JPH01213655A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance storage stability and to form a dye image superior in sharpness in a short time by incorporating as bleaching agent at least one of the ferric complex salts of specified compounds and that of 1,3- diaminopropane tetraacetate in a specified ratio in a processing solution having bleaching ability. CONSTITUTION:The photosensitive material having a <=2mol.% average silver iodine content of photosensitive silver halide grains in each photosensitive layers is color developed and processed with a processing solution having bleaching ability containing as the bleaching agents at least one of the compounds selected from the ferric complex salts of the compounds A; ethylenediamine tetraacetate A-1, diethylenetriamine pentaacetate A-2, cyclohexanediamine tetraacetate A-3, and 1,2-propylenediamine tetraacetate A-4, and that of 1,3-diaminopropane tetraacetate B in a molar ratio A/B of <=3:1, thus permitting superior color reproduction performance and image sharpness to be maintained and rapid simple color development processing to be executed.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic light-sensitive materials. The present invention relates to a method for processing a silver halide color photographic material that can be formed over time. Further, the present invention relates to rapid processing, and in particular to an improved processing method capable of accelerating bleaching action and shortening processing time.

(Prior Art) Since the development of silver halide color light-sensitive materials, improvements have been made to achieve higher sensitivity, better image quality, and rapid and simpler color development processing. Instant photography is a type of photographic material, and has formed a field due to its high sensitivity and quick and easy processing. However, the format is fixed, making it difficult to print multiple copies at the same time, and there is room for improvement in terms of image quality and price.

Regular color photographic paper provides excellent image quality with two- or three-bath processing; VC3C 3 minutes and 0 seconds before color reversal photographic paper yields approximately 1 liter in minilab processing.

The development process has been completed. However, these photographic papers cannot be used for photography due to their extremely low sensitivity. Kodak's C-at processing made color negative light-sensitive materials much faster, but it still took 17 minutes and 20 seconds, and by integrating the bleaching and fixing functions, the bleach-fixing process also took 72 minutes using jJroc. vinegar. Even if patch-type development processing is performed forcibly at IO resolution, continuous processing cannot be achieved. Even if a rapid desilvering process is adopted in the mini lab, continuous processing takes 11 minutes and 30 minutes at 1t0c.
It takes seconds. On the other hand, in the market where a desired number of prints of excellent image quality can be obtained at a reasonably low cost, the color negative/positive system is a quick and simple continuous color development process that allows prints to be obtained anywhere, anytime. desired. For this purpose, it is necessary to develop a quick and simple color development processing method that takes advantage of the excellent image quality such as color reproducibility, image sharpness, and graininess, and high sensitivity of color negative light-sensitive materials. Currently, in order to obtain high image quality, all commercially available color negative light-sensitive materials use KDIR couplers (couplers that react with the oxidized product of a color developing agent and release a development inhibitor). DIR couplers are also known to retard color development. Furthermore, in order to provide high sensitivity, suppress fogging, and control the progress of development, it is common to use a photosensitive silver halide emulsion containing more than one mole of silver iodide.

Furthermore, in recent years, there has been a strong demand in the industry for speeding up processing, that is, shortening the time required for processing, and shortening the desilvering process, which accounts for nearly half of the conventional processing time, has become a major issue. ing. For this reason, improvements have been made to the desilvering process, including two steps: a bleaching bath and a fixing bath, and a simplified bleach-fixing bath containing both bleach and fixing agents. It is being said.

As a bleaching agent, a bleaching treatment method based on a ferric ion complex salt (for example, an aminopolycarboxylic acid ferric ion complex salt, etc., especially an ethylenediaminetetraacetic acid iron (II) complex salt) is used.

However, since ferric ion complex salts have a relatively small oxidizing power and a bleaching blade is insufficient, products using this as a bleaching agent are, for example, low-sensitivity silver halide color photographs based on silver chlorobromide emulsions. When bleaching or bleach-fixing the material, it is possible to achieve the desired purpose, but it is possible to achieve the desired purpose by bleaching or bleach-fixing the material. When processing silver oxide color photographic materials, especially color reversal photographic materials and color negative photographic materials that use high-silver emulsions, the bleaching effect may be insufficient and desilvering may fail, or the bleaching may fail. It has the disadvantage of requiring a long time.

Furthermore, compounds that release the aforementioned development inhibitors have the disadvantage that they often inhibit the bleaching of silver.

In color light-sensitive materials, sensitizing dyes are generally used for the purpose of color sensitization. In particular, when tabular grains with high silver or high 7-spectral ratio are used with the aim of achieving high sensitivity, the sensitizing dye adsorbed on the silver halide surface inhibits the bleaching of the silver produced during development of the silver halide. A problem arises.

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

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

In contrast, Research Disclosure 21702
3 (/Yt 44th year), JP-A-Sho t0-2306j3
No. 1, etc., a treatment method using a combination of two or more of various ferric aminopolycarboxylic acid complex salts is described, but these methods cannot be said to have sufficient bleaching ability.

(Problems to be Solved by the Present Invention) The first object of the present invention is to provide excellent color reproducibility and image quality.
To provide a color photographic material and a method for developing the same, which can maintain sharpness and enable rapid and simple color development to a degree that has not been achieved heretofore. The second object is to provide a color photographic material whose gradation is less dependent on development time while maintaining high sensitivity as a photographic material, and a developing method thereof. The third objective is to provide a processing method with high desilvering speed.

Other objects will become apparent from the description.

The aspects of the present invention include blue-sensitive, green-sensitive and red-sensitive light-sensitive layers on a transparent support, i) each of these light-sensitive layers having at least one negative-working silver halide emulsion layer containing a dye-forming coupler; and ii) a silver halide color photograph in which the average silver iodide content of the light-sensitive silver halide grains in the silver halide emulsion layer or layer group in these photosensitive layers is 2 mole or less. A method of processing a photosensitive material with a processing solution having bleaching ability after color development, the processing solution having bleaching ability containing at least one ferric complex salt of a compound selected from the following compound group (A) as a bleaching agent. and a ferrous complex salt of 1,3-diaminopropanetetraacetic acid, the molar ratio of the former to the latter being 3 or less (including O). It was achieved by this method.

Compound (A) A-/ Ethylenediaminetetraacetic acid A-co Diethylenetriaminepentaacetic acid A-3 Cyclohexanediaminetetraacetic acid A-4 C/, J-Propylenediaminetetraacetic acid Also, in the present invention, a high-sensitivity photographic material with a large coating amount of silver Effective for KjI, set this to the lower limit and upper limit of ISO sensitivity ≠ 00
And so. Below 15 OJj, the effect of the present invention is not particularly noticeable and is too low for ordinary photographic purposes. 18044400
Although the present invention can be applied to the above-mentioned sensitive materials, the handling is complicated and impractical considering the influence of natural radiation, so the upper limit was set, but implementation is possible even with xsotaoo or more.

The present invention provides a silver halide photosensitive material according to a color development method and a development processing method thereof. The color development method is a currently widely used color photographic method in which an image dye is formed by a coupling reaction between an oxidized product of a paraphenylenediamine color developing agent and a so-called photographic coupler. Principle aT.

The Theory of the by H. James
Photographic Process (3rd
Edition) Macmillan Publishing, Chapter 77, published in /rit6, JtJ
- It is described in Jiri Sanga. The present invention does not concern color light-sensitive materials according to the dye developer system or the diffusible dye releasing compound system. These methods do not require a desilvering step to completely physically separate the developed silver from the color image, and are irrelevant to the present invention, which aims to shorten this step. .

A major object of the present invention is to provide a negative-type color photographic material. Color light-sensitive materials are usually provided with two or more silver halide emulsion layers that are sensitive to two or more wavelengths in different visible regions. A silver halide photosensitive material having three color sensitivities, blue sensitivity, green sensitivity and red sensitivity, represents a typical combination of color sensitivities of the present invention. Not only false color systems, but also systems that perform image processing from photographing objects to printing, use combinations of nine different color sensitivities, such as green sensitivity and red sensitivity, to reproduce natural colors. , the combination of three near-infrared sensitive emulsion layers, etc. can be changed as appropriate.

In a preferred embodiment of the present invention, each of the blue-sensitive, green-sensitive and red-sensitive emulsion layers contains a yellow-coloring, magenta-coloring and cyan-coloring coupler, as is widely practiced in color photography using the Ti subtraction method. be.

The color coupler is Research Disclosure, 11
No. 7/1, et al., and are well known to those skilled in the art.

In the present invention, it is desirable to have a wide latitude so that even if the exposure deviates from the appropriate value during photographing, the gradation can be reproduced. Furthermore, in order to improve sensitivity and graininess, it is preferable to provide a plurality of emulsion layers having substantially the same color sensitivity but different sensitivities. The blue, green, and red color-sensitive emulsion layers are formed into high-speed and low-sensitivity emulsion layers, and more preferably, the green-sensitive layer and the red-sensitive layer are formed into three layers of high, medium, and low sensitivity.

In the present invention, the average silver iodide content of one of the blue-sensitive, green-sensitive and red-sensitive light-sensitive silver halide emulsion layers is reduced to about 2 molt or less, preferably 1 molt or less, so that the halogen of that color sensitivity is reduced. Since the color development of the silver halide emulsion layer can be promoted and the inhibitory effect of naturally occurring ions on other layers can be reduced, the progress of development of the silver halide emulsion in all layers can be accelerated. When the silver iodide content of the three color-sensitive photosensitive silver halides is set to less than the average λ moltch, preferably 1 molt or less, this development accelerating effect is particularly large, and in addition, a suitable interlayer effect (inter-1ayer'
effects) can be obtained. In addition,
It is also a major discovery that the developed silver that is formed can be easily desilvered, and the present invention was arrived at based on these discoveries.

A major feature of the present invention lies in the silver halide emulsion used, particularly the silver halide grain composition.

That is, use of a silver halide emulsion in which the content of silver iodide is reduced to such an extent that it does not substantially inhibit the bleaching and fixing of reduced silver, or no silver iodide is used at all, and the inhibition of bleaching and fixing by DIR compounds and sensitizing dyes. The aim is to use a bleaching bath that has strong bleaching ability against.

The limit amount of silver iodide that can be used depends on the type of development inhibitor used,
Although it depends on the type of antifoggant and stabilizer and the amount used, Fi
, o, t molti or less, if possible, it should not be contained substantially. In order to obtain high sensitivity with an emulsion having a low silver iodide content, the improved silver iodine grain preformation method and the same techniques for improving image sharpness and graininess as described above may be used in combination.

At present, there are no color negative light-sensitive materials for photography or color reversal light-sensitive materials in which silver iodide is contained in a silver iodide emulsion of less than about -molt, preferably less than 1 molt, or substantially free of /% silver iodide. Generally speaking, silver iodobromide emulsions are used as high-sensitivity negative-type silver halide emulsions, and silver chlorobromide or silver chloride emulsions are used as low-sensitivity silver halide emulsions for photographic paper. For example, the description on pages 17 to 11 of chapter 1 of Photo Chemistry by Makoto Kikuchi, Kyoritsu Shuppan (1920), Pie
Photography by rre Glafkides
cChemistry Volume 1 Fountain Pre
SS Publishing (/SR) No. 1~-0 Chapters 327-3
T? Page information, especially edited by the Photographic Society of Japan, Fundamentals of Photographic Engineering, Silver Halide Photography, Coronasha Publishing (1985), 3rd Edition
This is clear from the descriptions in chapters 1 and 2, pages 103-2.

Highly sensitive silver halide emulsions according to the present invention include silver iodobromide emulsions containing less than about 2 moles of silver iodide, preferably less than 1 moles of silver iodide;
Preferred examples of silver iodochlorobromide emulsions include silver bromide emulsions and silver chlorobromide emulsions. In order to obtain high sensitivity, many defects are added to the crystal lattice during the grain formation process, such as grains with many twin planes, and multi-structured grains and grains created by changing PAg or halogen composition during the grain formation process. Particles in which the direction of crystal growth is changed by adding substances adsorbed to other silver halogenides during the process, and particles that change the direction of crystal growth by adding substances adsorbed to other silver halogenides, and in the process of crystal formation, different metal ion complexes or salts such as salts, copper chloride, iridium chloride complexes, gold chloride complexes , silver halide grains to which palladium chloride complexes, rhodium chloride complexes, etc. have been added as necessary, and compounds that become silver halide solvents in the crystal formation process, especially in the later stages, such as thiocyanate, thioether compounds, hypo, etc. are added, and the surface is etched. particles with irregular growth, particles with different crystals bonded by epitaxial bonding, particles with high silver iodide high sensitivity crystals bonded to a low silver iodide crystal substrate, particles with irregularities on the surface. Particles with increased surface area, particles subjected to multiple chemical sensitizations during the particle formation process, particles spectrally sensitized by adsorbing sensitizing dyes during the crystal growth process or before chemical sensitization; Particles in which the photosensitive nuclei are concentrated and strengthened by selectively using a small amount of a chemical sensitizer are preferably used.

A highly sensitive silver halide emulsion according to the present invention can be obtained by selecting from these various silver halide grains and chemically sensitizing them appropriately in accordance with the characteristics of the silver halide grains.

The silver halide grains used have a diameter of about 0.2 μ to jμ. For example, British Patent No. 10 Core/4LA, No. 203t7 Octopus, U.S. Patent No. 330!061, No. 3! No. 3, second≠, j
4cP 4th λ, second ≠ 32jφ7, second 5th. ≠
33. j, No. 01, No. 1 bow 30t7, No. Jtj4
No. 942, No. J? ! No. 2067, JP-A-ShojF-162
! No. Q, No. 4111-101!26, No. 31-
///Ri No. 33, Yuaki! ! -///No.73, Yukiaki! r
-／／／No. 937, special request! Suggestions of the basic technology are given in the descriptions such as t-J reference 4L4. If necessary, a small grain emulsion of Q, λμ or less can be mixed and used. A method for making such an emulsion is described in U.S. Patent No. J, 7
No. 744, 4, No. 3゜t! ! ,! Tada and British Patent No. 1,1113°7171.

Maku Patent Show μr-rtoo issue, same! /-39027,
same! /-430F7, same 13. -/37/33 issue 1,
Same za-at! t2/issue, 7$-2717? No., same,
jr, -J743! Monodispersed emulsions such as those described and published in No. 2931 of the same JT Reference No. 2931 can also be preferably used in the present invention. It is used in the present invention. Tabular grains are described by Gato 7, Photographic Science and Engineering Tomoe Ring (Cu.
toff, Photographic 5ci
ence and ,, -E,ngineer
, ing), Vol. 74C, p. 211-2-37 (t
y y, o year); U.S. Patent No. DA, 蓼, J4I, COCO No. 6, same reference-7≠,! , /q, same≠, 4133゜0hiroj, same da, 43ri, jko0夛 and British Patent No. 2. According to the descriptions and methods in llco, No. 717, etc., it is easy to write, compose, and write many items! When using 4-grain particles, the interest rate of the sensitizing dye, such as the improvement of single-color sensitization efficiency, the improvement of graininess, and the increase in sharpness, is that Patent, No. 3, Ko.

It is described in detail in issue 26.

The silver halide emulsion according to the present invention is produced by controlling OpAg in the liquid phase to generate and grow silver halide grains, controlling the temperature and stirring to a predetermined temperature, sodium chloride, potassium bromide, potassium iodide, etc. It is manufactured using a double-jet emulsion manufacturing equipment that controls the addition of halides and silver nitrate.

For the production of the silver halide emulsion used in the present invention, research disclosure, /7A4 (j: same, tlyi6
A compound described in is used. A fine grain emulsion in which silver halide grains have a diameter of o, oi-o, or 2 microns can also be used in the protective layer and intermediate layer.

When the iodine content of the silver halide emulsion is low, especially when it is less than -Morti, light absorption in the KFi blue wavelength range decreases,
Lack of sensitivity in the blue wavelength range tends to occur. In order to compensate for the lack of sensitivity caused by this decrease in light absorption, the particle size/surface area ratio is small, and a diameter/thickness ratio that allows addition of a large amount of sensitizing dye for short-wave sensitization and increases light absorption is required. In the present invention, it is preferable to use three or more tabular grains.

In addition, silver halide grains include regular grains with regular crystal bodies such as cubes, octahedrons, and dodecahedrons, but when the iodine content is low, the number of crystal defects decreases, resulting in a decrease in sensitivity. occurs.

Therefore, it is preferable to intentionally introduce crystal defects into the emulsion used in the present invention. In the process of grain formation, a silver halide adsorbent material, a different kind of halogen, a different kind of metal ion is added to introduce crystal defects, and nine grains are preferably used.

When the light-sensitive material of the present invention is composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity and different sensitivities, the silver halide grains in the emulsion layer having the highest sensitivity among these emulsion layers are The average particle size is greater than or equal to 0.3 microns, preferably greater than or equal to 0.6 microns. Here the average particle size is
It shall be determined by the average of the circular diameter of the projected area by an electron microscope.

The characteristics of the present invention are that color development progresses quickly, in particular, development is weakly suppressed in gradation areas in the early stages of development, and as development progresses, K
If the effect is strong, DIR-coupler or IR hydroquinone, which has little or no inhibitory effect on the bleach-fixing of developed silver, is selected and DXR-compound (DIR coupler and DIR (meaning hydroquinone) must be used.

The problem that must be solved in order to quickly and easily color develop photographic color photosensitive materials is to speed up the desilvering process (bleaching and fixing) of reduced silver. The first factor that inhibits the desilvering process of reduced silver is adsorption of a development inhibitor released from a commonly used DIR coupler to reduced silver and iodide ions generated during development, and photosensitive halogenation. The present inventors have discovered that the problem lies in the adsorption of sensitizing dyes used for spectral sensitization of silver emulsions.

The first Ic is silver iodide contained in silver halide grains, and the second Ic is the adsorption of sensitizing dyes used for spectral sensitization. however,
The silver iodide contained in the silver halide grains appropriately controls the progress of gradation development, and also provides silver halide with excellent functions such as high sensitivity, suppressing capri, and improving graininess. Therefore, it is necessary to introduce new K technology to reduce the amount of silver iodide used.

The inventors have discovered that by using the light-sensitive material of the present invention, a color development processing method that takes an unprecedented time of about 2 minutes, particularly a short time of about 3 minutes and 30 seconds, preferably FiJ minutes to 1 minute, can be carried out. I found out that it is possible. In the present invention, DIR
In the color development process, the compound reacts with the halogenated form of the color developing agent to release a development inhibitor, and in an amount that does not substantially inhibit KmJlk, for example, the amount used in the coupler used to form a color image.
It is preferable to use a color light-sensitive material that does not use a substrate of less than one mol, preferably less than one mol, at all.

In the present invention, the following general formula [I] or the general formula [I
] is used. Among them, it is preferable to use DIR compounds.

General formula (1) % formula % - Grand total (II) A -(Ll)-Z2-((Lg)-Y:]ba
When the formula C is used as an aromatic primary amine color developing agent, it reacts with its oxidized form to form -(Ll) -8-Zl-((Lg) -Y)b or a C -(Ll) -Zz-[(Lg) -Y) b Residue leaving, IL e Ll is timing group, Lg is linking group, Y represents cation, hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group . zl represents a heterocyclic group, arylene group, or alkylene group, and Z2 represents a heterocyclic group. a and C represent 0 or /, b represents 0, l or ko. However - ((Lg
) -Y)b K contains a hydrophilic group, a water-soluble group, or a precursor residue thereof. When b is λ, −((L
g) c Y) The residues may be the same or different. b
When is 00, it represents a hydrogen atom.

In general formula [I] or (II), zl or zl
is a heterocyclic residue, it is particularly useful as a DIR compound. However, it is not limited to this. In particular, in (1), zl is an arylene group or an alkylene group, which is advantageous for speeding up the desilvering process and is preferably used in the present invention.

DIR compounds have the property of suppressing the desilvering process when natural ions and sensitizing dyes coexist. It is preferable to use a DIR compound and a compound in which 21 is an arylene group or an alkylene group.

A is, for example, U.S. Pat. No. 3,432,3171! t
Ri No. 23 and Tokukai Sho! This is a coupler residue described in t/-14cde27, JP-A-Kokai Shojko/l/2J7'fk, etc.

As the color coupler residue, the following can be used. Yellow color coupler residues represented by A include piparoylacetanilide type, benzoylacetanilide type, malondiester-malondiamine type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type, and penzotizolylacetate type. coupler residues of type, benzoxacylylacetamide type, benzoxacylylacetate type, benzimidazolylacetamide type or benzimidazolylacetate type, and heterocycle-substituted acetamides or heterocycle-substituted acetates contained in U.S. Pat. or a coupler residue derived from U.S. Pat. No. 3,770. uμ6, British Patent No. 7. noon! ? , /7/
No. 2, West German Patent (OLS) No. 2. JOS, OR2, Japanese published patent! Coupler residues derived from acylacetamides described in No. 0-/J, No. 73 or Research Disclosure/J-737, or U.S. Pat.
The heterocyclic-substituted coupler residues described in No. 4, No. 04c4, No. 17 are preferred.

Examples of magenta color coupler residues represented by A include oxocobyrazoline nucleus, pyrazolo-[t, 5-a
) Coupler residues having a benzimidazole nucleus, a cyanoacetophenone type coupler residue or a pyrazolotriazole nucleus are preferred.

The cyan color coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus.

Furthermore, the human coupler residue may not form substantially any dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. Coupler residues of this type, represented by A, include U.S. Patent Nos. ≠, 0!2. Ko No. 13, Same No. Da, o'tr, ≠ No. 21, Same No. 3,432.34cj
No. 3. the law of nature! t, 2F3 or the same No. 3. Examples include coupler residues described in Rij/ and Rij No.2.

In other words, A reacts with the oxidized product of the color developing agent to form S Zl
-((Lx) -Y)b residue, ta-Zz-((L
z)-Y) is the coupler residue releasing the b residue.

Ll is a timing group and a represents Q or l.

Examples of the linking group represented by Ll include those shown below. For example, 10CH2- (linking group described in U.S. Pat. Hydrogen atom, halogen atom, alkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group,
represents a cyano group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, cycloalkyl group, alkanesulfonyl group, arylsulfonyl group or acyl group, R22 is a hydrogen atom, an alkyl group group, alkenyl group, aralkyl group, cycloalkyl group or aryl group.

pSq represents l or Fi-, respectively.

When q is co, R21s may form a fused ring.

zl represents a b-1-/valent linking group such as a heterocycle, unsubstituted or substituted arylene, linear or branched alkylene. When expressed as -5-zl-, for example, -8-CH2-CH-CH2-1 嘗-8-CH2-CH2-CH2-CH2--8-CH=
CH-CH2-CH2- C2H5- ' -8-0M2CH2-0-CH, -CH2-2
2 represents a heterocyclic residue.

L2 represents the consecutive winnings. For example, -(CH2 tube coo- 1l - (CH2) d-QC- double crown o-((,:M2 d(υ Lee- -(CH2)p-COOCH2CH2So2- W and dFiO to IO1 preferably represent an integer of 0-1.

Wl is a hydrogen atom, a halogen atom, an alkyl group with a carbon number of /-10, preferably /-j, an alkanamide group with a carbon number of l-10, preferably /-6, a carbon number /-10, preferably /-j Alkoxy group, carbon number 7-10. Preferably an alkoxycarbonyl group, an aryloxycarbonyl group, an alkanesulfonamide group, an aryl group, a carbamoyl group, having carbon atoms of 1 to 1, preferably /-1, preferably /-j,
It has 1 to 10 carbon atoms, preferably selected from #i/-tON-7h+lucarpamoyl group, nitro group, cyano group, arylsulfonamide group, sulfamoyl group, and imide group.

W2 represents a hydrogen atom, an alkyl group having a carbon number of -4, an aryl group or an alkenyl group, W3Fi a hydrogen atom, a halogen atom, a nitro group, an alkoxy group having a carbon number of -4,
or represents an alkyl group, and p represents an integer from 0 to 6.

Y represents a cation, a hydrogen atom, an alkyl group or an alkenyl group, preferably a linear, branched or cyclic alkyl group, alkenyl group, aryl group or heterocyclic group having a carbon number of /-10, preferably /-j; , preferably has a substituent, and examples of the substituent include a halogen atom, a nitro group, a carbon atom alkoxy group, and a carbon number 6 to 10.
Aryloxy group, alkanesulfonyl group with carbon number 1A-hiro, arylsulfonyl group with carbon number t to 10, alkanamide group with carbon number/-j, anilino group, benzamide group, alkyl-substituted carbamoyl group with carbon number/-4 group, carbamoyl group, aryl-substituted carbamoyl group with t to 10 carbon atoms, alkylsulfonamide group with carbon numbers/~≠, arylsulfonamide group with 4-10 carbon atoms, lA carbon atoms
-≠ alkylthio group, arylthio group having 6 to 10 carbon atoms, phthalimide group, succinimide group, imidazolyl group, 1,λ,≠-triazolyl group, pyrazolyl group, benztriazolyl group, furyl group, benzthiazolyl group,
Alkylamino group with carbon number l-μ, alkanoyl group with carbon number l-≠, benzoyl group, alkanoyloxy group with carbon number/-#, benzoyloxy group, perfluoroalkyl group with carbon a/~da, cyan group, Tetrazolyl group, droxy group, carboxyl group, mercapto group, sulfo group,
Amino group, alkylsulfamoyl group with carbon number/~da,
Arylcarbonyl group having 6 to 1 Q carbon atoms, t to 1 carbon atoms
0 aryloxy-substituted carbonyl group, imidazolidinyl group, or alkylidene amino group having carbon number/-4.

The aryl group represented by Y represents a phenyl group or a naphthyl group, and the substituent is selected from the substituents listed above for the alkyl group or alkenyl group or an alkyl group having 1-d carbon atoms.

The heterocyclic group represented by Y includes a diazolyl group (2-imidazolyl group, Hiro-pyrazolyl group, etc.), triazolyl group (/, 2.≠-triazol-3-yl group, etc.), thiazolyl group (2-benzothiazolyl group, etc.) ), oxacylyl group (1,3-oxazole-koyl group, etc.), pyrrolyl group, pyridyl group, diazonyl group (1,e-diazine-koyl group, etc.), triazinyl group (/, z, p-
Triazine! -yl group, etc.), 7lyl group, diazolinyl group (imidazolinyl group, etc.), pyrrolinyl group, thienyl group, etc.

The -(R2)-Y residue has a hydrophilic group, a water-soluble group, or a precursor thereof. Examples of hydrophilic groups, water-soluble groups, or precursors thereof are shown below.
COOC2F2H3, European carboxylic acid ester group, sulfonamide group such as -NH802CH3, -ku αΣ
Carbamide groups such as H3, -NHCα)C2H, -0H1-
NH2 -so2NH2, a kyl group, R2 is a linear or branched alkyl group with 1 carbon number, and the total number of carbon atoms of R1 and R2 is t or less) Next, specific examples of the compound represented by the general formula [1] are shown below. give. However, it is not limited to this.

uf12t,;f12-A;LXjL;l”3S-CH
2CH2-COOH CH2CH2C0OH Activated C11゜＼ 1=■ The DIR coupler used in the present invention has the above-mentioned development inhibiting properties and a tendency not to substantially inhibit silver bleaching properties, and in particular, the following general Formula (I[[), [■
], (V1, ([4), [■], [■] ~ (X!V ]
Compounds represented by K are preferred.

- Grand total [■] 〇 General formula (IV) General formula (V) General formula [■] General formula [■] General formula (IK) General formula (X) ((υ Li-11b - Grand total (XI) R11 -CO-CH-CO-NH-R
X represents a hydrogen atom or a substituent, and those listed as substituents for Y are selected.

For example, the same or different groups such as a halogen atom, an alkyl group, a nitro group, a cyano group, an alkoxy group, an alkanamido group, an aryl group, a heterocyclic group, etc., and U represents an integer of 0.11 and co.

In the formula, R11 represents an aliphatic group, an aromatic group, an alkoxy group, or a heterocyclic group, and R12 and R13 each represent an aromatic group or a heterocyclic group.

In the formula, the aliphatic group represented by R11 preferably has 7 to 22 carbon atoms, is substituted or unsubstituted, linear or cyclic,
It may be either. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and an atom atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as R11 are: isoprobyl, -isobutyl, tert-butyl, inamyl, tart-7mil, 1,l-dimethylbutyl. base, 1
, l-dimethylhexyl group, /j/-diethylhexyl group, dodecyl group, hexadecyl group, ophtateryl group, cyclohexyl group, -1methoxyinpropyl group, cofdinoxyisopropyl group, J-p-tert-7” tyl Phenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)inpropyl group, α-(succinimide)isopropyl group, α-(phthalimide),
These include inopropyl group, α-(benzenesulfonamido)inopropyl group, and the like.

When R11% R12 or R13 is an aromatic group (%K phenyl group), the aromatic group may be substituted! stomach. Aromatic groups such as phenyl groups include alkyl groups having 3-2 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, and alkylsulfonamide groups. The alkyl group may be substituted with a group, an alkylureido group, an alkyl-substituted succinimide group, etc. In this case, the alkyl group may be substituted with an aromatic group such as a phenylene group in the chain. It may be substituted with a phenyl group, an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, a 7-lylsulfonamide group, an arylureido group, etc. The 7-aryl group may be further substituted with one or more alkyl groups having a total number of carbon atoms of / to λ.

The phenyl group represented by R11, R12 or R13 may further include an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, a thiocyano group, including those substituted with a lower alkyl group having carbon number/-4. It may be substituted with a halogen atom.

Rli s R12 or R13 is a substituent in which a phenyl group is fused with another ring, such as a naphthyl group,
) group, inquinolyl group, chromanyl group, chromanyl group, tetrahydronaphthyl group, etc. These substituents may themselves have further substituents.

When R11 represents an alkoxy group, the alkyl moiety represents a linear or branched alkyl group, an alkenyl group, a cyclic alkyl group, or a cyclic alkenyl group having from / to 410 carbon atoms, preferably from / to 22 carbon atoms. It may be substituted with a halogen atom, an aryl group, an alkoxy group, etc.

When R111, Rrzl or R13 represents a heterocyclic group, the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the nitrogen atom of the amide group of the heterocyclic group is connected via one of the carbon atoms forming the term, respectively. Combine with. Such heterocycles include thiophene, 7ran,
Pyran, virol, pyrazole, pyridine, pyrazine,
Examples include pyrimidi/, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thia'diano, and oxazino.These may further have a substituent on the ring.

- Monna (V: l, RIS is carbon number l to rto,
Preferably 1-22 linear or branched alkyl groups (
For example, methyl, isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (for example, allyl group, etc.), cyclic Al*Al (for example, ttf cycloynthyl group, cyclohexyl group, norbornyl group, etc.), aralkyl! = (N, t benzyl, β phenylether group, etc.)
, represents a cyclic alkenyl group (e.g. cyclointenyl, cyclohexenyl group, etc.), and these are halogen atoms,
Nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, 7 diacylamide groups, ureido group, urethane group 1. Thiourethane group, sulfonamide group, heterocyclic group, arylarylsulfonyl group, alkylsulfonyl group, arylthio group,
It may be substituted with an alkylthio group, an alkylamino group, a dialkylamino group, an aniline group, an N-arylaniline group, an N-alkylaniline group, an N-acylamino group, a hydroxy group, a mercapto group, or the like.

Furthermore, R15 is an aryl group (e.g. phenyl group, α-
or β-su7tyl group). The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom,
Nitro group, cyano group, aryl group, alkoxy group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, Sulfo/amide group,
Heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-7 sylanilino group, hydroxy group, mercapto group, etc.

More preferable R5 is at least 7 or 1 at the ortho position.
A phenyl group in which one of the atoms is substituted with an alkyl group, an alkoxy group, or a nitrogen atom, and is useful because the coupler remaining in the film is less likely to fade due to light or heat.

Furthermore, RIS is a heterocyclic group (for example, a !-membered or 6-membered heterocyclic group containing a nitrogen atom, a surron atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group) , oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.), heterocyclic group substituted with the substituents listed above, aliphatic t le+-1 aromatic acyl group, alkylsulfonyl group, arylsulfonyl group , an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group.

In the formula, R14 is a hydrogen atom, carbon number 1 to 4to, preferably a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl group (these groups are listed for R, !1 above) Aryl groups and heterocyclic groups (which may have substituents listed above for R151C), alkoxycarbonyl groups (for example, methoxycarbonyl groups,
ethoxycarbonyl group, stearyloxycarbonyl group, etc.), aralkyloxycarbonyl group (e.g. benzyloxycarbonyl group, etc.), alkoxy group (e.g. methoxy group, ethoxy group, heptadecyloxy group, etc.),
Aryloxy groups (e.g., phenoxy group, tolyloxy group, etc.), alkylthio groups (e.g., ethylthio group, dodecylthio group, etc.), arylthio groups (e.g., phenylthio group, α-su7thylthio group, etc.), carboxy groups, acylamino groups (e.g., acylamino group) , j-((λ, tert-amylphenoxy)acetamide]be/zamide group, etc.), diacylamino group < N-furkylacylamino group (for example, N-methylpropionamide group, etc.), N-arylacylamino group (side-light N-phenylacetamide group, etc.), ureido group (e.g. ureido,
N-arylureido, N-furkylureido groups, etc.)
, urethane group, thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylaniline group, 2-chloro-j
-tetradecanamideanili group, etc.), alkylamino group (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino group (e.g. pyrrolidino group, pyrrolidino group, etc.), heterocyclic amino group (e.g. derpyridylamino group, etc.), group, copenzooxazolyl amino group, etc.), alkylcarbonyl group (e.g., methylcarbonyl group, etc.), arylcarbonyl group (e.g., phenylcarbonyl group, etc.), sulfo/amide group (e.g., alkylsulfonamide group, arylsulfo/amide group, etc.) group), carbamoyl group (e.g. ethylcarbamoyl group,
dimethylcarbamoyl group, N-/tylphenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl MC Examples: Lb N-arylalkylsulfamoyl group, N.

N-dialkylsulfamoyl group, N-arylsulfamoyl L N-alkyl-N-arylsulfamoyl group, N,? 'J-diarylsulfamoyl group, etc.)
, a cyano group, a hydroxyl group, a methcapto group, a halogen atom, or a sulfo group.

In the formula, R17 represents a hydrogen atom or a linear or branched alkyl group having 7 to 3 λ carbon atoms, preferably / to 2-carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group; is the above R15Vc
may have the substituents listed above. □ R17 may also represent an aryl group or a heterocyclic group, and these may have the substituents listed for R15 above.

R17 is a cyan group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group,
Sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group , N-
It may also represent an arylanilino group, an N-furkyanilino group, a hydroxy group or a mercapto group.

R18, R19 and R2O each represent a group commonly used in glue-equivalent phenol or α-7 toll couplers; specifically, R18 is a hydrogen atom,
Halogen atoms, aliphatic hydrocarbon residues, acylamino groups,
-0-R3, or -8-R31 (where R31 is an aliphatic hydrocarbon residue) in the same molecule! more than R
When R18 is present, two or more R18s may be different groups, and aliphatic hydrocarbon residues include those having substituents. R19 and R2O are aliphatic hydrocarbon residues. , an aryl group, and a heterocyclic residue, or one of these groups may be a hydrogen atom, and these groups include those having a substituent. Further, R19 and R20 may jointly form a nitrogen-containing heterocyclic nucleus. r is an integer from / to
An integer of ~3, t is an integer of ./~even. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic. and preferably alkyl groups (e.g. methyl, ethyl, propyl, isozolobyl, butyl, t
-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl, etc.), alkenyl groups (
For example, allyl, octenyl, etc. Aryl groups include phenyl, naphthyl, etc.; heterocyclic residues include pyridinyl, quinolyl, thienyl,
Typical examples of bi are lysyl, imidazolyl and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms, nitro,
Hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, acyloxy, acylamino, carbamoyl, ester, acyl, acyloxy, sulfo/amide, sulfamoyl, sulfonyl, morpholino, etc. Each group is mentioned.

R11 R12% R13s R14% R of the substituents of couplers represented by general formulas (III) to (XIV)
15%R17N R18, R19, R20 may be bonded to each other) or any one of them may be a divalent group to form a symmetrical or asymmetrical composite coupler.

Examples of couplers used in the present invention include the following compounds, but the compounds are not limited thereto.

More specifically, the special application 1974-//J! Examples include the compounds listed in Item B.

The DIR coupler used in the present invention includes the above-mentioned RD, /
744LJ, patents described in sections ■ to F, JP-A-Sho! 7-
Synthesized according to the method described in /j/W4t4, No. 17-/j Hiroko 3, No. 3, No. 12, US Pat. be able to.

The color coupler used in the invention is RD/74$
3. ■It is described in the patent described in -〇-G.

As a yellow coupler, for example, U.S. Pat.
No. 3,101, No. 4Ao-1, No. 620, No. 732
No. 3021, No. 410/7!2, Tokko Akira! ! -1
No. 073P, British Patent No. 1. ≠2! , No. 020, No. 1
．． ≠Those described in No. 76740 are preferred. Either or a combination of piparoylacetanilide yellow couplers and indiylacetanilide yellow couplers may be used.

As a magenta coupler! -Pyrazolone and pyrazoloazole compounds are preferred.

U.S. Patent No. 3106/R, U.S. Pat.
European Patent No. 73434, US Patent No. 30.474Cj
No. J, No. 3721067, RDA Komu Coco Q (1st year of publication), 1st issue of JP-A-4O-33/1, RD Yako-san 230 (/Free of charge in June 2013), JP-A Showa 6 O-u36! No. 1, U.S. Patent No. A, tOO, No. 630, No. J4! o
Particularly preferred are those described in the tsg issue.

Cyan couplers include phenolic and naphthol couplers. US Patent No. Hiroshi Q! cocoa 2
No. ≠ lμ632, No. Kokoko r233, No. 3 Kotakko OQ, No. 236 Tata λri, No. 21
0//7/ issue, Core 7th and 16th issue, Core number 16! t
Jt No. 377, 00, 3711301, 33140/, 327173,
West German Patent Publication No. 332 7 Kota, European Patent No. 12/3
tjA, U.S. Patent No. 3μ4 (j4 Coco, U.S. Patent No. A33
3Yri No. 2, same No. 4c4AJ/j! No. 2, No. 41a2
Those described in European Patent No. 7,767, European Patent No. 1t/, tAtA, etc. are preferred. Particularly preferred are polymer couplers and monoequivalent couplers.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in the ■-G section of RDA/74 Ko3 and U.S. Patent No. ≠/43.
No. 470, Special Publication No. 7-32-73, U.S. Patent No. 0
0 Hiro Octopus No. 2, Hiro No. 3t, Jjt No. 1, British Patent No. 1
/4ttjtt issue etc. are preferred.

Examples of couplers in which coloring dyes have appropriate diffusivity include U.S. Patent No. ≠ JAA, No. 2J7, and British Patent No. 1λj17.
No. 0, European Patent No. 26370, West German Patent (Publication) No. 3
, 23≠j33 is preferred.

Typical examples of polymerized color couplers are U.S. Pat. oto Jl No. 1, Oto Tei J47Jf, No. 2, British Patent No. 2i.

It is described in No. 2173, etc.

The amount of color coupler used is about 0.00 to 1 mole per 7 moles of silver halide, preferably 0.01 to Q for yellow coupler.

3 moles, 0.003' for magenta coupler! Stone 0
．． 3 mole or cyan coupler Fio, oo or 0
．． It is about 3 moles.

General formula [1) according to the present invention! (Some compounds represented by INK act as DIR-compounds, while others act rather to speed up the desilvering process. DL
The R-compound is preferably used in combination with the DIR-compound and other compounds that speed up the desilvering process in such amounts that it does not substantially inhibit desilvering. Preferably, the color coupler is used in an amount of 7 molti, more preferably 3 molti or less.

When the DIR compound represented by the general formula (1) and the compound (1) according to the present invention is used together with another compound represented by the general formula [I], the standard of the amount that does not inhibit desilvering is raised to about /Qmolti It has the advantage of being able to do both. This effect becomes remarkable when used in combination with the sensitizing dye according to the present invention.

Particularly preferred DIR couplers for use in the present invention are:
It is a DIR coupler that releases a development inhibitor having a carboxylic acid ester bond, such as the above-mentioned exemplified compounds (2), (3), (4), and (6). When these couplers are separated in the emulsion film during development, their low molecular weight makes them highly diffusive and brings about a favorable glabella multilayer effect. Additionally, DIR couplers are less likely to inhibit desilvering due to rounding, which when transferred to a developer, undergoes alkaline hydrolysis and becomes a harmless compound.

In the light-sensitive material of the present invention, the coating amount of the DIR compound is j x 10 per 1.0 g of silver equivalent coating amount of photosensitive silver halide.
-4 mol or less, preferably / Even if this happens, it is advantageous in preventing inhibition of desilvering.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, it is dissolved in either a high-boiling organic solvent with a boiling point of 1yz0c or more and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, and after death, water or an aqueous gelatin solution is prepared in the presence of a surfactant. finely dispersed in aqueous media. Examples of high boiling point organic solvents are described in U.S. Pat. No. 2,302,027 and others.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Examples of the process, effects, and latex for impregnation of latex dispersion methods are described in U.S. Pat.

No. 363, West German patent application (OLS) no. u/.

274! No. and No. 2 of the same. ! It is described in Hiroshi No. 1,230, etc.

The compound represented by the general formula [1] or [■] not only has little or no inhibitory effect on the bleach-fixing of reduced silver, but also has a weak inhibitory effect on the progress of development in gradation areas, particularly in the legs, during color development. It has the advantage that the multilayer effect works effectively in the mid-tone to high-density areas.

When a DIR coupler is not used, the bleaching and fixing inhibiting effect of reduced silver is extremely small, so that the bleaching and fixing process of the color light-sensitive material of the present invention can be completed in about 1 minute under fractional separation. Reinforcement of weak points caused by not using DIR-coupler, such as multilayer effect, image sharpness, etc.
It is desirable to supplement the granularity improvement with other means. The multilayer effect is achieved by applying a masking method using colored couplers.
For example, an overlaying effect from a red-sensitive layer to a magenta-producing green-sensitive layer can be imparted by adding a magenta dye release compound to the red-sensitive layer. Image sharpness can be imparted by using a colored coupler or the like that imparts a blur mask. Grain improvement can be supplemented, for example, by the combination of competing couplers or by the combination of a portion of a coupler forming a somewhat diffusive chromophoric dye.

There are sensitizing dyes that are preferably combined with the present invention. Sensitizing dyes that do not inhibit color development or inhibit the bleaching and fixing effects of reduced silver are preferably used. The types of sensitizing dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, hemicyanine dyes, merocyanine-7 dyes, and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline group, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
A benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or complex merocyanine dyes contain a pyrazolin-j-one nucleus, a thiohydantoin nucleus, a cortioxazolidine-2,
4cm dione nucleus, thiazolidine-2, Hiro-dione nucleus, rhodanine nucleus, thiobarbyl acid group, etc.! ~ can be applied to the member heterosegmental ring nucleus.

The sensitizing dye that has the effect of inhibiting color development, bleaching of reduced silver, and fixing, especially the latter, is a cationic cyanine dye, especially a sensitizing dye adsorbed in the form of a J aggregate. However, when a substituent having a water-soluble group is introduced into the cyanide dye ON-substituent or C-substituent, the inhibitory effect is significantly reduced. Anionic cyanine dyes have almost no inhibitory effect.

The same properties are shown for hemicyanine dyes and rhodacyanine dyes; merocyanine dyes have less inhibitory effect than cationic cyanine dyes, but similarly, the inhibitory effect can be almost eliminated by introducing a substituent with a water-soluble group. Can be done.

In the present invention, a sensitizing dye having a substituent having a precursor of a water-soluble group is used in a raw color light-sensitive material, and during image exposure and color development, it is hydrolyzed and converted into a substituent having a water-soluble group. The bleach-fixing inhibiting effect of reduced silver can be eliminated. These sensitizing dyes are preferably used in combination.

In particular, in color light-sensitive materials for photography, monomethine cyanine dyes, trimethine cyanine dyes, simple merocyanine dyes, dimethine merocyanine dyes are used, and pentamethine cyanine dyes and hemicyanine dyes may also be used. A substituent is introduced into the N atom or C atom of this bone nucleus. The sensitizing dye KFi used in the present invention is preferably one having a substituent represented by the following general formula (XV) introduced with &<K.

General formula CXV) -(L2)-Y In the formula, L2, Y and C are general formula (1) or (II)
It has the same meaning as that of , and includes a hydrophilic group, a water-soluble group, and its precursor in the residue of . L2 is especially an alkylene group,
Linking groups such as arylene groups and divalent heterocyclic residues are preferred.

A specific example is shown below. However, it is not limited to this.

-CH2-C0OH.

-CH2-COOC2H5, -CH2CH2-OH.

-CH2CH2-8O3H.

-CH2CH2CH2-8O3H.

OH3 -CH2CH2CH-CH2-8O3H.

-CH2-CH2-CH2-COOCH3, -COOC
H3, -CH2CH2CH2So2CH3, etc.

Preferably, it is a group that can be hydrolyzed in a color developing solution and converted into a strong water-soluble group.

Next, specific examples of sensitizing dyes used in the present invention will be given. However, it is not limited to this.

(CH2)3SO3-(CH2)3SO3-H (PTS:p-) luenesulfonate) tlFj The sensitizing dye used in the present invention is, for example, disclosed in JP-A Shoj/, -J
O72 ≠ issue, 滝昭J! - Kota l co-issue, Yukiaki! /-29
1st issue, Toshiaki! /-/μoi issue and special public Shosan 〇-7
≠//J issue, Yusho≠0-23≠67, Yusho 4c3-μ
ri 31, 滝昭μ≠-233t2, 滝昭4Lt-2J
tj No.2, Yushoat-23413, Yusho≠2-≠6μ
/No. 4, Showa 77-≠Hiroshi 3ty issue, Tokukai Show≠2-4tJ
JO No. 1/37013, Hiroko 17.
No. 2, No. 1110223, No. 7! j011-No.? r02j No. 41, No. 107tYrlA, No. 1O
IIA≠No.3j, etc., and patent application No. 4/-/j/
This is a sensitizing dye in which a substituent represented by the general formula (XV) according to the present invention is introduced into the dye core of the sensitizing dye described in JR No. 3. Select from the group of these sensitizing dyes for use. be able to.

The sensitizing dye used in the present invention can be added after being dissolved in a water-soluble organic solvent. It can also be added after being solubilized in a surfactant. It can also be added to a chemically sensitized silver halide emulsion in an amount of 1.times.10@-5 to 1.times.10@-3 mol per mol of silver. In the present invention, in particular, before chemical sensitization or in the middle of grain formation, 7 mol of silver/X
It is preferable to add in an amount of 10-5 to /x10-2 mol.

By this method, high sensitivity can be achieved in silver halide containing less than about 1 mole of silver iodide or zero. The sensitizing dye according to the present invention can be added in a larger amount than usual, and can provide spectral sensitization as well as the effect of preventing irradiation.

The amount of coated silver in the photosensitive material of the present invention is preferably as small as possible from the viewpoint of shortening the bleaching and fixing steps, and from the viewpoint of image quality such as sensitivity and graininess, it is preferable to have a large amount; From a comprehensive viewpoint to maintain sensitivity and graininess, the weight should be 2 g or more and izg or less, preferably l, per 1 m2 of support.

g or less, more preferably rgg or less, more preferably 6
g or less is good.

The photosensitive material of the present invention can be designed to have an ISO sensitivity of 2j or more and 6x0Q or less, and can be made into a negative type photographic photosensitive material. Preferably ISO sensitivity is 100
and 1too, 15Otoo, aoo
, goo, 1ooo.

It can be designed to have a sensitivity of 1too.

The light-sensitive material of the present invention uses a transparent support. Appropriate thickness of cellulose acetate film, polyethylene terephthalate λ-axis stretched film, etc., for example.

Film thicknesses from 10 pm to 200 μm can be used.

Photographic additives that can be used in the light-sensitive materials of the present invention are described in the following Research Disclosures /74/17/1 at specific locations and in the patents cited therein.

/ Chemical sensitizers Page 23 i Page 4 right column λ Sensitivity increasing agents Same as above ≠ Brightening agents Coμ Page 7 Anti-stinting agents Page 25 right column t! o page left to right column t
Dye image stabilizer Page 25 Hardener Cot" Rtri left column lO Binder Page Same as above / l Plasticizer, lubricant
Page 27 tzo Right column The processing bath having bleaching ability of the present invention will be described below.

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

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

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

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

3-diaminopro/ferric tetraacetic acid complex salt is used in combination at a molar ratio of 3 or less. The preferred molar ratio is /,! -0,1. If the molar ratio exceeds 13, the bleaching strength will decrease and desilvering will be poor.

Furthermore, if the proportion of ferrous salt of 1,3-diaminopropanetetraacetic acid becomes significantly high, a slight bleaching edge may occur.

The amount of the bleaching agent of the present invention added is 1/
0.0j mol to 1 mol per liter, preferably 0,7
(Mole ~ o, z moles.

Other Invention In addition to the above-mentioned aminopolycarboxylic acid iron (DI) complex, an aminopolycarboxylic acid salt can be added to the treatment solution IIc having bleaching ability. In particular, the compound group (A
) is preferably added. : The preferable addition amount is 0.0001 mol to 0.1 mol/l, preferably 0.003 mol to o,os mol/l.

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

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

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

Such bleach accelerators are described, for example, in US Pat. 3. t, tt specification, German patent cylinder 1. Kota No. 0,11 specification, British patent cylinder 1゜ixr, tax specification, Japanese Patent Application Laid-Open No. 3-41430, Research Disclosure No. 1712 (Li 7, July issue)
Compounds having a mercapto group or disulfide group as described in JP-A No. 10-1440122, thiazolidine derivatives as described in US Pat. No. J, 706,16/, JP-A-Sho! Iodide described in r-/Ako 3j publication, German patent tsutsuko, 7≠t, 4c3
Polyethylene oxides described in the specification of No. 0, polyamine compounds described in Japanese Patent Publication No. Shoat-teJt, etc. can be used. Particularly preferred is British Patent Tube 1. /
31. The more mercapto compounds described in the specification of r#co are preferred.

In particular, in the present invention, from the following general formula (IA) to (VI
The bleaching accelerator represented by A) can be preferably used because it has excellent bleaching ability and causes little bleaching fog.

General formula (IA) RIA-8-MIA In the formula, MIA represents a hydrogen atom, an alkali metal atom, or ammonium. RIA represents an alkyl group, an alkylene group, an aryl group, or a heterocyclic residue. The preferable number of carbon atoms in the alkyl group is from Fi/ to j, and most preferably 3. The preferred number of carbon atoms in the alkylene group is from co to j.
It is. Examples of the aryl group include phenyl and naphthyl groups, with phenyl being particularly preferred. As the heterocyclic residue, nitrogen-containing rings such as pyridine and triazine, and nitrogen-containing rA rings such as azonyl, pyrazole, triazole, and thiadiazole are preferable, but among them, two or more of the ring-forming atoms are nitrogen atoms. It is particularly preferable. RIA may be further substituted with a substituent. Examples of substituents include alkyl groups, alkylene groups, alkoxy groups, aryl groups, carboxy groups, sulfo groups, amino groups, alkylamino groups, dialkylamino groups, hydroxy groups, carbamoyl groups, sulfamoyl groups, sulfonamide groups, etc. Can be done.

Among general formulas (mA), preferred are general formulas (IA
-/) to (IA-see).

General formula (IA-/) In the formula, R2A, R3A, and R4A may be the same or different, and include a hydrogen atom, a substituted or unsubstituted lower alkyl group (
Preferably carbon number l to jl, especially methyl group, ethyl group,
(preferably a propyl group) or an acyl group (preferably carbon number/to 3, such as an acetyl group or a propionyl group), and kA is an integer from 1 to 3. zlA is an anion (chloride ion, bromide ion, nitrate ion, sulfate ion, p-)luenesulfonate, oxalate, etc.)
represents. kA is 0, II'it, 1AFiQ or 1. It is preferable to use a bleaching accelerator in the bleaching solution.

As bleaching accelerators, compounds represented by general formulas (IA) to (MA) are preferred.

General formula (IA) R"A-8-MIA In the formula, MlA represents a hydrogen atom, an alkali metal atom, or ammonium. RIA represents an alkyl group, an alkylene group, an aryl group, or a heterocyclic residue. The preferred number of carbon atoms is from IIi/ to j, most preferably from 1 to 3.The preferred number of carbon atoms for the alkylene group is from - to !Aryl groups include phenyl groups and naphthyl groups, but especially phenyl groups. As the heterocyclic residue, nitrogen-containing 6-membered rings such as pyridine and triazine, and nitrogen-containing J-membered rings such as azole, -pyrazole, triazole, and thiadiazole are preferred. It is particularly preferable that at least one of the nitrogen atoms is a nitrogen atom.RIA may be further substituted with a substituent. Examples of the substituent include an alkyl group, an alkylene group,
Alkoxy group, aryl group, carboxy group, sulfo group,
Examples include an amino group, an alkylamino group, a dialkylamino group, a hydroxy group, a carbamoyl group, a sulfamoyl group, and a sulfonamide group.

The most preferable formula (IA) is the general formula (IA).
-/) to (IA-Hiroshi).

General formula (IA-/) In the formula, R2AXR3A and R4A may be the same or different, and may be a hydrogen atom, a substituted or unsubstituted lower alkyl group (
Preferably carbon number/ to 1X, especially methyl group, ethyl group,
(preferably a propyl group) or an acyl group (preferably having 1 to 3 carbon atoms, such as an acetyl group or a propionyl group), and kA is an integer from / to 3. 2 is an anion (chloride ion, bromide ion, nitrate ion, sulfate ion, p-)luenesulfonate, oxalate, etc.)
represents. kA represents 0 or 11 iA represents 0 or l.

R and R may be linked to each other to form a ring. R2^
R3A and R4A are preferably a hydrogen atom or a substituted or unsubstituted lower alkyl group.

Here, as the substituent that R2A and R3AXR4A have, a hydroxy group, a carboxy group, a sulfo group, an amino group, etc. are preferable.

General formula (IA-J) General formula (IA-J) General formula (l A-1) In the formula, R5A is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an amino group, a substituted or unsubstituted Lower alkyl groups (preferably 1 to 1 carbon atoms, particularly methyl, ethyl, and propyl groups), amino groups having alkyl groups (methylamino, ethylamino,
Represents a substituted or unsubstituted alkylthio group (dimethylamino group, diethylamino group, etc.).

The substituents that Komude 15A has include a hydroxy group,
Examples include a carboxy group, a sulfo group, an amino group, and an amino group having an alkyl group.

General formula (I[A) RIA-8-8-R6A In the formula, BIA is the same as HIA of general formula (IA),
R6A is synonymous with RIA. RIA and R6A may be the same or different.

Among general formulas (IIA), preferred ones are general formulas (H
A-/).

General formula (uA-/) In the formula, R7AXR8A, R9A is R2AXH3A,
It is synonymous with R4^. hA, kA and zlA are expressed by the general formula (I
A-/) OhA and kA, ZlA and Lfh. 1Bt
Represents i0, l or ko.

General formula (III) In the formula, BIOA and HIIA may be the same or different, and each represents a hydrogen atom, an alkyl group that may have a substituent (preferably a lower alkyl group, such as a methyl group, an ethyl group, a propyl group) ), a phenyl group which may have a substituent,
or a heterocyclic residue which may have a substituent (more specifically, a heterocyclic group containing at least one heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc., such as a pyridine ring,
thiophene ring, thiazolidine ring, benzoxazole ring, benzotriazole ring, thiazole ring, imidazole ring, etc.). R12A represents a hydrogen atom or a lower alkyl group which may have a substituent (for example, a methyl group, an ethyl group, etc., preferably having 1 to 3 carbon atoms).

11 from RIOA here! Examples of the substituent that A has include a hydroxy group, a carboxy group, a sulfo group, an amino group, and a lower alkyl group.

R13A represents a hydrogen atom, an alkyl group, or a carboxy group.

- Grand Total (■A) In the formula, R14A, R15A, and H16A#i may be the same or different, and each has a hydrogen atom or a lower alkyl group (eg, a methyl group, an ethyl group, etc.), and preferably has a carbon number of / to 3. ). Represents an integer from kBril to j.

XIA represents an amino group, a sulfo group, a hydroxy group, a carboxy group, or a hydrogen atom which may have a substituent. The substituent is a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, hydroxyalkyl group, alkoxyalkyl group, carboxyalkyl group, etc.), and two alkyl groups may form a ring.

R14A, R15A, and R16A may be linked to each other to form a ring. As R14A, B16A,
In particular, a hydrogen atom, a methyl group or an ethyl group is preferable, and XI
A is preferably an amino group or a dialkylamino group.

General formula (MA) A1AFin-valent aliphatic linking group, aromatic linking group,
A heterocyclic linking group (When n=/, AIA represents a simple aliphatic group, aromatic group, or heterocyclic group.) The aliphatic linking group represented by A I A has 3 carbon atoms. -lλ alkylene groups (eg trimethylene, hexamethylene, cyclohexylene).

Examples of the aromatic linking group include arylene groups having 6 to tr carbon atoms (eg, phenylene, naphthylene, etc.).

Examples of the heterocyclic linking group include a heterocyclic group consisting of one or more heteroatoms (e.g., oxygen atom, sulfur atom, nitrogen atom) (e.g., thiophene, furantriazine, pyridine,
Biirisin, etc.).

Here, the number of aliphatic linking groups, aromatic linking groups, and heterocyclic linking groups is usually one, but two or more may be linked, and the linkage may be direct or with a divalent linking group (for example, - 〇－
1-S-1R20A 802-1-N-1 100- or a linking group formed from these linking groups<, 120A represents a lower alk or kyl group. ) may be connected via.

Further, the aliphatic linking group, aromatic linking group, and heterocyclic linking group may have a substituent.

Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a sulfonamide group, and a sulfamoyl group.

21A X 2 A represents 10-1-S-1-N- and R21
A is a lower alkyl group (e.g. methyl group, ethyl group, etc.)
), R17A, and R18A represent substituted or unsubstituted lower alkyl groups (e.g., methyl group, ethyl group, propyl group, inpyropyl group, pentyl group, etc.), and examples of substituents include hydroxy group, lower alkoxy group (For example, methoxy group, methoxyethoxy group, hydroxyethoxy group, etc.) and amino group (For example, unsubstituted amino group, dimethylamino group, N-hydroxyethyl-N-methylamino group, etc.) are preferable. Here, when there are two or more substituents, they may be the same or different.

R19A represents a lower alkylene group with carbon number/-j (methylene, ethylene, trimethylene, methylmethylene, etc.), and 2 represents an anion ( )/ride ion (chloride ion, bromide ion, etc.), nitrate ion, sulfate ion, p- toluenesulfonate, oxalate, etc.).

Further, R17A and R18A are connected via a carbon atom or a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom),
! A membered or 6-membered heterocycle (for example, a pyrrolidine ring, a lysine ring, a morpholine ring, a triazine ring, an imidazolidine ring, etc.) may be formed.

R17A (4-ring riR18A) and AFi are connected via a carbon atom or a hetero atom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom), and a j-membered or t-membered heterocyclic ring (e.g., a hydroxyquinoline ring, a hydroxyindole ring, an isocarbon may form an indoline ring, etc.).

Further, R (or R) and R are connected via a carbon atom or a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom), and a j-membered or 6-membered heterocycle (e.g., py is a lysine ring). , pyrrolidine ring, morpholine ring, etc.).

lA is 0 or /, mhtiO or /, nA is /, J or 3, pA is Q or 11 and qA is 0, /, 2, or 1
”represents i3.

General formula (VIA) 22A X1A (CHz) kn-N -C-8-M2A In the formula, X
``A and kB are the same as XIA and kB in the general formula (F/A).

M2A is a hydrogen atom, an alkali metal atom, or an ammonia atom. R
represents a hydrogen atom or a lower alkyl group (having l to j carbon atoms and optionally having a substituent).

Specific examples of compounds of general formulas (IA) to (MA) are shown below.

(IA)-(1) (IA)-(2) (lA)-(3) (IA)-(4) (IA)-(5) ()A)-(6) (lA)-(7) (IA) - (8) (IA) - (9) (IA) - αQ (IA) - (14) (IA) - (i5 (IA) - (19 bk'1 (IA) - ■ (IIA) - (1) (HA) - (2) (IA) - (3) (MA) - (4) (mA) - (5) (IA) - (6) (IIA) - (7) (HA) - (8) (mA) - (9) (IIA) - member (IA) - υ (mA) - (13 (IIA) - (1) h (mA) - (2) (IA) - (3) ( IIA) -(4) (IIIA) -(5) (IIIA) -(6) (VA)-(x) (VA)-(z) (!V'A)-(J) (IVA) -(4 ) (IVA) - (5) (VA) - (6) (VA) - (7) (WA) - (8) (11/A) - (9) (F/A) -Q groan (IVA) - (lυ (VA) - (1) (VA) - (2) C) (MA) - (3) (MA) - (4) (VA) - (5) (VA) - (6) (VA) - (7) (MA) - (8) H3 薯H3 (VA) - (11 H3 (MA) - (le (MA) - (1"3 (VA) - (1 mouth (MA) - (14) ( VA) - (1!9 (VA) - (le (VA) - (1'rI (VA) - (1 second (VA) - a9 (VA) - 4tecte (VA) - 0υ (VA) - @ (VA) - (2) TSe (VA) - (Foundation) tect0 (VA) - (C) (MA) - (1) (MA) - (2) (VIA) - (3) (VIA) - (4 ) (MA) -(5) Among the above bleach accelerators, particularly preferred compounds are IA-co, I
A-s, I A-/J, I A-/Hiroshi, 1A-
l! , IA-i6, IA-i, IA-/.

1 [A-//, VA-i, wA-i, and MA-J
It is.

The amount of the bleaching accelerator added is 0.00000000000000000000000000000000000000000000
0/g to coog, preferably 0. /g~lOg.

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

The concentration of the rehalogenating agent is from 0.1 to 3 mol per liter of bleach solution, preferably from Fio,t to 3 mol. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid-sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc.
Additives known to be commonly used in bleaching solutions, such as inorganic acids of IS class or higher having H buffering capacity, organic acids, and salts thereof, can be added.

The pH of the bath having bleaching ability of the present invention is generally 6 to 1, preferably Fij, I-/, t, and most preferably Fij, j to co. In a preferred pH range, there is little bleaching edge blur and excellent desilvering performance.

The replenishment amount of the bleaching bath of the present invention is 7 m2 of photosensitive material! tOrnl ~ko000m1 preferably 1010
0ml-1000.

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

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

The bath having fixing ability according to the present invention 1 refers to a bleach-fixing bath and a fixing bath.

Fixing agents for baths having these fixing abilities include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and sodium thiosulfate; Urea, thioether, etc. can be used. The amount of these fixing agents is 0.3 mol to 3 mol per liter of processing solution, preferably Q.

The amount is t mol to 2 mol.

The fixing bath contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adducts of hydroxylamine, hydrazine, aldehyde compounds, such as acetaldehyde sodium bisulfite. be able to. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as preservatives, it is possible to contain
It is preferable to use the sulfinic acid compounds described in No. 21313O.

The replenishment amount of the bath having fixing ability is preferably 9 JOOml to JOOml, more preferably 3 JOOml to 10,100ml per m2 of the photosensitive material.

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

The total time of the desilvering process of the present invention is short, and the effect of the basic invention can be significantly obtained. The preferred time is / minute ~ da minute, j! It is preferably 1 minute 30 seconds to 3 minutes.

Also, the processing source Flu J so-z ooC, good'! I
,,<d3z0C-pt'c. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

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

A specific method for strengthening stirring is described in JP-A-62-7rJut.
The method of impinging a jet of a processing liquid on the emulsion surface of a photosensitive material as described in No. 6 Cor./No.
A method of increasing the stirring effect using a rotating means of 1ts≠61, and furthermore, moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include methods of increasing the circulation flow rate of the entire processing liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. Improving agitation is achieved by adding bleach into the emulsion film,
It is believed that this speeds up the supply of fixing agent and, as a result, increases the desilvering rate.

Further, the agitation improvement means is more effective when a bleach accelerator is used, and it is possible to eliminate the fixing inhibiting effect caused by the bleach accelerator, which significantly increases the accelerating effect.

The automatic developing machine used in the present invention is
It is preferable to have a photosensitive material conveying means described in No. 257, No. 15'/Cojt, and No. 1/P/Coj. As described in the above-mentioned Japanese Patent Application Laid-Open No. 2003-110001, such a conveyance means can significantly reduce the carry-over of the processing liquid from the front bath to the rear bath, and has the effect of preventing the performance price of the processing liquid from increasing. expensive.

Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The color developer neutralizer used in the present invention contains known aromatic primary amine color developing agents.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-tN, N-diethyl-p-phinyl diamine D-J Coamino! -Diethylaminotoluene D-32-amino-β-(N-ethyl-N-laurylamino)toluene D-4! Reference-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-z Comethyl-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-z
-hydroxyethyl)aminocoaniline D -1μm amino-3-methyl-N-ethyl-N-[
β-(methanesulfonamide)ethyl-to-aniline D-7N-(-monoamino!-diethylaminophenylethyl)methanesulfonamide D-tN, N-dimethyl-p-phenyl-diamine D-tadaamino-3-methyl-N -ethyl-N-
Methoxyethylaniline D-to Hiro-amino-3-methyl-N-ethyl-N
-β-Ethoxyethylaniline D-ii 4! -amino-3-methyl-N-ethyl-
Among the above-mentioned -phenylenediamine derivatives of N-β-duthoxyethylaniline, exemplary compound D-z is particularly preferred.

These p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. The amount of the aromatic-grade amine developing agent to be used is preferably about 0.05% per liter of developer solution. /g~approx.-Ogz
More preferably, the concentration is about Q.jg to about 10 g.

In addition, sulfites such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts are added to the color developer as preservatives as necessary. be able to.

The preferable addition amount is 1. Color development, solution/l υ0゜7g
-10g, more preferably 7g-jg.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 4/11611
Hydronasamic acids described in No. 2, hydrazines described in No. j/-/70716, and 1. Hydrazides, same 4/-/
1! ? ≠ No. 2 and phenols described in No. 61-Co032!3, No. 4. It is preferable to add α-human 70 xyketones and α-7 minoketones described in No. /-1117141, and/or various saccharides described in No. j/-/r06/. In addition, in combination with the above compounds, Japanese Patent Application No. 6/≠7t23, No.4/-/j≦t7, No.61-/
636ko No. 1, 61-/A4L! T/! No., same/f
, /-/7071 No., and monoamines described in the same No. 4/-/73j No. 5, and the same al-itttsf, etc.
Diamines described in the l-itaziz issue, the same j/-/fftsto issue, etc., the same A/-/A! t6j/issue, and t6j/4
/-/4 Def t-de polyamines described in the same ti-it
Polyamines described in RTI No. J/-/27760
Nitroxy radicals described in No. 6i-itztt
Alcohols listed in No., and No./-/F'7F/ri,
Same 6/-/flIP! Oximes described in No. 7 and No. 6
/-26! It is preferable to use the tertiary amines described in No. TI4ct.

Other preservatives include Tokukai Sho! Various metals described in No. 7-≠Tei1≠j and the same No. 7-ta 374cW, salicylic acids described in No. 7-Ta 110j1, JP-A-Show! ≠−3
Alkanolamines described in J32, JP-A-Sho jtt-
Polyethyleneimines described in Tough 3≠, US Patent No. j
,? 4A7. If necessary, the aromatic polyhydroxy compound described in j4A≠ may be contained. Particularly preferred is the addition of an aromatic polyhydroxy compound.

The color developer used in the present invention preferably has a pH of 2
It is preferably ~//, preferably ~//, 0, and the color developer may contain other known developer component compounds.

It is preferable to use various buffering agents for rounding to maintain the above pH.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, O-
Sodium hydroxybenzoate (sodium salicylate), '-Potassium hydroxybenzoate,! - Surho J
-sodium hydroxybenzoate (!-sodium sulfosalicylate), j-sulfohydroxybenzoic potassium (!-potassium sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/!
It is preferably at least 41 K o , i mol/l -0, and e mol/l, particularly preferably.

In addition, various chelating agents can be used in the color developer as an anti-settling agent for calcium or magnesium or to improve the stability of the color developer.

As the chelating agent, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

Specific examples are shown below, but the invention is not limited to these.

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-)rimethylenephosphonic acid, ethylenediamine-N,N,N/.

N'-tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, greenyl ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, J-phosphonobutane-7, Tricarbon II, /-hydroxyethylidene-1,l-diphosphonic acid, N,N/-bis(cohydroxyindyl)ethylenediamine-N,N/-diacetic acid Two or more of these chelating agents may be used as necessary. May be used together.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example /l
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary. However, the color developer of the present invention preferably does not substantially contain benzyl alcohol from the viewpoints of pollution, liquid preparation properties, and prevention of color staining. Here, "substantially" means not more than 2 rnJ per liter of dissolved liquid/l, preferably not at all.

As the low development accelerator, Japanese Patent Publications No. 37-/4ort, No. 37-j2!7, No. 31-7126, and No. 4! Hiro-/No. 2310, same≠! -T0/R and U.S. Patent No. J
, r/J, No. 2447, etc., % Kaisho JJ-1 R Kota No. and the same! TO-111
p-phenyne/diamine compound represented by No. 117, 4! Kaisho 10-137726, special public show≠≠-300
No. 7μ, JP-A No. 6-istrat and JP-A No. 6-istrat, J, 2-I
Grade ammonium salts represented by No. J4cJ2, etc.
US Patent No. 2. Thank you, ? No. 03, same 3. /21゜1
No. 12, same reference, No. 230,796, same 3, 2j3, ri/
No. 3, Special Publication No. 4AI-llμ37, U.S. Patent No. 2. Reference 12. Jvt No. 2,326,226 and the same! ,!
tco, amine compounds described in No. 34C4, etc.,
Issue 7-/601, same≠Ko2! KoO1, U.S. Patent No. 3. /21,113, Japanese Patent Publication No. 44/-//4c3/, Gouko, No. 23rrs and U.S. Patent No. J, 132
．． Polyalkylene oxide represented by No. 10/ etc.,
Other l-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any anti-capri agent can be added as required. As anti-capri agents, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide and organic anti-capri agents can be used. Examples of organic anti-capri agents include benzotriazole, t-nitrobenzimidazole, j-nitroisoindazole, t-methylbenzotriazole, etc. - Nitrobenzotriazole,! Typical examples include nitrogen-containing heterocyclic compounds such as -chlorobenzotriazole, cochiazolyl-benzimidazole, -monothiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

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

≠'-diamino-λ,2'-disulfostilbene compounds are preferred. The amount added is O-jg/l, preferably 0. /
g to μg/l.

Furthermore, various surfactants such as alkyl sulfonic acids, ary-phosphonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids can be added as needed.

The processing temperature Fi of the color developer of the present invention is 20~! O0C
Preferably it is 3Q-Hiros 0C. Processing time is 0 seconds! The preferred time is 130 seconds to 3 minutes.

It is preferable that the amount of replenishment is small, but 1 per m2 of photosensitive material.
00~/! 00ml, preferably lO0~r00ml. More preferably, it is 100ml to μooml.

Further, the color developing bath may be divided into co-baths or more as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment.

The processing method of the present invention can also be used for color reversal processing. In the present invention, the black-and-white developer used at this time can be a so-called black-and-white first developer used in the reversal processing of color photographic light-sensitive materials, which is commonly known, or a developer used in the processing of black-and-white light-sensitive materials. In addition, various well-known additives that are generally added to black and white developers can be included.

Typical additives include /-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Examples include inorganic or organic inhibitors such as potassium bromide, comethylbenzimidazole, and methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. be able to.

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

ζIn this case, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally carried out, but after the bath that has fixing ability, stabilization processing is performed without substantially washing with water. It is also possible to use a simple processing method that performs the following.

The rinsing water used in the rinsing step may contain known additives, if necessary. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Disinfectants and fungicides (e.g., isothiazolone, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, and surfactant shavings that prevent dryness and unevenness can be used. . Or L, E.

West, 'Water Quality Cr1t
eria”.

Phot, Set, and Eng,, vol1,
ri, flat 6゜page j daμ~3! Compounds described in RI(/RIA, t) etc. can also be used.

As the stabilizing liquid used in the stabilizing step, a processing liquid that can stabilize a dye image is used. For example, a liquid having a buffering capacity of pH J to B, a liquid containing an aldehyde (for example, formalin), etc. can be used. The stabilizing liquid may optionally contain ammonium compounds, metal compounds such as Bi and AJ, optical brighteners, chelating agents (for example, l-hydroxyethylidene-1,1-diphosphonic acid), bactericides, fungicides, A hardening agent, a surfactant, etc. can be used.

Further, the water washing step and the stabilization step are preferably performed using a multistage countercurrent method, and the number of stages is preferably 2 to 2 stages. The amount of replenishment is 7 to 50 times, preferably 2 to 30 times, more preferably 2 to /j times the amount brought in from the previous bath per unit area.

The water used in these washing steps or stabilization steps includes tap water, as well as Ca
It is preferable to use water that has been deionized to have a Mg concentration of z mg/l or less, water that has been sterilized using a no-rogen, an ultraviolet germicidal lamp, or the like.

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

Further, the amount of waste liquid can be reduced by using a method in which the O/(-flow liquid in the water washing step or the stabilization step is allowed to flow into a pre-bath having a fixing ability.

(Example) The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

Example 1 (Reference Example) Sample 10/ was prepared on a cellulose triacetate support, consisting of each layer having the composition shown below.

1st layer: Emulsion layer Pure silver bromide emulsion (grain size 0.7μ, octahedral grains)
Silver coating amount g, oog/m2 Coupler A 0 x 10-2 mol per mol of silver Second layer: Protective layer polymethyl methacrylate particles (diameter l.

In addition to the above composition, a gelatin hardening agent H-/ and a surfactant were added to each gelatin layer including 32m).

Compound coupler A used to create the sample: α H-/: (CH2=CH8O2CH2CONHCH2-)y Next, to sample 10/, DIR coupler was added, or grain size and size were added instead of pure silver bromide emulsion. By using emulsions having the same distribution and uniformly containing iodine of 1 mole, λ mole, and ≠ mole, samples 102 to 1 were prepared with the compositions shown in Table 1.

DIR Coupler B H3 DIR Coupler C DIR Cub-Poor D DIR Casoler E After exposing the sample prepared in this way so that the amount of developed silver produced in the color development process would be /±Q, θjg/m2, It was processed as follows.

Table -/-2 Process Processing time Processing temperature Color development 3 minutes/! Seconds 310C Bleaching 7 minutes 310C Fixing 2 minutes 310C All steps 2 minutes/j seconds The composition of the processing solution used is as follows.

(Color developer) Diethylenetriaminepentaacetic acid /,0/-hydroxyethylidene-i,i-diphosphonic acid 3.0 Sodium sulfite G.O Potassium carbonate
30.0 Potassium Bromide
7.4t hydroxylamine sulfate
ko, 4t<t-(N-ethyl-β-hydroxyethylamino)-2-methylaniline sulfate ta, j Add water /, OLp H/ o,
θj (Bleach solution) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 70.0 Ammonium bromide /g 0.0 Ammonium nitrate 30. Qa, ammonia water (27chi)
4”, add 7m water
/・0L pH4,0 (Fixer) Ethylenediaminetetraacetic acid disodium salt 0.6 Sodium sulfite 7.0 Sodium bisulfite j,0 Ammonium thiosulfate aqueous solution (7o%) /7o, Add 0ml water /, θLpH4,7 The amount of developed silver in this example is the amount of silver remaining in the sample when the next treatment is carried out, measured by fluorescent X-ray method.

Table-/-3 Process Processing time Processing temperature Color development 3 minutes/j seconds 3r”c Stop 7 minutes 3♂0C fixation
2 minutes 310C water washing 7 minutes
30° C.1 The color developing solution and fixing solution used in this processing step are the same as those described above, and the stop solution is as described below.

(Stopping solution) Add acetic acid /jml water and measure the amount of silver remaining in each sample after the treatment shown in Table-7-2 using the fluorescent X-ray method.The results are shown in Table-λ Published in.

(Incidentally, all the silver amounts in the examples of the present invention are determined by the fluorescent X-ray method.) From Table 2/) DI
When R coupler is added, the amount of residual silver increases; 2.
) The amount of residual silver increases significantly when the development-inhibiting group of the DIR coupler does not have a water-soluble group; 3) The above trends of l) and λ) become even more pronounced as the iodine content of the emulsion increases. This shows that simply lowering the iodine content is insufficient. Therefore, the effectiveness of the bleaching agent of the present invention was tested in Example 1 using samples containing a large amount of DIR coupler.

Example λ After imagewise exposure of the sample/ltK of Example 1, continuous processing (running test) was performed in the following processing steps until twice the tank capacity of the color developer was replenished. However, the composition of the bleaching solution was changed as shown in Table 3, and the test was conducted for each of them.

The automatic developing machine used was JP-A-60-7-12!7.
The belt conveyance method described in the issue is used, and each treatment bath is
The jet stirring method described in No. 1134460 was used.

The processing steps are shown below.

Color development 3 minutes lj seconds Jf'C3tml bleaching 7 minutes jr oc hiroml fixed
Arrive 1 minute 3y6CJOml stable l stable 0 seconds 3
t0C- Stable 20 seconds JjoC- Stable 3 0 seconds 3r0C3jml" Drying 1 minute 1! seconds jQ~70°C - *The weak solution was a 3-tank countercurrent system of stable 3 → stable 1 → stable 1.

The composition of each treatment liquid used is shown below.

(Color developer) Mother solution (g) Replenisher (b) Diethylenetriaminepentaacetic acid J, Q 6.0 Sodium sulfite ≠, 0 Hiro, ≠ Potassium carbonate
30. OJ7.117 Potassium Bromide
/, 3 0.2 Potassium iodide 7.2 mg
-Hydroxylamine sulfate λ, 0 2. lrder [N
-Ethyl-N-β-hydroxyethylamino] monocomethylaniline sulfate Hiroshi, 7 3.3 Add water t, oL 1. oLpH10,001
0, Oj (Bleach solution) Mother solution Replenisher/3-diaminopropanetetraacetic acid Hiroshi, Og j, 0g Ammonium bromide 100. Og 160.0g Ammonium nitrate 30.0g jO, 0g Ammonia water (27%) 20.0ml λj, Om
jl Acetic acid (91r%), Oml 16.0
Add ml water and make t, oL/, (7L
See pH Table 3 (fixer) Mother solution Replenisher l-Hydroxyethylidene-/,/- Diphosphonic acid 6.0g 1,,0g Sodium sulfite 7.0g r,0g Sodium bisulfite 6.0g j,jg Thiosulfuric acid Ammotau aqueous solution (70%)/70.0ml Add 200.0ml water t,oL t,oLpH&,
7 1. ．． 6 (Stabilizing solution) Mother solution, replenisher common formalin <37%) t, arnl 1 chloro 2-methyl-inteazolin-3-one 6.0 mg co-methyl-μm inteazolin-3-one 3.0 mg surfactant 0. ≠Ethylene glycol
/, add 0 water
/, 0L pH 3,0-7,0 After exposing the sample to 700M5, it was treated with each running equilibrium solution, and the amount of residual silver was determined by fluorescent X-ray method.

The results obtained are shown in Table 3, demonstrating the effectiveness of the bleaching bath of the present invention.

Similar effects were obtained for other samples of Example 1, indicating that the bleaching bath of the present invention is effective when iodine is present or when desilvering is inhibited by a DIR coupler.

Example 3 For sample 10/, the sensitizing dyes shown in Table D were added at 1A per mole of silver during emulsion preparation. 10-4 mol of tX was added to prepare samples 202--/7.

Sensitizing Dye A After the treatment described in Table 2 in the same manner as in Example 1, the amount of silver remaining in each sample was measured by fluorescent X-ray method, and the results shown in Table 9 were obtained. From Table DA, sensitizing dye F that does not have a water-soluble group
It can be seen that this tendency is remarkable when an emulsion containing a large amount of iodine is used.

In addition, in sample 201VC, the sensitizing dyes cg and txl
Addition of o-4 mol/silver 1 mol, sensitizing dye I/
A sample was obtained by adding 10-3 mol of X/1 mol of silver. No increase in the amount of residual silver was observed with an increase in sensitivity.

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Example 4 Primed cellulose triacetate film support
Sample 3oi, which is a multilayer color light-sensitive material consisting of each layer having five compositions as shown below, was prepared.

(Composition of the photosensitive layer) The coating amount is the amount expressed in g/(H2 unit) of silver applied for silver halide and colloidal silver, and the amount expressed in g/m2 unit for couplers, additives and gelatin. For sensitizing dyes, silver halide in the same layer7
Expressed in moles per mole.

1st layer (antihalation layer) Black colloidal silver...0.2 Gelatin...7.3 Colored coupler C-/...o, θg ultraviolet absorber UV-/
...0. /Same as above UV-2...0.2 Dispersion oil 0il-/...θ, θ/Same as above 0i
1-2 ... θ, θ/ -th layer (intermediate layer) Particulate bromide (average particle size θ, 07μ) ・ ・ ・ ・ θ , /! Gelatin.../, 0 Colored coupler C-2...0.02 Dispersion oil 0il-
/ ...0. /Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 9 molti, average grain size 0.3μ) ...0.4t silver gelatin ...0.1 sensitizing dye ■
.../, 0X10-4 sensitizing dye ■...
・・J, 0X10-4 sensitizing dye■ ・・・・・
/X/θ″′″5 coupler C-s...
・0.06 coupler C-a...0.
06 coupler C-, r...0.0<
1 Coupler C-2...0.03 Dispersion oil 0il-/...O', 03 Same as above 0
i1-j...θ, 0/2 Second layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide j morch, average grain size θ, jμ)...0.7 sensitization Pigment ■
.../X10-4 sensitizing dye■
...3x/θ-4 sensitizing dye■ ...
・/X/θ-5 coupler C-3...0. -9 Coupler C-ta...0. ．． 24t coupler C-cr...0.0<Coupler C-2...o, o4t DIR coupler D...O, O4 dispersed in oil 0il-/...0. /j ditto 0il-
s ・---o, oa th! Layer (3rd red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 molt, average grain size 0.2μ)...Silver/, 0 gelatin
... /, 0 sensitizing dye I
... /X10-4 sensitizing dye■ ...
... j X /'0-4 sensitizing dye■ ...
・ /×/θ-5 coupler C-t...
・0. Oj coupler C-7... θ, / Dispersion oil 0il-/ ...0. Q/same as above 0
i1-2...0.0! 6th layer (middle layer) Gelatin...i.

Compound Cpd-A...0.03 Dispersion oil 0il-/...θ, Oj 2nd layer (1st
Green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide mortar, average grain size 0.3μ) ...0.30 sensitizing dye■
... jXlo-4 sensitizing dye ■°
...0.3 x 10-4 sensitizing dye V ...
・λ×10""4 gelatin...
・1. θ coupler C-9...0.2 DIR coupler D...Q, θ/♂ coupler C-/...0.03 Dispersion oil 0i
l-/ ...... 0.3 th male layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! Morch, average grain size 0.jμ) .... Sensitizes σ, 4 Dye■ ...jXlo-4 sensitizing dye■
... jXlo-4 sensitizing dye■ ...
0.3X10-4 coupler (-1...θ, Coj coupler (-/...-θ, Oj coupler C-10...0.0/j 1) IR coupler D...0 .02 Dispersion oil 0il-/ ...-0,2 2nd layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 4 molt, average grain size θ, 7μ) ...Silver O0♂ j gelatin
.../-0 sensitizing dye ■
...j, j x 70-4 sensitizing dye■ ...
・/, 4t×/θ-4 coupler C-// ・
...0.01 Casoler C-72...Q, θ3 Coupler C-73...O, CoQ coupler C-t...θ, 0.2 Dispersion oil 0il-/...・0.20 0il-2・
...0. OjT 1st O layer (yellow filter layer) Gelatin.../, Yellow colloidal silver...Q, Ot compound Cpd-B
...0. /Dispersion oil 0il-/
...0.3 1st/layer (first blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide q morch, average grain size σ, 3
μ) ...Silver Q, lt gelatin
... /, 0 sensitizing dye■ ...
λX10”4 Casolar C-t group...
0.9DIR coupler D...θ, θI dispersion oil 0il-/...0. 1st layer (second blue-sensitive emulsion layer) Silver iodobromide (silver iodide 10 molti, average grain size/, jμ) ・・・Silver 0.6 gelatin
... (7,6 sensitizing dye■
... /X/θ-4 turnip 9- (-/ 4t
....θ, 26 dispersion oil 0il-/
...0.07 73rd layer (first protective layer) Gelatin / ... θ, ultraviolet absorber UV- / ... θ, / same as above UV-2
...0.2 Dispersion oil 0il-/ ...θ, θ/Dispersion oil 0il-2...Q, 0/Layer 14 (second protective layer) Fine grain silver bromide (average grain Diameter σ, 07μ) -・・・・0,j Gelatin...0.4tj Polymethyl methacrylate particles (diameter/, jμ)...0. = Hardener H
-/...-0,4t Formaldehyde scavenger S-/... ・ ・ θ , j Formaldehyde scavenger, -8-a...
・Q, j In addition to the above-mentioned components, a surfactant was added as a coating aid to each layer. The sample prepared as above was designated as 30/.

Next, the DIR coupler D of the 9th layer, the 2nd layer, the 1st layer, and the 1st layer of the sample 3θ/ was reduced to //3, respectively.
Prepared as λ.

DI of 7th layer, 7th layer, 2nd layer, 1st/layer of sample 30/
Sample 3σ3 was prepared from which R Casoler D was removed.

9th layer, 7th layer, 1st layer, 1st/layer DI of sample 3Q
Sample 3θg was prepared by changing R coupler D to equimolar amount of DIR coupler CtC.

Next, the silver iodobromide emulsion (3rd layer, 7th layer) of sample 303 (
Silver iodide damolti, average grain size 0. jμ) and pure silver bromide emulsion (
Silver iodobromide emulsion (9th layer, 2nd layer) (average grain size 0.3μ) was mixed with silver iodobromide emulsion (silver iodide q, average grain size 0.jμ).・!Morch, average particle size 0.jμ)K,
(5th layer, 2nd layer) silver iodobromide emulsion (silver iodide 6 molt 1
．． Silver iodobromide emulsion (silver iodide 1 molch, average grain size 0.7 μm) (average grain size 0° 2μ), first/layer monodisperse silver iodobromide emulsion (silver iodide μ molch, average grain size 0.3 μ) was used as a silver iodobromide tabular emulsion (silver iodide 0.3 mol, average grain size 0).
．． 3μ) K11 sensitizer ■ was added to 3×/θ−4 moles per mole of silver, and the first λ layer silver iodobromide emulsion (silver iodide lθ mole,
A tabular silver iodobromide emulsion (1 mole of silver iodide, average grain size /, jμ) with an asquid ratio J (1 mole of silver iodide, average grain size /, jμ) was used, and a sensitizing dye (■) was added to a silver iodide emulsion of 7.0% per mole of silver. Sample 3Q was changed to zxlo-4 mol! It was prepared as follows.

The chemical structural formulas or chemical names of the compounds used below are shown below: UV-/X/y=7/J (weight ratio) UV-2 Oil-/tricresyl phosphate 0i1-2 diptyl 7-talate 0i1- 37 bis(2-ethylhexyl)talate C-/C-Co-J C-Reference H2 C(CHs)s C-7 C-♂ m=23- mo 1- wt, about 20. oθθ α C-// C-/ λ α C-/ Gu cpa A Cpd B Sensitizing dye l Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ 2H5 Sensitizing dye ■ Sensitizing dye ■ (CH2 )2δ(J3N a Sensitizing dye ■ Sensitizing dye ■ H-/ CH2=CH-8O2-CH2-CONH-CH2CH
2=CH-8O2-CH2-CONH-CH2W S-co DIR coupler C DIR coupler D After cutting the sample thus prepared into J j m/m widths, the amount of developed silver was l±0, Oj g. /r
Exposure was applied so that n2 was obtained, and the processing described in Example 1 was carried out.

The results obtained with bleach solution A are shown in the table below.

Table-! The results obtained using sample 303 in bleaching baths A and I are shown in the table below.

The effects of the present invention have been demonstrated above.

Example j A silver chlorobromide emulsion (A) (chloride content: 50 mol%) was prepared as follows.

(1) Liquid water roomy
Naα ≠, jg gelatin
Kozg (2) Solution The following compound (1 aqueous solution) jmltH3 Tatami H3 (3) Solution KBr t, 71□
gNa (j O, add 16g water / 0ml 1l (4) liquid AgN
O3j, 0g Add water to lda0rnl(5) liquid
KBr ≠7.2gNaα
Add water
320m (6) liquid AgNO3120g Add water to 320m1 (1)*
After heating j'cK and adding liquid (2), liquid (3) and (
4) were added simultaneously over a period of 10 minutes. After another VCIQ minute, liquids (5) and (6) were added simultaneously over a period of 3j minutes.

Five minutes after the addition was completed, the temperature was lowered and desalination was carried out.

An aqueous gelatin solution for dispersion was added and the pH was adjusted to 6.2 to obtain a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.7-μ. The emulsion was optimally chemically sensitized by adding sodium thiosulfate, chloroauric acid and rhodan ammonium at zt 0c.

Next, by changing the halide composition ratios of KBr and Naα in liquids (3) and (5), silver chlorobromide emulsion (B) (chloride content 7.
3 mol %) was obtained in the same manner as emulsion (A).

Average particle size 0.6! It was a monodisperse cubic emulsion of μ.

Using the emulsions (A) and (B) prepared as described above, the samples shown in Table 6 were prepared in the same manner as in Example.

After the treatment shown in Table 7-2, the amount of silver remaining in each sample was measured by fluorescent X-ray method in the same manner as in Example 1, and the results shown in Table 6 were obtained. Table 6 shows that in this example, which has a high silver chloride content, the amount of residual silver is extremely small, although the sensitizing dye FXH, which does not have a water-soluble group, tends to have a slight increase in the amount of residual silver. Proven.

Table - Bleaching bath of Example-E using sample≠02.

When the same treatment as in Example C was carried out using H, the residual silver amount was less than Q, -μg/cm 2 in all cases, confirming the effect of the present invention.

Patent applicant: Fuji Photo Film Co., Ltd.

Claims (1)

[Scope of Claims] (1) having blue-sensitive, green-sensitive and red-sensitive light-sensitive layers on a transparent support; i) each of these light-sensitive layers is a negative-working silver halide emulsion layer containing a dye-forming coupler; and ii) a halogen compound in which the average silver iodide content of the photosensitive silver halide grains in the silver halide emulsion layer or layer group in these photosensitive layers is 2 mol % or less. A method of processing a silver oxide color photographic light-sensitive material with a processing liquid having a bleaching ability after color development, the processing liquid having a bleaching ability containing a ferric compound selected from the following compound group (A) as a bleaching agent. A silver halide color photograph comprising at least one complex salt and a ferric 1,3-diaminopropanetetraacetic acid complex salt in a molar ratio of the former to the latter of 3 or less (including 0). How to process photosensitive materials. Compound (A) A-1 Ethylenediaminetetraacetic acid A-2 Diethylenetriaminepentaacetic acid A-3 Cyclohexanediaminetetraacetic acid A-4 1,2-propylenediaminetetraacetic acid (2) Claim in which the photographic speed is from ISO25 to ISO6400 (
Processing method for a silver halide color photographic light-sensitive material described in 1) (3) Containing at least one compound selected from the compounds represented by the following general formula [I] or [II] A method for processing a silver halide color photographic material according to claim (1) or claim (2). General formula [I] A-(L_1)_a-S-Z_1■L_2)_c-Y]
_b General formula [II] A-(L_1)_a-Z_2-[(L_2)_c-Y]
_b In the formula, A reacts with an oxidized product of an aromatic primary amine to form -(L_1)_a-S-Z_1-[(L_2)_c-Y
]_b or -(L_1)_a-Z_2-[(L_2)
The residue leaving _c-Y]_b, L_1, is a timing group, L_2 is a linking group, and Y represents a hydrogen atom, a cation, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. Z_1 represents a heterocyclic group, arylene group, or alkylene group, and Z_2 represents a heterocyclic group. a and c are 0 or 1,
b represents 0, 1 or 2. However - [(L_2)_c
-Y]_b contains a hydrophilic group, a water-soluble group, or a precursor residue thereof. When b is 2 - [(L_2)
_c-Y] residues may be the same or different. When b is 0, it represents a hydrogen atom. 4) A silver halide color photographic light-sensitive material according to claims (1) to (3) that contains a sensitizing dye containing a residue represented by the following general formula [XV] General formula [XV] -(L_2)_c-Y In the formula, L_2, Y and c have the same meanings as those in general formula [I] or general formula [II].