out, but after the bath having fixing ability, the stabilizing treatment is carried out without substantially washing with water. A simple treatment method to be carried out can also be used.

The washing water used in the washing step may contain known additives, if necessary. For example, hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, bactericides and antifungal agents that prevent the growth of various bacteria and algae (eg, isothiazolone, organochlorine bactericides, benzotriazole, etc.) , A drying load, and a surfactant for preventing unevenness can be used. Or LE
West, “Water Quality Criteria”, Phot.Sci.and Eng., V
The compounds described in ol. 9, No. 6, pages 344 to 359 (1965) and the like can also be used.

As the stabilizing solution used in the stabilizing step, a processing solution that stabilizes the dye image is used. For example, a liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), and the like can be used. In the stabilizing solution, if necessary, an ammonium compound, Bi, a metal compound such as Al,
A fluorescent whitening agent, a chelating agent (for example, 1-hydroxyethylidene-1,1-diphosphonic acid), a bactericidal agent, an antifungal agent, a hardener, a surfactant and the like can be used.

The washing step and the stabilizing step are preferably a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. The amount of replenishment is 1 to 50 times, preferably 2 to 30 times, more preferably 2 to 15 times, the amount carried in from the previous bath per unit area.

As the water used in these washing step or stabilizing step, in addition to tap water, Ca by an ion exchange resin,
Water, halogen, deionized to a Mg concentration of 5 mg / l or less,
It is preferable to use water sterilized by an ultraviolet sterilization lamp or the like.

In each of the above processing steps of the photosensitive material, when the continuous processing by the automatic developing machine is performed, the processing solution may be concentrated by evaporation, especially when the processing amount is small or the opening area of the processing solution is large. Will be noticeable. In order to correct such concentration of the treatment liquid, it is preferable to replenish an appropriate amount of water or the correction liquid.

Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid of the washing process or the stabilizing process is caused to flow into a bath having a fixing ability as a pre-bath.

〔Example〕

 Hereinafter, the present invention will be specifically described with reference to examples.

Example 1 On a subbed cellulose triacetate film support,
A sample, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) First layer (antihalation layer) Black colloidal silver 0.3 Gelatin 1.0 UV absorber UV-1 0.1 Same as UV-2 0.1 Same as UV-3 0.1 Dispersed oil Oil-1 0.2 Same as Oil-2 0.1 Second Layer (Intermediate layer) Gelatin 1.0 Colored coupler C-2 0.02 Dispersed oil Oil-1 0.01 4th layer (intermediate layer) Gelatin 1.0 Compound A 0.1 6th layer (intermediate layer) Gelatin 1.0 Compound A 0.1 Eighth layer (intermediate layer) Gelatin 1.0 Compound A 0.1 10th layer (intermediate layer) gelatin 1.0 coupler C-5 0.2 compound A 0.1 12th layer (intermediate layer) Fine grain silver bromide emulsion (average grain size 0.07μ) 2.0 Gelatin 1.2 Compound A 0.1 14th layer (1st protective layer) Coupler C-7 0.1 UV absorber UV-1 0.05 Same as above UV-2 0.05 Same as above UV-3 0.05 Same as above UV-4 0.05 Same as above UV-5 0.05 Gelatin 0.6 Dispersion oil Oil-4 0.1 15 layers (second protective layer) Gelatin 0.5 polymethylmethacrylate particles (diameter 1.5 μm) In addition to the above components, surfactant W-1 was added as a coating aid to each layer. In addition, formalin scavenger was added.

The amount added to the light-sensitive material is shown in grams per m ² , and the silver halide emulsion and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in a molar ratio with silver halide. It was

Compounds used in the examples This photosensitive material is referred to as sample 101. In addition, the third of this sample
Of the naphthol cyan coupler contained in the layer and the ninth layer,
The ratio of all cyan couplers contained in this layer (hereinafter referred to as naphthol content) is 6% and 34%, respectively.
Met. The specific photographic sensitivity of Sample 101 was calculated to be 1200
It was.

Next, the sample 101 was subjected to continuous processing (running test) after imagewise exposure until the tank was replenished with twice the tank capacity of the color developer in the following processing step. However, the composition of the bleaching solution is the first
Changes were made as shown in the table, and each of them was performed.

The automatic developing machine used was a belt-conveying system described in JP-A-60-191257, and each processing bath was a jet-stirring system described in JP-A-62-183460.

The processing steps are shown below.

The composition of each treatment liquid used is shown below.

(Stabilizer) Common for mother liquor and replenisher Formalin (37%) 1.2 ml 5-Chloro-2-methyl-4-isothiazolin-3-one 6.3 mg 2-Methyl-4-isothiazolin-3-one 3.0 mg Surfactant 0.4 [ C ₁₀ H ₂₁ -OCH ₂ CH ₂ O ₁₀ H] Ethylene glycol 10 Water was added to 1.0 L pH 5.0-7.0 The sample was exposed to 5 CMS, then treated with each running equilibrium solution, and the residual silver content was measured by the fluorescent X-ray method. I asked for. Residual silver amount is first
Indicated in the right column of the table.

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

Example 2 A sample 201 was prepared in exactly the same manner as in Example 1 except that the coupler C-1 in the third layer of Example 1 was changed to the coupler (a) having the following structure and an equimolar amount to C-1 was used. .

Further, a sample 202 was prepared in exactly the same manner as in Example 1, except that the coupler C-8 in the ninth layer was changed to the coupler (b) having the following structure and used in an equimolar amount to C-8.

The same processing as in Example 1 was performed using Samples 101, 201 and 202. However, the bleaching baths were A and E, the exposure was carried out imagewise with 5 CMS, and the residual silver amount was determined by uniformly exposing with another sample 5 CMS. As the cyan density, the density for the exposure amount that gives a density of 1.5 in Sample 202 was determined. The stain was represented by an increase in yellow density in the bleaching baths A and E based on the yellow density when the bleaching solution J described below was used.

<Bleaching bath J> Mother liquor / replenisher common ethylenediaminetetraacetic acid ferric ammonium salt 120.0g ethylenediaminetetraacetic acid disodium salt 10.0g ammonium nitrate 10.0g ammonium bromide 100.0g bleaching accelerator 5 × 10 ^-3 mol Ammonia water was added to pH 6.3 Water was added to 1.0 l From the above, it has been found that the combination of the naphthol coupler of the present invention and the bleaching bath of the present invention gives the best results.

Example 3 Sample 301, which is a multi-layer color light-sensitive material consisting of each layer having the following composition, was prepared on an undercoated cellulose triacetate film support.

1st layer (anti-halation layer) Black colloidal silver 0.3 Gelatin 1.0 UV absorber UV-1 0.1 Same as above UV-2 0.1 Same as above UV-3 0.1 Dispersed oil Oil-1 0.2 Same as above Oil-2 0.1 Second layer (intermediate layer) Gelatin 1.0 Colored coupler C-1 0.02 Dispersion oil Oil-1 0.01 Third layer (low-sensitivity red-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 8 mol%, average grain size 1.0
μ) 1.4 Gelatin 1.1 Sensitizing dye I 1.4 × 10 ^-4 Sensitizing dye II 7 × 10 ^-5 Coupler C-2 0.5 Coupler C-3 0.05 Coupler C-4 0.05 Dispersion oil Oil-3 0.03 Dispersion oil Oil-4 0.03 Fourth layer (intermediate layer) Gelatin 1.0 Dispersion oil Oil-1 0.05 Coupler C-5 0.15 Fifth layer (low sensitivity green sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 8 mol%, average grain size 1.0)
μ) 1.5 Monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 0.3
μ) 0.3 Gelatin 0.8 Sensitizing dye III 3 × 10 ^-4 Sensitizing dye IV 1 × 10 ^-4 Sensitizing dye V 1 × 10 ^-4 Sensitizing dye VI 1 × 10 ^-4 Coupler C-6 0.4 Coupler C-1 0.1 Dispersion oil Oil-3 0.1 Sixth layer (intermediate layer) Gelatin 1.0 Dispersion oil Oil-1 0.05 Coupler C-5 0.15 Seventh layer (low-sensitivity blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide 8 Mol%, average particle size 1.0
μ) 0.9 Gelatin 1.0 Sensitizing dye VII 2 × 10 ^-4 Sensitizing dye VIII 2 × 10 ^-4 Coupler C-7 0.9 Dispersion oil Oil-1 0.1 8th layer (intermediate layer) Seratin 1.0 Coupler C-5 0.15 9th Layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 5.5 mol average grain size 2.0 μ) 2.1 Silver iodobromide emulsion (silver iodide 8 mol average grain size 1.2 μ) 0.8 Silver iodobromide emulsion (Silver iodide 2.5 molar average particle size 0.5 μ) 0.3 Gelatin 1.2 Sensitizing dye I 7 × 10 ^-5 Sensitizing dye II 2 × 10 ^-5 Coupler C-8 0.1 Coupler C-4 0.2 Dispersion oil Oil-4 0.2 10 layers (intermediate layer) gelatin 1.0 Coupler C-5 0.1 11th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (5.5 mol% silver iodide, average grain size 2.0 μ) 1.2 Silver iodobromide emulsion (iodine Silver halide 8 mol% 1.0μ) 0.8 Gelatin 1.0 Sensitizing dye III 1.5 × 10 ^-4 〃 IV 5 × 10 ^-5 〃 V 5 × 10 ^-5 〃 VI 5 × 10 ^-5 〃 IX 1 × 10 ^-5 Coupler C -6 0.2 Coupler C-1 0.05 Dispersion oil Le Oil-1 0.4 12th layer (intermediate layer) Fine grain silver bromide emulsion (average grain size 0.07μ) 2.0 Gelatin 1.2 Dispersion oil Oil-1 0.05 Coupler C-5 0.1 13th layer (high-sensitivity blue-sensitive emulsion layer) Single Dispersed silver iodobromide emulsion (6 mol% silver iodide, average grain size 2.1
μ) 1.8 Monodisperse silver iodobromide emulsion (8 mol% silver iodide, average grain size 1.2)
μ) 0.5 monodisperse silver iodobromide emulsion (3 mol% silver iodide, average grain size 0.3
0.2) Fine grain silver iodobromide emulsion (average grain size 0.09μ) 0.2 Gelatin 1.2 Sensitizing dye VII 3 × 10 ^-4 Sensitizing dye VIII 1 × 10 ^-4 Coupler C-7 0.3 Dispersion oil Oil-1 0.06 14th Layer (1st protection layer) UV absorber UV-1 0.05 Same as above UV-2 0.05 Same as above UV-3 0.05 Same as above UV-4 0.05 Same as above UV-5 0.05 Gelatin 0.6 Dispersion oil Oil-4 0.1 15th layer (2nd protection layer) ) Gelatin 0.5 Polymethylmethacrylate particles (diameter 1.5μ) In each layer, in addition to the above components, surfactant WA-1 was added in a total amount of 0.25.
0.4 g of hardener H-1 was used. In addition, formalin scavenger was added.

The amount added to the light-sensitive material is shown in grams per m ² , and the silver halide emulsion and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in a molar ratio with silver halide. It was The naphthol contents of the third layer and the ninth layer were 13% and 100%, respectively.

Compounds used in the examples Sample 302 was prepared by changing the coupler C-2 of the third layer of Sample 301 to C-8 and using equimolar amounts.

Further, the coupler C-8 of the ninth layer of the sample 301 was changed to C-2, the coupler C-4 of the ninth and third layers was changed to the coupler (b) of Example 2, and each had the same mole as 301. Sample 303 (comparative) was made in quantity.

When the same treatments as in Example 2 were performed using these samples 301 to 303, the same results as in Example 2 were obtained.

Example 4 Samples 401 to 405 were prepared by changing the kind and amount of the surfactant of Sample 301 of Example 3 as follows.

The samples 401 to 405 were passed through the processing step of Example 1 (E in the bleaching bath). This process is called process α. A running test is carried out using the above-mentioned light-sensitive material, and the process that passes through the process of Example 1 after continuous processing until the tank is filled with the color developing solution by 4 times is designated as β.

It is considered that the treatment amounts α and β are different from each other in the continuous treatment amount by a factor of 2, and β is the fatigue of the bleaching solution. 5C for Samples 401-405
After the imagewise exposure of MS, the treatments α and β were performed. Processing α
The cyan densities of the processed β were read with the exposure amount that gives a cyan density of 1.5 at. In addition, the sample after treatment β is 60 ℃ 70
It was stored under% RH for 1 week, and the increase in yellow density was measured and shown in the table below.

By comparing Samples 401 and 405 with Samples 402 to 404, Sample 40
You can see that 1 and 405 are excellent.

Claims (2)

[Claims] 1. A blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layer, at least one of which is composed of two or more layers having different sensitivities. When viewed from the side of the support, at least one silver halide emulsion layer having different color sensitivity is arranged in order from the low-sensitivity layer to the high-sensitivity layer. In the method of processing a color light-sensitive material containing at least one naphthol coupler in an amount of 20 mol% or more based on all cyan couplers in the same layer after color development, the emulsion layer is treated with a processing solution having a bleaching ability. The treatment liquid has a bleaching agent containing at least one ferric complex salt of a compound selected from the following compound group (A) and 1,3-diaminopropanetetraacetic acid ferric complex salt in a molar ratio of the former to the latter. Ha containing at a ratio of 3 or less Processing method of Gen halide color photographic light-sensitive material. Compound group (A) A-1 ethylenediaminetetraacetic acid A-2 diethylenetriaminepentaacetic acid A-3 cyclohexanediaminetetraacetic acid A-4 1,2-propylenediaminetetraacetic acid 2. The total amount of surfactants in the light-sensitive material is 0.
The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the amount of the surfactant is 5 g / m ² or less and 60% or more of the total amount of the surfactant is a naphthalenesulfonic acid derivative.