JPH03158852A - Method for processing silver halide color photographic sensitive material and composition having fixing ability - Google Patents

Abstract

PURPOSE:To enhance stability of a fixing solution or a bleach fixing solution and storage stability of a color photographic image by adding a hydrogen sulfite adduct of a specified compound in a processing solution containing thiosulfate as a fixing agent. CONSTITUTION:The imagewise exposed silver halide photographic sensitive material is color developed and then processed with the bleach fixing solution and/or the fixing solution containing the following compounds: (1) thiosulfate, (2) at least one of the hydrogen sulfite adducts of the compounds represented by general formula (A), (B), (C), and (D). When this compound is allowed to form the adduct with the hydrogen sulfite, free hydrogen sulfite ions are lowered in concentration, made difficult to undergo oxidation, and the processing solution is enhanced in stability, therefore, this compound may be added separately from the hydrogen sulfite or the sulfite into the bleach fixing solution or the fixing solution.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention reduces deterioration of the processing liquid over time in continuous processing, and
The present invention relates to a method for processing silver halide color photographic materials that has excellent desilvering properties, reduces the increase in staining of the obtained images over time, and improves the preservation of the processing work environment.

(Prior Art) In the processing of silver halide color photographic materials, it has become an important issue to provide more stable and good photographic images than before. Especially now that there is a strong demand for speeding up processing and reducing the amount of replenishment to reduce waste, it is becoming more difficult to achieve the two objectives. In providing stable and good photographic images, the Photography Department J'I! ! The most important issue is that the liquid is stable against deterioration over time due to air oxidation and the like. In particular, in current color photographic processing where reducing the amount of washing water or stabilizing treatment is widely carried out, it is an important problem to improve the stability over time of the bleach-fixing solution or fixing solution and the subsequent washing solution or stabilizing solution. be.

As a means for improving the stability of such bleach-fixing solutions or fixing solutions, carbonyl compound bisulfite adducts have been conventionally provided as bleach-fixing solutions or fixing solution preservatives. Regarding these carbonyl compound bisulfite adducts, JP-A-48-42733, JP-A-50-51326,
No. 56-107244, West German Patent No. 2,102.713
The method of using it as a bleach-fix solution or a fix solution preservative is described in the specifications of No. 1, etc. However, although carbonyl compound bisulfite adducts have excellent performance as preservatives for bleach-fix solutions and fix solutions, they have various problems and have not been put into practical use to date. In particular, when conventional photographic materials were processed with a bleach-fix solution using a carbonyl compound bisulfite (lr) as a preservative, a problem arose in that the image storage properties of the materials deteriorated. That is, as the processed photosensitive material is stored over time, a problem arises in that the minimum 4 degrees (Dsin) of the uncolored portion of the photosensitive material increases. Further, when the conventional carbonyl compound is a lower aliphatic aldehyde, its vapor pressure is low, and there are also problems in terms of environmental protection such as handling and odor.

Therefore, there is a strong demand for a method for processing silver halide color photographic materials that solves these problems, has excellent stability of bleach-fix solutions and fix solutions, and does not deteriorate image storage stability.

On the other hand, it has been proposed to perform bleaching or bleach-fixing using a bleaching agent with stronger oxidizing power instead of the ferric complex salt of ethylenediaminetetraacetic acid that has been conventionally used as a bleaching agent. As a result, it has become possible to shorten processing time or reduce the amount of photographic processing waste liquid discharged. In other words, by using a strong oxidizing agent as a bleaching agent, the bleaching reaction rate in the bleaching or bleach-fixing process can be increased and the above processing steps can be accelerated, or the bleaching solution or bleach-fixing solution can be used as an oxidizing agent during processing. By maintaining excellent bleaching performance even when the amount of bleach (bleaching agent) decreases and silver ions and halogen ions accumulate, it is possible to reduce the amount of replenishment of the processing solution. . However, as mentioned above, strong oxidizing agents (bleach)
In the case of bleach processing, the stability of the subsequent fixing solution over time decreases due to the introduction of the bleach solution, and in the case of bleach-fixing processing, the stability of the bleach-fix solution itself over time decreases significantly. It has become clear that it delays bleaching and desilvering reactions. As a result, it has become clear that the liquid stability over time of the subsequent washing bath or stabilizing bath is also reduced.

Therefore, there has been a growing demand for techniques to improve the stability of bleaching solutions or fixing solutions over time.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material in which the fixer or bleach-fixer has excellent stability.

A second object of the present invention is to provide a processing method that provides excellent image preservation of the obtained color photographic images. A third object of the present invention is to provide a processing method capable of rapid desilvering.A fourth object of the invention is to provide a processing method with improved environmental protection. A fifth object of the invention is to provide a treatment method with excellent liquid stability over time in a washing bath or stabilizing bath.

(Means for solving B!ff) As a result of intensive studies, the present inventors solved the above problems by using the following processing method and the following composition for silver halide color photographic light-sensitive materials. I found out that it can be done.

That is, (1) in a processing method in which a silver halide color photographic light-sensitive material is imagewise exposed, subjected to color development treatment, and then treated with a bleach-fix solution and/or fixer, the bleach-fix solution and/or fixer is A method for processing a silver-genide color photographic material, characterized by containing the compounds of [1] and [2] and/or [3].

(2) A fixing composition containing the following compounds [1], [2] and/or [3].

■ Thiosulfate ■ At least one compound represented by the following general formula (Δ), (B), (C) or (D) and
At least one compound selected from the group consisting of i sulfate, 1Ili 6#i acid salt, and metabisulfite.

■ The following general formula (A), (B), (C) or (D)
At least one bisulfite adduct of the compound represented by
seed.

General formula (A) where R1 is an alkenyl group, an aryl group, an alkynyl group,
Represents a cycloalkyl group, aralkyl group, heterocyclic group, carboxylic acid group, ester group, acyl group or carbamoyl group, R2 is a hydrogen atom, an alkyl group, an alkenyl group,
It represents an alkynyl group, an aralkyl group, an aryl group, a nocroalkyl group, or a heterocyclic group, and R and Rt may be combined to form a ring.

However, when R5 represents an aryl group, R8 is never a hydrogen atom.

General formula (B) In the formula, R, , R, , R each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group,
It represents a cycloalkyl group, an aryl group, a heterocyclic group, a carboxylic acid group, an ester group, an acyl group, a halogen group, an ether group, a sulfo group, a sulfinyl group, a sulfonyl group, a cyano group, a nitro group, a carbamoyl group, or a sulfamoyl group.

R1 represents an electron-withdrawing group. Further, R1 and R4, R4 and Rs, Rs and R, R, and R5 may be combined to form a ring.

In the formula, R, , R, , R each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group,
alkylamino group, arylamino group, carboxylic acid group,
It represents an ester group, an acyl group, an ether group, a hydroxyl group, an alkylthio group or an alkylthio group, X represents an anion, and n represents O or l.

Furthermore, R7 and R, R1 and R9, and Rv and R1 may be combined to form a ring.

General formula (D) 7゛Z” R+.

In the formula, R3 represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group or a heterocyclic group. Further, Z represents an atom constituting a ring, Y represents an anion, m represents O or 1, and RIO may combine atoms in Z to form a ring.

Next, general formulas (A) to (D) will be explained in detail.

General formula (A) where R1 is an alkenyl group, an aryl group, an alkynyl group,
Represents a cycloalkyl group, aralkyl group, heterocyclic group, carboxylic acid group, ester group, acyl group or carbamoyl group, R2 is a hydrogen atom, an alkyl group, an alkenyl group,
It represents an alkynyl group, an aralkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group, and R and R2 may be combined to form a ring.

However, when R1 represents aryl 25, R2 is not necessarily a hydrogen atom.

General formula (A) will be explained in detail.

Each of R, , R, may have a substituent.

1'? Examples of the substituted or unsubstituted alkyl group of -propenyl group,
l-octynyl W, etc. are listed, and substituted or unsubstituted alkynyl moieties include ethynyl group, l-propynyl group,
Examples of substituted or unsubstituted Schiff [1-alkyl groups include noclopropyl group, nclopentyl group, nclohexynol group, etc., and examples of substituted or unsubstituted aryl groups include phenyl group, naphthyl group, etc. Substituted or unsubstituted aralkyl groups include:
Examples include Hensyl group, phenethyl group, etc. Substituted or unsubstituted heterocyclic groups include pyridyl group, piperidyl group,
Examples include thienyl group, pyrrolyl group, indolyl group, furyl group, fluoryl group, etc., and substituted or unsubstituted ester groups include methyloquinecarbonyl group, ethyloxycarbonyl group, isopropyloxycarbonyl group, Examples of the substituted or unsubstituted acyl group include an acetyl group, a hendyl group, a butanoyl group, and the like, and examples of the substituted or unsubstituted carbamoyl group include an octylcarbamoyl group, a dimethylcarbamoyl group, a phenylcarbamoyl group, and the like.

R,,I? may have a substituent, and examples of the substituent include a substituted or unsubstituted alkyl group, a halogen group, a hydroxy group, a carbonyl group, a substituted or unsubstituted ether group, a carboxy group, a substituted or unsubstituted ester group,
Mercapto group, substituted or unsubstituted thioether group, sulfino group, sulfo group, substituted or unsubstituted sulfinyl group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted sulfamoyl group, substituted or unsubstituted amino group, substituted or unsubstituted ammonio group, cyano group, phosphono group, substituted or unsubstituted hydroxyimino group, substituted or unsubstituted acylamino group, substituted or unsubstituted carbamoyl group, nitro group, substituted or unsubstituted hydrazino group, Substituted or unsubstituted ureido groups, substituted or unsubstituted amidino groups, substituted or unsubstituted guanidino groups, and substituted or unsubstituted heterocyclic groups such as 2-pyrrolyl groups, 2-pyridyl groups, and 4-piperidyl groups. etc.

-C In formula (A), R1 preferably represents an aryl group or a heterocyclic group, and R1 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. However, when R1 and R1 are an aryl group or an aromatic heterocyclic group, the substituents have a total Hammett's σ value of -l, 2 or more and 1. 0 or less, and preferably has at least one hydrophilic group in the substituent. What is Hammett's σ value here? [Journal of Medicinal Chemistry] (J.
It refers to the σ value described in Med, Chem, 1207 (1973) and 304 (1977).

In addition, the above-mentioned hydrophilic group consists of an atom selected from a sulfo group, a sulfino group, a carboxy group, a phosphono group, an amino group, an ammonio group, and a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a hydrogen atom having these groups. Represents an organic group having up to IO carbon atoms.

The following general formula (A') is more preferred than general formula (A).

General Formula (A') In the formula, R5' represents a heterocyclic group consisting of a substituted or unsubstituted carbon atom, nitrogen atom, oxygen atom, sulfur atom, or hydrogen atom. Preferred heterocyclic groups include pyridyl, thienyl, furyl, pyrrolyl, and indolyl.

Further, R1' represents a hydrogen atom or a substituted or unsubstituted lower alkyl group.

General substitute (B) In the formula, R,, L, I? each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carboxylic acid group, an ester group, an acyl group, a halogen group, an ether group, a sulfo group , sulfinyl group, sulfonyl group, noano group, nitro group, carbamoyl W or sulfamoyl group.

However, R6 represents an electron-withdrawing group, and R1 and R,,f
? , and Rs, Rs and I'? ,,R, and R,L! - may be incorporated to form a ring.

General formula ([3)] will be explained in detail.

In the formula, each of R3 to R8 may have a substituent.

In the formula, the alkyl W of R1 to R6 is, for example, methyl!
S, ethyl group, A methyl group, examples of alkenyl group include vinyl group, allyl group, 1-propenyl group, l-cyclohexenyl group, etc., and examples of alkynyl group include ethynyl group, l-propynyl group, Examples of the aralkyl group include a benzyl group and a phenethyl group; examples of the cycloalkyl group include a cyclopropyl group, a cycloalkyl group, and a ncrobentyl group; examples of the aryl group include phenyl, Examples of hetero F2M include 2-pyridyl group, 4-piperidyl group, 2-furyl group, furfuryl group, etc., and examples of ester groups include methoxycarbonyl group, ethquincarbonyl group, Examples of the acyl group include an acetyl group, hendyl group, and oftenoyl group; examples of the halogen atom include a chlorine atom and a bromine atom; examples of the ether group include a methocino group, Examples of the sulfinyl group include methylsulfinyl group, hexylsulfinyl group, phenylsulfinyl group, etc.; examples of the sulfonyl group include ethylsulfonyl L, butylsulfonyl group, phenylsulfonyl group, etc. and as the electron-withdrawing group for R4,
It has a Hammett's σ value of 0.0 to 1.0, and includes, for example, a nitro group, a cyano group, a sulfonyl group, an acyl group, and an ester group. However, this σ value is determined by the general formula (A)
It is synonymous with the σ value used in . When Rs to R1 have a substituent, it represents a synonym of the substituent of R1.

Preferably, R, , R, and R are a carboxylic acid group, a cyan group, or an argyl group, an aryl group, a heterocyclic group, an ester group, or an acyl group with hydrogen atoms substituted or unsubstituted, respectively;
, is a nitro group, cyan group, acyl group, or ester group.

More preferably, R3, Ra, and Rs are a carboxylic acid group, a cyano group, a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or an acyl group, and R4 is a nitro group,
They are cyano group and acyl group.

R in the ceremony? , Rg and Rq each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an amino group, an alkylamino group, an arylamino group, a carboxylic acid group, It represents an ester group, an acyl group, an ether group, a hydroxyl group, an alkylthio group, an arylthio group, or a carbamoyl group, X represents an anion, and n represents O or 1.

Furthermore, R1 and Rs, Re and R9, and R7 and R7 may be combined to form a ring.

-a Formula (C) will be explained in detail.

R in the ceremony? , Rs and R9 may each have a substituent.

Examples of the alkyl group for Rt, Rs, R9 include methyl group, ethyl group, isobutyl group, dodecyl group, etc.
Examples of alkenyl groups include vinyl group, allyl group, 1-propenyl group, ■-octenyl group, etc. Examples of alkyl groups include ethynyl group, l-propynyl group, etc., and cycloalkyl groups include cyclopropyl group. Examples of the aralkyl group include a hensyl group and a phenethyl group; examples of the aryl group include a phenyl group and a naphthyl group; and examples of the hetero radical include a 2-pyridyl group, 4-piperidyl method, 2-
Examples of the alkylamino group include a dimylamino group and a butylamino group; examples of the arylamino group include an anilino group and a toluidino group; Examples include Luponylno S, Ethoxycarbonyl W, etc.
Examples of the anru group include acetyl group, octanoyl 2S, benzoyl group, etc., and examples of ether)S include methokino group, phenokitno S, isopropoquine group, etc.
Examples of the arylthio group include a phenylthio group and a naphthylthio group, and examples of the carbamoyl group include an octylcarbamoyl group and a trimethylcarbamoyl group. , phenylcarbamoyl group, etc., and examples of X include a chlorine atom, a bromine atom, a paratoluenesulfonate anion, a perchlorate anion, and the like. When R,, R,, R, has a substituent, R1
represents a substituent and a synonym.

Preferably Rt, Re, and R9 are hydrogen atoms and have 2 carbon atoms.
Substituted/unsubstituted alkyl groups, cycloalkyl groups, aralkyl groups, aryl groups, hetero fO)i up to 0
:, amino group, alkylamino group, arylamine group.

More preferably, rl, , R, and R are a hydrogen atom, a substituted or unsubstituted alkyl group having up to IO carbon atoms, an aryl group, a heterocyclic group, an amino group, or an alkylamino group.

General formula (D) 7-Z.

In the formula R1°, R1° represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a heterocyclic group. Further, Z represents an atom constituting a ring, Y represents an anion, and m represents O or 1. Moreover, RIO may combine atoms in Z to form a ring.

-C Formula (D) will be explained in detail.

In the formula, R1° and Z may have a substituent.

Examples of the alkyl group for R7° include a methyl group, ethyl group, isobutyl group, and dodecyl group; examples of the alkenyl group include a vinyl group, ■-propenyl group, and l-octenyl group; Examples of the aryl group include ethynyl group, l-propynyl group, l-octenyl group, etc., cycloalkyl group includes cyclopropyl group, cyclopentyl group, nclohexyl group, etc., and aryl group includes phenyl group, naphthyl group, etc. mentioned,
Examples of the aralkyl group include a hensyl group and a phenethyl group, and examples of the heterocyclic group include a 2-pyridyl group and a 4-
Examples include piperidyl group, 2-furyl group, furfuryl group, and the like.

Further, Y is a general organic or inorganic anion, such as a halogen anion such as a chlorine ion, an organic anion such as a paratoluenesulfonate anion, and a perchlorate anion.

In addition, Z is a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom,
A ring consisting of a hydrogen atom, which may be substituted with a substituent or fused with another ring, such as a pyridinium ring, an imidazolium ring,
Quinolinium ring, oxacillium salt, thiazolium ring,
Examples include benzimidazolium ring. When R1° and Z have a substituent, it represents a synonym of the substituent of R1.

Preferably, R1° is a substituted or unsubstituted alkyl group, aralkyl group, or cycloalkyl group, respectively, and Z is a substituted or unsubstituted 5- or 6-membered ring consisting of a carbon atom, a sulfur atom, a hydrogen atom, or a nitrogen atom. and other rings may be fused.

More preferably, Rlo is a substituted or =W-substituted alkyl group having up to 10 carbon atoms, and Z is an imidazolium ring, a henzimidazolium ring, or a pyridinium ring.

Next, specific examples of the compound of formula (A) used in the present invention will be shown, but the present invention is not limited thereto.

-5 -1 -2 -9 -12 -13 -17 -19 Js -16 -8 -22 23 4 5 6 7 8 υ(L; HzJ4Sυ1 υ(Lllt) Go>u, Bt -34 5 C1+□ CHCl1zCHO CHICHC)IzCHO -36 7- 9 0 1 -29 0 1 2 3 ,N(lkono3 I'35U 2 -43 4 -45 -46 -47 :liU3Na Next, the general formula used in the present invention (B) compound of A specific example is shown below. The present invention is limited to these It's not a thing.

N Next, the general formula used in the present invention () A specific example is shown below. The present invention is limited to these It's not a thing.

0 Next, the general formula used in the present invention () A specific example is shown below. The present invention is limited to these It's not a thing.

1 2 -13 4 II -15 -16 CI+3 D-4 C,)I.

-8 -9 -5 CIIzC)lzcIIzclhsOJ-6- 7 C, +1 5 IIF. ○ C, II.

Many of these compounds are commercially available and can be used as is. In addition, other compounds can be synthesized using known organic chemical reactions.
For example, to compound example-15, A-I LA-27 is “
Organic Synthesis
hesee) J- CollecLiveνoluI
IIc 1109 pages, Journal of the Chemical Society 4 (J.Chem.Soc.) 3 8 4
2 (1954) Journal on American Chemical Society (J.8-, Che
m. Soc. ) -7ーー〇−, 1557 (1
It can be synthesized according to the method described in 945).

In addition, compound example B-6 “Organic Relaxations (
Organic reactions) J Volume 16 1~
It can be synthesized according to the method described on page 438 (1968).

Moreover, compound examples C-1 to C-6 are S. R. Sandra
and enemy. Caro (S.R.Sardler; W. ar
o) Author: “Organic Functional Group
Preparations (Organic Parctin)
al graupPreparations) J 2nd
It can be synthesized according to the method described in ed., Vol. 2, pp. 291-322 (1986).

Moreover, compounds D-9 to D-14 are S. R. Sandra and d. Karo (S.R.Sardler; W.Karo)
Author: “Organic FarcLinal Groups”
aup Preparations) J Volume 3, 20
It can be synthesized according to the method described on pages 5-240 (1972).

Examples of compositions having fixing ability include fixing compositions (for example, fixing solutions), bleach-fixing compositions (for example, bleach-fixing solutions), and the like.

These compounds may be added to the bleach-fixer or fixer separately from the bisulfite or sulfite, or -M
The compounds of formulas (A) to (D) may be added in the form of adducts.

When compounds of general formulas (A) to (D) form adducts with bisulfite, the concentration of free bisulfite ions becomes low, making them less susceptible to oxidation and improving the stability of the processing solution. Conceivable.

The bleach-fixing solution or fixing solution of the present invention has general formulas (A) to (
When adding the compound D), -II(A) to (D)
The molar ratio of the compound and bisulfite or sulfite is 3
Can be used at 0:1-1:30, 5:1-1:
The ratio is preferably 10, particularly preferably 1:1 to 1:5. Further, the amount of the compound of general formulas (A) to (D) added to the bleach-fix solution or fixer of the present invention is from 1 to 1 mol of IXIO-' per 11 of the bleach-fix solution or fixer.
It can be used at 0 mol/Il, preferably from ■×10-3 mol/l to 5 mol/l, particularly 1×10-2 mol/l.
1-1 mol/I! It is preferable that

As the bleaching agent used in the bleaching solution and/or bleach-fixing solution, ferric complex salts of aminopolycarboxylic acids, peroxides (for example, persulfate), etc. can be used, but the following general substances (III) can be used. It is preferable to use an aminopolycarboxylic acid represented by:

General formula (III)
eRffl, old, representing W denoted by C11-.

Rzt, Rii, and R34 each represent a hydrogen atom or an alkyl group, but R31 and R3! or R'l and R
o may be linked to each other to form a cycloalkylene ring; l, m, and n each represent an integer of 0 to 4; a represents an integer of 1 to 3; k, 7! , m, and n are 2 or more.

General formula (I[I) will be explained in more detail.

In general formula ([11), Ll is preferably an oxygen atom, a sulfur atom, or an alkylene group having 6 or less carbon atoms, but in the case of an alkylene group, a methylene group, an ethylene group, a propylene group, or a butylene group is particularly preferable. R11, R3! , R31c
Regarding Rffl, a hydrogen atom and an alkyl group having 6 or less carbon atoms are preferable, but in the case of an alkyl group, particularly a methyl group,
Ethyl group, n-propyl group and 1so-propyl group are preferred.

In addition, a is 1, and R31, Rffl, R33, Rff
l is each a hydrogen atom, and the total of l, m, and n is 2
It is preferred that the bleaching rate is less than 100%, as this allows the bleaching rate to be optimized.

Specific examples of the aminopolycarboxylic acid compound represented by the -C formula (III) are shown below, but the invention is not limited thereto.

α-1: 1.3-diaminopropanetetraacetic acid α-2 nigericol ether diamine tetraacetic acid α-3 dichlorohexanediaminetetraacetic acid α-4: 1.4-diaminobutanetetraacetic acid α-5: 1.2- Propylene diamine tetraacetic acid α-6: Thioglycol ether diamine tetraacetic acid α-7: 1,3-
Butylenediaminetetraacetic acid α-8; ethylenediaminetetraacetic acid The amount of the bleaching agent of the present invention added is 0.05 mol to 1 mol, preferably 0.1 mol to 0.5 mol, per 12 of the bleach solution or bleach-fix solution. . Further, the above-mentioned ferric aminopolycarboxylic acid complex salt and ferric ethylenediaminetetraacetic acid complex salt can be used in combination as a bleaching agent. In this case, the mixing ratio of the two is preferably 1:1 O-toot, and the total concentration of the iron complex salts of the two is the treatment liquid lI! , 0.05 mol to 1 mol, preferably 0.1 to 0.5 mol.

In addition to the above-mentioned 18 iron aminopolycarboxylic acids (Ill), an aminopolycarboxylic acid or a salt thereof can be added to the bleaching solution and/or bleach-fixing solution of the invention.

The preferable addition amount is o, oooi mol to 0.1 mol/l,
More preferably, it is 0.003 to 0.05 mol/l.

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

Further, the bleach solution and/or bleach-fix solution containing the above-mentioned ferric complex salt may contain complex salts of metal ions other than iron, such as cobalt and copper.

Examples of thiosulfates that can be used in the present invention include ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, calcium thiosulfate, and magnesium thiosulfate, which have good solubility and the highest fixing speed. Ammonium thiosulfate is preferable, and the amount of thiosulfate added is 0.1 mol/2 to 3 mol/I! , and preferably 0°3 mol/l-2 mol/l.

In addition to the above-mentioned thiosulfates, thiocyanic acid compounds (especially ammonium salts), thioureas, thioethers, ureas, etc. can be used as fixing agents or fixing accelerators in the bleach-fixing solution and/or fixing solution of the present invention. The concentration of these auxiliary fixing agents or fixing accelerators, together with the thiosulfate, is 1.

11 to 3.0 mol/l, preferably 1. 4-2
, 8 mol/l.

Various bleach accelerators can be added to the bleach solution and/or bleach-fix solution of the present invention.

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
．． 812 specification, British Patent No. 1138 842 specification, JP-A-53-95 (i30), Research Disclosure No. 17129 (July 1978 issue) Compounds having a mercapto group or nosulfide group , thiazurinone derivatives described in JP-A No. 50-140129, thiourea derivatives described in U.S. Pat. No. 3,706.561, iodides described in JP-A-58-16235, German Patent No. Polyethylene oxides described in specification No. 2,748.430, Japanese Patent Publication No. 1974-
Polyamine compounds described in Japanese Patent No. 8836 can be used. Particularly preferred is British Patent No. 1.138.
Mercapto compounds such as those described in '842 are preferred.

The amount of bleaching accelerator added is O per liquid having bleaching ability,
01 g to 20 g, preferably 0.1 g to 10 g.

In addition to bleaching agents and the above-mentioned compounds, the bleaching solution and/or bleach-fixing solution constituting the present invention may contain bromides such as potassium bromide, sodium bromide, ammonium bromide or chlorides such as potassium chloride, sodium chloride, Rehalogenating agents such as ammonium chloride can be included. The concentration of the rehalogenating agent is between 0.1 and 5 moles, preferably between 0.5 and 3 moles per 11 parts of the bleaching solution. 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 F4 acid, citric acid, sodium citrate, tartaric acid, etc. pHI! Known additives that can be used in conventional bleaching solutions, such as one or more types of non-I acids, IR acids, and salts thereof, having an oxidation capacity can be added.

The bleach-fix solution and/or fix solution of the present invention may contain sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, hydroxylamine, hydrazine, and the like. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, methanol, and other 81 solvents can be contained, but in particular, as preservatives, patent application No. 60-2838
It is preferable to use the sulfinic acid compounds described in No. 31.

Further, for the purpose of stabilizing the liquid, it is preferable to add various aminopolycarboxylic acids and organic phosphon taM.

Particularly effective is 1-hydroxyethylidene-1,1-diphosphonic acid. The amount of these additions is 0.01 to 0.
．． 3 morph g, preferably 0.05 to 0.2 mol/l, and is particularly effective in fixers.

The pH of the bleaching solution and/or bleach-fixing solution of the present invention is generally 9 to 1, preferably 7.5 to 1.5, and most preferably 7.0 to 2.0.

For bleaching solutions, 5.0 to 2.0 is particularly preferred.

In a preferred pH range, there is little bleaching fog (and
It also has excellent desilvering performance.

The pH of the fixer of the present invention is generally 9.0 to 5.0, particularly preferably 7.5 to 5.5.

The amount of replenishment of the bleaching solution and/or bleach-fixing solution of the present invention is 50d to 3000-preferably 1 per r41 rrl of photosensitive material.
00- to 1000-.

The amount of fixer replenishment is preferably from 300 to 3000, more preferably from 300 to 1000, per 1 d of toe material.

However, the above-mentioned replenishment amount can be reduced to a smaller amount if, for example, a regeneration treatment is performed, such as oxidation regeneration of the processing solution and silver recovery treatment.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

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

B-IN, N-diethyl-p-phenylenediamine B-22-amino-5-diethylaminotoluene 8-32-amino-5-(N-ethyl-N-laurylamino)toluene θ-44-(N-ethyl- N-(β-hydroxyethyl)aminocoaniline 2-methyl-4-[N-ethyl-N- (β-hydroxyethyl)aminocoaniline 4-amino-3-methyl-N-ethyl-N-(β- (methanesulfonamide)ethylcouaniline B-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide B-8N, N-dimethyl-p-phenylenediamine 4-amino-3-methyl-N-ethyl- N-methoxy'diethylaniline θ-104-amino-3-methyl-N-ethyl--6 -9 -5 N-β-ethoxyethylaniline B-114-amino-3-/thi-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compounds 8-2, θ-4, B-5 and 8-6 are particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. Preferably about 0.1g to about 20g
, more preferably at a concentration of about 0.5 g to Log.

In addition, the color developer contains sodium sulfite, potassium sulfite, sodium bisulfite, and bisulfite P-rl as preservatives.
Sulfites such as i-potassium, sodium metasulfite, potassium metasulfite, and the carbonyl compound sulfite adduct of the present invention can be added as necessary.

The preferable addition amount is 0.5 g to 1.0 g per 11 color developing solutions.
0g, more preferably 1g to 5g.

In addition, as compounds that directly preserve the color developing agent, various hydroxylamines, Japanese Patent Application No. 61-18655
Described in No. 9 (DhiYo-+SuLfaB, 61-1707
Hydrazines described in No. 56, hydrazines, No. 61-
Phenols described in No. 188742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61
It is preferable to add various tIMs described in Japanese Patent Application No. 180616, and in combination with the above compounds.
No. 823, No. 61-166674, No. 61-1656
No. 21, No. 61-164515, No. 61-17078
No. 9, monoamines described in No. 61-168159, etc., No. 61-173595, No. 61-164515
Diamines described in No. 61-186560, polyamines described in No. 61-165621 and No. 61-169789, polyamines described in No. 61-188619, nitroxy as described in No. 61-197760. Radicals, No. 61-186561, and No. 61-197
Alcohols described in No. 419, No. 61-18874 i
! It is preferable to use II oximes and tertiary amines described in No. 61-265149.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
Polyethyleneimines described in No. 349, U.S. Patent No. 3,
The aromatic polyhydroxy compound described in No. 746.544 may be included if necessary, and addition of an aromatic polyhydroxy compound is particularly preferred.

The color developer used in the present invention preferably has a pH of 9
-12, more preferably 9-11.0, and the color developer may contain other known developer component compounds.

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

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, O-
Sodium hydroxybenzoate (sodium satylylate), potassium O-hydroxybenzoate, 5-sulfo-2
-Hydroxyamne, sodium -fragrant (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like can be mentioned. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferable that the amount is more than 0.1 mol/1 to 0.1 mol/1.
Particularly preferred is 4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer.

As the chelating agent, acid compounds are preferred, such as aminopolycarbonate aJ, 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, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1, 2,4-
) Ricarboxylic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, N,N"-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid, and two or more of these chelating agents may be used in combination as necessary.

The amount of these chelating agents added may be sufficient as long as the amount is sufficient to sequester metal ions in the color developer. For example, 11
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, formulation properties, and prevention of color staining. Here, "substantially" means 2. - Hereinafter, it means preferably not containing at all.

Other development accelerators include Japanese Patent Publications No. 37-16088, No. 37-5987, No. 38-7826, No. 44-
No. 12380, No. 45-9019 and U.S. Patent Series 3,
813,247, etc., p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-Sho 44-30074, JP-A-56-156826 and JP-A No. 52-43429,
Quaternary ammonium salts represented by U.S. patent system 2.
No. 494,903, No. 3,128゜182, No. 4,2
No. 30,796, No. 3,253.919, Special Publication No. 1977
-11431, U.S. Patent No. 2.482,546, 2. 596. 926 and 3,582.346, etc., Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, U.S. Patent No. 3,128,18
No. 3, Special Publication No. 41-11431, No. 42-23883
and U.S. Patent No. 3,532.501, and other l-phenyl-3-
Pyrazolidones, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added according to a. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and nucleating antifoggants can be used. Examples of antifoggants include benzotriazole, 6-
Nidropenzimitazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-
Representative examples include nitrogen-containing heterocyclic compounds such as thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

A fluorescent brightener may be added to the color developer used in the present invention. As the fluorescent brightener, 4゜4゛-diamino-2,2゛-disulfostilbene type compounds are preferred. , the amount added is O~Sg/l, preferably 0.1g~4g/l
It is.

Further, various surfactants such as alkylsulfonic acid, ary-phosphonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added as necessary.

The processing temperature of the color developer of the present invention is 20 to 50°C, preferably 30 to 40°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. It is preferable to replenish a small amount, but the amount of toe material is not enough. 100 to 1500 d per unit, preferably 100 to 800 d, more preferably 100
-~400-.

Further, the color developing bath may be divided into two or more baths 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 is commonly known as the black and white first developer used for the reversal processing of color photographic light-sensitive materials, or Those used for processing black and white angry light materials can be used. In addition, various well-known additives that are generally added to black and white developers can be included.

Typical additives include: -Developing agents such as -phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate and potassium carbonate;
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzothiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. I can give it to you.

The processing steps for the silver halide color light-sensitive material of the present invention will be explained.

After exposure, the color photosensitive material of the present invention is subjected to a color development process, a desilvering process, and a water washing process.

As the desilvering step, instead of the bleaching step using a bleaching solution and the processing step using a fixing solution, a bleach-fixing step may be performed using a bleach-fixing solution, or a bleaching step, a fixing step, The bleach-fixing treatment steps may be combined arbitrarily.

Examples of the desilvering step of the present invention include, but are not limited to, the following steps.

■ Bleach-fix ■ Bleach-bleach-fix ■ Bleach-bleach-fix ■ Bleach-Water wash constant-fix ■ Bleach-fix constant ■ Bleach-fix ■ Bleach-fix-bleach fix The color photosensitive material of the present invention is subjected to bleaching treatment or bleaching treatment after color development. Bleach-fixing processing is performed, but these processings may be performed immediately without going through the color development recovery process, or
In order to prevent unnecessary post-development and air fog, and to eliminate color developer from being carried into the derailment process, it is also impregnated into sensitive material components such as aggravating pigments and dyes contained in photographic toe materials and photographic window light materials. In order to wash out the color developing agent and render it harmless, the color developing agent may be subjected to processing steps such as stopping, adjusting, and washing with water, and then subjected to a bleaching treatment or a bleach-fixing treatment.

If necessary, a stabilization treatment step may be performed after the water washing step, or a stabilization treatment step may be performed instead of the water washing step.In combination with these treatment steps, a pre-hardening treatment step, A neutralization process, a stop-fixing process, etc. may be performed.
A washing step and a rinsing step may be optionally provided between these steps.

In addition, as for the replenishment method for the detining process mentioned above, it is normal to replenish each treatment bath with the corresponding replenisher and dispose of the overflow liquid as waste. For example, the overflow of the washing water or stabilizing bath may be introduced into the fixing bath or the bleach-fixing bath. can.

Regarding the total time of the desilvering step of the present invention, the effects of the water-sprinkling invention can be significantly obtained. The preferred time is 1 minute to 10 minutes, more preferably 1 minute to 6 minutes. In addition, the processing temperature is 25℃ ~
The temperature is 50°C, preferably 35°C to 45°C. In a preferred temperature range, the derailment speed is improved and the occurrence of staining after treatment 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 disclosed in JP-A-62-18346.
No. 0, No. 62-183461, U.S. Patent No. 4,758
, 858, a method of impinging a jet of processing liquid on the emulsion surface of the toe material, a method of increasing the stirring effect using a rotating means of JP-A No. 62-183461, and a method of increasing the stirring effect by using a rotating means of JP-A-62-183461. Examples of methods include a method of improving the stirring effect by moving the tip material without bringing the wiper blade into contact with the emulsion surface to create turbulence on the emulsion surface, and a method of increasing the circulation flow rate of the entire processing solution. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of the bleaching net and fixing agent into the emulsion film, resulting in an increase in the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the acceleration results and eliminate the fixing inhibiting effect caused by the bleach accelerator.

The automatic developing machine used in the present invention is JP-A-60-191
No. 257, No. 60-191258, No. 60-1912
No. 59, Re5earch DisclosureIt
e■ Case 29118 (July 1988), U.S. Pat. No. 4,758,858.
As described in No. 1257, such a conveying means can significantly reduce the carrying of the processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of the performance of the processing liquid.The means described in the above RD is also preferable. This effect is particularly effective in shortening the processing time in each process and reducing the amount of processing solution replenishment.These methods of improving agitation are also effective in addition to the desilvering process, and are useful in the washing process and developing process. It is desirable to shorten the processing time and reduce the amount of replenishment.

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

Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. A simple treatment method can also be used.

The rinsing water used in the rinsing process may contain known additives as required. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid;
It is possible to use disinfectants and antifungal agents to prevent the growth of various bacteria and algae (e.g., isothiazolone, organochlorine disinfectants, benzotriazole, etc.), surfactants to prevent dry load and unevenness, etc. . Or L, E
Jeit.

Flater Quality Cr1teria'',
Phot, Sci, and Eng.

vol, 9, N16. Pages 344-359 (
Compounds described in 1965) and the like can also be used.

As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, gel tar aldehyde), etc. Can be used. Formalin is undesirable from a pollution standpoint, and the stabilizing liquid may contain ammonium compounds, metal compounds such as Bi, At, etc. as necessary.
Optical brighteners, chelating agents (e.g. EDTA 1-hydroxyethylidene-1,1-diphosphonic acid), rice-killing agents, anti-fungal agents, 11! Film agents, surfactants, etc. can be used. As fungicides, thiazolone compounds such as 5-chloro-2-methyl-isothiazolin-3-one and 1°2-benzisothiaprin-3-one are effective.

Further, as the surfactant, a silicone compound represented by the following general formula is preferable because it has an effect of preventing water droplet unevenness and defoaming.

Here, a, b, d, and e are integers of 5 to 30, C is an integer of 2 to 5, or R is an alkyl group having 3 to 6 carbon atoms.

In addition, the stabilizing solution also contains thio[
The use of alkanolamines is described in US Pat. No. 4,786,583, where the addition of alkanolamines is preferred to prevent sulfidation of one ion.

Also, formalin is used as a stabilizing liquid when fishing on a boat, but
It is preferable not to use it in the present invention.

The pH of the stabilizer of the present invention is 3-8, preferably 5-7.

The temperature of the stabilizing liquid is preferably 5°C to 45°C, more preferably 10°C to 40°C.

In addition, the water washing step and the stabilization step are preferably carried out in a multi-stage countercurrent system, and the number of stages is preferably 2 to 4. Two or more types of stabilizing solutions may be used in multiple stages, and the replenishment amount is from the pre-bath per unit area. The amount is 1 to 50 times, preferably 2 to 30 times, and more preferably 2 to 15 times the amount brought in.

The effect of the water-sprinkling invention is that the processing time of the water-washing and stabilization steps is short, and from the viewpoint of rapid processing, the total processing time of the water-washing and stabilization steps is preferably 10 to 50 seconds, and the effect is particularly remarkable when the processing time is 10 to 30 seconds.

In addition, the amount of replenishment in water washing and stabilization steps is small, and the effect of the water washing invention is large, so that the amount is preferably 50 to 400, particularly preferably 50 to 200, per 1 rrr of the photosensitive material.

In addition to tap water, the water used in these washing steps or stabilization steps is
It is preferable to use water that has been deionized to have a Mg concentration of 5 .mu./E or less, water that has been sterilized with halogen, ultraviolet sterilization lamps, or the like.

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

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

It is preferable that the silver halide color photographic light-sensitive material of the present invention contains at least one magenta coupler represented by the following general formula (1) or (II). It is possible to greatly reduce stain, especially magenta stain and yellow stain.

x (wherein, Ro represents a carbonamide group, anilino group, or ureido group, R11 represents a phenyl group, and X represents a group that can be supereliminated by a camping reaction with an oxidized aromatic primary amine developer.) / / / / / General formula (n) (In the formula, RlI represents a hydrogen atom or a single substituent, and X8 is a hydrogen atom or a group that can be separated by a camping reaction with an oxidized aromatic primary amine developer. Za, Z
b and Zc are methine, substituted methine, -N- or -N
Represents H-; 7. One of the a-zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. ) Next, general formula (1) will be explained in detail. In the formula, Ro represents a carbonamide group, anilino group or ureido group, R12 represents a phenyl group, and X+ represents a combination with an oxidized aromatic primary amine developer. Represents a group that can leave by campling reaction (hereinafter referred to as a leaving group).

xl is an active carbon and aliphatic group, aromatic group, heterocyclic group, aliphatic/aromatic or heterocyclic sulfonyl group, aliphatic/aromatic or A group that binds a heterocyclic carbonyl group, a carbamoyl group, an alkoxycarbonyl group and a monoyloxycarbonyl group, a halogen atom,
Aliphatic, aromatic or heterocyclic groups, RII and F2+z contained in eXl, such as aromatic azo groups and heterocyclic groups, may be further substituted, such as halogen atoms (e.g. fluorine atoms, chlorine atoms, bromine atom), alkyl groups (e.g. methyl, t-octyl, dodecyl, trifluoromethyl), alkenyl groups (e.g. allyl, octadecenyl), aryl groups (e.g. phenyl, p-tolyl,
naphthyl), alkoxy groups (e.g. methoxy, benzyloxy, methoxyethoxy), aryloxy groups (e.g. phenoxy, 2,4-di-tert-amylphenoxy, 3-tart-butyl-4-hydroxyphenoxy), acyl groups (e.g. acetyl, benzoyl), sulfonyl groups (e.g. methanesulfonyl, toluenesulfonyl), carboxy groups, sulfo groups, cyano groups, hydroxy groups, amino groups (e.g. amino, dimethylamino), carbonamide groups (e.g. acetamide, trifluoroacetamide). , tetradecanamide, benzamide), sulfonamide groups (e.g. methanesulfonamide, hexadecanesulfonamide, p-toluenesulfonamide),
Acyloxy groups (e.g. acetoxy), sulfonyloxy groups (e.g. methanesulfonyloxy), alkoxycarbonyl groups (e.g. dodecyloxycarbonyl), carbonyl groups (e.g. phenoxycarbonyl), carbamoyl groups (e.g. dimethylcarbamoyl, tetradecylcarbamoyl). ), sulfamoyl groups (e.g. methylsulfamoyl, hexadecylsulfamoyl)
, imido groups (e.g. succinimide, phthalimide, octadecenylsuccinimide), heterocyclic groups (2-pyridyl, 2-furyl, 2-thienyl), alkylthio groups (e.g. methylthio), arylthio groups (e.g. phenylthio). Can be done.

Specific examples of Xl include halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), alkoxy groups (e.g. benzyloxy), aryloxy groups (e.g. 4-chlorophenoxy, 4-methoxyphenoxy), acyloxy groups ( (e.g. acetoxy, tetrazocallyoxy, benzoyloxy), arylamido groups, aliphatic or aromatic sulfonyloxy groups (e.g. methanesulfonyloxy, toluenesulfonyloxy), carbonamide groups (
(e.g. dichloroacetamide group, trifluoroacetamide), aliphatic or aromatic sulfonamide groups (e.g. methanesulfonamide, p-)luenesulfonamide), alkoxycarponyloquine groups (e.g. ethoxycarbonyloxy, benzyloxycarbonyloxy),
Aryloxycarbonyloxy groups (e.g. phenoxycarbonyloxy), aliphatic/aromatic or heterocyclic thio groups (e.g. ethylthio, hexadecylthio, 4-dodecylphenylthio, pyridylthio), ureido groups (e.g. methylureido, phenylureido), 5-membered or a 6-membered nitrogen-containing heterocyclic group (e.g. imidazolyl, pyrazolyl, triazolyl, tetrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide group (e.g. succinimide, phthalimide, hydantoinyl), aromatic azo group (for example, phenylazo), etc. Furthermore, there are so-called bis-type couplers obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom.

Any one of Ro, R11, or Polymeric couplers may also be formed.

General formula [! ] Compound examples, synthesis methods, etc. of the compound represented by the formula are described in, for example, JP-A No. 1-111631 and JP-A No. 1-111631, No. 54-4854.
0, 55-62454, 55-118034, 5
6-38043, 56-80045, 56-126
833, 57-4044, 57-35858, 5
No. 7-94752, No. 5B-17440, No. 5B-5
No. 0537, No. 58-85432, No. 58-1175
No. 46, No. 58-126530, No. 58-14594
No. 4, No. 5B-205151, Special Publication No. 54-170, No. 54-10491, No. 5421258, No. 53
-46452, 53-46453, 57-36
No. 577, Japanese Patent Application No. 58-110596, No. 5B-13
No. 2134, No. 59-26729, U.S. Patent No. 3,22
No. 7,554, No. 3,432,521, No. 4,310
No. 618, No. 4,351,897, WOlo 47
It is described in the specification of No. 95, etc.

In the present invention, among the 5-pyrazolone 2-equivalent magenta couplers represented by the general formula (1), those in which the leaving group is via an ionic atom and those that leave an azole compound are preferred, and those that leave an azole compound are particularly preferred. .

Next, the magenta coupler represented by the general formula (■) of the present invention will be explained.

-a In the formula (■), R□ represents a hydrogen atom or a substituent, and X□ represents a hydrogen atom or a group that can be separated by a campling reaction with an oxidized aromatic primary amine developer *Za, Zb and Zc is methine, substituted methine, -
Represents N- or -NH-, and combines Za-Zb bond and Zb-
One of the Zc bonds is a double bond and the other is a single bond.

When Zb-Zc is a carbon/-carbon double bond, including the case where it is part of an aromatic ring, further R, or X! So 2
ZasZ
When b or Zc is a substituted methine, it also includes the case where the substituted methine forms a dimer or more multimer.

Substituents for RlI include halogen atoms, alkyl groups,
Aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group , carbamoylamino group, furkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonylamino 7 group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, 7-syl group,
Examples include a sulfamoyl group, a sulfinyl group, an alkoxycarbonyl group, and a 7-aryloxycarbonyl group.

X represents a hydrogen atom, a halogen atom, a carboxy group, or a group that is bonded to a carbon at the campsite position via an oxygen atom, an i-atomic atom, or a sulfur atom and undergoes cambling separation.

In the general formula (n), the multimer means one having two or more groups represented by the general formula (n) in one molecule, and includes bis forms and polymer couplers. Here, the polymer coupler is a monomer having a moiety represented by general formula (n) (preferably one having a vinyl group,
A homopolymer consisting only of vinyl monomer (hereinafter referred to as vinyl monomer) may be used, or a copolymer may be prepared together with a non-color-forming ethylene ladder monomer that does not couple with the oxidation product of the aromatic-grade amine developing straw.

The compound represented by the general formula (n) is a 5-membered ring-5-membered ring fused nitrogen heterocyclic coupler, and its chromogenic nucleus exhibits isoelectronic aromaticity with naphthalene, and is usually collectively referred to as azapentalene. It has a chemical structure. Among couplers represented by general formula (n), preferred compounds are IH-imidazo(1,2-b)pyrazoles, IH-pyrazolo(1,2-b)
5-b) Pyrazole, IH-pyrazolo (5,1-c)
(1,2,4)) Riazole, IH-pyrazolo (1,
5-b)(1,2,4)) liazoles, IH-pyrazolo(1,5-d)tetrazoles and IH-pyrazolo(1,5-a)benzimidazoles, each having the general formula (I[ a) CIlb) (III c) (I[
d) Represented by (II a) and (Iff). Among these, particularly preferred compounds are (■a), (Ilc
) and (Ild).

(f[a) (IIb) (IIc) (Ild) CIIe) (III) Substituents R1, RlJ of general formulas (Ua) to (■[),
R14 and Ro are synonymous with RlI, and Xll is synonymous with x8. The case where RxiSR*s, Rza, R3, or XZ+ becomes a divalent group and forms a bis body is also included. Moreover, when the moiety represented by the general formula Cma) to (rlf) is present in the vinyl monomer, Ro, R1! Or R14 represents a simple bond or a linking group, via which the general formula (
The moieties represented by R1) to (■[) and the vinyl group are bonded.

More specifically, R1beRyuki8, Ro, Ro and R□ are hydrogen atoms, halogen atoms (e.g. chlorine, bromine), alkyl15 (e.g. methyl, propyl, i-propyl,
t-butyl, trifluoromethyl, tridecyl, 3-
(2,4-di-t-amylphenoxy)propyl, 2-
dodecyloxyethyl, 3-phenoxypropyl, 2-
hexylsulfonyl-ethyl, cyclopentyl, benzyl), aryl groups (e.g. phenyl, 4-t-butylphenyl, 2,4-di-t-amyl phenyl, 4-tetradecanamidophenyl), heterocyclic groups (e.g. 2 −
furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), alkoxy groups (e.g., methoxy, ethoxy, 2-methoxyethoxy, 2-dodecyloxyethoxy, 2-phenoxyethoxy, 2-methanesulfonylethoxy), ryoloxy groups (e.g. phenoxy,
2-methylphenoxy, 4-t-butylphenoxy),
Heterocyclic oxy groups (e.g., 2-benzimidazolyloxy), 7-syloxy groups (e.g., acetoxy, hexadecanoyloxy), carbamoyloxy groups (e.g.,
N-phenylcarbamoyloxy, N-ethylcarbamoyloxy), silyloxy groups (e.g. trimethylsilyloxy), sulfonyloxy groups (e.g. dodecylsulfonyloxy), acylamino groups (e.g. acetamide, benzamide, tetradecaneamide, α-(2
, 4-di-t-amylphenoxy)butyramide, γ-
(3-t-butyl-4-hydroxyphenoxy)butyramide, α-(4-(4-hydroxyphenylsulfonyl)phenoxy)decaneamide), anilino groups (e.g., phenylamino, 2-chloroanilino, 2-chloro-
5-tetradecanamide anilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5-(α-(3-1-butyl-4-hydroxyphenoxy)dodecanamide)anilino ), ureido groups (e.g. phenylureido, N-butyl-N
゛-methylureido, methylureido, N,N-dibutylureido), imide groups (e.g., N-succinimide, 3-penzylhydantoinyl, 4-(2-ethylhexanoylamino)phthalimide), sulfamoylamino groups (e.g., N,N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino)
, carbamoylamino groups (e.g. carbamoylamino, N,N-dimethylcarbamoylamino), alkylthio groups (e.g. methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-(4-t -butylphenoxy)propylthio), arylthio groups (e.g. phenylthio, 2
-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio,
4-tetradecanamidophenylthio), heterocyclic thio groups (e.g. 2-benzothiazolylthio), alkoxycarbonylamino groups (e.g. methoxycarbonylamino, tetradecyloxycarbonylamino), aryloxycarbonylamino groups (e.g. phenoxy carbonylamino, 2,4-tar t-butylphenoxycarbonylamino), sulfonamide groups (e.g. methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-)luenesulfonamide,
Octadecanesulfonamide, 2-methyloxy-5-
t-butyl bezizenesulfonamide), carbamoyl groups (e.g., N-ethylcarbamoyl, N,N-dibutylcarbamoyl, N-(2-dodecyloxyethyl)carbamoyl, N-methyl-N-dodecylcarbamoyl,
N-(3-(2°4-di-tert-amylphenoxy)propyl)carbamoyl), acyl 15 (e.g. acetyl, (2,4-di-tert-amylphenoxy)
acetyl, benzoyl), sulfamoyl group (e.g.
N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-(2-dodecyloxyethyl)sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N
, N-diethylsulfamoyl), sulfinyl groups (e.g., octanesulfinyl, dodecylsulfinyl,
phenylsulfinyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, butyloxycarbonyl,
(dodecyloxycarbonyl, octadecyloxycarbonyl), aryloxycarbonyl group (eg, phenyloxycarbonyl, 3-pentadecyl phenyloxy-carbonyl).

X! (X□) is a hydrogen atom, a halogen atom (for example,
chlorine, bromine, iodine), a carboxyl group, or a group linked by an oxygen atom (e.g., acetoxy, propanoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, bilbinyloxy, cinnamoyloxy, Phenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2
-phenethyloxy, 2-phenoxyethoxy, 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), groups linked via a nitrogen atom (e.g., benzenesulfonamide, N-ethyltoluenesulfonamide, heptafluorobutanamide) , 2,3.4.5,6.-pentafluorobenzamide, octanesulfonamide, p-
Cyanophenylureido, N,N-diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl-2,
4-dioxo-3-oxazolidinyl, 1-benzyl-
Ethoxy-3-hydantoinyl, 2N-1,1-dioxo-3(2H)-oxo-1,2-benzisothiazolyl, 2-oxo-1,2-dihydro-1-pyridinyl,
imidazolyl, pyrazolyl, 3,5-diethyl-1゜2
．． 4-triazol-1-yl, 5- or 6-furomobenzotriazol-1-yl, 5-methyl-1,2
, 3,4-triazol-1-yl, benzimidazolyl, 3-benzyl-1-hydantoynyl, 1-benzyl-5-hexadecyloxy-3-hydantoytriyl, 5-
methyl-1-tetrazolyl, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), groups linked via a sulfur atom (e.g., phenylthio, 2-carboxyphenylthio, 2-butoxy-5-, t-octylphenylthio, 4-methanesulfonamidophenylthio, 2,5-
dibutoxyphenylthio, 4-methanesulfonylphetrithio, 4-octanesulfonamidophenylthio, 2
-butoxyphenylthio, 4-dodecyloxyphenylthio, 2-(2-hexanesulfonylethyl)-5-t
ert-octylphenylthio, benzylthio, 2-cyanoethylthio, l-ethoxycarbonyltridecylthio, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolylthio, 2-dodecylthio, 2-
dodecylthio-5-thiophenylthio, 2-phenyl-
3-dodecyl-1゜2.4-)riazolyl-5-thio)
Preferably, the halogen atom or leaving group is via an oxygen or sulfur atom.

R1 Rf! , Ro, R14, Ro or X! (X□)
When becomes a divalent group to form a bis body, the divalent group can be described in more detail as a substituted or unsubstituted alkylene group (e.g., methylene, ethylene, 1.10-decylene, -CHz CHx -0-CH* CHz -), a substituted or unsubstituted phenylene group (for example, 1,4-phenylene, 1,3-7 enylene, or an unsubstituted alkylene group or phenylene group), etc. .

R1, Ro, Rta or R when the compound represented by general formulas (na) to (ff f) is present in the vinyl monomer
The linking group represented by □ is an alkylene group (e.g., methylene, ethylene, 1.10-decylene, -CHgCHz
OCHtCHz-), phenylene group (e.g. 1,4
-phenylene, 1,3-phenylene, -NHCO--CONH--0--0CO- and aralkylene aft (for example, N HCO-R* h -CON H- group (Rzi is a combination of substituted or Including groups that hold true.

The vinyl group in the vinyl monomer has the general formula (Ha)
Preferred substituents, including those having substituents other than those represented by (■f), are hydrogen atoms, chlorine atoms,
Or it is a lower alkyl group having 1 to 4 carbon atoms.

Acrylic acid, α
-chloroacrylic acid, α-alacrylic acid (e.g., methacrylic acid) and esters or amides derived from these acrylic acids (e.g., acrylic acid, lylamido, n-butylacrylamide, t-butylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, t-
butyl acrylate, iso-butyl acrylate,
11-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxy methacrylate), methylene dibis acrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate) and vinyl urarate), acrylonitrile, methacrylatetrile, aromatic vinyl compounds (e.g. styrene and its u-form, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid,
Crotonic acid, vinylidenk.

Examples include loride, vinylfurkyl ether (eg, vinyl ethyl ether), maleic acid, maleic anhydride, maleic ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. It also includes the case where two or more of the non-color-forming ethylene-like undiagnosed monomers used herein are used in one boar.

Compound examples and synthesis methods of couplers represented by the above general formulas (Ha) to CII r) are described in the documents listed below.

The compound of general formula (Ha) is disclosed in JP-A No. 59-162548.
The compound of general formula (nb) is disclosed in Japanese Patent Application Laid-open No. 1986-4.
3659, etc., the compound of general formula (Ilc) is described in Japanese Patent Publication No. 47-27411, etc., and the compound of general formula (Ild) is described in Japanese Patent Publication No. 59-171956 and Japanese Patent Publication No. 60-1729.
No. 82, etc., the compound of general formula (■e) is disclosed in JP-A-60-
No. 33552, etc., and the compound of general formula (Ilf) is
The synthesis methods are also described in US Pat. No. 3,061,432 and the like.

Also, JP-A-58-42045, JP-A No. 59-21485
The highly color-forming ballast group described in No. 4, No. 59-177553, No. 59177544, No. 59-177557, etc. is applicable to any of the compounds of the above general formulas (Ila) to (nr). .

-C type [! ], (If) specific examples of couplers are listed below.

(I-1) (l CI-3) (I-’+) (I-5) CHl I CI(.

As the magenta coupler of the present invention, it is preferable to use a colorless magenta coupler that is mainly contained in the emulsion layer.So-called colored couplers are colored and cannot be added in large quantities, so the effects of the present invention will not be significant. As the group, a 7-ionic leaving group is preferable, and among colorless magenta couplers, the leaving group inhibits development,
A photographically inert leaving group that does not have the effect of accelerating development or accelerating bleaching is most effective in the present invention.

Two or more types of magenta couplers of the present invention can be contained in the same layer. The same compound may be contained in two or more different layers.

The magenta coupler of the present invention is generally 1M1 in the emulsion layer.
It is added from 2X10-' moles to 5X10-' moles, preferably from 1X10-' moles to 5X10-' moles, per mole. When used in combination, it is preferable that the total amount added falls within the above range. .

In order to introduce the above-mentioned couplers into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2,322.027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate,
triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), etc., or with a boiling point of about 30°C to 1°C
Organic solvents at 50°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl fropionate,
Secondary butyl alcohol, methyl isobutyl ketone, β-
After being dissolved in ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above high boiling point f! A mixture of a l solvent and a low boiling point m solvent may be used.

For details of these 8g solvents with high boiling points, please refer to JP-A-6
2-215272 Publication Specification, page 137, bottom right corner ~1
Other types of high-boiling organic solvents that can be effectively used in the couplers of the present invention described in the upper right column of page 44 include N,N-dialkylaniline derivatives. Among these, those in which an alkoxy group is bonded to the ortho position of the IN,N-dialkylamino group are preferred, and specific examples include the following compounds.

This type of high boiling point solvent is useful to prevent the formation of magentastin over time on the white background of color prints during processing, and also to prevent fog during development. The amount used is generally 10 mol% to 500 mol%, preferably 20 mol% to 300 mol%, per coupler.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a polymer (for example, US Pat. No. 4,203,716) or by dissolving it in a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. WO3B100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

Also, Japanese Patent Publication No. 51-39853, Japanese Patent Publication No. 5159943
It is also possible to use the dispersion method using polymers described in No.

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

Any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide may be used as the silver halide contained in the photographic emulsion layer of the photographic photosensitive material used in the present invention. can.

Silver halide grains in photographic emulsions include those that have regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those that have regular crystal shapes such as spherical and plate shapes, and those that have 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 microns or less or large grains with a projected area diameter of up to 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), Volume 17643.
(December 1978), pp. 22-23, “!, Emulsion ρreparation andt
ypes)”, and 1Ikl+8716 (19
(November 1979).

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 Gutoff, Photographic Science and Engineering.
nce and en! 1neeriB), Volume 14,
pp. 248-257 (1970); U.S. Patent System 4, 43
4゜226, 4,414. '310, 4,43
3.048, 4,439.520 and British Patent No. 2.112.157.

The crystal structure may be similar, or the inside and outside may have different halide compositions (it may have a layered structure, or silver halides with different compositions may be bonded together by epitaxial bonding). Alternatively, it may be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

A mixture of grains of various crystal forms may also be used.Silver halide emulsions that have been subjected to physical ripening, chemical ripening and spectral sensitization are usually used. Additives used in such processes are described in Research Disclosure 17643 and Kaimagne 18716, and the relevant sections 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.

Additive type 1i RD17643 RD187
161 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity increasing agents Same as above 4 Whitening agents Page 24 Right column 8 Dye image stabilizers Page 25 91i! Ill agent page 26 page 651 left column 10 binder page 26 same as above 11 plasticizer, lubricant page 27 page 650 right column mild color couplers can be used in the present invention,
A specific example of this is the aforementioned Research Disclosure (R
D) It is described in the patent described in Ih17643, ■-〇-G.

As a yellow coupler, for example, US patent series 3.93
．． 3.501, 4.022.620, 4.
．． No. 326.024, No. 4.401゜752, Japanese Patent Publication No. 58-10739, British Patent System No. 1.425,020
No. 1. 476, 760, etc. are preferred.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Patent No. 4°052.212.
No. 4.146.396, No. 4.228.23
No. 3, No. 4.296,200, No. 2,369.92
No. 9, No. 2,801゜171, No. 2,772.16
No. 2, No. 2゜895.826, No. 3,772.0
No. 02, No. 3,758.308, No. 4. 334
．． No. 011, No. 4.327,173, West German Patent Publication No. 3,329.729, European Patent No. 121°365
A, U.S. Patent No. 3,446,622, U.S. Patent No. 4,33
No. 3,999, No. 4.451,559, No. 4.4
27,767, European Patent No. 161.626A, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure-17643.
- Section G, U.S. Patent No. 4.163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4. 138. No. 258, British Patent No. 1,146,
The one described in No. 368 is preferred.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2.125.
．． Preferred are those described in German Patent No. 570, European Patent No. 96,570, and German Patent Publication No. 1 3,234,533.

Typical examples of polymerized dye-forming couplers are disclosed in U.S. Pat. No. 3,451,820, 4. o80.211, 4.367.282, British Patent No. 2,102,1
It is described in No. 73, etc.

Couplers that release photographically useful residues upon camping are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 60-184248
Preferred are those described in U.S. Pat. No. 4,248,962.

Couplers that release a nucleating agent or a development accelerator in an imagewise manner during development include - British Patent No. 2. o97.140, No. 2,131,188, JP-A-59-15763
No. 8 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include the competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , long equivalent couplers described in JP-A No. 4,310,618, etc., DIR redofuchs compound-releasing couplers described in JP-A-60-185950, etc., and dyes that fade after separation described in European Patent No. 173.302A. Examples include couplers that emit light.

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 US Pat. No. 2,322;027 and the like.

There is also a method of using a polymer as a coupler dispersion medium, as described in Japanese Patent Publication No. 48-30494 and U.S. Patent No. 3,619.
No. 195, West German Patent No. 1,957゜467, Special Publication No. 1973
There are various descriptions in No.-39835.

The steps and effects of latex dispersion methods, and specific examples of latex for impregnation, can be found in U.S. Pat. It is written in the number etc.

As a statinic prevention agent, especially the patent application No. 60-2490
21, 61-32462, the fluorine-containing surfactant or polymer described in JP-A-60-76742, JP-A-60-80846, JP-A-60-80848, JP-A-6σ-
No. 80839, No. 60-76741, No. 58-208
No. 743, Japanese Patent Application No. 61-13398, No. 61-160
56, M61-32462, etc., or JP-A-57-20
Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in No. 4540 and Japanese Patent Application No. 61-32462 can be preferably used. Among them, JP 44-16238, JP 50-5467
No. 2, No. 54-1398, U.S. Patent No. 4,118.2
No. 31, No. 3.988.158, Patent Application 1982-130
No. 841, No. 53-140100, No. 53-1416
Cationic latex polymers described in No. 11, No. 53-14086, No. 53-17130, etc. are preferred.
Inorganic antistatic agents include ammonium, alkali metal, alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, acetates, phosphorus rJ salts, thio/anate salts, etc. Preferably, conductive tin oxide, zinc oxide, or a composite oxide prepared by doping antimony or the like into these metal oxides described in JP-A-57-118242 and the like can be used. Furthermore, various ffl cargo transfer complexes, π-conjugated polymers and their doped materials, organometallic compounds, intercalation compounds, etc. can also be used as antistatic agents, such as TCNQ/T.
Examples include TF, polyacetylene, and polypyrrole. These are Morita et al., Science and Industry 5'' ■3), 103-III (
19, 85), 1i (4), 146-152 (198
5).

In the present invention, fluorine-containing compounds and silicon-containing compounds can also be used as antistatic, antiadhesive, slippery or coating aids to improve the properties of the sensitive material. These fluorine-containing compounds and silicon-containing compounds may be either low-molecular compounds or high-molecular compounds.For example, known compounds including those described in JP-A-62-215272 may be used depending on the purpose. Can be applied.

Polymers can also be used in the present invention. The polymer can also be used as a polymer latex. In the present invention, the polymer is useful for exhibiting the following functions.

・In gelatin Improves dimensional stability and flexibility, and lowers Fg friction resistance.

Reduces the tendency of dispersed materials to aggregate due to metal salts.

・Reduces static electricity by increasing conductivity.

・Accelerate drying speed.

e Prevention of destruction of color material layer ・Improve the thermal strength of photographic paper.

・Improves the coating protection power of dispersed materials.

- Speed up development.

・Eliminates high temperature fog.

・Increase color density.

・Reduces numbness.

A patent with such a description is, for example, Japanese Patent Application Laid-open No. 6221521.
Examples include those described in No. 2, and other known polymers can be used depending on the purpose.

In the present invention, it is also possible to use improving agents related to coating properties and physical properties of the film, such as surfactants, slippers, thickeners, antistatic agents, and matting agents. As these compounds, any of the known compounds including those described in JP-A No. 62-215272 may be used depending on the purpose.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, page 28 of 17643, and 6 of 18716
It is described from the right column on page 47 to the left column on page 648.

The present invention can be applied to various color photosensitive materials. Color photosensitive materials described in JP-A-64-59351 and JP-A-63-129341 may also be used.

In the photographic 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, and the film swelling rate TI/Y is preferably 30 seconds or less.
The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate T1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr) by Green et al.

Sci,! ! ng, ), Volume 19, No. 2, 124-12
It can be measured by using a swellometer (swelling membrane) of the type described on page 9, and the TI/! The saturated film thickness is defined as 90% of the maximum swelling film thickness reached when the color photosensitive material is treated with a color developing solution at 30°C for 3 minutes and 15 seconds, and 1 of this saturated film thickness is
It is defined as the time required to reach a film thickness of /2.

The film swelling rate T1/: can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions of the coating solution. Further, the swelling rate is preferably 150 to 400%.

The swelling rate is calculated from the maximum swollen film thickness under the conditions described above, using the formula: (maximum swollen film thickness - film thickness)/II! It can be calculated according to the thickness.

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

Example 1 The back layer was undercoated with a dispersion of silica and methyl methacrylate/dodecyl methacrylate copolymer using cellulose diacetate and a low boiling point organic solvent. On the cellulose triacetate film support produced by the production method,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/n of silver for silver halide and colloidal silver, and the amount expressed in g/% for coupler additives and gelatin, and the amount expressed in g/n of silver for silver halide and colloidal silver. For dyes, the number of moles is expressed per mole of silver halide in the same layer.The symbols indicating additives have the meanings shown below.However, if the additive has an effect of 31, one of them. Posted on behalf of.

UV, ultraviolet absorber, 5olvH high boiling point 8!1 solvent,
ExF: Dye, ExSH thickening dye, ExC: Cyan coupler, ExM *Magenta coupler ExY: Yellow coupler, Cpd: Additive split tube 11 (Haley silane prevention layer) Black colloid! ]! 0.15 gelatin 2.9tJV-10,
03 UV-20,06 UV-30,07 Solv-20,08 ExF-10,01 ExF-20,01 2nd layer (low pestilence red sensitivity emulsion) Silver iodobromide emulsion (Ag14 mol%, uniformly Agl Type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles,
Diameter/thickness ratio 3.0) Coated silver amount 0.4 Gelatin 0.8ExS-12
,3X10-'ExS-21,4xlO-'ExS-52,3X10-'ExS-78,0XIO-' ExC-30,13 3rd layer (mid-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag16 mol% , internal Agl type with core-shell ratio 2:l, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/W-view ratio 2.o) Coated silver amount 0.65 Iodor Silveride emulsion (Ag14-T″le% average-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/thickness ratio 3.0) Coated silver amount 0.1 Gelatin i.

xS-I xS-2 xS-5 xS-7 2X10-'1.2X10-' 2 X 10-'7X10-' ExC-30,06 Fourth layer (high sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion ( Ag 16 mol%, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μm, coefficient of variation of 1 sphere equivalent diameter 25%, plate-shaped particles, diameter/thickness ratio 2.5) Coated silver amount 0.9 0. 8 1, 6X10-'1.6X10-'1.6X10-'6X10-' 0,07 0.05 Gelatin xS-I xS-2 xS-5 xS-7 ExC-I ExC-4 5olv-10,07 Solv -20,20 Cpd-74,6xlO-' 5th N (middle layer) Gelatin 0.6UV-40,
03 UV-50,04 Cpd-10,,1 Polyethyl acrylate latex o, o13Solv-
10,05 6th layer (low pestilence) 3 emulsion N) Silver iodobromide emulsion (Ag 14 mol%, uniform-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like grains,
Diameter/rg ratio 2.0)! ! ! ! Silkworm amount 0.18 Gelatin 0.4ExS-32
X10-'ExS-47xio-' ExS-51xlO°4 xM-5 xM-7 xY-8 3o1v I Solv-4 7th layer (mid-sensitivity green emulsion layer) Iodobromide 1! Emulsion (Ag 14 mol%, core shell ratio 1:1
Surface cavity Agl type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 4.0) Coating dose 0, 27 0.6 2 X 1 0-' 7X10- ' 1 x 10°4 0, 17 0, 04 0, 02 0, 21 0, 02 Gelatin xS-3 xS-4 xS-5 xM-5 xM-7 xY-8 Solv-I Solv-4 8th layer ( High-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 18.7 mol%, silver ratio 3:4:2
Multi-layer structured particles, Agl content from inside to 24 mol, 0 mol, 3 mol%, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 1.6) Coated silver Amount 0.7 0.8 5.2X10-'lXl0-'0.3X10"' 0.1 0, 03 0, 02 0, 02 0, 01 0, 25 0, 06 0, 01 1 Gelatin xS-4 xS-5 xS-8 xM-5 xM-6 xY-8 xC-I xC-4 o1v-I Solv-'I Solv-4 pd-7 9th layer (middle layer) Gelatin 0.6Cpd- 10
,04 Polyethyl acrylate latex 0.12Solv-1
0,02 101st! (Donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag 16 mol%, internal high Agl type with core-shell ratio 2:1, equivalent sphere diameter 0.7 μm, coefficient of variation of 1 sphere equivalent diameter 25%, plate-like grains) , diameter/W-view ratio 2.0) Coated silver amount 0.68 Silver iodobromide emulsion (AgI 4 mol%, uniform-Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of one sphere equivalent diameter 37%, plate-like grains ,
Diameter/thickness ratio 3.0)! ! ! ! City bank amount 0.19 Gelatin 1.0ExS-35
xto-' ExM-100,19 Solv-10,20 No. 11N (Yellow Filter F Yellow Colloidal Silver 0,06 Gelatin 0.8Cpd-20,13 Solv-10,13 Cpd-10,07 Cpd-60,002 H -10,13 12th N (low pestilence vestibule emulsion layer) Silver iodobromide emulsion (Ag 14.5 mol%, homogeneous gI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like Grains, diameter/thickness ratio 7.0) Coated silver amount 0.3° Silver iodobromide emulsion (13 mol % of silver, uniform GL type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 30%, plate-like particles,
Diameter/thickness ratio 7.0) Coated silver it O,15 Gelatin 1.8ExS-69
xio-' ExC-10,06 xC-4 0,03 xY-9 0,14 13th layer (middle F gelatin 0,7EXY-12
0,20 Solv-10,34 No. 14N (highly blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag 110 mol%, internal high Agl type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, multiple Twin platelet particles, diameter/thickness ratio 2.0) Coated silver amount 0.5 Gelatin 0.5E
xS-6txto-' EXY-90,01 olv-1 0,12 15th layer (first protective layer) Fine grain silver iodobromide hole side (Ag 12 mol%, homogeneous Agl type,
Equivalent sphere diameter 0.07μm) Coated silver amount 0.12 Gelatin 0.9UV-40,
11 UV-50,16 Solv-50,02 H-10,13 Cpd-50,10' Polyethyl acrylate latex 0.09 16th layer (
2nd protective layer) Fine-grain silver iodobromide emulsion (Ag 12 mol%, uniform-Agl type,
Equivalent sphere diameter: 0.07 μm) Coated silver amount: 0.36 Gelatin 0.55 Polymethyl methacrylate particles (diameter: 1.5 μm) 0.2H-10・
17 In addition to the above components, each layer contains emulsion stabilizer Cpd-3.
(0,07g/m), surfactant cpd-4 (0,0
3 g/n() was added as a coating aid.

V-1 H (t)cei.

V-2 H (t) CeL V-3 H (t)Celt UV-4 ExF-1 x:y-70:30 (Kat%) UV-S ExF-2 0IV-1 tricresyl phosphate olv-2 dibutyl phthalate 0IV-4 olv-5 trihexyl phosphate xS-1 xS-5 xS-6 xS-7 xS-4 88N〉-...j-...(;force., N(C,)IS).

(CHz)ssOJ-N(CJs)s ExC-1 ExC-2 xM-5 xM-6 H H CHl ExC-3 H ExC-4 H (i)COH,0CONH OCHzGHzSCI(xco□H xM-7 1 xM-10 ExY-9 ExY-11 pd pd ■ 6H1ff pd-2 Hff ExY 2 xC ExY-14 r ρ pd-5 pd-5 pd-3 pd-4 ■ CIl□=Cl-5o□-〇1b-CONH -CHHzC
H! Next, as sample 102, the magenta coupler ExM-5 of the present invention used in the 6.7.8 and 10th layers was compared with the structural formula shown below. Equimolar li (Ex
A sample was prepared in the same manner without making any changes except for replacing (calculated based on the molecular weight converted to a unit containing one molecule of pyrazolone core of M-5).

Comparative Magenta Coupler (1) These prepared samples 101 and 102 were cut and processed into 35 mm width, one sample remained unexposed, and the other sample f4 gave a gray density of 2.0. Exposure was given at a light exposure amount of tA as shown above, and processing was carried out in an amount of 1:1 using a Cinebu automatic developing machine according to the processing steps and processing solution composition shown below. However, the samples to be evaluated for performance were subjected to imagewise exposure until the cumulative replenishment amount of the color developing solution reached three times the volume of the mother solution tank, and then the samples were processed.

Processing process Processing time Processing temperature Replenishment amount 9 Color development 3 minutes 15 seconds 37.8°C2M! Bleach 40 seconds 38.0'C5InfI.

Fixation 1 minute 30 seconds 38.0℃ 3
011 Water washing (1130 seconds 38.0°C Water washing (2) 30 seconds 38.0°C stable 30 seconds 38.0'C drying 1
Minutes 55°C° The replenishment amount is the amount per 1 meter length in 35 ml.Water washing is from (2) to (1) for the self-flow method, the amount of developer carried into the bleaching process, and the fixer washing process -1 The amount of carry-on is 2.5-12.5 mm per 1 meter length of photosensitive material with a width of 35 mm. It was Od.

0Id Tank capacity 01 2 107! 2 1 2 0d Further, the crossover time is 5 seconds in each case, and this time is included in the processing time of the previous step.

The contact area between the treatment liquid and air in each treatment tank was 500 cm''.

The composition of the treatment liquid is shown below.

(Color developer) Mother solution (g) Replenisher (
6) Diethylenetriamine 1.0 1.1 Pentaacetic acid 1-hydroxyethyrythene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 30.0 Potassium bromide
1.4 Potassium iodide 1.5■Hydroxylamine sulfate 2.4 3.64-[N
-ethyl-N β-hydroxyethylamino]-2- methylaniline sulfate 4.5
6.4 Water woka t-c x, op
1. opp H10,0510,10 (bleaching solution) 1.3-diaminopropanetetraacetic acid ferric ammonium hydrate (1,3-DPTA-Fe (■)) 1.3-diaminopropanetetraacetic acid ammonium bromide ammonium nitrate Acetic acid (98%) Add water and pH (adjust with ammonia water (27%)) Mother liquor (g) Replenisher solution (□□□ 144.0 2.8 84.0 90.0 63.0 1, Ol 4. 0 206.0 4.0 120.0 125.0 90.0 1.0! 3.2 (Fixer) Common to mother liquor and replenisher (g) Ethylenediaminetetraacetic acid diammonium salt 1,7 Preservative
See Table 1 ammonium thiosulfate water + 8 liquids (700g/f) 340. Add 0 ml of water to pH 7.0 (Washing water) Mother liquor, replenisher common tap water to II pear type strong acid cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type strong base anion exchange resin. Resin (Amberlite I RA)
Water was passed through a mixed bed column packed with sodium isocyanurate dichloride 20 to reduce the concentration of calcium and magfucilam ions to 3 mg/ffi or less.
mg/p and 150 mg//2 of sodium quartzite were added.

The pH of this liquid was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 1.2m Surfactant 0. 4(C+ oHz I
-0+ CI (zcHzO-+-r-?rIt) Ethylene glycol 1.0 Add water
1.01 pH 5.0 to 7.0 Next, the bleaching solution was changed to the bleaching solution composition shown below, the processing temperature was 38°C, the processing time was 40 seconds, and the amount of replenisher was 25 all.
/35 am width and 1 m length, and the fixing treatment after bleaching was carried out in the same manner as before, and other treatments were carried out in the same manner as above.

(Comparative bleaching solution (1)) Mother liquor (g) Replenisher solution ((to) Sodium ferric ethylenediaminetetraacetic acid trihydrate (EDT^・Fe(I[l)) 100.0
! 20.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 Ammonium bromide 140.0 160.0 Ammonium nitrate 30.0 35.0 Aqueous ammonia (27%) 6.5 m 4.0 Add aqueous solution 1. Of 1. Of H 6,05,7 was investigated.

These results are shown in Table 1.

The processed samples thus obtained were uniformly exposed to light so that the gray density was 2.0°, and the amount of silver remaining in the sensitive material after processing was determined by fluorescent X-ray method. On the other hand, the treated unexposed sample was stored under the conditions of high temperature and high humidity shown below, and the staining (increase in density when measured with blue light) that occurred was examined.

Storage conditions = 60°C, 170% RH, 135 days The evaluation of the stain was shown as the difference (ΔD and ΔDG) between the density under blue light measured before storage under the above conditions and the density under blue and green light measured after storage. .

ΔD, = (Concentration of blue light after storage) - (Concentration of blue light before storage) △DG = (Concentration of green light after storage) - (Concentration of green light before storage) Also, fixing solution, water washing Presence of precipitation in the fixing solution and stabilizing solution As is clear from Table 1, when the compound of the present invention is used in the fixing solution, no precipitation occurs in the processing solution after the fixing solution, and the stability of the solution is improved. I was able to improve my skills. Although the compound of the present invention was used in the fixing solution, the stability of the subsequent washing solution and stabilizing solution was also improved.

The cause is thought to be components brought in from the fixer. Furthermore, compared to conventionally known acetaldehyde bisulfite adducts (described in JP-A No. 48-42733, for example), the image storage stability of the processed sample could be improved. The compounds of the present invention can improve the stability of liquids over time compared to acetaldehyde bisulfite adducts, but this is because acetaldehyde decreases due to oxidative deterioration, evaporation, etc. This is thought to be because the preservative itself has excellent stability without being affected by Also, 2 equivalent magenta force puller ExM
-5, a preferable result was obtained in which the image storage stability was further improved.Example 2 Magenta coupler ExM-5 was added to the 2-equivalent magenta coupler of the present invention with equimolar il (ExM-5
A sample was prepared in the same manner without making any changes except that the molecular weight was calculated based on the molecular weight converted to a constituent unit containing one molecule of pyrazolone core. The two-equivalent magenta couplers of the present invention used are shown in Table 2-1.

Next, a sample was prepared in exactly the same manner as above using a coupler having the structural formula shown below as a comparative coupler.

Comparative magenta coupler (2) C1 Comparative magenta coupler (3) Comparative magenta coupler (4) All of these prepared samples were cut and processed within 35 seconds.
One group of these samples was left unexposed, and the other group of samples was given n) 11: by changing the light intensity of 6 to m so as to give a gray density of 2.0 degrees. Continuous treatment was carried out according to the treatment steps of Ha 3 and Ha 5. Regarding the obtained sample, the density change (ΔD,) of the yellow image of the processed sample was examined in the same manner as in Example 1. The results obtained are shown in Table 2.

As shown in Table 2, when treated with a fixer containing the compound of the present invention, conventionally known acetaldehyde (for example, JP-A-48-4273
44) have shown favorable results in that yellow images have superior storage stability compared to those described in No. 3), and particularly when processed with light-sensitive materials containing 2-equivalent magenta couplers (1), the image storage properties are even better. Excellent quality, yellow stain (△D
A more favorable result with lower I) was obtained.

Example 3 According to the processing steps of Example 1, Ntll, the preservative of the fixer was changed as shown in Table 3, and J! Further treatments were performed, and the formation of precipitates or turbidity in each of the fixing, washing, and stabilizing treatment tanks was investigated. The results are shown in Table 3.

As shown in Table 3, when treated with a fixing solution containing each preservative of the present invention, conventional sodium sulfite, acetaldehyde bisulfite (e.g., JP-A-48-427
33), the stability of the processing solution after the fixing solution over time is improved, especially for the exemplified compound A-1-A-
The compounds represented by 15 and D2 to D-6 further include -
It was found that the layer liquid has excellent stability over time. The problem with stability over time, in which precipitates form in the liquid after the fixer, arises because of the constant M brought in from the fixer tank during the processing process.
This is thought to be caused by deterioration of the liquid over time.

Example 4 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support which was laminated on both sides with polyethylene and coated with colloidal glue and colloidal alumina on the back side. The coating solution was prepared as follows.

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and color image stabilizer (Cpd-7)
) to 0.7 g, 27.2 cc of ethyl acetate and solvent (So
lv-3) 8.2g was added and dissolved, and this solution was mixed with 10% sodium dodecylhenzenesulfonate containing 8cc.
% gelatin aqueous solution (185 cc). On the other hand, S11 mol of the blue-sensitive sensitizing dye shown below was added to a block silver bromide emulsion (cubic average grain size 0.88μ, grain size distribution coefficient of variation 0.08, containing 0.2 mol% silver bromide on the grain surface). A sulfur sensitized product was prepared by adding 2.0×10 −′ moles per sample, respectively. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first layer coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-5-) riazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer and 03-5OJ-N (CJs)! (Halogenated!! Each 2゜OX 10-' mole per mole) Green-sensitive emulsion layer SO2- 5OJ4 (CJs)s (7.0X10-s mole per mole of silver halide) Red-sensitive emulsion layer C, lIs I - J11 (Halogenated!!0.9X10""mol per mol)
For the red-sensitive emulsion layer, the following compounds are halogenated.
2.6×10 −3 moles were added per mole of barb.

(Halogenation!!! 4°OX 10-' mole per mole) 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer. Each is halogenated! ! 8.5 x 10-' mol per 1-vol, 7.7XIO-' mol, 2. 5 x 10-':el was added.

The following dyes were added to the emulsion layer to prevent irradiation.

So, K SO2 and (layer structure) The composition of each layer is shown below, the number is the coating amount (g/r+?)
The silver halide emulsion that represents 1! Represents the converted coating amount.

Support polyethylene Z-laminated paper [The polyethylene on the first layer side contains a white pigment (Tilt) and a bluish dye (ulmarine)] -th layer (blue-sensitive layer) Silver chlorobromide hole side (the hole side > -0 ,30 Gelatin 1.86 Yellow coupler (ExY) 0.82 Color image stabilization (Cp
d-1) 0.19 solvent (Solv-3)
0.35 color image stabilizer (Cpd-7)
0.06 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-
1) 0.16 solvent (Solv-4)
0.08 third J! (Green layer) Chlorobromide emulsion (1=3 mixture (Ag mole ratio) of one with a cubic average particle size of 0.55μ and one with a cubic average particle size of 0.39μ) 0
Coefficient of variation of particle size distribution 0.10.0.08 each, Ag
0.12 Gelatin 1924 magenta coupler (Ex M) Color image stabilizer (Cpd-3) Color image stabilizer jFI (Cpd ~ 8) Color image stabilizer ( Cpd-9) Solvent (SOIV-2) 0, 2 doo 0, l 5 0, 02 0, 03 0, 46 4th F! (Ultraviolet absorbing layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (Cp
d-5) 0.05 solvent (Solv-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (1=4 mixture of cubic average grain size 0.58μ and 0.45μ (Ag molar ratio) 0 Coefficient of variation of grain size distribution, each 0.09.0.11, AgB
r0.6 mol% was locally contained in a part of the particle surface)0
．． 23 1.34 0.32 0.17 0.04 0.40 0.15 Gelatin cyan coupler (Ex C) Color image stabilizer (Cpd-6) Color image stabilizer (Cpd-1σ) Color image stabilizer ( Cpd-7) Solvent (SOIV-6) Sixth layer (ultraviolet absorption layer) Gelatin 0, 53 Ultraviolet absorber (UV-1) Color mixing inhibitor (Cpd-5) Solvent (Solv-5) Seventh layer (protective layer) ) Acrylic modified copolymer of gelatin polyvinyl alcohol (degree of modification 17%) Liquid paraffin Ol 0゜0゜1゜0゜0゜ (ExY) Yellow coupler 6 8 3 7 3 (Ex M) Magenta coupler (Ex C ) Cyan coupler 1 R '' C z H s C. H9 H l mixture of 2=4:4 by weight (Cpd-1) Color image stabilizer ((pd-6) Color image stabilizer H cJ*(D (Cpd-3) Color image stabilizer H CeL(t) H (Cpd-5) Color mixture inhibitor H 2; 4; 4 mixture (weight ratio) (Cpd-7) Color image stabilizer (UV-1) Ultraviolet light Absorbent ÷ CH!-CH-)-.

H CONHC, H*(t) average molecular weight 60° 00 CJ++(t) (Cpd-8) color image stabilizer 01( Rai, (t) H (Cpd-9) color image stabilizer cen, (t) 4:2:4 mixture (weight ratio) of (Cpd-IQ) Color image stabilizer (Solv-1) fIi medium H (S.

1v-23 2:1 mixture of solvents (volume ratio) (Solv-3) Solvent 0-P÷OC,H+*(igo))s(Solv-4
) Solvent (S.

■-5) Solvent COOC*Hlff ■ (CHt)* Gi COOC＊　Hr　t magenta coupler Color image stabilizer (Cpd 11) Solvent (S.

IV-7) J.S. O=P +0CHtCHCaHq ).

(S.

IV-6) solvent The prepared sample is referred to as sample 601.

Next, a sample was prepared by changing the third layer (green-sensitive layer) as shown below and leaving the other layers unchanged. This will be referred to as sample 602.

Third layer (green feel N) Coating amount (g/rr Silver chlorobromide emulsion (same as the third layer of sample 601) 0.18 Gelatin 1.24 Magenta coupler 0, 32 Color image stabilizer (Cpd-3) ) 0.09 Color image stabilizer (Cpd-11) 0.06 Solvent (Solv
-7) 0.30 solvent (Solv-8)
0.17 Solvent (SolV-8) The sample 401 prepared above was cut and processed, subjected to imagewise exposure, and then refilled in an amount three times the tank capacity for color development in the following processing step using a paper processing machine. After continuous processing (running test) was performed until the color density reached 2.0, some of the samples remained unexposed, and the other sample had a gray density of 2. The exposure amount was adjusted so that the exposure amount was 0, and the sample was processed with uniform exposure.

Preparation process I cliff 1°? 1 color development 38℃ 45 seconds 109d 17f
fi bleach fixing 35℃ 45 seconds 30d 17ff
i-rinse ■ 35℃ 30 seconds -10ffi
Rinse ■ 35°C 30 seconds -10ffi Rinse ■ 35°C 30 seconds 364d lON drying 80'C 60 seconds
21m) will be replenished.

3-tank counter-current method for umbrella rinse ■-・■ The contact area between the air and the treatment liquid in each treatment tank is 1700 rr? Met.

The composition of each treatment liquid is as follows.

Shooting::Development i +ymu ecstasy 1
m water 800m1
800ml Ethylenediamine-N NNN-tetramethylenephosphonic acid 3.0g 3.0g Triethanolamine 5.0g 5.0
g Potassium chloride 3.1 g Potassium bromide 0.015 g Potassium carbonate 25 g 25 g Hydrazinoniacetic acid 5.0 g 7.0 gN-
Ethyl-N-(β-methanesulfonamidoethyl)-3 Methyl-4-aminoaniline sulfate Fluorescent brightener (5.0g ITEX4 5.0g Add water 1.0 QOOd pH (Add potassium hydroxide) 1Q , 05 1 engineering 1 shiken Kotsukami water
60〇-Ammonium thiosulfate solution H (700g/l) 100d preservative (
Table 4) 0.2t$ ammonium sulfite
0.2u Ethylenediaminetetraacetic acid iron ([11) ammonium 55g Ethylenediaminetetraacetic acid 3.0g Ammonium bromide 30g 9.5g 2.5 00M 10.60 Kannomei 50d 45I11 0.5u 095 mole 35g 8.0g 5g Add water 1000d 1000
idp H5,505,20 - history ≦ 1 moxibustion (tank solution and replenisher are the same) ion exchange water (calcium, magnesium each 3 pρ - or less) Next, add the carbonyl compound bisulfite adduct of the present invention to the bleach-fix solution. Treatments were carried out using various compounds as shown in Table 6 so that the concentration was 0.4 mol/2.

Among the processed samples, those that were exposed to light to obtain a gray density of 2.0 were quantified by fluorescent X-ray method to determine the amount of silver remaining on the photosensitive material after processing, and were also bleach-fixed. The formation of precipitates in the bleach-fix solution and the washing solution was investigated.
[1] The same treatment was performed in place of ammonium. The results obtained are shown in Table 4.

As shown in Table 4, the compounds of the present invention are also effective when used as preservatives in bleach-fix solutions, as well as conventional ammonium sulfite and acetaldehyde (e.g., JP-A No. 48-42
733), it was possible to improve the retention of processing solutions after the bleach-fix solution.

In particular, when 1,3-propanediaminetetraacetic acid ferric complex salt is used as a bleaching agent, the stability over time of the processing solution after the bleach-fix solution deteriorates significantly. It was possible to improve the stability of the solution, and it was possible to achieve both rapid desilvering performance and stability of the solution.

In addition, similarly to Example 3, exemplary compounds A-1 to A of the present invention
-15 and compounds D-3 and D-4 gave particularly good results with excellent liquid stability.

Example 5 Paper support laminated on both sides with polyethylene (thickness 10
A color photographic material (sample F4501) was prepared by coating the next 4th layer of strategist on the front side of 0 micron) and the 5th layer of strategist to 6th layer of strategist on the back side. The polyethylene on the coating side of the first layer contains titanium oxide as a white pigment and a trace amount of ultramarine as a bluish dye (the chromaticity of the surface of the support is 880, -0 in I, 'a'', b' systems). .20, -〇, 7
It was 5. ).

(Photosensitive layer composition) Ingredients and coating below! +i'Jl (g/+d jp position) is shown. For silver halide, the amount of fabric in terms of silver is not shown.

The emulsions used in each layer were made by following the manufacturing method of emulsion EMI. However, the emulsions for the first to fourth layers were Lippmann emulsions that do not cause surface character enhancement.

1st layer (anti-Halley 797 layer) 11! Color code [Id silver 0.1
0 gelatin 0.70 second layer (
middle layer) Gelatin 0.70 3rd layer (
Low-grade red-light layer) Bromide spectrally sensitized with red sensitizing dyes (ExS-1, 2, 3)! ! (Average particle size 0.25μ, size distribution [coefficient of variation] 8%, octahedral) 0,04 Chlorobromide i! spectrally sensitized with red enhancing dyes (ExS-1, 2, 3)! (Silver chloride 5 mol%, average grain size 0.4
0 μ, size distribution 10%, octahedral),
0.08 gelatin
1.00 cyan coupler (ExC-12 1:1) 0
．． 30 Anti-fading agent (Cpd-1'<2.3.4 equivalents) 0.18 Anti-stinting agent (CPd-5) 0.003 Power puller dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1 . Distribution 15%
, octahedron) 0.14 gelatin
1.00 cyan coupler (ExC-1,2 to 1
:l) 0, 30 Antifading agent (Cpd-1, 2, 3, 4 equivalents) 0, 18 Coupler dispersion medium (Cpd-6) 0.03 Cuffler solvent (SQIV-1, 2, 3 equivalents) 0 , 12 Fifth layer (middle layer) Gelatin 1. OO color mixing inhibitor (Cpd-7>0.08 color mixing inhibitor solvent (S
olV-4,5 equivalent) 0,16 Polymer latex (Cbd-8) 0.10 No. 67i (
Silver bromide spectrally sensitized with a green enhancing dye (ExS-4)
Average particle size 0.25μ, size distribution 8%, octahedral)
-0,04 Silver chlorobromide (silver chloride 5 mol%, average grain size 0.40 μ, size distribution 10%, octahedral) spectrally sensitized with a green brightening dye (ExS-4) 0,06 Gelatin 0・ 80 magenta coupler (EXM-1, 2, 3 equivalent) 0, 10 Anti-fading agent (equal amount of Cpd-9, 26) 0, 15 Anti-stain agent (equal amount of Cpd-10, 11, 12, 13)
0 near:7:1 ratio) 0.025 force puller dispersion medium%
Cpd-, 6) 0.05, l'J 7" la-t
8 medium (Solv-4, 6 equivalent) 0, 15 7th layer (high-range green sensitive layer) Silver bromide (spectral sensitized with green sensitizing dye (EXS-t)
Average particle size 0.65μ, size distribution 16%, octahedral) 0.10 gelatin
0.80 magenta coupler (ExM-1, 2, 3
Equivalent amount) 0, 10 Anti-fading agent (Cpd-9,266 equivalent amount 0, 15 Anti-stain agent (Cpd-10, 11, 12, 13 in l)
(at a 7:1 ratio) 0. (125 force puller dispersion medium (Cpd-6) 0.05 coupler solvent (Sol
v-4,6 equivalent) 0° 8th layer (intermediate layer) 9th layer (yellow filter layer) same as the 5th layer Yellow colloidal silver gelatin Color mixing prevention agent (Cpd-7) Color mixing prevention side solvent (Solv-4 , Polymer latex 0, 12 0, 07 0, 03 5 etc. 1E) 0.10 0, 07 10th layer (intermediate layer) 5th J! Same as (Cpd-8) 11th N (low sensitivity front window layer) Silver bromide spectrally sensitized with blue sensitizing dye (EXS-5, 6) (average grain size 0.40μ, size distribution 89A, octahedral ) 0.07 blue enhancement dye (ExS-5
, 6) spectrally sensitized with chlorobromide 5FA (chloride 118 mol%, average particle size 0.60μ, size distribution 119A,
Octahedron) 0.14 Gelatin 0.80 Yellow coupler (ExY-1,2 equivalent) 0.35 Anti-fade agent (Cpd-14) 0.10 Anti-stain agent (Cpd-5,15 in a 1:5 ratio) )
0.007 force puller dispersion medium (Cp
d-6) O,OS coupler solvent (Solv-'
2) 0.10 12th layer (high-grade venereal layer) Silver bromide spectrally sensitized with a blue sensitizing dye (Ex S -5,6) (average grain size 0.85μ, size distribution 18
%, octahedral) 0.15 gelatin yellow coupler antifade agent (Cpd-14) stain inhibitor (Cpd-5, at) coupler dispersion medium (Cpd-6) coupler solvent (SolV-2) No. 137N (UV absorbing layer ) Gelatin UV absorber (Cpd-2, 4, 16 equivalents) (ExY-L 0, 60 2 equivalents) 0, 30 0, 10 15 to 1:5 ratio 0.00? 0,05 0,10 1,(t.

0,50 Color mixing inhibitor (Cpd-7,17 equivalent) 0.03 Dispersion medium (Cpd-6) 0.02 Ultraviolet absorber solvent (3otv-2,7 equivalent) 0.08 Irradiation inhibitor dye R (Cpd -18, 19, 20
, 21, 27 in a 10:10:13:15:20 ratio)
O, OS 14th layer (protection N) Fine particle chloride bromide (chloride!! 97 mol%, average size 0
．． 1 μ > 0.03 Acrylic modified copolymer of polyvinyl alcohol 0.01 Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
0.05 gelatin
1.80 gelatin hardener (H-1, H-2 equivalent) 0.
18 15th layer (back layer) Gelatin 2.50 Ultraviolet absorber (Cpd-2, 4, 16 equivalents) 0.50 Dye (Cpd-18, Ig, 20, 21, 27 equivalents)
0.06 16th layer (X-plane protective layer) Polymethyl methacrylate particles (average particle size 2.4
μ) and silicon oxide (average particle size 5μ) equivalent amount
0.05 gelatin
2.00 Gelatin hardener (H-1, H-2 equivalent) 0.
14 How to make emulsion EM-1 An aqueous solution of potassium bromide and 81M nitrate was simultaneously added to an aqueous gelatin solution over 15 minutes at 75°C with vigorous stirring to form octahedral silver bromide grains with an average grain size of 0.40μ. I got it. In this emulsion, 0.3 g of 3.4-dimethyl-
Chemical aggravation treatment was performed by sequentially adding 1,3-thiazoline-2-thione, 6 ml of sodium thiosulfate, and 7 N chloroauric acid (tetrahydrate) and heating at 75° C. for 80 minutes.

Using the thus obtained grains as cores, they were further grown in the same precipitation environment as the first time, and finally an octahedral monodisperse cob/shell silver bromide emulsion with an average grain size of 0.7μ was obtained. The coefficient of variation was approximately 10%. To this emulsion, 1.5 μ of sodium thiosulfate and 1.5 μ of chloroauric acid (tetrahydrate) were added per mol of 1 mole and heated at 60°C for 60 minutes to perform chemical aggravation treatment, resulting in internal active halogenation. One emulsion was obtained.

Each toe layer contains EXZK-1 and ExZK- as the nucleating side.
2 to 10110-''% by weight of silver halide, respectively.
, Cpd-22 was used as a nucleation accelerator in an amount of 10% by weight.Alkanol
C (Dupon) and sodium alkylbenzenesulfonate, succinate ester and Ma as coating aids.
gefac F-120 (manufactured by Dainippon Ink Co., Ltd.) was used. Silver halide and colloidal silver gold layers were used as stabilizers (Cpd-23, 24, 25). This sample was designated as sample number DA01. The compounds used in the examples are shown below.

xS-1 xS-4 xS-2 xS-5 xS-6 5OJ-N (C!Hs) 2 xS-3 Cpd-1 Cpd-5 0 H p d-2 H Cpd-6 CONHC,H,(t) Cpd-3 Cpd-7 H Cpd-4 H Cpd-8 I'll do n, do, r+1゜ +CHl-CH-)-.

C00C,H5 Cpd-9 Cpd-12 1 Cpd-13 Cpd-10 H H C,d-14 Cpd-11 Cpd-15 H Cpd-16 Cpd-17 H H Cpd-18 SO,K SO,K Cpd-22 Cpd-23 (ld-24 Cpd-25 11 Cpd-26 Cpd-19 Cpd-20 Cpd-21 So, K Cpd-27 xC-1 I xC-2 H to SOi ExM-1 ExM-3 xY-1 I ExM -2 xY-2 Cρ olv-1 olv-2 olv-3 olv-4 olv-5 olv-6 olv-7 -1 -2 ExZK-1 Di(2-ethylhexyl) sebacate trinonyl phosphate di(3-methyl hexyl) phthalate μ -tricresyl phosphate dibutyl phthalate trioctyl phosphate di(2-ethylhexyl) phthalate 1.2-bis(vinylsulfonylacetamido)ethane 4.6-dichloro-2-hydroxy-1,3,5 -Triazine Na salt 7-(3-zthoxythiocarponylaminobenzamide)-9-methyl-10-prohagiru 1,2゜3.4-tetrahydroacridinilam trifluoromethanesulfonateExZK-22-(4-(3- (3-(3-(5-[3
-(2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl)phenylrubamoyl)-4-hydroxy- 1-naphthylthio)tetrazol-1-yl]phenyl)ureido] benzenesulfonamido)phenyl]-1-formyl Hydrazine After cutting and processing the silver halide color photographic light-sensitive material prepared as described above and imagewise exposure, the cumulative replenishment amount of the color developing solution is determined by the method described below using an automatic developing machine. Continuous treatment was carried out until the amount increased to three times the amount. Thereafter, the exposure amount was adjusted so that the unexposed sample and the gray density became 2.0, and the sample to which negative light was applied was processed.

Color development 135 seconds 38℃ 1sx 300
1i# bleach fixing 40# 331 3# 300
#Water washing (1140 seconds 33°C 31 Water washing (2140 seconds 33°C 31 320d
/ Po 30 8 °C The method of replenishing the washing water is to replenish the washing water into the washing bath (2) and
A so-called countercurrent replenishment system was adopted in which the overflow liquid of 2) was led to the washing bath (1). At this time, carry the bleach-fixing solution from the bleach-fixing bath using the optical material to the water washing bath (1).
5mff1/+d, and the ratio of washing water replenishment h1 to the amount of bleach-fix solution brought in was 9.1.

The contact area between the air and the treatment liquid in each treatment tank was 75 cm''.

The composition of each treatment liquid was as follows.

Light color ■Dark Skin-stains J+li filled ethylenediaminetetrakismethylenephosphonic acid 1.58 1.5g diethylene glycol 10ml 110d Hensyl alcohol l 2, Oml 14, 4
m1 Potassium Bromide Hensitriazole Sodium Sulfite Glucose N,N-bis(carboxymethyl)hydrazineTriethanolamine N-Ethyl-N-(β Methanesulfonamidoethyl)-3-Methyl 4-Aminoaniline Sulfate Potassium Carbonate Optical Brightener (WIIITEX-4, manufactured by Sumitomo Chemical) pH (25'C) Reduction ■ Akebono 1-ethylenediaminetetraacetic acid 0.70 g 0.003 g 2.4 g 2.5 g 0.004 g 2.9 g 3.0 g 4. 0 g 4.8 g 6.0 g 7.2 g 6.0 g 7.2 g 30.0 g 25.0 g l, 0 g 10.25 1.2 g 10.85・Dihydrate 4.0g Ethylenediaminetetraacetic acid・Fe(l[l) ・Ammonium dihydrate ammonium thiosulfate (700gl1) Sodium P-toluenesulfinate 20.0g Preservative (see Table 6) Ammonium sulfite 5 -Mercapto = 1,3゜4-triazole ammonium nitrate 0.2 morph 0.0 g 1110d 0.5 g 10.0 g 0.3 mol Washing water Both the mother liquor and replenisher were mixed with tap water and H-type strongly acidic cation exchange resin (ROHM Water was passed through a hotbed column filled with Amberlite IR-120B (manufactured by Andhaas) and an OH-type anion exchange resin (Amberlite IR-400) to reduce the concentration of calcium and magnesium ions to 31 g/l or less, Subsequently, 20 g/l of sodium isocyanurate dichloride and 1.5 g/l of sodium nitrate were added. The pH of this solution is 6.5~
It was in the range of 7°5.

The amount of silver remaining on the light-sensitive material after processing was determined by the fluorescence XvA method for the samples that had been exposed to light to give a gray density of 2.0.

Furthermore, the color density was measured using red light.The same sample was then used in Example 1. Soaked in the bleach solution used in N117 for 30 minutes,
After washing with water for 1 minute and drying, the color density was measured using red light.
Inspected for poor color restoration.

Inadequate color recovery (ΔDI) = (color density measured with red light after re-bleaching) - (color density measured with red light after treatment) In addition, the formation of precipitates in the bleach-fix solution and washing solution was investigated. Ta.

The results obtained are shown in Table 5.

As shown in Table 5, when processing with a small automatic processor in which the contact area between each processing solution and air is 75 cm, using conventional ammonium sulfite as a preservative will cause poor color recovery. In photosensitive materials after processing, the cyan image dye converts into leuco form, resulting in a decrease in color density, but when the compound of the present invention is used, a favorable result is that such color reproduction defects do not occur. Obtained.

This effect was particularly remarkable in exemplified compounds A-1 to A-8 and D-4 and D-5.

(Effects of the Invention) It has been shown that the compounds represented by formulas (A) to (D) have excellent performance as preservatives for fixing solutions or bleach-fixing solutions that use thiosulfate as a fixing agent.

These compounds are used to process color photographic materials containing 2-equivalent magenta couplers, and as bleaching agents with the general formula (
Even more favorable results are obtained in combination with the use of a ferric complex salt of the chelating agent represented by III).

Claims (5)

[Claims] (1) In a processing method in which a silver halide color photographic material is imagewise exposed, subjected to color development treatment, and then treated with a bleach-fix solution and/or a fixer solution, the bleach-fix solution and/or fixer solution contains the following [ 1. A method for processing a silver halide color photographic material, comprising the compounds of [1], [2] and/or [3]. [1] Thiosulfate [2] General formula (A), (B), (C) or (D) below
and at least one compound selected from the group consisting of bisulfites, sulfites, and metabisulfites. [3] The following general formula (A), (B), (C) or (D)
At least one bisulfite adduct of the compound represented by
seed. General formula (A) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is an alkenyl group, an aryl group, an alkynyl group, a cycloalkyl group, an aralkyl group, a heterocyclic group, a carboxylic acid group, an ester group, an acyl group, or Represents a carbamoyl group, and R_2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group. R_1 and R_2 may be combined to form a ring. ) However, when R_1 represents an aryl group, R_2 is never a hydrogen atom. General formula (B) ▲ Numerical formulas, chemical formulas, tables, etc. , heterocyclic group,
Carboxylic acid group, ester group, acyl group, halogen group, ether group, sulfo group, sulfinyl group, sulfonyl group,
Represents a cyano group, nitro group, carbamoyl group or sulfamoyl group. R_4 represents an electron-withdrawing group. Also, R_3 and R_4,
R_4 and R_5, R_5 and R_6, and R_6 and R_3 may be combined to form a ring. General formula (C) ▲ Numerical formulas, chemical formulas, tables, etc. Heterocyclic group, amino group, alkylamino group, arylamino group, carboxylic acid group, ester group, acyl group, ether group, hydroxyl group,
It represents an alkylthio group or an arylthio group, X represents an anion, and n represents 0 or 1. Also, R_7 and R_8, R_8 and R_9, R_7 and R_
9 may be integrated to form a ring. ) General formula (D) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_0 represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a heterocyclic group. Represents an atom constituting a ring, Y represents an anion, m represents 0 or 1. R_1_0 may also form a ring by bonding atoms in Z.) (2) The halogenated silver halide color photographic light-sensitive material according to claim (1), wherein the silver halide color photographic light-sensitive material contains at least one magenta coupler represented by the following general formula (I) or (II). Processing method for silver color photographic materials. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_1 is a carbonamide group, anilino group, or ureido group, R_1_2 is a phenyl group, X_1
represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2_1 represents a hydrogen atom or a substituent, and
_2 represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. Z
a, Zb and Zc represent methine, substituted methine, =N- or -NH-, and one of the Za-Zb bond and Zb-Zc bond is a double bond and the other is a single bond. ) (3) The silver halide according to claim (1), wherein the bleach-fix solution contains at least one ferric complex salt of an aminopolycarboxylic acid represented by the following general formula (III). A method of processing color photographic materials. General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, L_1 represents an oxygen atom, a sulfur atom, an alkyl group, or a group shown by ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R_3_1, R_3_2, R_3_3, R_3_4
each represents a hydrogen atom or an alkyl group, but R_
3_1 and R_3_2 or R_3_3 and R_3_2 may be linked to each other to form a cycloalkyl ring. k,
l, m, n each represent an integer from 0 to 4, and a is from 1 to
It represents an integer of 3, but the sum of k, l, m, and n is 2 or more. (4) Silver halide color photographic light-sensitive material is prepared by the following general formula (
A method for processing a silver halide color photographic light-sensitive material according to claim (1), which comprises processing with a bleaching solution containing at least one ferric aminopolycarboxylic acid complex salt represented by III). . General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, L_1 represents an oxygen atom, a sulfur atom, an alkyl group, or a group shown by ▲There are mathematical formulas, chemical formulas, tables, etc.▼. R_3_1, R_3_2, R_3_3, R_3_4
each represents a hydrogen atom or an alkyl group, but R_
3_1 and R_3_2 or R_3_3 and R_3_2 may be linked to each other to form a cycloalkyl ring. k,
l, m, n each represent an integer from 0 to 4, and a is from 1 to
It represents an integer of 3, but the sum of k, l, m, and n is 2 or more. (5) A composition having fixing ability containing the following compounds [1], [2] and/or [3] [1] Thiosulfate [2] The following general formulas (A), (B), ( C) or (D)
At least one compound represented by the following formula (A), (B), ( C) or (D)
At least one bisulfite adduct of the compound represented by
Species general formula (A) ▲ Numerical formulas, chemical formulas, tables, etc. or represents a carbamoyl group, and R_2 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a cycloalkyl group, or a heterocyclic group.Also, R_1 and R_2 may be combined to form a ring. (Good.) However, when R_1 represents an aryl group, R_2 is not a hydrogen atom. General formula (B) ▲ Numerical formulas, chemical formulas, tables, etc. , heterocyclic group,
Carboxylic acid group, ester group, acyl group, halogen group, ether group, sulfo group, sulfinyl group, sulfonyl group,
Represents a cyano group, nitro group, carbamoyl group or sulfamoyl group. R_4 represents an electron-withdrawing group. Also, R_3 and R_4,
R_4 and R_5, R_5 and R_6, and R_6 and R_3 may be combined to form a ring. ) General formula (C) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, R_7, R_8, and R_9 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, and an aryl group. , heterocyclic group, amino group, alkylamino group, arylamino group, carboxylic acid group, ester group, acyl group, ether group, hydroxyl group,
It represents an alkylthio group or an arylthio group, X represents an anion, and n represents 0 or 1. Also, R_7 and R_8, R_8 and R_9, R_7 and R_
9 may be integrated to form a ring. ) General formula (D) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_0 represents an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a heterocyclic group. Represents an atom constituting a ring, Y represents an anion, m represents 0 or 1. R_1_0 may also form a ring by bonding atoms in Z.)