EP0271061B1

EP0271061B1 - Silver halide color photographic material and method for processing the same

Info

Publication number: EP0271061B1
Application number: EP87118164A
Authority: EP
Inventors: Shinpei Fuji Photo Film Co. Ltd. Ikenoue; Toshihiro Fuji Photo Film Co. Ltd. Nishikawa; Akira Fuji Photo Film Co. Ltd. Abe; Shunji Fuji Photo Film Co. Ltd. Takada; Keisuke Fuji Photo Film Co. Ltd. Shiba
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1986-12-09
Filing date: 1987-12-08
Publication date: 1995-03-29
Anticipated expiration: 2007-12-08
Also published as: DE3751199T2; EP0271061A3; EP0271061A2; DE3751199D1

Description

The present invention relates to a silver halide color photographic material and a method for processing same.
Many attempts have been made to achieve higher sensitivity, better image quality and rapid and simple color development processing since silver halide color photographic materials were developed. Instant photographic materials which are one kind of photographic materials require high sensitivity and rapid and simple development processing. However, instant photographic materials cause some problems because the format thereof is fixed and a large number of prints is hard to obtain simultaneously. Also improvements in image quality and price are desired.
Color images of excellent image quality can be obtained within 3 minutes and 40 seconds by development processing using two baths or three baths in the case of conventional color paper or for about 10 minutes of development processing using a mini-labo system in the case of color reversal paper. However, these color papers can not be employed for photographing because of their low sensitivities. Processing of color negative photographic light-sensitive materials can be rapidly conducted with C-41 Processing of Eastman Kodak Co. but still requires a period of 17 minutes and 20 seconds. Also, it requires 12 minutes at 38°C even when a bleach-fixing step which is a combined step of a bleaching function and a fixing function is used. It is possible to conduct development processing of a batch system for about 10 minutes by force, but it can not be applied to continuous processing. In the case of adopting a rapid desilvering step in a mini-labo system, it takes 11 minutes and 30 seconds for continuous processing at 38°C.
On the other hand, a color negative/positive system can provide color prints of excellent image quality in desired numbers and at a reasonably low price. Also the market desires a rapid and simple continuous color development processing in order to obtain color prints at any time and anywhere according to the color negative/positive system. For this purpose, it is necessary to utilize excellent image quality, for example, color reproducibility, sharpness and graininess, and high sensitivity of color negative photographic light-sensitive materials and to develop a method for rapid and simple color development processing.
At present, all of the color negative photographic light-sensitive materials for obtaining high image quality, which are commercially available, employ DIR couplers (couplers capable of releasing development inhibitors upon the reaction with oxidation products of color developing agents). It is also known that DIR couplers act to retard the progress of color development. Further, in order to provide high sensitivity, to inhibit the formation of fog and to control the progress of development, light-sensitive silver halide emulsions containing 4 mol% or more of silver iodide are ordinarily employed.
EP-A-0070183 discloses light-sensitive color photographic materials having a support and coated thereon at least two light-sensitive silver halide emulsion layers respectively sensitive to lights of different spectral regions, each of said light-sensitive layers having different light sensitivities and containing negative type light-sensitive silver halide crystals essentially consisting of silver iodobromide containing silver iodide at a proportion not higher than 4 mole %.
It is the object of the present invention to provide a color photographic light-sensitive material which can be subjected to a rapid and simple color development processing while maintaining excellent color reproducibility and image sharpness, said material having little change in gradation depending on the developing time while maintaining a high sensitivity and a method for processing the color photographic light-sensitive material.
This object of the present invention has been achieved by a silver halide color photographic material comprising a transparent support having thereon a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, wherein

(1) at least one of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer comprises at least one negative type silver halide emulsion layer containing a dye forming coupler, each of the green-sensitive layer and the red-sensitive layer comprising at least three negative type silver halide emulsion layers which have different sensitivities from each other and the blue-sensitive layer comprising at least two negative type silver halide emulsion layers which have different sensitivities from each other,
(2) the average silver iodide content of the light-sensitive silver halide grains contained in at least one of the silver halide emulsion layer is less than 2 mol% and
(3) the photographic sensitivity is from ISO 25 to ISO 6400.

A method for processing such a silver halide color photographic material comprising the steps of exposing, color developing, desilvering and water washing or stabilizing, wherein the processing time is from 1 minute to 9 minutes, is also provided.
The present invention is particulary effective for a photographic light-sensitive material having a high sensitivity which has a large coating amount of silver. The sensitivity of the photographic light-sensitive material is from ISO 25 to ISO 6400. When the sensitivity is lower than ISO 25, the effect of the present invention is not particularly significant and such a sensitivity is too low for the purposes of conventional photographing. While the present invention can be applied to a photographic light-sensitive material having a sensitivity of more than 6400, the handling thereof is complicated and practically different in view of the influence of natural radioactivity. Therefore, the upper limit of sensitivity is defined as described above.
The term "DIR compound" used herein includes a DIR coupler and a DIR hydroquinone.
The term "processing time" as used herein means the time for the steps of color development, desilvering and water washing or stabilizing, and it does not include the time for drying.
The terminology "desilvering hindrance does not substantially occur" is described in detail hereinafter.
In accordance with the present invention a silver halide photographic material and a method for processing thereof using a chromogenic development method are provided. The chromogenic development method is the color photographic method which is most widely employed at present and in which an image dye is formed upon a coupling reaction of a so-called photographic coupler with an oxidation product of a paraphenylene- diamine type color developing agent. The principle thereof is described in T.H. James, The Theory of the Photographic Process, Third Edition, Chapter 17, pages 383 to 394 (The Macmillan Co., 1966).
The present invention does not relate to color photographic light-sensitive materials according to a dye developer system ora diffusible dye releasing compound system. In these systems, a desilvering step for physically separating developed silver from color images is not necessary, and thus they are irrelevant to the present invention which attempts to reduce the time of the desilvering step.
The present invention provides a negative type color photographic light-sensitive material for photographing. Acolor photographic light-sensitive material usually comprises a support having thereon at least two silver halide emulsion layers sensitive to different spectral ranges. Asilver halide photographic material having three different spectral sensitivities, i.e., blue sensitivity, green sensitivity and red sensitivity shows the representative combination of spectral sensitivities according to the present invention. In a system wherein the spectral energy distribution of the object to be photographed is converted using an appropriate electronic circuit, a different combination of spectral sensitivities, for example, a combination of three emulsion layers sensitive to green light, red light and infrared light, etc. can be employed, if desired, in order to reproduce natural color.
Further, as widely practiced in color photography using a subtractive process, to incorporate a yellow color forming coupler, a magenta color forming coupler and a cyan color forming coupler into a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer, respectively is a preferred embodiment of the present invention.
In the present invention, the photographic light sensitive material desirably has a wide latitude of exposure so as to reproduce sufficiently gradation even when the exposure amount deviates from the optimum value at the time of photographing. Each of the green-sensitive emulsion layer and the red-sensitive emulsion layer is composed of at least three negative type silver halide emulsion layers, i.e., a high sensitive layer, a medium- sensitive layer and a low-sensitive layer, and the blue-sensitive layer is composed of at least two negative type silver halide emulsion layers, i.e., a high-sensitive layer and a low-sensitive layer.
In the photographic light-sensitive material of the present invention, the average silver iodide content of the light-sensitive silver halide grains contained in at least one of the light-sensitive silver halide emulsion layers selected from the blue-sensitive, green-sensitive and red-sensitive emulsion layers is less than 2 mol%, preferably not more than 1 mol%. As a result, color development of the silver halide emulsion layer(s) of such a spectral sensitivity can proceed and the development inhibiting effect of iodide ions on other layers can also be reduced, and consequently the progress of development in all silver halide emulsion layers can be increased. When the average silver iodide content of the light-sensitive silver halide grains in three spectrally different light-sensitive layers is less than 2 mol%, preferably not more than 1 mol%, the development accelerating effect is particularly large, and in addition, an appropriate interlayer effect can be obtained. Moreover, it has been found that desilveration of developed silver which forms can be easily conducted.
In the present invention, the term "desilvering step" used herein means a step for removing undesirable developed silver which is formed upon color development. This step may be ordinarily composed of two steps of bleaching and fixing or performed as a mono-bath bleach-fixing step. Further, two baths of bleaching and then bleach-fixing, two baths of fixing and then bleach-fixing and two bleach-fixing baths are also employed, if desired. The bleach-fixing step is explained as a representative example for the desilvering step hereinafter.
The development processing time of from 1 minute to 9 minutes does not include the time for drying as defined above.
An important feature of the present invention resides in the silver halide emulsion used, particularly the halogen composition of the silver halide particles. Specifically, a silver halide emulsion in which the content of silver iodide is reduced to a level wherein the hindrance function on bleaching and fixing of reduced silver does not substantially occur or which does not contain silver iodide is employed. The upper limit of silver iodide content of the silver halide grains contained in at least one of the silver halide emulsion layers can be varied depending on the kinds and amounts of development inhibitors, antifoggants and stabilizers to be used, but is less than 2 mol%, preferably not more than 1 mol%, more preferably not more than 0.5 mol%, and substantially no silver iodide, if possible. In order to achieve high sensitivity using a silver halide emulsion of a low silver iodide content, an improved method for forming silver halide particles may be employed in combination with techniques for improving image sharpness and graininess as described above.
According to a generally accepted idea, silver iodobromide emulsions are employed as negative type silver halide emulsions of high sensitivity and silver chlorobromide emulsions or silver chloride emulsions are employed as silver halide emulsions for printing paper of low sensitivity. These facts are apparent from descriptions, for example, in Shin-ichi Kikuchi, Shashin Kagaku, Chaper 1, pages 17 to 19 (Kyoritsu Shuppan 1974), Pierre Glafkides, Photographic Chemistry, Vol. 1, chapters 19 and 20, pages 327 to 368 (Fountain Press, 1958), and particularly Shashin Kogaku no Kiso edited by Nippon Shashin Gakkai, Edition on Silver Salt Photography, Forth Edition, Chapter 3, Section 1.2, pages 103 to 104 (Corona, 1985).
The high-sensitive silver halide emulsion used in the present invention includes a silver iodobromide emulsion and a silver iodochlorobromide emulsion each containing silver iodide in an amount of less than 2 mol%, preferably not more than 1 mol% and preferably a silver bromide emulsion and a silver chlorobromide emulsion. In order to obtain high sensitivity, silver halide particles in which many lattice defects are formed in the process of particle formation, for example, particles having many twin planes, multiphase structure particles obtained by alteration of the pAg or alteration of the halogen composition, in the process of particle formation, particles obtained by changing the direction of crystal growth due to addition of other substances which adsorb to silver halide during the process of particle formation, silver halide particles obtained by adding other metal ion complexes or salts, for example, lead chloride, an iridium chloride complex, a gold chloride complex, a palladium chloride complex or a rhodium chloride complex, in the process of crystal formation, particles obtained by irregular crystal growth due to etching the surfaces thereof by adding a silver halide solvent, for example, a thiocyanate, a thioether compound or hypo. In the process of crystal formation, particularly in the latter period, particles connected with other crystals upon epitaxial junctions, particles connected to high-sensitive crystals of a high silver iodide content on base crystals of low silver iodide, crystals wherein the surface areas are increased by forming unevenness on their surfaces, particles which are subjected to multiple chemical sensitization in the process of particle formation, spectrally sensitized particles by adsorbing sensitizing dyes in the process of crystal growth or before conducting chemical sensitization, and particles which are subjected to centralization and intensification of light-sensitive nuclei by selective use of a small amount of chemical sensitizer, are preferably employed.
The silver halide emulsion having a high-sensitivity used in the present invention can be obtained by selecting appropriate silver halide particles from the various kinds of silver halide particles as described above and subjecting them to proper chemical sensitization conforming to the characteristics of the silver halide particles.
The diameter of silver halide grains used is generally from about 0.2 µm to 5 µm. Fundamental techniques are described, for example, in British Patents 1,027,146 and 2,038,792, U.S. Patents 3,505,068, 4,444,877, 4,094,684,4,142,900,4,459,353,4,349,622,4,395,478,4,433,501,4,463,087, 3,656,962 and 3,852,067, Japanese Patent Application (OPI) Nos. 162540/84, 108526/83, 111935/83, 111936/83, 111937/83 and 143331/85. Further, a small particle emulsion having a diameter of less than 0.2 µm may be employed in a mixture, if desired. Methods for preparation of such emulsions are described in U.S. Patents 3,574,628 and 3,655,394, British Patent 1,413,748. Further, monodispersed emulsions as described in Japanese Patent Application (OPI) Nos. 8600/73, 39027/76, 83097/76, 137133/78, 48521/79, 99419/79, 37635/83 and 49938/83, can be preferably employed in the present invention.
Moreover, tabular silver halide grains having an aspect (diameter/thickness) ratio of about 5 or more can be employed in the present invention. The tabular grains may be simply prepared by the method as described in Gutoff, Photographic Science and Engineering, Vol. 14, Pages 248 to 257 (1970), U.S. Patents 4,434,226, 4,414,310,4,433,048 and 4,439,520, British Patent 2,112,157. In the case of employing the tabular silver halide grains, it is described in detail that many advantages, for example, increase in spectral sensitizing efficiency with a sensitizing dye, improvement in graininess and improvement in sharpness, are obtained in U.S. Patent 4,434,226 mentioned above.
The silver halide emulsion used in the present invention can be prepared using an emulsion production device of a double jet process in which the pAg, temperature and stirring in a liquid phase in which silver halide particles are formed and grown are controlled in a fixed pattern and in which additions of a halide such as sodium chloride, potassium bromide and potassium iodide, and silver nitrate are controlled.
In the production of the silver halide emulsion used in the present invention, compounds as described in Research Disclosure, No. 17643 and ibid., No. 18716 can be employed. A fine grain emulsion wherein the diameter of the silver halide grains is 0.01 µm to 0.2 µm may be employed in a protective layer or an intermediate layer.
When a silver halide emulsion of a silver iodine content of less than 2 mol% is used light absorption in the blue wavelength range decreases, and thus sensitivity of the blue wavelength range tends to be insufficient. In view of compensation for the insufficient sensitivity due to the decrease in light absorption, it is preferred in the present invention to employ tabular grains having a diameter/thickness ratio of 5 or more which are small in a particle size/surface area ratio and capable of having added thereto a large amount of sensitizing dyes for sensitizing a short wavelength range to increase light absorption.
Further, in the case of silver halide grains having a regular crystal form, for example, cubic, octahedral or tetradecahedral, when the iodide content is small, the number of crystal defects decreases and a reduction of sensitivity occurs. Therefore, it is preferred for the emulsion used in the present invention to introduce intentionally crystal defects. Silver halide particles in which crystal defects are formed by adding, in a process of the formation of silver halide particles, substances which adsorb to silver halide, other halogens or other metal ions are preferably employed.
In the case wherein the photographic light-sensitive material according to the present invention is composed of plural silver halide emulsion layers which have substantially the same spectral sensitivity but different sensitivities from each other, silver halide particles used in an emulsion layer having the highest sensitivity among these emulsion layers have an average particle size of 0.3 f..lm or more, preferably 0.6 f..lm or more. The average particle size is obtained by the mean diameter calculated as a sphere based on the projected area using an electron microscope.
The present invention is characterized by the rapid progress of color development. More specifically, the feature resides in that a DIR compound (a DIR coupler or a DIR hydroquinone) which has a weak development inhibiting function on a gradation part at the beginning of development, but exhibits a strong development inhibiting function as the development proceeds and particularly has no or a small hindrance function against bleach-fixing of developed silver is selected and employed or a DIR compound is not employed.
The first aspect to be solved for the purpose of performing more rapidly and simply color development processing of color photographic light-sensitive materials for photographing is to carry out a rapid desilvering process (bleaching and fixing) of reduced silver. It has been found that the main factors which act on hindrance of the desilvering process of reduced silver are adsorption of development inhibitors released from DIR couplers ordinarily used on reduced silver, iodine ions formed upon development and adsorption of sensitizing dyes used for spectral sensitization of light-sensitive silver halide emulsions on silver halide particles.
Further, with respect to factors which disturb the progress of color development, the first one is the amount of silver iodide contained in the silver halide particles and the second one is adsorption of sensitizing dyes used for spectral sensitization on silver halide particles. However, silver iodide contained in silver halide particles has excellent functions, for example, appropriate control of processing of development on a gradation part, high sensitivity of the silver halide, restraint of fog, and improvement in graininess. Accordingly, the introduction of a new technique is required in order to reduce the amount of silver iodide used.
It has been found that color development processing of a short period within about 9 minutes can be performed using the photographic light-sensitive material according to the present invention. Specifically, it is possible to conduct short period desilveration of about 3 minutes and 30 seconds or less, preferably from 1 minute to 3 minutes. In the present invention, it is preferred to employ a color photographic light-sensitive material which contains a DIR compound capable of releasing a development inhibitor upon reaction with an oxidation product of a color developing agent in the course of color development in an amount which does not substantially hinder desilveration, for example, 5 mol% or less, preferably 2 mol% or less based on the total amount of couplers used for forming color images, or a color photographic light-sensitive material which does not contain a DIR compound at all.
Of the DIR compounds, those represented by the following general formulae (I) or (II) are preferably employed.

wherein A represents a color coupler residue or a coupler residue which does not form a colored dye upon a reaction with an oxidation product of a developing agent; L₁ represents a timing group; a represents 0 or 1; Z₁ represents a linking group selected from a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted arylene group or a substituted or unsubstituted, straight chain or branched chain alkylene group; Z₂ represents a substituted or unsubstituted heterocyclic group; L₂ represents a linking group; X and Y each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, a mercapto group, and at least one of X and Y includes a water-soluble group or a precursor thereof; b represents 0, 1 or 2; and c represents 0 or 1.
The DIR compounds represented by the general formulae (I) or (II) are described in more detail below.
Suitable examples of the coupler residue which does not form a colored dye upon a reaction with an oxidation product of a developing agent include those as described, for example, in U.S. Patent 3,632,345 and 3,958,993, Japanese Patent Application (OPI) Nos. 64927/76 and 161237/77.
Suitable examples of the color coupler residue are described below. Preferred examples of yellow color coupler residues represented by A include those of the pivaloyl acetanilide type, benzoyl acetanilide type, malonic diester type, malondiimide type, dibenzoylmethane type, benzothiazolyl acetamide type, malonic ester monoamide type, benzothiazolyl acetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, benzimidazolyl acetamide type and benzimidazolyl acetate type; the coupler residues derived from hetero ring-substituted acetamides or hetero ring-substituted acetates described in U.S. Patent 3,841,880; the coupler residues derived from the acyl acetamides as described in U.S. Patent 3,770,446, British Patent 1,459,171, West German Patent Application (OLS) No. 2,503,099, Japanese Patent Application (OPI) No. 139738/75 and Research Disclosure, No. 15737; and the hetero ring substituted type coupler residues as described in U.S. Patent 4,046,574.
Preferred examples of magenta color coupler residues represented by A include those of the 5-oxo-2-pyrazoline type, the pyrazolo[1,5-a]benzimidazole type and the cyanoacetophenone type; and coupler residues having a pyrazolotriazole nucleus.
Preferred examples of cyan color coupler residues represented by A include those having a phenol nucleus or an a-naphthol nucleus.
Further, the coupler residues represented by A are those which release a development inhibitor upon coupling with an oxidation product of a developing agent and substantially do not form a dye. Suitable examples of such a type of coupler residues represented by A include the coupler residues as described in U.S. Patents 4,052,213, 4,088,491, 3,632,345, 3,958,993, and 3,961,959.
In short, A is a coupler residue capable of releasing a moiety of
or a moiety of
upon the reaction with an oxidation product of a color developing agent.
Suitable examples of the timing group represented by L₁ in the general formulae (I) or (II) are set forth below.
(a linking group as described in U.S. Patent 4,146,396)
(a linking group as described in West German Patent Application (OLS) No. 2,626,315)
(a linking group as described in West German Patent Application (OLS) No. 2,855,697; c represents an integer of 0, 1, or 2)
In the above described formulae, R₂₁ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, a ureido group, a cyano group, a nitro group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a cycloalkyl group, an alkanesulfonyl group, an arylsulfonyl group or an acyl group; R₂₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group; c represents 0, 1 or 2; q represents 1 or 2, and when q represents 2, the two R₂₁ groups may be bonded to each other to form a condensed ring.
Suitable examples of the linking group represented by Z₁ in the general formula (I) include a (2+b)-valent heterocyclic group, a substituted or unsubstituted arylene group and a straight chain or branched chain alkylene group. Specific examples thereof are set forth below in the form of -S-Z₁-.
Preferably, Z₁ represents a 5-tetrazolyl group, a 2-(1,3,4-thiadiazolyl) group, or a 2-(1-methyl-1,3,4-thiazolyl group.
Suitable examples of the (2+b)-valent heterocyclic group represented by Z₂ in the general formula (II) are set forth below in the form of -S-Z₁-.
Suitable examples of the linking group represented by L₂ in the general formulae (I) or (II) are set forth below.
In the above described formulae, d represents an integerfrom 0 to 10, preferably from 0 to 5; W_i represents a hydrogen atom, a halogen atom, an alkyl group having from 1 to 10, preferably from 1 to 5 carbon atoms, an alkanamido group having from 1 to 10, preferably from 1 to 5 carbon atoms, an alkoxy group having from 1 to 10, preferably from 1 to 5 carbon atoms, an alkoxycarbonyl group having from 1 to 10, preferably from 1 to 5 carbon atoms, an aryloxycarbonyl group, an alkanesulfonamido group having from 1 to 10, preferably 1 to 5 carbon atoms, an aryl group, a carbamoyl group, an N-alkylcarbamoyl group having from 1 to 10, preferably from 1 to 5 carbon atoms, a nitro group, a cyano group, an arylsulfonamido group, a sulfamoyl group or an imido group; W₂ represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, an aryl group or an alkenyl group; W₃ represents a hydrogen atom, a halogen atom, a nitro group, an alkoxy group having from 1 to 6 carbon atoms or an alkyl group having from 1 to 6 carbon atoms; and p represents an integer from 0 to 6.
The alkyl group or the alkenyl group represented by X or Y in the general formulae (I) or (II) specifically represents a straight chain, branched chain or cyclic alkyl group or alkenyl group having 1 to 10, preferably 1 to 5 carbon atoms, and preferably has a substituent. Examples of the substituents include a halogen atom, a nitro group, an alkoxy group having from 1 to 4 carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, an alkanesulfonyl group having from 1 to 4 carbon atoms, an arylsulfonyl group having from 6 to 10 carbon atoms, an alkanamido group having from 1 to 5 carbon atoms, an anilino group, a benzamido group, a carbamoyl group, a carbamoyl group substituted with an alkyl group having from 1 to 6 carbon atoms, a carbamoyl group substituted with an aryl group having from 6 to 10 carbon atoms, an alkylsulfonamido group having from 1 to 4 carbon atoms, an arylsulfonamido group having from 6 to 10 carbon atoms, an alkylthio group having from 1 to 4 carbon atoms, an arylthio group having from 6 to 10 carbon atoms, a phthalimido group, a succinimido group, an imidazolyl group, a 1,2,4-triazolyl group, a pyrazolyl group, a benzotriazolyl group, a furyl group, a benzothiazolyl group, an alkylamino group having from 1 to 4 carbon atoms, an alkanoyl group having from 1 to 4 carbon atoms, a benzoyl group, an alkanoyloxy group having from 1 to 4 carbon atoms, a benzoyl oxy group, a perfluoroalkyl group having from 1 to 4 carbon atoms, a cyano group, a tetrazolyl group, a hydroxy group, a carboxy group, a mercapto group, a sulfo group, an amino group, an alkylsulfamoyl group having from 1 to 4 carbon atoms, an arylcarbonyl group substituted with an aryloxy group having from 6 to 10 carbon atoms, an imidazolidinyl group or an alkylideneamino group having from 1 to 6 carbon atoms.
Y may represent an aryl group, and specifically represents a phenyl group or a naphthyl group which may be substituted. Examples of the substituents are selected from the substituents as defined for the above described alkyl group or alkenyl group and an alkyl group having from 1 to 4 carbon atoms.
Y may represent a heterocyclic group, and includes a diazolyl group (for example, a 2-imidazolyl group, a 4-pyrazolyl group), a triazolyl group (for example, a 1,2,4-triazol-3-yl group), a thiazolyl group (for example, a 2-benzothiazolyl group), an oxazolyl group (for example, a 1,3-oxazol-2-yl group), a pyrrolyl group, a pyridyl group, a diazinyl group (for example, a 1,4-diazin-2-yl group), a triazinyl group (for example, a 1,2,4-triazin-5- ylgroup), a furyl group, a diazolinyl group (for example, an imidazolin-2-yl group), a pyrrolinyl group, ora thienyl group.
At least one of X or -(L₂)-Y includes a water-soluble group or a precursor thereof. Suitable examples of the water-soluble group and a precursor thereof are set forth below.

-SO₃H or a salt thereof,
-COOH or a salt thereof,
a carboxylic acid ester group such as -COOCH₃, -COOCF₃, -COOC₂H₅, -COOC₂F₂H₃,
a sulfonamido group such as -NHS0₂CH₃,
a carbamido aroup such as -NHCOOCH₃. -NHCOOC₂H₅.

(wherein R₁ represents a hydrogen atom or a straight chain or branched chain alkyl group having from 1 to 4 carbon atoms; R₂ represents a straight chain or branched chain alkyl group having from 1 to 4 carbon atoms; and the total number of carbon atoms included in R₁ and R₂ is not more than 8)

Specific examples of the compound represented by the general formula (I) which can be used in the present invention are set forth below.
The DIR couplers which can be employed in the present invention have the suitable development inhibiting function as described above and a tendency which does not substantially hinder the bleaching of silver. Of the DIR couplers, those represented by the following general formulae (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII) or (XIV) are preferred.
In the above described formulae, Z₁, X, Y and b each has the same meaning as defined in the general formulae (I) or (II), and R₂₁ and R₂₂ each has the same meaning as defined above.
In the above described general formulae, R₁₁ represents an aliphatic group, an aromatic group, an alkoxy group or a heterocyclic group or a group formed by condensing a phenyl group and another ring; and R₁₂ and R₁₃ each represents an aromatic group or a heterocyclic group or a group formed by condensing a phenyl group and another ring.
The aliphatic group represented by R₁₁ is preferably an aliphatic group containing from 1 to 22 carbon atoms, and may have substituents or not, and further, may have a chain form or a cyclic form. Preferable substituents therefor include an alkoxy group, an aryloxy group, an amino group, an acylamino group, a halogen atom, each of which may further have substituent(s). Specific examples of aliphatic groups useful for R₁₁ include an isopropyl group, an isobutyl group, a tert-butyl group, an isoamyl group, a tert-amyl group, a 1,1-dimethylbutyl group, a 1,1-dimethylhexyl group, a 1,1-diethylhexyl group, a dodecyl group, a hexadecyl group, an octadecyl group, a cyclohexyl group, a 2-methoxyisopropyl group, a 2-phenoxyisopropyl group, a 2-p-tert-butylphenoxyisopropyl group, an a-aminoisopropyl group, an a-(diethylamino)isopropyl group, an a-(succinimido)isopropyl group, an a-(phthalimido)isopropyl group, an a-(benzenesulfonamido)isopropyl group.
In the case that R_11' R₁₂ or R₁₃ represents an aromatic group (especially a phenyl group), it may have a substituent. The aromatic group such as a phenyl group, may be substituted with an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonylamino group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkyl-substituted succinimido group, each containing 32 or less carbon atoms. The alkyl group therein may include an alkyl group which contains an aromatic group such as phenylene in its chain. Further, a phenyl group represented by R_11' R₁₂, or R₁₃ may be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, the aryl moiety of which groups each may be substituted with one or more alkyl groups wherein the number of carbon atoms is from 1 to 22 in total.
Furthermore, a phenyl group represented by R₁₁, R₁₂ or R₁₃ may be substituted with an amino group which may include an amino group substituted with a lower alkyl group having from 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group or a halogen atom.
In addition, R₁₁, R₁₂ or R₁₃ may represent a substituent formed by condensing a phenyl group and another ring, to form, for example, a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a cou- maranyl group, a tetrahydronaphthyl group. These substituents may further have substituents in themselves.
In the case that R₁₁ represents an alkoxy group, the alkyl moiety thereof represents a straight chain or branched chain alkyl group having from 1 to 40 carbon atoms, preferably from 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group or a cyclic alkenyl group, each of which may be substituted with a halogen atom, an aryl group, an alkoxy group.
In the case that R₁₁, R₁₂ or R₁₃ represents a heterocyclic group, the heterocyclic group is bonded to the carbon atom of the carbonyl group of the acyl moiety or the nitrogen atom of the amido moiety of an a-acyla- cetamido group through one of the carbon atoms forming the ring. Examples of such heterocyclic rings include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazole, oxazine. These rings may further have substituents on the individual rings.
In the above-described formula (V), R₁₅ represents a straight chain or branched chain alkyl group having from 1 to 40 carbon atoms, preferably from 1 to 22 carbon atoms (e.g., a methyl group, an isopropyl group, a tert-butyl group, a hexyl group, a dodecyl group), an alkenyl group (e.g., an allyl group), a cyclic alkyl group (e.g., a cyclopentyl group, a cyclohexyl group, a norbornyl group), an aralkyl group (e.g., a benzyl group, a (3-phenylethyl group), a cyclic alkenyl group (e.g., a cyclopentenyl group, a cyclohexenyl group) which groups each may be substituted with a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an alkylthiocarbonyl group, an arylthiocarbonyl group, an alkoxy carbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a thiourethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group.
R₁₅ may further represent an aryl group (e.g., a phenyl group, an a- or (3-naphthyl group). The aryl group may have one or more substituents. Specific examples of the substituents include an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-alkylanilino group, an N-arylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group. A more preferable group for R₁₅ is a phenyl group which is substituted with an alkyl group, an alkoxy group, a halogen atom, at at least one of the o-positions, because it is effective to restrain discoloration of couplers remaining in film layers due to light or heat.
Furthermore, R₁₅ may represent a heterocyclic group (e.g., a 5-membered or 6-membered heterocyclic ring containing as a hetero atom a nitrogen atom, an oxygen atom or a sulfuratom, or a condensed ring thereof, specific examples including a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a naphthoxazolyl group), a heterocyclic group substituted with one or more substituents as defined for the above-described aryl group, an aliphatic acyl group, an aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.
In the above-described formulae, R₁₄ represents a hydrogen atom, a straight chain or branched chain alkyl group having from 1 to 40 carbon atoms, preferably from 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group (each of which may have one or more substituents as defined for the above-described substituents R₁₅), an aryl group or a heterocyclic group (which each also may have one or more substituents as defined for the above-described substituent R₁₅), an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, a stearyloxycarbonyl group), an aralkyloxycarbonyl group (e.g., a benzyloxycarbonyl group), an alkoxy group (e.g., a methoxy group, an ethoxy group, a heptadecyloxy group), an aryloxy group (e.g., a phenoxy group, a tolyloxy group), an alkylthio group (e.g., an ethylthio group, a dodecylthio group), an arylthio group (e.g., a phenylthio group, an a-naphthylthio group), a carboxy group, an acylamino group (e.g., an acetylamino group, a 3-[(2,4-di-tert-amylphenoxy)acetamido]benzamido group), a diacylamino group, an N-alkylacylamino group (e.g., an N-methylpropionamido group), an N-arylacylamino group (e.g., an N-phenylacetamido group), a ureido group (e.g., a ureido group, an N-arylureido group, an N-alkylureido group), a urethane group, a thiourethane group, an arylamino group (e.g., a phenylamino group, an N-methylanilino group, a diphanylanino group, an N-acetylanilino group, a 2-chloro-5-tetradecanamidoanilino group), an alkylamino group (e.g., a n-butylamino group, a methylamino group, a cy- clohexylamino group), a cycloamino group (e.g., a piperidino group, a pyrrolidino group), a heterocyclic amino group (e.g., a 4-pyridylamino group, a 2-benzoxazolylamino group), an alkylcarbonyl group (e.g., a methylcar- bonyl group), an arylcarbonyl group, a sulfonamido group (e.g., an alkylsulfonamido group, an arylsulfonamido group), a carbamoyl group (e.g., an ethylcarbamoyl group, a dimethylcarbamoyl group, an N-methylphenyl- carbamoyl group, an N-phenylcarbamoyl group), a sulfamoyl group (e.g., an N-alkylsulfamoyl group, an N,N-dialkylsulfamoyl group, an N-arylarylsulfamoyl group, an N-alkyl-N-arylsulfamoyl group, an N,N-diarylsulfa- moyl group), a cyano group, a hydroxy group, a mercapto group, a halogen atom or a sulfo group.
In the above-described formula, R₁₇ represents a hydrogen atom, or a straight chain or branched chain alkyl group having from 1 to 32 carbon atoms, preferably from 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group or a cyclic alkenyl group, each of which may have one or more substituents as defined from the above-described substituents R_15'
Further, R₁₇ may represent an aryl group or a heterocyclic group, which each may have one or more substituents as defined for the above-described substituent R₁₅.
Furthermore, R₁₇ may represent a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an n-alkylanilino group, a hydroxy group or a mercapto group.
In the above-described formulae, R₁₈, R₁₉ and R₂₀ each represents a group of a type which has been employed in conventional 4-equivalent type phenol or a-naphthol couplers.
Specifically, R₁₈ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an acylamino group, an -O-R₃₁ group or an -S-R₃₁ group (wherein R₃₁ is an aliphatic hydrocarbon residue). When two or more of the R₁₈ groups are present in one molecule, they may be different from each other. The above-described aliphatic hydrocarbon groups include those having substituents.
R₁₉ and R₂₀ each represents an aliphatic hydrocarbon group, an aryl group cr a heterocyclic group. Either of them may be a hydrogen atom. The above-described groups for R₁₉ and R₂₀ may further have certain substituents. Furthermore, R₁₉ and R₂₀ may combine with each other and form a nitrogen-containing heterocyclic nucleus. More specifically, the above-described aliphatic hydrocarbon residues include both saturated and unsaturated residues, wherein each may have a straight chain form, a branched chain form or a cyclic form. Preferred examples thereof include an alkyl group (e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, an isobutyl group, a dodecyl group, an octadecyl group, a cyclobutyl group, a cyclohexyl group) and an alkenyl group (e.g., an allyl group, an octenyl group). The above-described aryl group includes a phenyl group, a naphthyl group. Representative examples of the above-described heterocyclic groups include a pyridinyl group, a quinolyl group, a thienyl group, a piperidyl group, an imidazolyl group. These aliphatic hydrocarbon groups, aryl groups and heterocyclic groups each may be substituted with a halogen atom, a nitro group, a hydroxy group, a carboxy group, an amino group, a substituted amino group, a sulfo group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an arylthio group, an arylazo group, an acylamino group, a carbamoyl group, an ester group, an acyl group, an acyloxy group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a morpholino group. r represents an integer of 1 to 4 ; s represents an integer of 1 to 3 ; and t represents an integer of 1 to 5.
Substituents R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₇, R₁₈, R₁₉ and R₂₀ in the couplers represented by the general formulae (II) to (XIV) may combine with each other or each of them may make a divalent group to form symmetric or asymmetric complex couplers.
The DIR couplers used in the present invention can be prepared by the methods described in the patent publication described in Research Disclosure, No. 17643, VII-F, Japanese Patent Application (OIP) Nos. 151944/82, 154234/82 and 184248/85, U.S. Patent 4,248,962, and methods similar thereto.
Particularly preferred DIR couplers which can be used in the present invention are DIR couplers capable of releasing a development inhibitor having a carboxylic acid ester group, for example, Compounds (2), (3), (4) and (6) as described above. These couplers release a development inhibitor as development progress in an emulsion layer. The development inhibitor thus-released has a large diffusibility due to its low molecular weight and provides a preferred interlayer effect. Further, when it is discharged into a color developing solution, it is subjected to alkali hydrolysis to be converted to a harmless compound. Therefore, these DIR couplers exhibit small desilvering hindrance.
It is advantageous to prevent desilvering hindrance, even if the bleach-fixing time is about 3 minutes or less, when the coating amount of the DIR compound is 5 x 10-⁴ mol or less, preferably 1 x 10-⁴ mol or less per 1.0 g of the coating amount of light-sensitive silver halide calculated as silver, and the silver iodide content in at least one of the light-sensitive silver halide emulsion layer is 2 mol% or less, preferably 1 mol% or less in the photographic light-sensitive material of the present invention.
The color couplers used in the present invention are described, e.g., in the patent publications described in Research Disclosure, No . 17643,VII-C to G.
Preferred examples of the yellow coupler include those described in U.S. Patents 3,933,501, 4,022,620, 4,326,024, and 4,401,752, Japanese Patent Publication No. 10739/73, British Patents 1,425,020 and 1,476,760.
Preferred examples of the magenta coupler include 5-pyrazolone type compounds and pyrazoloazole type compounds. More preferred examples thereof include those described in U.S. Patents 4,310,619 and 4,351,897, European Patent 73,636, U.S. Patents 3,061,432 and 3,725,067, Reserch Disclosure, No. 24220 (June 1984), Japanese Patent Application (OPI) No. 33552/85, Reserch Disclosure, No. 24230 (June 1984), Japanese Patent Application (OPI) No. 43659/85, U.S. Patents 4,500,630 and 4,540,654 (the term "OPI" as used herein refers to a "published unexamined application").
Examples of the cyan coupler include phenol type couplers and naphthol type couplers. Preferred examples thereof include those described in U.S. Patents 4,052,212, 4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002, 3,758,308, 4,334,011 and 4,324,173, West German Patent Application (OLS) No. 3,329,729, European Patent Application 121,365A, U.S. Patents 3,446,622, 4,333,999, 4,451,559 and 4,427,767, European Patent Application 161,626A.
Preferred examples of the colored couplerwhich compensates unnecessary absorption of the colored dye include those described in Reserch Disclosure, No. 17643, VII-G, U.S. Patent4,163,670, Japanese Patent Publication No. 39413/82, U.S. Patents 4,004,929 and 4,138,258, British Patent 1,146,368.
Examples of the coupler in which the colored dye has a suitable diffusibility include those described in U.S. Patent 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent Application (OLS) No. 3,234,533.
Typical examples of the polymerized color forming coupler include those described in U.S. Patents 3,451,820, 4,080,211 and 4,367,282, British Patent 2,102,173.
In general, the amount used of the color coupler is from 0.001 to 1 mol per mol of the silver halide, and preferably, from 0.01 to 0.5 mol for yellow couplers, from 0.003 to 0.3 mol for magenta couplers, and from 0.002 to 0.3 mol for cyan couplers per mol of the silver halide.
The couplers which can be used in the present invention can be introduced into the photographic light-sensitive material according to various known dispersing methods. Typical examples of the dispersing methods include a solid dispersing method, an alkali dispersing method, preferably a latex dispersing method and more preferably an oil droplet in water type dispersion method. By means of the oil droplet in water type dispersing method, couplers are dissolved in either an organic solvent having a high boiling point of 175°C or more, a so-called auxiliary solvent having a low boiling point, or a mixture thereof and then the solution is finely dispersed in an aqueous medium such as water or an aqueous gelatin solution, in the presence of a surface active agent. Specific examples of the organic solvents having a high boiling point are described in U.S. Patent 2,322,027. In order to prepare a dispersion, phase inversion may be included. Further, dispersions are utilized for coating after removing or reducing the auxiliary solvent therein by distillation, noodle washing or ultra-filtration, if desired.
The processes and effects of latex dispersing methods and the specific examples of latexes for loading are described in U.S. Patent 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
The compounds represented by the general formulae (I) or (II) have only a small hindrance function on bleaching and fixing of reduced silver or no hindrance function, they have a small hindrance function on the progress of development at a gradation part, particularly in a toe portion, at color development and effectively provide an interlayer effect at an intermediate tone area and a high density area.
In the case wherein the DIR coupler is not employed, the bleaching and fixing step for processing the color photographic light-sensitive material can be completed in about 2 minutes or less and even in 1 minute since the effect on hindrance to bleaching and fixing of reduced silver is very small. The supplement for defects which occur according to the non-use of a DIR coupler, for example, improvement in interlayer effect, image sharpness and graininess, are desirably conducted by means of other procedures. The interlayer effect can be obtained by applying a masking method using a colored coupler. For example, an interlayer effect from a red-sensitive layer to a magenta color forming green-sensitive layer can be achieved by adding a compound capable of releasing a magenta dye to the red-sensitive layer. Image sharpness can be improved using a colored coupler which forms a fade mask. Further, improvement in graininess can be conducted, for example, using together with a competing coupler or using partially a coupler which forms a colored dye having some diffusibility.
Sensitizing dyes which are preferably employed in the present invention are those which do not restrain the progress of color development and do not hinder the bleaching and fixing function on reduced silver. Suitable sensitizing dyes to be used include cyanine, dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonole dyes. Particularly useful dyes are cyanine dyes, hemicyanine dyes, merocyanine dyes and complex merocyanine dyes. To these dyes can be applied any nuclei which are usually utilized for cyanine dyes. Examples of these nuclei are pyr- roline nuclei, oxazoline nuclei, thiazoline nuclei, pyrrole nuclei, oxazole nuclei, thiazole nuclei, selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei; the nucleus formed by fusing alicyclic hydrocarbon rings to the above-described nuclei; and the nuclei formed by fusing aromatic hydrocarbon rings to the above-described nuclei, such as indolenine nuclei, benzindolenine nuclei, indole nuclei, benzoxazole nuclei, naphthoxazole nuclei, benzothiazole nuclei, naphthothiazole nuclei, benzoselenazole nuclei, benzimidazole nuclei, quinoline nuclei. These nuclei may be substituted on carbon atoms.
For the merocyanine dyes or complex merocyanine dyes can be applied 5-membered or 6-membered heterocyclic nuclei such as pyrazolin-5-one nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei.
Sensitizing dyes which have a restraining function on the progress of color development and particularly those which have a hindering function on the bleaching and fixing of reduced silver are cation type cyanine dyes, particularly sensitizing dyes adsorbed on the silver halide grains in the form of a J-aggrogate. However, the hindering function is remarkably decreased, when a substituent having a water-soluble group is introduced into an N-substituent or a C-substituent of a cyanine dye. Anion type cyanine dyes show almost no such hindering function. With respect to hemicyanine dyes and rhodacyanine dyes, the same characteristics are observed. While merocyanine dyes have smaller hindering functions than cation type cyanine dyes, the hindering function can be almost eliminated by the introduction of a substituent having a water-soluble group just as for cyanine dyes.
In the present invention, a sensitizing dye having a substituent containing a precursor of a water-soluble group is incorporated into a color photographic light-sensitive material, and in the process of color development after imagewise exposure, the precursor is converted to a substituent having a water-soluble group upon hydrolysis to remove the hindering function of reduced silver on bleaching and fixing. These sensitizing dyes are preferably employed in combination.
Particularly, in color photographic light-sensitive materials for photographing, monomethinecyanine dyes, trimethinecyanine dyes, simple merocyanine dyes, and dimethinecyanine dyes are employed. Further, pen- tamethinecyanine dyes and hemicyanine dyes are used in some cases. To an N-atom or a C-atom of the nucleus, a substituent can be introduced. As sensitizing dyes which can be used in the present invention, those having a substituent represented by the general formula (XV) shown below are particularly preferred.
wherein Z₁ represents the same meaning as defined for the general formula (I), and preferably an alkylene group or an alkoxyalkylene group each having from 1 to 8 carbon atoms as described above; L₂ and c each has the same meaning as defined for the general formula (I); Y represents a hydrogen atom or a group selected from the same group as defined for the general formula (I); the group represented by the general formula (XV) has a water-soluble group or a precursor thereof; and e represents 0 or 1.
Specific examples of the substituent represented. by the general formula (XV) are set forth below.
A group which can be converted to a highly water-soluble group upon hydrolysis in the color developing solution is preferred.
The sensitizing dyes used in the present invention can be prepared by the methods described, e.g., in Japanese Patent Application (OPI) No. 104917/77, Japanese Patent Publucation Nos. 22884/68, 25652/73 and 22368/82, F.M. Hamer, Heterocyclic Compounds - Cyanine dyes and related compounds (John Wiley & Sons 1964), D.M. Sturmer, Heterocyclic Compounds - Special topics in heterocyclic chemistry, chapter Vlll, sec. IV, pages 482 to 515 (John Wiley & Sons 1977).
Specific examples of the sensitizing dyes which can be employed in the present invention are set forth below.
( PSTθ:
The sensitizing dyes which can be used in the present invention are described, for example, in Japanese Patent Application (OPI) Nos. 30724/76, 29128/76, 29129/76 and 14019/76, Japanese Patent Publication Nos. 14112/65, 23467/65, 4931/68, 23389/69, 25652/73, 25653/73, 46416/74 and 44368/80, Japanese Patent Application (OPI) Nos. 66330/74, British Patents 1,137,083, 742,112, 840,223, 975,504, 980,254, 1,077,984 and 1,084,435. Further, the sensitizing dyes include those obtained by introducing a substituent represented by the general formula (XV) described above into dye skeletons of sensitizing dyes as described in Japanese Patent Application No. 131583/86. In the present invention, the sensitizing dyes to be employed are appropriately selected from these groups of sensitizing dyes.
The sensitizing dye used in the present invention can be added to an emulsion by dissolving it in an organic solvent which is soluble in water. Further, it can be added by solubilizing in a surface active agent. The sensitizing dye may be added to a silver halide emulsion subjected to chemical sensitization in an amount of 1 x 10-smoi to 1 x 10-² mol per mol of silver. It is particularly preferred in the present invention that the sensitizing dye is added to a silver halide emulsion before chemical sensitization or during the formation of particles in an amount of 1 x 10-⁵ mol to 1 x 10-³ mol per mol of silver. According to this method, high sensitivity can be obtained with silver halide containing about 1 mol% or less of silver iodide or no silver iodide. The sensitizing dyes used in the present invention can be added in a large amount as compared with conventional sensitizing dyes and they can exhibit an irradiation prevention effect in addition to spectral sensitization.
It is preferred that the coating amount of silver be as small as possible in view of the reduction of bleaching and fixing steps. However, from the standpoint of sensitivity and image quality such as graininess a large coating amount of silver is preferred. Therefore, considering collectively the reduction of processing time and maintaining the sensitivity and graininess, the coating amount of silver is not less than 2 g and not more than 15 g, preferably not more than 10 g, more preferably not more than 8 g and further more preferably not more than 6 g per m² of the support.
The photographic light-sensitive material of the present invention is designed to have an ISO sensitivity of 25 to 6400 and can be employed as a negative photographic light-sensitive material for photographing. Preferably, the ISO sensitivity is in a range from 100 to 1600, such as ISO 100, 200, 400, 1000 and 1600.
A transparent support is employed in the photographic light-sensitive material of the present invention. For example, a cellulose acetate film, a biaxially drawn polyethyleneterephthalate film, each having a thickness of from 10 to 200 µm, preferably from 60 to 120 µm, can be employed.
Photographic additives which can be used in the photographic light-sensitive material of the present invention are described in the items of Research Disclosure, No. 17643 and ibid., No. 18716 and the patents cited therein.
A color developing solution which can be used in development processing of the color photographic light-sensitive material according to the present invention is an alkaline aqueous solution containing preferably an aromatic primary amine type color developing agent as a main component. As the color developing agent, while an aminophenol type compound is useful, a p-phenylenediamine type compound is preferably employed. Typical examples of the p-phenylenediamine type compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-(3-methanesulfonamidoethylani- line, 3-methyl-4-amino-N-ethyl-N-(3-methoxyethylaniline, or sulfate, hydrochloride or p-toluenesulfonate thereof. These diamines are preferably employed in the form of salts since the salts are generally more stable than their free forms.
The color developing solution can usually contain pH buffering agents, such as carbonates, borates or phosphates of alkali metals; and development inhibitors or antifogging agents such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Further, if necessary, the color developing solution may contain preservatives such as hydroxylamine, sulfites; organic solvents such as triethanolamine, diethylene glycol; development accelerators such as benzylalcohol, polyethyleneglycol, quaternary ammonium salts, amines; dye forming couplers; competing couplers; nucleating agents such as sodium borohydride; auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity imparting agents; and various chelating agents as represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids and phosphonocarboxylic acids; and antioxidants as described in West German PatentApplication (OLS) No. 2,622,950.
In the case of development processing for reversal color photographic light-sensitive materials, color development is usually conducted after black-and-white development. In a black-and-white developing solution, known black-and-white developing agents, for example, dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol, may be employed individually or in combination.
After color development, the photographic emulsion layer is usually subjected to a bleach processing. The bleach processing can be carried out simultaneously with or separately from a fix processing. Further, in order to perform a rapid processing, a processing method in which a bleach-fix processing is conducted after a bleach processing can be employed.
Examples of bleaching agents which can be employed include compounds of a multivalent metal such as iron (II), cobalt (III), chromium (VI), copper (II); peracids; quinones; nitroso compounds. Representative examples of the bleaching agents include ferricyanides; dichloromates; organic complex salts of iron (III) or cobalt (III), (for example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, cyclohexanediaminetetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, malic acid); persulfates; bromates; permanganates.
Preferred methods of using bleaching agents in view of rapid bleaching include a method using an iron (III) salt which has a high oxidation reduction potential (a strong oxidizing power) such as 1,3-diaminopropanetetraacetic acid iron (III) complex salt, iron (III) salt of citric acid or tartaric acid, in a bleaching solution, or a method using an aminopolycarboxylic acid iron (III) complex salt which has a relatively low oxidation reduction potential such as ethylenediaminetetraacetic acid iron (III) complex salt together with a compound which can rapidly oxidize the reduction product thereof, for example, a persulfate and a bromate, as described above.
Further, the use of a bleach-fixing solution which performs simultaneously bleaching and fixing is a preferred embodiment of the rapid processing. Preferred bleaching agents which can be used in the bleach-fixing solution are required not only to have strong oxidizing power but also to be coexistent with fixing agents to a certain degree of stability. Examples of such bleaching agents include iron (III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid.
In a bleaching solution, a bleach-fixing solution or a prebath thereof, a bleach accelerating agent can be preferably used. Specific examples of the bleach accelerating agents which can be used include compounds having a mercapto group or a disulfide group as described in U.S. Patent 3,893,858, West German Patents 1,290,812 and 2,059,988, Japanese Patent Application (OPI) Nos. 32736/78, 57831/78, 37418/78, 55732/78, 72623/78, 95631/78, 104232/78, 124424/78, 141623/78 and 28426/78, Japanese Patent Publication Nos. 19985/86 and 22295/86, Research Disclosure, No. 17129 (July, 1978), thiazolidine derivatives as described in Japanese Patent Application (OPI) No. 140129/75, thiourea derivatives as described in Japanese Patent Publication No. 8506/70, Japanese Patent Application (OPI) No. 20832/77 and 32735/78, U.S. Patent 3,706,561, iodides as described in West German Patent 1,127,715, Japanese Patent Application (OPI) No. 16235/83, polyethyleneoxides as described in West German Patents 966,410 and 2,748,430, polyamine compounds as described in Japanese Patent Publication No. 8836/70, compounds as described in Japanese Patent Application (OPI) Nos. 42434/74, 59644/74, 94927/78, 35727/79, 26506/80 and 163940/83, iodine ions, bromine ions. Of these compounds, the compounds having a mercapto group or a disulfide group are preferred in view of their large accelerating effects, and the compounds as described in U.S. Patent 3,893,858, West German Patent 1,290,812 and Japanese Patent Publication Nos. 19985/86 and 22295/86 are particularly preferred. Further, the compounds as described in U.S. Patent 4,552,834 are preferably employed. These bleach accelerating agents may be incorporated into the photographic light-sensitive material. These bleach accelerating agents are particularly effective in the case wherein color photographic light-sensitive materials for photographing are bleach-fixed.
Examples of fixing agents include thiosulfates, thiocyanates, thioethertype compounds, thioureas, a large amount of iodides. Of these compounds, thiosulfates are ordinarily employed. In the bleach-fixing solution or the fixing solution, sulfites, bisulfites, carbonylbisulfite adducts are preferably employed as preservatives.
In accordance with the present invention, it is preferred that bleaching and fixing are incorporated into a step of bleach-fixing (blixing).
The hindrance function on bleach-fixing can be determined by a method wherein a sample having a fixed amount of silver obtained by development of a film having coated thereon a silver halide emulsion layer is immersed in a certain bleach-fixing solution for a fixed time and then washed with water and thereafter the remaining silver amount of the sample is measured. The hindrance function of a compound can be determined by being coexistent the certain amount of the compound with silver halide in the silver halide emulsion layer and measuring the increase in the remaining silver amount.
A preferred desilvering step of developed silver after color development in the present invention is a step containing bleach-fixing (blixing). For example, steps of development - bleach-fixing → stabilizing or water washing or steps of development - bleaching → bleach-fixing → stabilizing or water washing, are employed.
The hindrance function on desilveration is evaluated with a bleach-fixing step. A sample having a light-sensitive silver halide emulsion layer on a film support is developed to form a fixed amount of reduced silver whereby a test sample is prepared. The test sample is immersed in a certain bleach-fixing solution for a fixed time and then washed with water and thereafter the remaining silver amount of the test sample is measured. On the other hand, a film sample is prepared by adding a compound to be tested to the silver halide emulsion in a certain amount, and is subjected to the same procedure as described above to form a test sample having the fixed amount of developed silver. Then the test sample is processed in the same bleach-fixing solution as described above, washed with water and the remaining silver amount is measured in the same manner as described above. By comparison of the remaining silver amount of the standard sample and that of the sample using the compound to be tested, the hindrance function of the compound on bleach-fixing can be evaluated. Further, with respect to various color photographic light-sensitive materials, remaining silver amounts after color development processing are determined, and the existence of desilvering hindrance can be evaluated by judgement whether it is within the allowed amount. The allowed amount of remaining silver is suitably about 5 wg/cm2 or less and preferably 3 wg/cm² or less.
In the present invention, the terminology "amount which does not substantially hinder a silver bleaching property" means an amount of the DIR compound used in order to maintain the amount of remaining silver after processing at about 5 wg/cm² or less in the case of using a color development processing time of from 1 minute to about 9 minutes excluding the time required for a drying step. According to a representative example, it can be said that the silver bleaching property or the desilvering property is not substantially hindered in the case wherein the amount of remaining silver at an area having the maximum amount of developed silver is not more than 5 wg/cm² when a bleach-fixing processing is continuously carried out at 35°C to 45°C for 1 minute to 2 minutes using an EDTA Iron (III) complex salt as a bleaching agent and ammonium thiosulfate as a fixing agent as represented by the bleach-fixing solutions described in Examples 1 and 3 hereinafter.
After a silver removing processing such as fixing or bleach-fixing, the silver halide color photographic material according to the present invention is generally subjected to a water washing step and/or a stabilizing step.
The amount of water required for the water washing step may be set in a wide range depending on the characteristics of the photographic light-sensitive materials (due to elements used therein, for example, couplers), uses thereof, temperature of washing water, the number of water washing tanks (stages), a replenishment system such as countercurrent or orderly current, or other various conditions. The relationship between the number of water washing tanks and the amount of water in a multi-stage countercurrent system can be determined based on the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pages 248 to 253 (May, 1955). Ordinarily, the number of stages used in the multi-stage countercurrent system is preferably from 2 to 6, particularly from 2 to 4.
According to the multi-stage countercurrent system, the amount of water for washing can be significantly reduced. For example, it is possible to use 0.5 to 1 liter or less per m² of the photographic light-sensitive material. However, an increase in staying time of water in a tank causes the propagation of bacteria and some problems such as adhesion of floatage formed on the photographic materials, occur. In the method for processing the silver halide color photographic material according to the present invention, a method for reducing amounts of calcium and magnesium as described in Japanese Patent Application No. 131632/86 can be particularly effectively employed in order to solve such problems. Further, sterilizers, for example, isothiazolone compounds as described in Japanese Patent Application (OPI) No. 8542/82, cyabendazoles, chlorine type sterilizers such as sodium chloroisocyanurate as described in Japanese Patent Application (OPI) No. 120145/86, benzotriazoles as described in Japanese Patent Application No. 105487/85, sterilizers as described in Hiroshi Horiguchi, Bokin-Bobai No Kagaku, Biseibutsu No Mekkin-, Sakiin-, Bobai-Gijutsu, edited by Eiseigijutsu Kai, Bokin-Bobaizai Jiten, edited by Nippon Bokin-Bobai Gakkai, can be employed.
Moreover, surface active agents as agents for uniform drying, and chelating agents represented by EDTA as water softeners may be employed in the washing water.
Following the water washing step or without conducting the water washing step, the color photographic material can be treated with a stabilizing solution. To the stabilizing solution are added compounds having the function of stabilizing images, for example, aldehyde compounds represented by formalin, buffers for adjusting the pH of the layer to a value suitable for stabilization of dyes formed, or ammonium compounds. Further, various sterilizers or antimold agents as described above can be employed in the stabilizing solution in order to prevent the propagation of bacteria in the solution and impart antimold properties to the photographic material after processing. Moreover, surface active agents, fluorescent whitening agents, hardeners may be added to the stabilizing solution.
For the purpose of simplification and acceleration of processing, a color developing agent may be incorporated into the silver halide color photographic material according to the present invention. In order to incorporate the color developing agent, it is preferred to employ various precursors of color developing agents. Suitable examples of the precursors of developing agents include indoaniline type compounds as described in U.S. Patent 3,342,597, Schiff's base type compounds as described in U.S. Patent 3,342,599 and Research Disclosure, No. 14850 and ibid., No. 15159, aldol compounds as described in Research Disclosure, No. 13924, metal salt complexes as described in U.S. patent 3,719,492, urethane type compounds as described in Japanese Patent Application (OPI) No. 135628/78, and various salt type precursors as described in Japanese Patent Application (OPI) No. 6235/81, 16133/81, 59232/81, 67842/81, 83734/81, 83735/81, 83736/81, 89735/81, 81837/81, 54430/81, 10624/81, 107236/81, 97531/82 and 83565/82.
Further, the silver halide color photographic material according to the present invention may contain, if desired, various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development. Typical examples of the compounds include those described in Japanese Patent Application (OPI) Nos. 64339/81, 144547/82, 211147/82, 50532/83, 50536/83, 50533/83, 50534/83, 50535/83 and 115438/83.
In the present invention, various kinds of processing solutions can be employed in a temperature range from 10°C to 50°C. Although a standard temperature is from 33°C to 38°C, it is possible to carry out the processing at higher temperatures in order to accelerate the processing whereby the processing time is shortened, or at lower temperatures in order to achieve improvement in image quality and to maintain stability of the processing solutions.
Further, for the purpose of saving the amount of silver employed in the color photographic light-sensitive material, the photographic processing may be conducted utilizing color intensification using cobalt or hydrogen peroxide as described in West German Patent Application (OLS) No. 2,226,770 or U.S. Patent 3,674,499.
In each of the processing baths, a heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating cover, a squeezer may be provided, if desired.
Moreover, in the case of continuous processing, the variation of composition in each processing solution can be prevented by using a replenisher for each processing solution, whereby a constant finish can be achieved. The amount of replenisher can be reduced to one half or less of the standard amount of replenishment for the purpose of reducing cost.
Specific examples of the processing steps according to the present invention are set forth below.

1. Color Development - Bleaching - (Water Washing) - Fixing - (Water Washing) - (Stabilizing)
2. Color Development - Bleach-Fixing - (Water Washing) - (Stabilizing)
3. Color Development - Bleaching - Bleach-Fixing - (Water Washing) - (Stabilizing)
4. Color Development - Bleaching - Bleach-Fixing - Fixing - (Water Washing) - (Stabilizing)
5. Color Development - Bleaching - Fixing - Bleach-Fixing - (Water Washing) - (Stabilizing)
6. Color Development - Fixing - Bleach-Fixing (Water Washing) - (Stabilizing)

In the above described processing steps, the steps described in the parentheses can be eliminated depending on the kinds, purposes and uses of the photographic light-sensitive materials, but it is not preferred to eliminate both Water Washing and Stabilizing at the same time in the processing method described above.
The silver halide photographic material according to the present invention wherein the silver iodide content in the light-sensitive layer is controlled to less than 2 mol%, preferably not more than 1 mol% and, if desired, a combination of selection of a DIR compound and decrease in the amount thereof to be employed is performed is suitable for a high-sensitive negative type photographic light-sensitive material capable of being conducted rapid development and rapid desilveration while maintaining excellent color reproducibility and sharpness. In particular, the reduction of iodine ions released from light-sensitive silver halide and development inhibitors formed from DIR compounds in the course of color development eliminates bleaching hindrance and fixing hindrance in the case of using an EDTA iron (III) salt and sodium thiosulfate, respectively, in the desilvering step and thus a rapid development processing of a high-sensitive negative type silver halide photographic material for photographing which has an especially large amount of coating silver becomes possible. The method for development processing of a silver halide color photographic material according to the present invention can be applied to mini-labs as well as large-scale labs and provide a negative processing which is completed without waiting time, and therefore it has a big economic effect.
The present invention is explained in greater detail with reference to the following examples.

EXAMPLE I (Comparative)

On a cellulose triacetate film support, each layer having the composition shown below was coated to prepare a color photographic light-sensitive material which was designated Sample 101.

First Layer: Emulsion Layer

Second Layer: Protective Layer

Gelatin layer containing polymethyl methacrylate particles (diameter: about 1.5 µm)
Each layer described above further contained Gelatin Hardener H-1 and a surface active agent in addition to the above described components.
The compounds used for the preparation of the sample are shown below:
Further, Samples 102 to 140 having the compositions shown in Table 1 below were prepared in the same manner as described for Sample 101 except adding a DIR coupler and/or using emulsions having particle sizes and particle size distribution the same as those of the pure silver bromide emulsion but uniformly containing iodide in amounts of 1 mol%, 2 mol% and 4 mol%, respectively, in place of the pure silver bromide emulsion.
The samples thus-prepared were exposed to light so as to make an amount of developed silver formed in a color development step (±0.05 g/m²) and then subjected to the color development processing according to the procedure shown below.
The composition of each processing solution used is illustrated below. Color Developing Solution:
Bleaching Solution:
Fixing Solution:
The amount of developed silver in this example was obtained by measuring the amount of remaining silver in each sample subjected to the processing steps shown in Table 1-3 below according to a fluorescence X-ray method.
The color developing solution and the fixing solution used in the above-described processing steps wer the same as those described above and the stopping solution used had the following composition.

Stopping Solution: e

After the development processing as described in Table 1-2, the amount of remaining silver in each sample was measured using a fluorescence X-ray method. The results thus-obtained are shown in Table 2 below. In the examples of the present invention, the amount of silver was measured using a fluorescence X-ray method.
From the results shown in Table 2, it is apparent (1) that the amount of remaining silver increases upon the addition of a DIR coupler, (2) that the increase in the amount of remaining silver is remarkable when a DIR coupler is one which does not have a water-soluble group in its development inhibiting group, and (3) that the above-described tendencies in (1) and (2) become larger as the iodide content of emulsion increases. Therefore, it can be understood how to achieve the effects according to the present invention.
Further, Samples 101 to 140 were exposed to light so as to make an amount of developed silver formed in a color development step 1 ± 0.05 g/m² and then subjected to the color development processing in accordance with the procedure shown below.
The composition of each processing solution used is illustrated below.

Color Developing Solution:

Bleach-Fixing Solution:
The amount of developed silver in this example means an amount of remaining silver in each sample subjected to the processing steps shown in Table 2-3 below. The desilvering property was compared at an area having the amount of remaining silver of 1.00 ± 0.05 g/m² in each sample.
The color developing solution used in the above-described processing step was the same as that described above and the stopping solution and the fixing solution used were the same as those described above.
After the development processing as described in Table 2-2, the amount of remaining silver in each sample was measured using a fluorescence X-ray method, and results similar to those described in Table 2 were obtained.

EXAMPLE 2 (Comparative)

Samples 202 to 217 were prepared in the same manner as described for Sample 101 except for adding the sensitizing dyes shown in Table 3 below in an amount of 4.5 x 10-⁴ mol per mol of silver at the time of preparation of the emulsion.
These samples were exposed and processed in the same manner as described in Example 1 using the color development processing shown in Table 1-2. The amount of remaining silver in each sample was measured using a fluorescence X-ray method. The results thus-obtained are shown in Table 4 below.
From the results shown in Table 4, it can be seen that the amount of remaining silver is large in the case of using Sensitizing Dyes F and H each of which does not have a water-soluble group and that this tendency becomes remarkable when emulsions having a high iodide content are employed.
Further, Sample 218 was obtained in the same manner as described for Sample 208 except adding Sensitizing Dye I in an amount of 1 x 10-³ mol per mol of silver in addition to 4.5 x 10-4 mol per mol of silver of Sensitizing Dye G. Increase in the amount of remaining silver was not observed which sensitivity of the sample was higher than that of Sample 208.
Moreover, the samples described in Table 3 were exposed and processed using the color development processing shown in Table 2-2. The amount of remaining silver in each sample was measured using a fluorescence X-ray method, and results similar to those described above in Table 4 were obtained.

EXAMPLE 3

On a cellulose triacetate film support having a subbing layer, each layer having the composition shown below was coated to prepare a multilayer color photographic light-sensitive material which was designated Sample 301.
In the following, the coated amounts of silver halide and colloidal silver are shown by g/m² units of silver, the coated amounts of couplers, additives and gelatin are shown by g/m² units, and the coated amounts of sensitizing dyes are shown by mol number per mol of silver halide in the same layer.

First Layer: Antihalation Layer
Second Layer: Intermediate Layer
Third Layer: First Red-Sensitive Emulsion Layer
Fourth Layer: Second Red-Sensitive Emulsion Layer
Fifth Layer: Third Red-Sensitive Emulsion Layer
Sixth Layer: Intermediate Layer
Seventh Layer: First Green-Sensitive Emulsion Layer
Eighth Layer: Second Green-Sensitive Emulsion Layer
Ninth Layer: Third Green-Sensitive Emulsion Layer
Tenth Layer: Yellow Filter Layer
Eleventh Layer: First Blue-Sensitive Emulsion Layer
Twelfth Layer: Second Blue-Sensitive Emulsion Layer
Thirteenth Layer: First Protective Layer
Fourteenth Layer: Second Protective Layer

Each layer described above further contained a surface active agent as a coating aid in addition to the above described components. Thus, Sample 301 was prepared.
Sample 302 was prepared in the same manner as described for Sample 301 except for reducing the amounts of DIR Coupler D used in the fourth layer, the seventh layer, the eighth layer and the eleventh layer to 1/3.
Sample 303 was prepared in the same manner as described for Sample 301 except for eliminating DIR Coupler D used in the fourth layer, the seventh layer, the eighth layer and the eleventh layer.
Sample 304 was prepared in the same manner as described for Sample 302 except for changing DIR Coupler D used in the fourth layer, the seventh layer, the eighth layer and the eleventh layer to equimolar amounts of DIR Coupler C.
Sample 305 was prepared in the same manner as described for Sample 303 except for changing the silver iodobromide emulsion (silver iodide: 4 mol%, mean grain size: 0.3 µm) used in the third layer and the seventh layer to a pure silver bromide emulsion (mean grain size: 0.3 pm), changing the silver iodobromide emulsion (silver iodide: 5 mol%, mean grain size: 0.5 µm) used in the fourth layer and the eighth layer to a silver iodobromide emulsion (silver iodide: 0.5 mol%, mean grain size: 0.5 pm), changing the silver iodobromide emulsion (silver iodide: 6 mol%, mean grain size: 0.7 µm) used in the fifth layer and the ninth layer to a silver iodobromide emulsion (silver iodide: 1 mol%, mean grain size: 0.7 pm), changing the monodispersed silver iodobromide emulsion (silver iodide: 4 mol%, mean grain size: 0.3 µm) used in the eleventh layer to a tabular silver iodobromide emulsion having an aspect ratio of 5 (silver iodide: 0.5 mol%, mean grain size: 0.3 pm), changing the amount of Sensitizing Dye IX used in the eleventh layer to 3 x 10-⁴ mol per mol of silver changing the silver iodobromide emulsion (silver iodide: 10 mol%, mean grain size: 1.5 µm) used in the twelfth layer to a tabular silver iodobromide emulsion having an aspect ratio of 5 (silver iodide: 1 mol%, mean grain size: 1.5 µm), and changing the amount of Sensitizing Dye IX used in the twelfth layer to 1.5 x 10-⁴ mol per mol of silver.
The compounds used in this example are shown below by the chemical structures or the chemical names:

Oil-1: Tricresyl phosphate
Oil-2: Dibutyl phthalate
Oil-3: Bis(2-ethylhexyl)phthalate

The samples thus prepared were cut into strips of a 35 mm width, exposes to light so as to make the amount of developed silver formed 1 ± 0.05 g/m² and then subjected to the color development processing according to the procedure shown in Table 5 below.
The color development processing was carried out using an automatic developing machine in a manner that each sample was processed with fresh processing solutions and continued until the accumulated replenishment amount of the bleach-fixing solution became three times the capacity of the bleach fixing tank.
The composition of each processing solution used is illustrated below.
Color Developing Solution:
Bleach-Fixing Solution: (both Mother Solution and Replenisher)

Washing Water: (both Mother Solution and Replenisher)

City water which was passed through a mixed bed type column filled with an H type strong acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm & Haas Co.) and an OH type anion exchange resin (Amberlite IR-400 manufactured by Rohm & Haas Co.) to reduce both calcium ions and magnesium ions at concentrations of not more than 3 mg per liter respectively, and then to which were added sodium dichloroisocyanurate in an amount of 20 mg per liter and sodium sulfate in an amount of 1.5 g per liter was used. The pH of the water was in a range of 6.5 to 7.5
The amount of developed silver in this example means an amount of remaining silver in each sample subjected to the processing steps shown in Table 5-2 below.
The color developing solution used in the above-described processing step was the mother solution of color developing solution described above in this example and the stopping solution and the fixing solution used were same as those described in Example 1.
After the development processing as described in Table 5 in the manner as set forth above, the amount of remaining silver in each sample at the end of processing was measured using a fluorescence X-ray method. The results thus-obtained are shown in Table 6 below.
From the results shown in Table 6, it can be seen that the sample according to the present invention exhibits an extremely small amount of remaining silver.
Sample 306 was prepared in the same manner as described for Sample 304 except for replacing the half amount of Coupler C-3 in the third layer with Compound (9), replacing the half amount of Coupler C-3 in the fourth layer with Compound (9), replacing DIR coupler C in the fourth layer with Compound (11), replacing DIR coupler C in the seventh and eighth layers with Compound (7), replacing Coupler C-12 in the ninth layer with Compound (8), and replacing the half amount of DIR coupler C with Compound (5).
Sample 307 was prepared in the same manner as described for Sample 304 except for replacing the half amount of Coupler C-3 in the third layer with Compound (9), replacing the half amount of Coupler C-3 in the fourth layer with Compound (9), replacing DIR coupler C in the fourth layer with Compound (11), replacing DIR coupler C in the seventh and eighth layers with Compound (7), replacing Coupler C-12 in the ninth layer with Compound (8), replacing the half amount of DIR coupler C with Compound (5), adding 0.08 g of Compound (3) to the eleventh layer, adding 0.05 g of Compound (11) to the sixth layer, and adding 0.10 g of Compound (11) to the tenth layer.
Samples 306 and 307 (Comparative) were subjected to the same treatment as Samples 301 to 305. As a result, the amount of remaining silver for Sample 306 was 3.1 µg/cm² and that for Sample 307 was less than 1 wg/cm2.

EXAMPLE 4 (Comparative)

The silver chlorobromide emulsion (A) (chloride content: 50 mol%) was prepared in the following manner.
Solution (1) was heated to and maintained at 55°C. Solution (2) was added thereto and thereafter Solution (3) and Solution (4) were simultaneously added over 10 minutes. After further 10 minutes, Solution (5) and Solution (6) were simultaneously added over 35 minutas. After the completion of the addition, the solution was cooled to room temperature and the excess salt was removed. An aqueous solution of gelatin for dispersion was added thereto, and the pH was adjusted to 6.2 so as to obtain a monodispersed cubic silver chlorobromide emulsion having an average grain size of 0.72 µm. Sodium thiosulfate, chloroauric acid, and ammonium rho- danide were added to thus-obtained emulsion so as to chemically sensitize optimally.
The compositions of Solutions (1) to (5) were as follows.

Solution (1)
Solution (2) 1% aqueous solution of
3 mi
Solution (3)
Solution (4)
Solution (5)
Solution (6)

The monodispersed cubic silver chlorobromide emulsion (B) (chloride content: 75 mol%, average grain size: 0.65 wm) was prepared in the same manner as in the preparation of the emulsion (A) except that the halide compsotions (KBr/NaCI) of Solutions (3) and (5) were changed.
By using the emulsions (A) and (B) obtained, Samples 401 to 418 shown in Table 7 below were prepared. Samples 401 to 418 were then treated in the same manner as in Example 1 (Table 1-2), and the remaining silver amount was measured by a fluorescence X-ray method. The results obtained are shown in Table 7.
From the results shown in Table 7, in the case of the high silver chloride content samples, the remaining silver amount is extremely low even though it slightly increases in samples using Sensitizing Dyes F and H which do not have a hydrophilic group.

EXAMPLE 5

Sample 501 was prepared in the same manner as in the preparation of Sample 304 in Example 3 except that the silver halide emulsions were replaced with silver chlorobromide emulsion (chloride content: 50 mol%) having an average grain size shown in Table 8 below.
The emulsions having various average grain sizes were prepared in the same manner as in Example 4 while varying the temperature during the grain formation.
Sample 501 was exposed to light so as to the developed silver formed be 1 ± 0.05 g/m², and then treated according to Table 5 in Example 3.
As a result, the final remained silver amount is 2.0 wg/cm². Therefore, it was found that Sample 501 according to the present invention can be desilvered extremely quickly.

EXAMPLE 6

Samples 304 and 501 were treated with the process shown in Table 5, and the ISO photographic sensitivity thereof was measured according to JIS K7614-1986 (method for measuring ISO speed of negative film for still photography). The photographic sensitivity of Sample 304 was ISO 125 and that of Sample 501 was ISO 80 which are sutisfactory for photographic light-sensitive materials.

Claims

1. A silver halide color photographic material comprising a transparent support having thereon a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, wherein

(1) at least one of the blue-sensitive layer, the green-sensitive layer and the red-sensitive layer comprises at least one negative type silver halide emulsion layer containing a dye forming coupler, each of the green-sensitive layer and the red-sensitive layer comprising at least three negative type silver halide emulsion layers which have different sensitivities from each other and the blue-sensitive layer comprising at least two negative type silver halide emulsion layers which have different sensitivities from each other,

(2) the average silver iodide content of the light-sensitive silver halide grains contained in at least one of the silver halide emulsion layer is less than 2 mol% and

(3) the photographic sensitivity is from ISO 25 to ISO 6400.

2. The silver halide color photographic material of claim 1, wherein the negative type silver halide emulsion layer contains silver halide grains selected from silver iodochlorobromide and silver iodobromide.

3. The silver halide color photographic material of claim 1, wherein the negative type silver halide emulsion layer contains silver halide grains selected from silver chlorobromide and silver bromide.

4. The silver halide color photographic material of claim 1, wherein the color photographic material comprises at least one blue-sensitive silver halide emulsion layer containing at least one yellow dye forming coupler, at least one green-sensitive silver halide emulsion layer containing at least one magenta dye forming coupler and at least one red-sensitive silver halide emulsion layer containing at least one cyan dye forming coupler.

5. The silver halide color photographic material of claim 1, wherein the silver halide emulsion layers having the highest sensitivity among each of the blue-sensitive layers, the green-sensitive layers and the red-sensitive layers each contain negative type silver halide grains having an average particle size of not less than 0.3 f..lm.

6. The silver halide color photographic material of claim 1, wherein the silver halide emulsion layers having the highest sensitivity among each of the blue-sensitive layers, the green-sensitive layers and the red-sensitive layers each contain negative type silver halide grains having an average particle size of not less than 0.6 µm.

7. The silver halide color photographic material of claim 1, wherein the total coating amount of light-sensitive silver halide is from 2 g to 15 g per m².

8. The silver halide color photographic material of claim 1, wherein the total coating amount of a DIR compound is not more than 5 x 10-⁴ mol per g of light-sensitive silver halide calculated as silver.

9. The silver halide color photographic material of claim 1, wherein the total coating amount of a DIR compound is not more than 5 mol% of the coating amount of image forming couplers per unit area.

10. The silver halide color photographic material of claim 1, wherein the average silver iodide content of light-sensitive silver halide grains contained in the blue-sensitive layer, the green-sensitive layer, and the red-sensitive layer is less than 2 mol%.

11. The silver halide color photographic material of claim 1, wherein the silver halide color photographic material contains a DIR compound selected from the compounds represented by the general formula (I) or (II):

wherein A represents a color coupler residue or a coupler residue which does not form a colored dye upon a reaction with an oxidation product of a developing agent; L₁ represents a timing group; a represents 0 or 1; Z₁ represents a linking group selected from a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted arylene group or a substituted or unsubstituted, straight chain or branched chain alkylene group; Z₂ represents a substituted or unsubstituted heterocyclic group; L₂ represents a linking group; X and Y each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a cyano group, a mercapto group, and at least one X and Y contains a water-soluble group or a precursor thereof; b represents 0, 1 or 2; and c represents 0 or 1.

12. The silver halide color photographic material of claim 11, wherein the color photographic material contains a DIR compound in an amount of not more than 5 mol% of image forming couplers including 0 mol%.

13. The silver halide color photographic material of claim 11, wherein the coupler residue represented by A is selected from a yellow color forming coupler residue, a magenta color forming coupler residue, a cyan color forming coupler residue and a non-color forming coupler residue.

14. The silver halide color photographic material of claim 11, wherein the timing group represented by L₁ is selected from -OCH₂-,

wherein R₂₁ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, a ureido group, a cyano group, a nitro group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a cycloalkyl group, an alkynesulfonyl group, an arylsulfonyl group or an acyl group; R₂₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group; c represents 0, 1 or2; q represents 1 or2, and when q represents 2, two R₂₁ groups may be bonded to each other to form a condensed ring.

15. The silver halide color photographic material of claim 11, wherein the DIR compound is represented by the following general formula (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), (XII), (XIII) or (XIV):

wherein X, Y, Z₁, and b each has the same meaning as defined in the general formula (I) or (II), R₂₁ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, a ureido group, a cyano group, a nitro group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a cycloalkyl group, an alkanesulfonyl group, an arylsulfonyl group or an acyl group; R₂₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group; R₁₁ represents an aliphatic group, an aromatic group, an alkoxy group, a heterocyclic group, or a group formed by condensing a phenyl group and another ring; R₁₂ and R₁₃ each represents an aromatic group, a heterocyclic group, or a group formed by condensing a phenyl group and another ring; R₁₅ represents a straight chain or branched chain alkyl group having from 1 to40 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group a cyclic alkenyl group, an aryl group, a heterocyclic group, a heterocyclic group substituted by one or more of an aliphatic acyl group, an aromatic acyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group; R₁₄ represents a hydrogen atom, a straight chain or branched chain alkyl group having from 1 to 40 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aralkyloxycarbonyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, a carboxy group, an acylamino group, a diacylamino group, an N-alkylacylamino group, an N-arylacylamino group, a ureido group, a urethane group, a thiourethane group, an arylamino group, an alkylamino group, a cycloamino group, a heterocyclic amino group, an alkylcarbonyl group, an arylcarbonyl group, a sulfonamido group, a carbamoyl group, a sulfamoyl group, a cyano group, a hydroxy group, a mercapto group, a halogen atom, or a sulfo group; R₁₇ represents a hydrogen atom, a straight chain or branched chain alkyl group having from 1 to 32 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, a ureido group, a urethane group, a sulfonamido group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, a dialkylamino group, an anilino group, an N-arylanilino group, an N-alkylanilino group, a hydroxy group or a mercapto group; R₁₈ represents a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue, an acylamino group, an -O-R³¹ group or an -S-R₃₁ group (wherein R₃₁ represents an aliphatic hydrocarbon group); R₁₉ and R₂₀ each represents an aliphatic hydrocarbon residue, an aryl group or a heterocyclic group, one of R₁₉ and R₂₀ may be a hydrogen atom, or R₁₉ and R₂₀ may combine with each other to form a nitrogen-containing heterocyclic nucleus; r represents an integer of 1 to 4; s represents an integer of 1 to 3; and t represents an integer of 1 to 5.

16. A method for processing a silver halide color photographic material comprising the steps of exposing, color developing, desilvering and water washing or stabilizing a silver halide color photographic material according to any of claims 1 to 15, wherein the processing time is from 1 to 9 minutes.

17. The method of claim 16, wherein the time required for the desilvering step is from 1 to 3 minutes.