JPH03127060A - Color image forming method - Google Patents

Abstract

PURPOSE:To enhance desilvering speed by exposing and color developing a photosensitive material having a silver halide emulsion layer and a hydrophilic colloidal layer containing the fine crystal dispersion of a specified compound on a support and processing it with a processing solution containing persulfate. CONSTITUTION:The photosensitive material having on the support the silver halide emulsion layer and the hydrophilic colloidal layer containing the fine crystal dispersion of the compound represented by formula I and the like is exposed and color developed and processed with the processing solution containing the persulfate. In formula I, A is an acid nucleus; R is H or alkyl; each of R1 and R2 is alkyl, aryl, acyl, or sulfonyl; each of R3 and R6 is H, OH, COOH, alkyl, alkoxy, or halogen; each of R4 and R5 is H or the like; and each of m and p is 0 or 1, thus permitting the image forming method superior in desilverability to be ensured even by using a bleaching process small in environmental pollution load.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a color image forming method, and more particularly to a color image forming method with improved desilvering properties.

(Prior art) Generally, the basic processing steps for color photosensitive materials are as follows:
These are a color development process and a desilvering process. That is, the exposed color photosensitive material #+ undergoes a color development process, in which silver dihalide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with the coloring agent to form a dye. gives an image of

After that, the color light-sensitive material enters a desilvering process, where the silver produced in the previous process is oxidized by the action of an oxidizing agent (commonly known as #4 whitening agent), and then the silver produced in the previous process is oxidized. It is cleaved by the ion complexing agent and removed from the photographic material. Therefore, only dye images are produced on color photosensitive materials. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary steps to preserve the photographic and physical quality of the image, or to improve the shelf life of the image. It is accompanied by Engineer 8. For example, a hardening bath to prevent excessive softening of the photosensitive layer during processing (to prevent film removal), a stop bath to effectively stop the development reaction, an image stabilizing bath to stabilize the image, or a support bath. Examples include a film removal bath for removing the dust/black layer.

Further, the above desilvering step may be carried out in a bleach-fixing bath containing both a bleaching agent and a fixing agent, or may be carried out in two steps, a bleaching bath and a fixing bath, using separate baths.

Generally, red blood salts, potassium dichromate, ferric iono complexes, persulfates, etc. are used as bleaching agents in bleaching solutions. Among these, the bleaching solution using red blood salt has an excellent bleaching effect, but it is discharged due to overflow during processing and carried into the washing water after bleaching. Cyanide ions may undergo photochemical oxidation and remove cyanide compounds, but
These cyanide compounds are highly toxic and cause great harm. Therefore, it is desirable to develop a bleaching agent to replace red blood salt.

Ferric iono complex salts are sometimes used as bleaching agents in bleach-fix solutions for color photographic paper (German Patent No. 166.6
Specification No. 0j, same No. 66. No. 10 Mei MB, British Patent No. 74't, A7 Specification, British Patent No. P33,0Irr
Specification of No. M11074'1326). However, since the bleaching solution or bleach-fixing solution F'i containing ferric ion complex salts has weak oxidizing power, it is difficult to process when used with photographic color light-sensitive materials containing a high concentration of silver halide and using silver bromide. It takes a long time.

In any case, bleaching methods that use metal ions such as red blood salts and ferric ionocomplex salts have a large pollution load on the waste liquid, so methods that do not use metal ions, specifically persulfuric acid bleaching methods, are more desirable. However, a disadvantage of persulfate bleach baths is that they have weaker bleaching blades than ferric ion complexes and require significantly longer times to bleach. Therefore, a new technique for promoting bleaching by persulfate is desired, especially for color photosensitive materials with photographic sensitivity that use a large amount of silver halide.

(Problem to be Solved by the Invention) Conventionally, methods of adding various bleach accelerators to bleach baths, bleach-fixing baths, or their pre-baths have been proposed as a method of increasing the bleaching blade in order to speed up the desilvering process. There is. Although such bleaching accelerators are described in Japanese Patent Application No. 43-g, +pt, etc., they have not yet reached a satisfactory level in terms of stability and effectiveness in bleaching baths.

A method in which these compounds are present in a light-sensitive material is also known, but this method also has many problems, including the fact that it has a large undesirable effect on photographic performance.

In contrast, Research Disclosure Kuroko#,
2u/issue, same//, ellri issue, and JP-A-67-0
The specification of No. 7 includes a description of a bleach accelerator-releasing coupler. The use of these compounds increases the desilvering rate, but there is a certain limit and even if these compounds are used, they are still insufficient from the viewpoint of shortening the desilvering process.

Previous methods for promoting persulfate bleaching include, for example, U.S. Pat. No. 3,772.0
No. 20, No. 3. ry3. rzr4+b and research
This is a method in which an amino compound described in Disclosure Jli/j, 70<-> is added to a processing bath (bleach bath, bleach-fix bath, or a pre-bath thereof).

However, this method requires a long period of time to achieve sufficient bleaching, and many of the above compounds have a bad odor, so it is not recommended to use them by adding them to the treatment bath. .

Furthermore, this method can be used to create colloidal silver layers such as yellow filter layers and antihalation layers! It has been difficult to sufficiently bleach color photosensitive materials containing a high amount of silver.

Therefore, it is an object of the present invention to provide a method of high desilvering rate while using persulfate bleaching.

(Means for Solving the Problem) As a result of intensive research, the present inventors have found that the object of the present invention can be achieved by the following means.

That is, a hydrophilic colloid comprising at least seven silver halide emulsion layers on a support and a microcrystalline dispersion of at least seven compounds selected from the group of compounds represented by the following general formulas (1) to Vl). After exposing and color-developing the silver halide color photographic light-sensitive material having the layer,
This is a color image forming method characterized by processing with a processing solution containing persulfate.

6 General formula (II[) AL, -(Lx proverb Ls), l-A' General formula (IV) A= (L+ -Lx) t--=B general formula (Vl) (wherein, A and A' may be the same or different, each represents an acidic nucleus, B represents a basic nucleus, X and Y may be the same or different, and each represents an electron-withdrawing group, R
represents a hydrogen atom or an alkyl group, R1 and R2 each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and Rt and R2 may be linked to form a 5- or 6-membered ring.

R1 and R6 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group, or a halogen atom, and R4 and R3 each represent a hydrogen atom, or R1 and R4 or Rt and R3 are linked to form a 5- or 6-membered ring. *Ll, Lt, and RI, which represent a group of nonmetallic atoms necessary for forming, each represent a methine group.

m represents O or 1, n and q each represent 0.1 or 2, P represents O or 1, and when P is 0, R1 represents a hydroxy group or a carboxyl group, and R4 and Rs represent hydrogen B', which represents an atom, represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group.

However, the compound represented by -m formula (1) or Vl) has a pKa in the range of 4 to 11 in a γ-containing solution in which the volume ratio of water and ethanol in one molecule is 1:1. It has at least one dissociable group. ) First, the compound represented by the general formula (1) or V[) will be explained in detail.

The acidic nucleus represented by A or A' is preferably 2-pyrazolin-5-one, rhodanine, hydantoin, thiohydantoin, 2,4-oxazolidinedione, isoxazolidinone, barbylic acid, thiobarbylic acid, indandione, pyrazolo. Represents pyridine or hydroxypyridone.

The basic nucleus represented by B preferably represents pyridine, quinoline, indolenine, oxazole, benzoxazole, naphthoxazole or pyrrole.

Examples of heterocycles of B' include pyrrole, indole,
Thiophene, furan, imidazole, pyrazole, indolizine, quinoline, carbazole, phenothiazine,
phenoxazine, indoline, thiazole, pyridine,
These include pyridazine, thiadiazine, biran, thiopyran, oxadiazole, benzoquinolidine, thiadiazole, pyrrolothiazole, pyrrolopyridazine, and tetrazole.

A group having a dissociable proton with a pKa (acid dissociation constant) in the range of 4 to 11 in a mixed solution of water and ethanol at a volume ratio of 1:1 makes the dye molecule substantially water-insoluble at pH 6 or below. There is no particular restriction on the type and substitution position on the dye molecule as long as it makes the dye molecule substantially water-soluble at pH 8 or above, but preferably a carboxyl group, a sulfamoyl group, a sulfonamide group, A more preferred hydroxy group is a carboxyl group. The dissociable group may not only be directly substituted on the dye molecule, but may also be Xta-substituted via a divalent linking group (for example, an alkylene group or a phenylene group).

Examples of connections via a divalent linking group include 4-carboxyphenyl, '2-methyl-3-carboxyphenyl.2.
4-dicarboxyphenyl, 3,5-dicarboxyphenyl, 3-carboxyphenyl, 2,5-dicarboxyphenyl, 3-ethylsulfamoylphenyl, 4-phenylsulfamoylphenyl, 2-carboxyethyl 6-dolyphenyl Hydroxyphenyl, 3-benzenesulfonamidophenyl, 4-(p-cyamibenzenesulfonamidophenyl) phenyl, 3-hydroxyphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2-hydroxy-4-carboxyphenyl, 3-Methoxy-4-carboxyphenyl, 2-methyl-4-phenylsulfamoylphenyl, 4-carboxybenzyl, 2-carboxybenzyl, 3-sulfamoylphenyl, 4-sulfamoylphenyl, 2,5-dis Examples include rufamoylphenyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 8-carboxyoctyl, and the like.

? The alkyl group represented by +Rs or Rh has 1 to 1 carbon atoms.
10 alkyl groups are preferred, and examples include groups such as methyl, ethyl, n-propyl, isoamyl, n-octyl and the like.

The alkyl group represented by R,, R, is an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, n-propyl, n-
-butyl, n-octyl, n-octadecyl, isobutyl, isopropyl) are preferred; 〉, alkoxycarbonyl group (e.g. methoxycarbonyl, i-propoxycarbonyl),
(e.g., phenoxy group), phenyl group, amido group (e.g., acetylamino, methanesulfonamide), carbamoyl group (e.g., methylcarbamoyl,
ethylcarbamoyl), sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl)].

The aryl group represented by R1 or R2 is preferably a phenyl group or a naphthyl group, and the substituents include the above R
The substituents of the alkyl groups represented by I and R2 include the groups and alkyl groups (eg, methyl, ethyl). ].

The acyl group represented by R5 or R2 is preferably an acyl group having 2 to 10 carbon atoms, and includes, for example, acetyl, propionyl, n-octanoyl, n-decayl, isobutanoyl, benzoyl, and the like. R1 or R
Examples of the alkylsulfonyl group or arylsulfonyl group represented by 2 include methanesulfonyl, ethanesulfonyl, n-butanesulfonyl, n-octanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, 0
-carboxybenzenesulfonyl and the like.

The alkoxy group represented by R1 or R6 has 1 to 1 carbon atoms.
0 alkoxy groups are preferred, such as methoxy, ethoxy, n-butoxy, n-octoxy, 2-ethylhexyloxy, isobutoxy, isopropoxy, etc. ++The halogen atom represented by R3 or R6 includes chlorine, bromine, etc. , fluorine.

Examples of the ring formed by linking RI and R4 or R8 and Rs include a julolidine ring.

Examples of the 5- or 6-membered ring formed by linking R1 and R2 include a piperidine ring, a morpholine ring, and a pyrrolidine ring.

The methine group represented by L+, Lx or ri has a substituent (
For example, methyl, ethyl, cyano, phenyl, chlorine atoms,
hydroxypropyl).

The electron-withdrawing groups represented by X or Y may be the same or different, and include a cyano group, a carboxy group, an alkylcarbonyl group (an alkylcarbonyl group that may be substituted, such as acetyl, propionyl, heptanoyl, dodecanoyl, hexadecanoyl, l-oxo-7-chloroheptyl), arylcarbonyl group (arylcarbonyl group that may be substituted, e.g. benzoyl, 4-ethoxycarbonylbenzoyl, 3-chlorobenzoyl)
, alkoxycarbonyl group (an alkoxycarbonyl group that may be substituted, such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, t-amyloxycarbonyl, hexyloxycarbonyl, 2-ethylhexyloxycarbonyl, octyloxycarbonyl, decyloxy Carbonyl, dodecyloxycarbonyl, hexadecyloxycarbonyl, octadecyloxycarbonyl, 2-butoxyethoxycarbonyl, 2-
Methylsulfonylethoxycarbonyl, 2-cyanoethoxycarbonyl, 2-(2-chloroethoxy)ethoxycarbonyl, 2-(2-(2-chloroethoxy)ethoxy]ethoxycarbonyl), aryloxycarbonyl group (optionally substituted aryloxy A carbonyl group, for example, phenoxycarbonyl, 3-ethylphenoxycarbonyl, 4-ethylphenoxycarbonyl, 4
-Fluorophenoxycarbonyl, 4-nitrophenoxycarbonyl, 4-methoxyphenoxycarbonyl, 2
．． 4-di(t-amyl)phenoxycarbonyl), carbamoyl group (carbamoyl group which may be substituted,
For example, carbamoyl groups ethylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, 4-methoxyphenylcarbamoyl, 2-bromophenylcarbamoyl, 4-chlorophenylcarbamoyl, 4-ethoxycarbonylphenylcarbamoyl, 4-propylsulfonylphenylcarbamoyl, 4-cyanophenylcarbamoyl, 3-methylphenylcarbamoyl, 4-hexyloxyphenylcarbamoyl, 2,4-di(t-amyl)phenylcarbamoyl, 2-chloro-3-(dodecyloxycarbamoyl)phenylcarbamoyl, 3-(hexyloxycarbonyl)phenylcarbamoyl ) Sulfonyl groups (e.g. methylsulfonyl, phenylsulfonyl), sulfamoyl &<'IttlAsh are acceptable sulfamoyl groups, for example sulfamoyl,
methylsulfamoyl).

Next, specific examples of dyes used in the present invention will be given.

-6- 7- -11 ■-13 ■-14 Hx ■ 5 -17 [-18 -19 -21 -25 ■ 6 ! -27 -28 n-2 El-3 -4 ○ ○ 1-5 ■ -2 1[1-3 -4 ■-5 11[-6 11-7 1[[-9 l1l-10 ■-11 ■-12 -14 [1-16 ■ 7 ■-18 ■-19 ■ 0 ■-21 +[[-22 ■-24 m-25 ■-29 Hs CH.

111-30 C,H.

C1Hs C,H.

HI zHs C-Hs C,H.

V-12 ■-15 C*Hs C2H4 CtHs CHl Hs CH2 CHl CH.

l-1 N Nll5OICI (I C, 11, C0OH OOH OQII VI-7 ■-9 cozcooH 1-10 ■-11 ■-12 C ool ■-13 The dye used in the present invention is covered by international patent wo8810479
No. 4, European Patent EPO 274723A1, No. 2
No. 76.566, No. 299.435, JP-A-52-9
No. 2716, No. 55-155350, No. 55-155
No. 351, No. 61-205934, No. 48-6862
No. 3, U.S. Pat. No. 2,527,583, U.S. Pat. No. 3,486,897
No. 3746539, No. 3933798, No. 41
30429, No. 4040841, etc., and the bottom can be easily formed according to the method.

In the present invention, the dye is formed into a solid fine powder dispersion for inclusion in a layer, such as a hydrophilic colloid layer, coated on a photographic element. The fine powder dispersion can be prepared by precipitating the dye in the form of a dispersion and/or in the presence of a dispersant by known micronization means, such as ball milling (ball mill, vibratory ball mill, planetary ball mill, etc.), sand milling, It can be formed by colloid milling, jet milling, roller milling, etc., in which case a solvent (for example, water, alcohol, etc.) may be present, or alternatively, after dissolving the dye in a suitable solvent, a non-solvent of the dye can be removed. A microcrystalline powder of the dye may be precipitated by adding a dispersing surfactant, or by controlling the pH of the dye.
It may be first dissolved and then crystallized by changing the pH.

The dye particles in the dispersion have an average particle size of 10 μm or less, more preferably 2 μm or less, and particularly preferably hao, sμ
m or less, and in some cases 0. More preferably, it is a fine powder of 1 μm or less.

The amount of dye used in the present invention is 1~1000nr.
Used in the range /-. Preferably 5■~800av
/rr! It is.

The dye dispersion of the present invention can be added to any layer, regardless of whether it is an emulsion layer or an intermediate layer.

The effects of the present invention are remarkable when a part or all of colloidal silver, which is commonly used in the yellow filter layer and/or the antihalation silver layer, is used as a substitute.

Next, the bleaching treatment used in the present invention will be explained in detail.

After color development, the photographic emulsion layer is bleached with persulfate. Bleaching treatment may be carried out simultaneously with fixing treatment,
It may also be done individually.

Persulfates used as bleaching agents in the present invention include alkali metal persulfates such as potassium persulfate and sodium persulfate, or ammonium persulfate. The preferred amount of the above bleaching agent is 0.50% per liter of bleaching solution. It's a record without Oj.

The bleach solution may contain chlorides such as potassium chloride, sodium chloride, ammonium chloride, bromides such as potassium bromide, sodium bromide, ammonium bromide, and the like. The preferred amount of the above halide is 0.00% per bleach solution/if. / or comor. The bleaching solution contains boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, sinorous acid, cynic acid, otrium phosphate, citric acid, sodium citrate, tartaric acid, etc. Seven or more types of inorganic acids, organic acids, and salts thereof that have a pH buffering capacity can be added. Also, salts such as sodium sulfate and potassium sulfate
It is also possible to adjust the salt concentration during bleaching by adding tn.

The bleach solution in the box was JP-A-7J-/17? An imide compound for preventing the generation of halogen gas described in PDA ψ is added in an amount of x10 to x10 mol per liter of bleaching solution, preferably in the range of ixio -<<xlo-2 mol. You may do so.

The pH of the bleaching solution is between 0 and 7.01 before use.
．． It is desirable that it becomes J~J,j.

Bleaching accelerators can also be used. For example, U.S. Patent No. 370737ψ, U.S. Pat.
1j1 No. 31-21227, JP-A No. 33-Tag No. 727, J3-F! No. 61/, special application f@13-F
7PrO issue, same! Bleaching accelerators such as mercapto compounds and ditheocarbamate compounds described in Research Disclosure Magazine/370g (March/777), No. 3-yryoi, are used.

The light-sensitive material used in the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of the silver emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material,
Generally, the unit photosensitive layers are arranged in the following order from the support: a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

For the primeval interlayer, JP-A-61-43748 and JP-A-59-1
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer configuration can be preferably used.

Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer.
No. 112751, No. 62-200350, No. 62-2
As described in Nos. 06541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support: low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL) /High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer (R)
or 1 of BH/BL/GL/GH/RH/RL
They can be installed in the order of 1 or BH/BL/GO/GL/RL/RH.

Furthermore, as described in Japanese Patent Publication No. 55-34932, blue-sensitive N/G)I/
R) They can also be arranged in the order of I/GL/RL. Alternatively, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/RH can be arranged in this order from the farthest side from the support. .

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, they may be arranged in the order of low-speed emulsion layer/medium-speed emulsion layer/high-speed emulsion layer, etc.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

To improve color reproduction, U.S. Patent No. 4,663゜2
No. 71, No. 4,705,744, No. 4.707.
No. 436, JP-A-62-160448, JP-A No. 63-89
The multilayer effect donor layer (C
L) is preferably arranged adjacent to or close to the main photosensitive layer.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 corons or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the light-sensitive material used in the present invention include, for example, Research Disclosure (R
D) 17643 (December 1978), 22-23
Page, ``1. Emulsion preparation
tion and types)”, and the same N1
118716 (November 1979), 648 pages,
“Physics and Chemistry of Photography” by Geafkides, published by Paul Montil (P, GIafkides, Chemie et al.
Ph1sique Photography-1que
, Paul Montel.

1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G.F. Duffin, Photogr.
aphic Emulsion ChemisLry
(Focal Press, 1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L., Zelikman et al.
l,,Making and Coating Ph
otographic Emul-5ion, Foc
al Press, 1964).

U.S. Patent Nos. 3,574,628 and 3,655,39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413,748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by GuLoff, Photographic Science and Engineering.
ence and Engineering), No. 14S248A-257 (1970); U.S. Pat. It can be easily made of steel by the method described in British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Alternatively, agglomerates of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure k1
7643 and Nα18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

RD17643 1 chemical sensitizer Page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 23~
Page 24 Page 648 Right 4vI-+-Supersensitizer
Page 649 right column 4 Brightener Page 24 5 Anti-fog i11 Page 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, page 25-26 Page 649 right column ~ Filter dye, Page 650 left column Ultraviolet absorption Agent 7 Anti-stain agent Page 25 right I Page 650 left to right column 8 Dye image stabilizer Page 25 9 Hardener page 26 Page 651 left column 10
Binder, page 26 Same as above 11 Plasticizer, lubricant, page 27 Page 650, right column 12 Coating aid, pages 26-27 Page 650, right column Surface active agent 13 Static, page 27 Same as above Inhibitor Also, deterioration of photographic performance due to formaldehyde gas In order to prevent
It is preferable to add to the light-sensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435.503.

Various color couplers can be used in the light-sensitive material used in the present invention, and specific examples thereof are given in the research paper mentioned above.
Disclosure (RD) Nα17643, ■-C-
It is described in the patent described in G.

As a yellow coupler, for example, U.S. Pat. No. 3,93
3.501, same No. 4,022,620, same No. 4,3
No. 26,024, No. 4,401,752, No. 4,
248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,020, British Patent No. 1.476.760, U.S. Patent No. 3,973.968, British Patent No. 4.314,
No. 023, No. 4,51L649, European Patent No. 249
．． No. 473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Pat.
No. 0,619, European Patent No. 4.351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432, European Patent No. 3.725.067, Research Disclosure 24220 (June 1984) month), JP-A-60-3
No. 3552, Research Disclosure Nα242
30 (June 1984), JP 60-43659, JP 61-72238, JP 60-35730, JP 5
No. 5-118034, No. 60-185951, U.S. Patent No. 4.500.630, U.S. Pat.
Particularly preferred are those described in No. 795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4', 052.21.
No. 2, No. 4,146,396, No. 4,228.2
No. 33, No. 4,296,200, No. 2,369,
929, 2.801, 171, 2.772
．． No. 162, No. 2,895,826, No. 3,77
2.002, 3.758.308, 4.3
No. 34.011, No. 4.327.173, West German Patent Publication No. 3゜329.729, European Patent No. 124,36
5A, 249°453A, U.S. Patent No. 3,44
No. 6,622, No. 4,333,999, No. 4,7
No. 75.616, No. 4.451,559, No. 4,
No. 427,767, No. 4,690,889, No. 4
, 254° 212, 4,296.199, JP-A-61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Research De, Section 1-G of Isclozier Toru 17643, U.S. Patent No. 4.163.670, Japanese Patent Publication No. 5
No. 7-39413, U.S. Patent No. 4,004,929,
No. 4.138,258, British Patent No. 1.146.3
The one described in No. 68 is preferred. Also, U.S. Patent No. 4,
No. 774,181, which uses a fluorescent dye released during coupling to correct unnecessary absorption of coloring dyes, and U.S. Pat. It is also preferred to use couplers having a dye precursor group as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,366.237 and British Patent No. 2,125.
．． Preferred are those described in No. 570, European Patent No. 96,570, and German Patent Publication No. 3,234.533.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4,576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17614.
3. Patents listed in sections ■ to F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, No. 63-37350,
U.S. Patent No. 4,248.962, U.S. Patent No. 4,782.012
Preferably, those listed in No.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound releasing couplers, DIR coupler releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc.,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European patent cylinder 173°3
No. 02A, No. 313.3084, a coupler releasing a dye that after-breaks after separation, R, D, Nα11449
, No. 24241, JP-A-61-201247, etc., bleach accelerator-releasing couplers, U.S. Pat. No. 4,553.4
Ligand releasing coupler described in No. 77 etc., JP-A-63-
75747, a leuco dye-releasing coupler;
Examples include couplers that emit fluorescent dyes as described in U.S. Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322.027 and the like.

It has a high boiling point of 175°C or higher at normal pressure, which is used in the oil-in-water dispersion method! Specific examples of the solvent include phthalate esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amylphenyl) phthalate, bis(2, esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphate, etc.)
, benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
hydroxybenzoate, etc.), amides (N, N-
diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2
, 4-di-tert-amylphenol, etc.), aliphatic carboxylic acid ester MC bis(2-ethylhexyl)
sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N-dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.).

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30°C or higher, preferably 50°C or higher and about 160°C or lower, can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of latex dispersion processes, effects, and latex for impregnation include U.S. Pat. It is described in.

The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
It is preferable to add various preservatives or antifungal agents such as 2-phenoxyethanol and 2-(4-thiazolyl)benzisodazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of NCL 17643, and the same N(L
18716, from the right column on page 647 to the left column on page 648.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 20 μm or less, and the film swelling rate is TI/book is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% ill humidity (2 days), and the film swelling rate T, t can be measured according to a method known in the art, e.g. , Photographic Science and Engineering (Photogr, Sci, Eng,) +199 by A. Green et al.
It can be measured by using a swellometer (swelling membrane) of the type described in , Issue No. 1, pp. 124-129, and the TI/1
The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when treated with a color developing solution at 30'C for 13 minutes and 15 seconds, and is defined as the time required to reach the saturated film thickness of 172.

The membrane swelling rate T1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color developing solution used in the development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline,
3-Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonate 3-methyl-4- AξNo N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-
Examples include +-luenesulfonate. Among these, 3-methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may contain pHi buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. In addition, various preservatives such as hydroxyl amine, diethylhydroxylamine, sulfite, hydrazines such as N,N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catechol sulfonic acids, ethylene solvents such as glycols, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone. , viscosity imparting agent, aminopolycarboxylic acid, aminopolyphosphonic acid,
Various calcinants such as alkylphosphonic acids and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1 , 1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N,N-tetramethylenephosphonic acid, ethylenediamine di(0-hydroxyphenylacetic acid), and salts thereof. It can be mentioned as follows.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than d. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, the above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
The slit development processing method described in Japanese Patent No. 216050 can be mentioned. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing, and stabilization.Also, the amount of replenishment can be reduced by using means to suppress the accumulation of bromide ions in the developer. .

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

Since the bleaching treatment after color development has been described above, it will be omitted here.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3.893.858, German Pat.
．． No. 290,812, No. 2,059,988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group described in JP-A No. 53-124424, No. 53-141623, No. 53-28426, Research Disclosure No. Nα17129 (July 1978), etc.; Thiazolidine derivatives described in No.
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 52-20832,
No. 53-32735, U.S. Patent No. 3,706,561
Thiourea derivatives described in West German Patent No. 1,127,7
No. 15, iodide salts described in JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748,430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; other JP-A-49
-42,434, 49-59,644, 53-
No. 94,927, No. 54-35,727, No. 55-2
Compounds described in No. 6,506 and No. 58-I63.940; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in U.S. Pat. No. 3,893,858.
No., West German Patent No. 1.290,812, Japanese Unexamined Patent Publication No. 1983-9
Preferred are the compounds described in US Pat. No. 5,630, and also preferred are the compounds described in US Pat. No. 4,552,834.

These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa>2).
-5, specifically acetic acid, propionic acid, etc. are preferred.

Examples of fixing agents used in fixing solutions and bleaching window solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are generally used. ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769A are preferred. Furthermore, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time for the desilvering process is preferably as short as possible without causing desilvering defects.The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50"C1 is preferably 35° C. to 45° C. In the preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring be as strong as possible.A specific method for strengthening the stirring is the treatment on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461. A method of colliding liquid jets, a method of increasing the stirring effect using a rotating means as described in JP-A No. 62-183461, and a method of moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid. , a method of improving the stirring effect by creating turbulence on the surface of the emulsion, and a method of increasing the circulation flow rate of the entire processing liquid. Such agitation enhancement means include bleaching solutions,
It is effective in both bleach-fixing solutions and fixing solutions. Improved stirring speeds up the supply of bleach and fixing agent into the emulsion film,
It is thought that this increases the desilvering rate as a result. Also,
The agitation improvement means described above are more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0491257, No. 60-191258, No. 60-
It is preferable to have a photosensitive material conveying means described in No. 191259.As described in the above-mentioned Japanese Patent Application Laid-Open No. 191257/1983, such a conveying means prevents the carrying of processing liquid from the front bath to the rear bath. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

In the present invention, after the desilvering treatment, it is common to undergo a water washing and/or stabilization step. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (stages), countercurrent flow, etc.
It can be set in a wide range depending on the replenishment method such as forward flow and various other conditions.

Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is based on the Jour-al of the 5ocie
Ty of Motion PicLure and
It can be determined by the method described in Te1e-vision Engineers, Vol. 64, P, 248-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, such problems were solved by the method disclosed in Japanese Patent Application Laid-open No. 52-28.
The method for reducing calcium ions and magnesium ions described in No. 8.838 can be used very effectively. In addition, chlorine-based disinfectants such as isothiazolone compounds, cyabendazole, and chlorinated sodium isocyanurate described in JP-A No. 57-8,542, and other chlorinated disinfectants such as hensitriazoles, etc. Chemistry” (19
1986) Sankyo Publishing, Hygiene Technology complete volume, "Microbial Sterilization, Bacteria, Sterilization, Anti-Mold Technology J (1982) Society of Industrial Engineers, Lecture of Japan Society for Anti-Bacterial and Anti-Mold Encyclopedia J (1986) The fungicides mentioned can also be used.

The pi (pi) of the washing water in the processing of the photosensitive material of the present invention is 4
-9, preferably 5-8. The washing time and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
Generally, a range of 20 seconds to 10 minutes at 15 to 45°C, preferably 30 seconds to 5 minutes at 25 to 40°C is selected.

Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Examples of dye stabilizers that can be used include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetratin, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process.

When the above-mentioned processing solutions are concentrated by evaporation during processing using an automatic processor or the like, it is preferable to add water to correct the shrinkage.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
Ship base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, and U.S. Patent No. 3
, 719.492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material used in the present invention may contain various 1-phenyl-3-pyrazolidones, if necessary, for the purpose of promoting color development.Typical compounds include Kaisho 56-64339, 57-144
No. 547, and No. 58-115438.

The various processing solutions used in the present invention are typically used at temperatures between 10°C and 33°C to 38°C, but higher temperatures may be used to accelerate the processing and shorten the processing time. Conversely, it is possible to improve the image quality and stability of the processing solution by lowering the temperature.

In addition, West German Patent No. 2,226,7 was issued for the purpose of saving light-sensitive materials.
70 or U.S. Pat. No. 3,674.499 using cobalt or hydrogen peroxide intensification.

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

Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color light-sensitive material, was prepared by coating each layer having the composition shown below with heavy nitrogen.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rd units, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of silver halide in the same layer.

(1 ton of sample) 1st i (antihalation layer) Black colloid i! ! 0.18 Gelatin 1.40 Second layer (middle layer) 2.5-di-t-pentadecylhydroquinone 0.18EX-
10,07 E Dye ■ -s 1.8 Dye I Sensitizing dye ■ Sensitizing dye ■ ■ X-3 Silver 1.60 5.4X10-'1.4X10-'2.4X10-' 0.010 o, os.

O,097 B5-1 B5-2 gelatin 6th layer (middle layer) X-5 B5-1 gelatin 7th layer (first green emulsion layer) Emulsion A Emulsion B Sensitizing dye V Sensitizing dye■ Sensitizing dye■ X-6 X-1 X-7 X-8 B5-1 B5-3 gelatin 0.22 0.10 1.63 0.040 0.020 0.80 Silver 0.15 Silver 0.15 3.0X10-' 1.0X10-' 3.8X10-' 0.260 0.021 0.030 0.025 0.100 0.010 0.63 8th N (second green emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye■ Sensitizing dye■ X-6 X-8 X-7 B5-1 B5-3 gelatin 9th layer (3rd green emulsion layer) Emulsion E Sensitizing dye V Sensitizing dye■ Sensitizing dye■ X-13 X-11 X-1 B5-1 Silver 0.45 2, lX1O-' 7, OX 10-' 2.6X10-' 0.094 0.018 0.026 0,160 o, ooa O150 Grudge 1.2 3.5X10-' 8, OX 1O-S 3.0X10-' 0.015 0.100 0.025 0.25 B5-2 gelatin 10th layer (yellow filter layer) yellow colloidal silver X-5 B5-1 gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion A Milk ax JB Emulsion F Sensitizing dye■ X-9 X-8 B5-1 gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye■ X-9 0,10 1,54 0,05 0,0B O2O3 0,95 Silver 0.08 Silver 0.07 Silver 0.07 3.5X10-' 0.721 0.042 0.28 1.10 0.45 2, lXl0-' 0.154 X-10 B5-1 gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion H Sensitizing dye■ X-9 B5-1 gelatin 14th layer (1st protective layer) Emulsion 2 -4 -5 B5-1 gelatin 15th layer (second protective layer) polymethyl acrylate particles (Diameter approximately 1.5μm) -1 gelatin 0.007 0.05 0.78 Silver 0.77 2゜2X10-' 0.20 0.07 0.69 0.20 0.11 0.17 0.05 1.00 0.54 0.20 1.20 In addition to the above ingredients, each layer contains gelatin hardener H-1 and a surfactant were added.

EX-1 EX-2 EX-3 +1)1 0)1 1 EX-4 EX EX-6 CJhshi) EX EX-8 EX-9 I EX-10 EX-12 c, u, osoρ EX 3 -2 I -4 Dye ■ -1 CH! ) (-1 Preparation of sample 70.2 In sample ioi, except for the yellow colloidal silver added to the first O layer, the amount of the dispersion S-/l-1-23 of the present invention added was O, Co, 2f. Sample 10/ was prepared in the same manner as Sample 10/, except that the amount of the sample 10/m was added.

Preparation of sample 103 In sample 10J, S-coy<
l-,2t added amount is 0. ．． It was prepared in the same manner as Sample 10, except that the amount was added at 2 tlf/m2.

Preparation of sample iou~10t In place of the black colloidal silver added to #1 in samples 10/~103, dye dispersion of the present invention S~3 gold [1-
The samples were prepared in the same manner as Test 1) 10/-103 except that the total amount of J and [1-/J was 0.2397 m2.

Preparation method of fine powder dye dispersion 8-i The dye was dispersed in a vibrating ball mill by the following method.

Water (co/, 7d) and 1% aqueous p-octylphenoxyethoxyethane sulfo/acid soda 3dX! % aqueous solution of p-octylphenoxypoly(polymerization*io)oxyethylene/ether θ,! The dye of the present invention (1-21)/00f and zirconium oxide beads (diameter/mm) were added to the mixture, and the contents were dispersed for 2 hours. The vibratory ball mill used was B(1)m manufactured by Chuo Kakosei.

Take out the contents and use a saw to remove J% gelatin aqueous solution Ir? and filtered the beads to obtain a dye gelatin dispersion.

In a similar manner, 5-2 (dye 1-J♂) and 5-3 (dye m-J/m-/co(ii quantity ratio/:/)) were prepared.

After exposing the sample ioi~1ota obtained by the above method with a step wedge, sample 10/ was subjected to the following treatment step (1) using bleaching solution (I), and sample 101~
106 in the following treatment step (1) with bleaching solution (II)'
sample l−/0/, ]]
1-10/~■-tbutton.

The residual @jl of the exposed portion of the aoCMS of the treated sample/pull was measured using fluorescent X-rays.

The results are shown in Table/.

As is clear from Table 7, when the present invention is used, even if a persulfuric acid bleaching method with a weak bleaching blade is used, the amount of residual silver is extremely small. In addition, colloidal silver for antihalation,
When both the colloidal silver for the yellow filter is replaced by the dye of the invention, the effect is - so pronounced.

(color developer) hydroxylthily Minoniacetic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate ← [N-ethyl-N -β-hydroxy ethylamino〕- comethylanili sulfate add water Mother liquid (b) J, 0 q, 0 30.0 /, 3 /, koη Ko, O Replenisher (ω 6, O ! ,Q 37.0 0, J 3.3 i, oy1o-2 mole f, 3x) O-2 mol /, Ol /, 0/1 pH io, o.

io, it Bleach solution I 32-13°C water red blood salt sodium bromide add water pH (27°C) Prescription value OO ←　O.

Ko ! .

/.

, J:l:O.

Ol 2 f Ol ! Bleach solution ■ ko l~jJ”C water gelatin sodium persulfate sodium chloride Sodium nitrate/acid (anhydrous) Phosphoric acid (rj%) add water pH (27°C) J Prescription value 00xt o, zy 33.0f iz, oy 7, O? 2,! me i,oB 3±Q, Ko (Fixer) /-Hydroxyethyl Ride7-/,/ji Honufonic acid Etele/Diamine 4 disodium acetate salt sodium sulfite sodium bisulfite Ammonyl thiosulfate Mu water @liquid (700f/l) Log/Ammonium Thiourea J, 6-Schier 7° ! −Octanegio rule add water ammonium acetate Add p H mother liquid@ J,Q 0, J 10.0 1, O /7(L,,0yn1 100.0 3.0 3.0 /, 01 6, j Replenisher (ω 7.0 0.7 /+2.0 70.0 2oo, 0zl ijo,.

J, 0! , O /, 0 (1 6,7 (stable solution) Formalin common to mother liquor and replenisher (37%) !-Chlorocomethyl-intiazolin-3-oncomethyl-guisotheazoline 3-o/ Interface Activator - Oη Oη Ethylene glycol/, 0 Add water to H/, 01 7, 0-7, 0 Example 2 As a sample, a multilayer consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support. Color photosensitive material 2
01 was produced.

1st layer; antihalation layer; black colloidal silver gelatin layer containing ultraviolet absorber C-1, ultraviolet absorber C-2, B5-2; second layer; intermediate layer compound H-1 coupler C B5-1 B5-2; 3rd gelatin layer containing; 1st red-sensitive emulsion layer Silver iodobromide emulsion ...Amount of coated silver (same below) 0.5
8 g/bo (silver iodide 5 mol%, average grain size 0.5 μm) 18
g/rd 04g/Po1 B g/Bo09g/Po3og/Po07g/Bo11g/Bo01 g/rd・Oo・0゜・0゜・Oo・0゜・06・O9・0゜sensitizing dye ■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Gelatin layer 4N containing coupler C-3 coupler C-4 coupler C-5; second red-sensitive emulsion layer silver iodobromide emulsion (silver iodide 6 mol% , Sensitizing dye! ... Sensitizing dye■ Sensitizing dye■ ・7.0X10-' mole per 1 mole of i-2.0XIO-' mole per 1 mole of silver・2.0XIO-' mole per 1 mole of silver 2.8X10-'mol・i 2.0xlO-s mol for 1 mole...0.26g/po...0.01g/rtf...0.01g/bo...・1.3g/average particle size 0.8μm) ・5.2XIO-'mol per 111mol ・1.5X10"mol per Im 1mol ・Sensitizing dye ■ Coupler per 1mol C-12 Coupler C-3 Coupler C-13 Coupler C-5 5th gelatin layer containing B5-1 B5-2; 3rd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, sensitized) Dye! ... Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ 2, lXl0-'mole・1.5X10-' mole for 1 mole of silver...0.06 g/bo...0 .04g/bo...o, otg/bo...0.03g/bo...0.12g/nf...0.l1g/rrr ・ ・ ・ ・0.9g/bo average Particle size: 1.0 μm) - 5.5 x 10-' mol per 1 mol of silver - 1.6 x 10-' mol per 1 mol of silver - 2.2 x 10-' mol per 1 mol of silver - 1 mol of primate On the other hand, the sixth gelatin layer containing coupler C-12 coupler C-3 B5-1 B5-2; the seventh gelatin layer containing intermediate layer compound H-1; the first green-sensitive emulsion layer silver iodobromide emulsion ( Silver iodide 5 mol%, Sensitizing dye V ... Sensitizing dye ■ Coupler coupler coupler coupler -6- 7- -4 1,6X10°5 mol・・0.04g/bo・・0.03g/bo・・0.06g/bo・・0.05g/bo・・・・0.02g/bo・・・・・1.54g/bo・・1.54g/bo・average particle size 0.5μm)・3,8×10-' per mole of silver 3, OXlo-' mole for 1 mole of mole S... 0.29 g/bo... 0.05 g/po... 0.08 g/bo...0.06 g/ BoHBS-1 ・ ・ ・ ・0.31
Gelatin layer 8th layer containing g/V; Second green-sensitive emulsion layer Silver iodobromide emulsion...0.61 g/% (silver iodide 6 mol%, average grain size 0.8 μm) Sensitizing dye V
... 2,7 x 10-' mol sensitizing dye for 1 mol of silver ■... Coupler C-6 Coupler C-9 Coupler C-8 Gelatin layer containing HBS-1 9th layer; 3rd green Sensitizing emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, sensitizing dye V... Sensitizing dye ■ 2, IXIO-' mol per silver mol 0.03 g/po O.OO 1 g /Po・O.OO1g/rl'r ・0.034g/Po・・・・0.1g/rd Average particle size 1.0μm) ・3 for 1 mole of silver, OXIO−′ mole for 1 mole of silver 2.4X10-' molar coupler C-6...0.03g/po coupler C
-8...O,001g/PoHBS-1
・ ・ ・ ・10th gelatin layer containing o, o4g/po; yellow filter layer 11th gelatin layer containing yellow colloidal silver compound H-1 coupler C-7/B5-1; first blue-sensitive emulsion layer Silver bromide emulsion...o, 34g/rtf (
Silver iodide 6 mol%, average grain size 0.5 μm) Coupler C-10...0.41 g/Bocablur C-14
・・・・o, o3g/BoHBS-1---0,16g
Gelatin layer 12i containing /rrr, second blue-sensitive emulsion layer silver iodobromide emulsion 49 g/po.0.036 g/po.0.10 g/po.0.08 g/bo.o, o9g/po.0° (Silver iodide 10 mol%, average grain size 0.9 μm) Coupler C-10...o, t5g/bo HBS-1.
... 13th gelatin layer containing o, osg/bo; 3rd blue-sensitive emulsion layer Silver iodobromide emulsion ...0.75 g/rr? (
Silver iodide 14 mol%, average grain size 1. 5μm) Sensitizing dye ■...2.3X10-' per mole of silver
Mol coupler C-10...0.05g/BoHBS-1
14th layer of gelatin layer containing ...0.02g/B; First protective layer UV absorber C-1...0.05g/B UV absorber C-2...0.24g/ BoHBS-2
・---・0.12g/rr! Gelatin layer 15th layer containing; second protective layer polymethyl methacrylate particles (diameter 1.5 μm)...
In addition to the above composition, 11 and a surfactant were added to each gelatin layer containing 0.05 g/bo.

This sample was designated as sample 201.

Gelatin hardening agent C- Produced as above The compounds used to prepare the samples are shown below.

-4 C CH.

Hs -6- 7- -9 0 -11
H t'lT'--12 C-14 Sensitizing dye ■ Sensitizing dye ■ xHs Sensitizing dye ■ Sensitizing dye ■ Preparation of sample KO/ In sample KO/, remove the yellow colloidal silver added to the first O layer. Sample 20/ was prepared in the same manner as Sample 20/, except that instead, the dispersion S-a of the present invention was added so that the amount of v-J added was a, 1117 m.

Preparation of sample-203 In the sample OJ, replace dispersion 8-u with 8-! 7
It was prepared in the same manner as sample JOJ except that l-7o was added in an amount of 06109/m2.

Preparation of sample 2041-JO6 In place of the black colloidal silver added to the first layer in samples 0/-03, the dye dispersion S-2 of the present invention was added to 11-J.
Samples JO/--A were prepared in the same manner as samples JO/--03, except that the total amount of O and -a was 32/m2.

Same, S-φ (dye ■-2), 5-j (dye ■-ri, 5-
6 (dye [1-J/■-4 (weight ratio/;/)) is S-/
It was adjusted in the same way.

After exposing the samples 207 to Jot obtained by the above method with a step wedge, the sample O/ was bleached in the following treatment step (n) using a bleaching solution (1), and the sample O/
~206 in the following treatment step (1) with bleaching solution (If)
sample I-koO/, ■-koO, respectively.
/~■-ko θ6.

The amount of residual silver in the portion of the treated sample exposed to 4AoCMS was measured using firefly X-rays.

The results are shown in Table 1.

As is clear from Table 1, when the present invention is used, even if a persulfuric acid bleaching method with a weak bleaching blade is used, the amount of residual silver is extremely small. Furthermore, the effect is even more remarkable when both colloidal silver for anti-injection and colloidal silver for yellow filter are replaced with the dye of the present invention.

Processing process ■ Processing process Temperature Time Development color development 44/'Cj minute stop Jf'C3d second water wash 〃 3d seconds before bath x 30 seconds bleaching
White 〃 Seasonal water
Wash / minute fixation
I water division washing 〃
The treatment solution used in the 10-second stabilization bath has the following composition.

Color developer aminotri(methylenephospho/acid)-3-sodium salt/, sodium bisulfite, θ sodium bromide
/, J Sodium carbonate
,2t,.

N-ethyl-N-β-meta/nulfonamide ether-3-methyl-φ-aminoanili/sesquisulfate monohydrate ←, add ot water to make total amount /, 01(p) (i
Stop solution Sulfuric acid (7N) Add water and pre-bath Sodium metabisulfite bleaching solution (described later) Fixing solution Amino tri(methylene phospho/acid) -! - Sodium salt Sodium thiosulfate (jff rumor) Sodium sulfite Add sodium bisulfite water to stabilize formaldehyde (37%) Otd Total amount i, op io, ot /.

Its.

10° T.

Total amount/.

! t one f I-2 1 0d add water Total amount i, ol Bleach solution I 3ko-da 311C water red blood salt sodium bromide add water pH (17°C) Prescription value Poo ml 4! o, oy Ko J, Ot /, Ol 6,! ±0.3 Bleach solution ■ Gelate/ sodium persulfate sodium chloride Sodium 1st/acid Phosphoric acid (rt rumor) add water 0.

31° /　j　.

2.

Ko .

Total amount/.

20? f2! -〇1 Example 3 Preparation of Sample 301 A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm, and designated as Sample 301. The numbers represent the amount added per -. Note that the effects of the added compound are not limited to the described uses.

1st layer; antihalation layer black colloidal silver 0.25g gelatin 1.9g ultraviolet absorber U-
10,04g Ultraviolet absorber U-20,1g Ultraviolet absorber U-30,1g Ultraviolet absorber U-60,Ig High boiling point organic solvent○1l-10,1g 2nd layer: Intermediate layer gelatin 0.40g Compound C
pd-D 10mg high boiling point organic solvent ○
11-340mg 3rd layer: Fine grain silver iodobromide emulsion covered with intermediate layer (average grain size 0.06 μm, Ag I content, It mol %) Si
! 0.05 g Gelatin 0.4 g 4th layer: Low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.4 μm, Ag I-containing N2. 1:1 mixture of 5 mol % monodisperse cubes and monodisperse cubes with average particle size 0.3 μm and Agl content 4.5 mol %) Silver content 0.4 g Gelatin 0.8 g Coupler C
-10,20g Coupler C-90,05g Compound Cpd-010mg High-boiling organic solvent Oil -20, Log 5th layer: Medium-sensitivity red-sensitive emulsion layer Spectrally sensitized with sensitizing dyes S-1 and S-2 Silver bromide emulsion (monodisperse cubic with average grain size 0.5 μm and Agl content 4 mol%) Silver amount 0.4 g gelatin
0.8g Coupler C-10.2g Coupler C-20.05g Coupler C-30.2g High boiling point organic solvent ○1l - 20.1g 6th layer: High sensitivity red-sensitive emulsion layer containing sensitizing dyes S- and S- Silver iodobromide emulsion spectrally sensitized with 2 (monodisperse twin grains with average grain size 0.7 μm and Agl content 2 mol%) Silver amount 0.4 g Gelatin 1.1 g Coupler C
-30.7g Coupler C-10.3g 7th layer: Intermediate layer gelatin 0.6g Dye D-1
0.02g 8th layer: Silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μm, Ag
l content 0.3 mol%) 0.02g gelatin
1.0g Konzoku inhibitor Cpd-A
o, 2g 9th layer: low-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size 0.4 μm, Ag I content 4.5 mol%) A 1:1 mixture of monodisperse cubes and monodisperse cubes with an average particle size of 0.2 μm and an Agl content of 4.5 mol%)
Silver amount 0.5g gelatin
0.5g Coupler C-40, 20g Coupler C-70, 10g Coupler C-80, 10g Compound Cpd-B O, 03g Compound Cpd-E 0.02g Compound Cpd
-F 0.02g Compound Cpd-G
O,02g Compound Cpd-H0,02
g High boiling point organic solvent ○1l-10,1g High boiling point organic solvent○1t-20,1g 10th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide spectrally sensitized with sensitizing dyes S-3 and S-4 Emulsion (monodispersed cubic with average grain size 0.5 μm and Agl content 3 mol%) Silver FiO, 4 g gelatin
0.6g Coupler C-40, 1g Coupler C-70, 1g Coupler C-80, 1g Compound Cpd-BO O, 03g Compound Cpd-E O, 02g Compound Cpd
-F 0.02g Compound Cpd-G
O,05g Compound Cpd-HO,05
g High boiling point organic solvent ○ 1 l - 20.01 g 11th layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (average grain size when converted to spheres: 0. 6 μm, monodispersed flat plate with an Agl content of 1.3 mol% and an average diameter/thickness of 7)
Silver amount 0.5g gelatin
1.0g Coupler C-40,4g Coupler C-70,2g Coupler C-80,2g Compound Cpd-B O,08g Compound Cpd-E 0. 02g Compound Cp
d-F, 0. 02g Compound Cpd
-G O,02g compound @IJcpd-
HO, 02g High boiling point organic solvent 0il-10,02g High boiling point organic solvent ○1l-20,02g 12th layer: Intermediate layer gelatin 0.6g Dye D-2
0. 05g 13th layer: Yellow filter layer Yellow colloid tI Silver amount 0.1g Gelatin 1.1g Color mixing prevention agent Cpd
-A O, O 1g 1g high boiler solvent 041-
1 0. 01g 14th layer: Intermediate layer gelatin 0.6g 15th layer:
Low-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
1:1 mixture of monodisperse cubes with an average particle size of 0.4 μm and an Agl content of 3 mol % and monodisperse cubes with an average particle size of 0.2 μm and an Agl content of 3 mol %) Amount of silver 0.6 g Gelatin 0.8 g Coupler C
-50.6g 8g solvent with high boiling point ○1l -20.02g 16th layer: Medium-sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Average particle size: 0.5 μm SAgT content: 2 mol %, monodisperse cubic) Silver: 10.4 g Gelatin
0.9g Coupler C-50.3g Coupler C-60.3g High-boiling organic solvent ○1f-20.02g 17th layer: Highly sensitive blue-sensitive emulsion layer Sensitized with sensitizing dyes S-5 and S-6 Silver iodobromide emulsion (
Average particle diameter in terms of spheres: 0.7 μm, Agl content: 1.5 mol%
, tabular grains with an average diameter/thickness value of 7)
Silver amount 0.4g gelatin
l. 2g coupler C-60.7g 18th layer: 1st protective layer gelatin 0.7g UV absorber U-10.04g UV absorber U-30.03g UV absorber U-40.03g UV absorber U- 50.05g Ultraviolet absorber U-60.05g High boiling point 89 solvent 04l-10.02g Formalin scavenger Cpd-C0.8g Dye D-30.05g 19th layer: Fine particles covered with the second protective layer Silveride emulsion (average grain size 0°06,
c+m, Agl content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g 20th layer: 3rd protective layer Gelatin 0.4 g Polymethyl methacrylate (average particle size 1.5 μm 0.1 g Methyl methacrylate and acrylic acid 4:6 copolymer (average particle size 1.5μm) 0.1g silicone oil 0.03g surfactant W-13.0
mg In addition to the above composition, a gelatin hardener H1, a coating surfactant, an emulsifying surfactant, and the like were added to each layer.

In addition, in the emulsion used here, monodisperse means that the coefficient of variation is 20% or less.

〉 -2 m3 H R R -4 (CHz-CHhT---1-i CHz-CHh1-5 6 Coupler C -9 H N 11-1 Dibutyl phthalate i1 Tricresyl phosphate Cpd H Cpd-8 Cpd-C Cpd -[1 H Cpd +1 +13 -1 U -3 (L) 4H -5 -6- -2 -4 -5 SOJN(CJs)s -1 -2 )υ3 to 3 CHz-CHSI)zCHzCONHCHzCTol
CH5O2CHzCONHCHt-1 l13 Hs Preparation of Sample 302 In Sample 30/, the yellow colloidal silver added to the 73rd layer was removed, and instead, the amount of the dispersion of the present invention 5-7f■-/J added was 0. ．． It was produced in the same manner as Sample 30/, except that the amount was added so that the ratio was 2/f/m2.

Preparation of sample JOJ In sample JQJKTh, S-r was added instead of dispersion S-7.
k ■ - / j nots addition iEO, / F f 7m
Sample 30 was prepared in the same manner as the sample 30 except that the amount of the sample was increased to 2.

Preparation of Samples 3017 to 306 In place of the black colloidal silver added to the seventh layer in Samples 307 to 303, the dye dispersion S-ta of the present invention was added in a total amount of 1-/ and [1-3 of 0. 2! Samples 30/~JOJ were prepared in the same manner as Samples 30/~JOJ, except that the addition was made to achieve P/m.

Same, 5-7 (dye 111-/3), 5-r (dye ■-7)
3), 5-2 (dye 1-//III-J (weight ratio/:/
)) was adjusted in the same manner as S-/.

After exposure with sample 30/~JO6'i step wedge obtained by the above method, sample 30/f was exposed in the following processing step (II
The bleaching of I) was carried out using bleaching solution (1), and the bleaching of samples 30/-304 was carried out using bleaching solution (If) t- of the following processing step (III), and each sample 1- 30
/, 1-30/~l [-304.

The amount of residual silver in the portion of the treated sample exposed to OCMS was measured using fluorescent X-rays.

The results are shown in Table 3.

As is clear from Table 3, when the present invention is used, even if a persulfuric acid bleaching method with a weak bleaching blade is used, the amount of residual silver is extremely small. In addition, colloidal silver for antihalation,
When both the colloidal silver for the yellow filter is replaced by the dye of the invention, the effect is - so pronounced.

The composition of each treatment liquid was as follows.

black and white development Nitrilo-N, N, N- Trimetere/Phospho/ Acid/J sodium salt sodium sulfite Hydrokino/Monos Potassium sulfonate potassium carbonate /-Phenyl-Gumethi Ruder Hydroxyme Chil-3-pyrazolide / potassium bromide potassium thiocyanate potassium iodide Ko, 02 30? , 20? 32 Ko, O2 Ko,! ? /, Jf +2. θη Ko, 02 30? +202 Jf Ko, Or /, 4t? / ,Ko? The pH is Adjusted with hydrochloric acid or potassium hydroxide.

reversal liquid Mother liquor replenisher Nitrilo-N, N, N- trimethylene phosphone acid/j sodium salt Tin chloride/J water salt p-aminophenol Sodium hydroxide glacial acetic acid 3.02 Same as mother liquor character /, 02 0, /2 2 /jxl pHA, o.

9H was prepared with hydrochloric acid or sodium hydroxide.

Color developer mother solution Replenisher Nitrilo-N, N, N- Trimethylenephosphonic acid trisodium salt Sodium sulfite trisodium chloride salt 2.0? 7.0f 36? 2.Of 7.02 36? Potassium bromide Potassium iodide Sodium hydroxide Sitondate N-ethyl-(β-methanesulfonamidoethyl)-3-methyl-φ monoaminoanili/sulfate 3.6-cythia/, l--octa/diol7. 02 RiO! l1i 3.02 / ,! t lnot i, oy 3, Of /, Jf //2 /, Of 98 //, rO/2.0
0 pH was adjusted with hydrochloric acid or potassium hydroxide.

Adjustment liquid Ethylenediaminetetraacetic acid ・λ Sodium Salt・Co water salt sodium sulfite r, oy Same as mother liquor character /JP /-thioglycerin O, goo Sorvita／・Ester※ 0, /f E) H≦, +20 p)l was adjusted with hydrochloric acid or sodium hydroxide.

Bleach solution I Prescription value 7.2-443'C water red blood salt sodium bromide add water 0H (17'C) OO φ　O.

+23.

7+ O2 2 p t, J:l:0. j Bleach solution ■ Kopi~3r’c water gelatin sodium persulfate sodium chloride Prescription value OO θ.

33.

7! .

Jf 2 f Monosodium phosphate (anhydrous) Phosphoric acid (rj%) Add water, 0f -2,7 mJ /, 04 pH (27°C) 3 ± O, ko fixing solution mother solution Replenisher thiosulfuric acid Ammonia water r, oy Sodium sulfite in mother liquor 1.0? Sodium bisulfite! , O? Water was added to bring the pH to 1000.1. The pH was adjusted with hydrochloric acid or aqueous ammonia.

Stabilizing liquid formali/(37 rumors) Polyoxyethele 7-p-monononylphenyl ether (average degree of polymerization J, Otd Same as mother liquor 0#tl io) Sorbitan ester* (w+x+y+z=+20) (Effect of the invention) According to the present invention For example, an image forming method with excellent desilvering properties can be obtained while using a bleaching method with low pollution load.

The practical advantages of the present invention are extremely large.

Claims (1)

[Scope of Claims] At least one silver halide emulsion layer and a microcrystalline dispersion of at least one compound selected from the group of compounds represented by the following general formulas (I) to (VI) are provided on a support. 1. A method for forming a color image, which comprises exposing and developing a silver halide color photographic material having a hydrophilic colloid layer containing a hydrophilic colloid, and then treating the material with a processing solution containing a persulfate. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (III) A=L_1-(L_2=L_3)_n-A' General formula (I
V) A=(L_1-L_2)_2_-_q=B General formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, A and A ' may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, and X and Y may be the same or different and each represents an electron-withdrawing group. R represents a hydrogen atom or an alkyl group, R_1 and R_2 each represent an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and R_1 and R_2 may be linked to form a 5- or 6-membered ring. R_3 and R_6 each represent a hydrogen atom, a hydroxy group, a carboxyl group, an alkyl group, an alkoxy group, or a halogen atom, and R_4 and R_5 each represent a hydrogen atom or R_1
represents a group of nonmetallic atoms necessary for R_4 or R_2 and R_5 to connect to form a 5- or 6-membered ring. L_1,
L_2 and L_3 each represent a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2, p represents 0 or 1, when p is 0, R_3 represents a hydroxy group or a carboxyl group, and R_4 and R_
5 represents a hydrogen atom. B' represents a heterocyclic group having a carboxyl group, a sulfamoyl group, or a sulfonamide group. However, the compounds represented by general formulas (I) to (VI) have dissociative properties that have a pKa in the range of 4 to 11 in a mixed solution with a volume ratio of water and ethanol in one molecule of 1:1. It has at least one group.