JPH01210957A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To rapidly bleach the title material, without generating a bleaching fog and a recoloring defect by processing the sensitive material contg. a specified antifoggant with a specified bleaching solution. CONSTITUTION:The sensitive material contg. the antifoggant shown by the formula is imagewisely exposed, and then processed with a bleaching solution having pH of <=5.5, followed by fixing it. And the bleaching agent (A) is composed of one or more kinds of the ferric complex salt (a) of a compd. selected from the group comprising ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, cyclohexane diamine tetraacetic acid and 1,2-propylene diamine tetraacetic acid and the ferric complex salt (b) of 1,3-diaminopropane tetraacetic acid in a mol. ratio of the component (a) to the component (b) of <=3.0. In the formula, Q is a prescribed heterocyclic ring residual group, M<1> is H atom or an alkaline metal, etc. The antifoggant shown by the formula is exemplified by a compd. shown by formula II. etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an exposed silver halide color photographic light-sensitive material (
The present invention relates to a processing method for color light-sensitive materials (hereinafter referred to as color light-sensitive materials), and particularly relates to an improved processing method that can perform sufficient desilvering in a short time and has excellent photographic properties.

(Prior art) In general, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. In the zero color development step, silver halide exposed to light is reduced by a color developing agent to produce silver, and is oxidized. In the zero-order RFT silver process, the color developing agent reacts with the color former (coupler) to form a dye image, and the silver produced in the color development process is oxidized by the action of an oxidizing agent (commonly called a bleaching agent). , which is then dissolved by a silver ion complexing agent commonly called a fixing agent. By going through this desilvering step, only a dye image is created on the color photosensitive material.

The above desilvering process is carried out in two baths: a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, or in one bath using a bleach-fixing bath containing both a bleaching agent and a fixing agent. There is.

In addition to the basic steps mentioned above, the actual development process includes various auxiliary steps, such as hardening, to maintain the photographic and physical quality of the image, or to improve the preservation of the image. These include membrane baths, stop baths, image stabilization baths, and water washing baths.

In the present invention, the term "bath having bleaching ability" refers to both the bleaching bath and the bleach-fixing bath, and examples of bleaching agents used in these baths having bleaching ability include red blood salt, dichromate, and dichloromethane. Known examples include diiron, ferric aminopolycarboxylic acid complex salts, and persulfates.

However, red blood salt and dichromate have pollution problems related to cyanide compounds and hexavalent chromium, and their use requires special treatment equipment. Furthermore, ferric chloride has problems in the production of iron hydroxide and staining during the subsequent washing process, which poses some practical problems. Persulfates have the disadvantage that their bleaching action is very weak and that they require a significantly long bleaching time. Regarding this, a method has been proposed to increase the bleaching effect by using a bleach accelerator in combination, but persulfate itself is regulated as a dangerous substance under the Fire Service Act, and various storage measures are required, making it difficult to put it into practical use. There are drawbacks.

Aminopolycarboxylic acid ferric complex salts are bleaching agents that are currently widely used in practical use because they have fewer pollution problems and do not have storage problems like persulfates. A large number of compounds are known as ferric aminopolycarboxylic acid complex salts, but from the standpoint of bleaching ability, cost, etc., ethylenediaminetetraacetic acid ferric acetic acid, diethylenetriaminepentaacetic acid ferric complex salt, cyclohexanediamine Ferric tetraacetic acid complex salts have been used as the preferred compound.

However, the bleaching blades of the ferric complex salts of ethylenedi7minetetraacetic acid and the ferric complex salts of diethylenetriaminepentaacetic acid that have been used in the past are not necessarily sufficient, and those using these as bleaching agents are When bleaching or bleach-fixing low-sensitivity silver halide color light-sensitive materials based on emulsions, it is possible to achieve the desired purpose, but it is possible to achieve the desired purpose, but it is possible to achieve the desired objective by bleaching or bleach-fixing low-sensitivity silver halide color light-sensitive materials based on emulsions. When processing high-sensitivity color light-sensitive materials that have been color-sensitized, especially color negative light-sensitive materials for photography and color reversal light-sensitive materials that use high-silver emulsions, desilvering defects may occur.
It has the disadvantage that it takes a long time to bleach.

As a means to enhance the bleaching power of such a ferric aminopolycarboxylic acid complex salt, it is known to lower the pH of the solution having bleaching ability, but this method has the drawback of causing poor recoloring of the cyan dye. It is also known to add various bleach accelerators, but their effects are not sufficient.

However, some aminopolycarboxylic acids also contain
Compounds with relatively strong bleaching properties such as 1,3-diaminopropanetetraacetic acid ferric complex salt and l,2-diaminopropanetetraacetic acid ferric complex salt described in No. 2252 are also known,
To achieve the speed of processing required in this industry,
It is still insufficient. Moreover, it has been revealed that the use of these compounds causes significant bleaching and blade burring.

(Problems to be Solved by the Invention) Therefore, the first object of the present invention is to provide a processing method that speeds up bleaching without causing problems such as bleaching fog or poor color recovery. The second objective is to provide a processing method that is free from environmental pollution and handling hazards.

(Means for Solving the Problems) The above object of the present invention is to provide a method for processing an exposed silver halide color photographic light-sensitive material with a solution having bleaching ability after color development processing, the silver halide color photographic light-sensitive material contains at least one compound represented by the following - Tsuzuriyo (ri), and the liquid having bleaching ability contains at least one ferric complex salt selected from the following compound group (A) as a bleaching agent;
．． 3-sia'minopropanetetraacetic acid ferric complex salt in a molar ratio of the former to the latter of 3 or less, and p
This was achieved by a method for processing a silver halide color photographic material characterized in that H is 5.5 or less.

Compound (A) A-1 Ethylenediaminetetraacetic acid ferric complex salt A-2 Diethylenetriaminepentaacetic acid ferric complex salt A-3 Cyclohexanediaminetetraacetic acid ferric complex salt A-41,2-Propylenediaminetetraacetic acid ferric complex salt General Formula (I) Q-3M! (In the formula, Q represents a heterocyclic residue directly or indirectly bound to at least one member selected from the group consisting of -3O5M'', -COOM'', -0H and -NR'R'',
, Ml independently represents a hydrogen atom, an alkali metal, a quaternary ammonium, or a quaternary phosphonium; R' and Rg independently represent a hydrogen atom or a substituted or unsubstituted alkyl group; investigated various processing solution compositions and photosensitive material compositions in order to shorten bleaching time, and found that aminopolycarboxylic acid of compound group (A) was used as a bleaching agent for ferric complex salt of 1,3-diaminopropanetetraacetic acid. the second of
When using a bleaching solution with a molar ratio of iron complex salts of 3 or less and a pH of 5.5 or less, and a compound of the general formula (H) as an antifoggant used in photosensitive materials, the bleaching rate is They have found the surprising effect of specifically increasing ferric complex salt of l,3-diaminopropanetetraacetic acid and eliminating the bleaching fog caused by the ferric complex salt of l,3-diaminopropanetetraacetic acid, and have arrived at the present invention.

Various antifoggants are used in silver halide color photographic materials to prevent fog during development processing and during storage before processing.

As such antifoggants, heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles, and mercaptopyrimidines are used; The compound 1) is also described in Japanese Patent Publication No. 58-9939 and is known as an antifoggant.

However, the effects of the present invention can only be obtained when the compound of -Tsuriyo (I) is used, and such effects are not described at all in the above-mentioned Japanese Patent Publication No. 58-9939.

Conventionally, l-phenyl-5-mercaptotetrazole has been known as a typical antifoggant, but this compound significantly inhibits bleaching and has different effects than the compound of formula -a (!). It shows.

Hereinafter, the treatment bath having bleaching ability of the present invention will be explained.

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

A processing bath having bleaching ability generally refers to a bleaching solution and a bleach-fixing solution, but in the present invention, a bleaching solution is preferable because it has an excellent bleaching blade, and the desilvering process of the present invention includes, for example, the following steps. However, it is not limited to these.

■ Bleach □ Fixing ■ Bleach □ Bleach-fixing ■ Bleach-fixing ■ Bleach-fixing □ Bleach-fixing ■ Bleach □ Washing □ Fixing In particular, steps □ and □ are preferred in order to exhibit the effects of the present invention.

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

3-diaminopropanetetraacetic acid ferric complex salt is used in combination at a molar ratio of 3 or less of the former to the latter.

A preferred molar ratio is 1.8 to 0.5.

If the molar ratio exceeds 3, the bleaching blade will deteriorate, resulting in poor desilvering, and if the ratio of 1,3-diaminopropanetetraacetic acid ferric salt is significantly high, a slight blurring of the bleaching blade may occur. be.

The amount of the bleaching agent of the present invention added is 0.05 mol to 1 mol, preferably 0.05 mol to 1 mol per 11 baths having bleaching ability. 1 mole ~ 0.5
It is a mole.

In addition to the above-mentioned aminopolycarboxylic acid iron (III) if form, an aminopolycarboxylate salt can be added to the treatment liquid having bleaching ability according to the invention.

In particular, it is preferable to add a compound of compound group (A).

The preferred amount added is 0.0001 mol to 0.1 mol/1
More preferably, it is 0.003 mol to 0.05 mol/1.

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

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

Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, German Patent No. 1,290.
．． Compounds having a mercapto group or a disulfide group described in Specification No. 812, British Patent No. 1 138.842, JP-A-53-95630, Research Disclosure No. 17129 (July 1978 issue) , thiazolidine 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 JP 8836 can be used.

Particularly preferred are mercapto compounds as described in British Patent No. 1,138,842.

In particular, in the present invention, from the following - binding allowance (IA) to (VI
The bleaching accelerator represented by A) can be preferably used because it has excellent bleaching ability and less brittleness of the bleaching blade.

General formula (IA) RI A -3-MI A In the formula, yl 1 A represents a hydrogen atom, an alkali metal atom, or ammonium. RI A represents an alkyl group, an alkylene group, an aryl group, or a heterocyclic residue. The preferred number of carbon atoms in the alkyl group is from 1 to J, most preferably from 1 to 3. The preferred number of carbon atoms in the alkylene group is from ! I'll go. Examples of the aryl group include phenyl and naphthyl groups, with phenyl being particularly preferred. Examples of heterocyclic residues include nitrogen-containing 6-membered rings such as pyridine and triazine, and nitrogen-containing rings such as azole, pyrazole, triazole, and thiadiazole! Although a membered ring is preferable, it is particularly preferable that two or more of the ring-forming atoms are nitrogen atoms. RI A may be further substituted with a substituent. Examples of substituents include alkyl groups, alkylene groups, alkoxy groups, aryl groups, carboxy groups, sulfo groups, abano groups, alkylamino groups, dialkylamino groups, hydroxy groups, carbamoyl groups, sulfamoyl groups,
Examples include sulfonamide groups.

- Preferable among the binding allowances (IA) are - binding allowances (IA)
−/ ) to (IA−≠).

-Archive (IA-/) In the formula, R2A%R3A and R4A may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably from 1 carbon number, especially a methyl group, an ethyl group) , a propyl group is preferred) or an acyl group (preferably having 1 to 3 carbon atoms, such as an acetyl group or a propionyl group), and kA is an integer from / to 3. z
1A represents an anion (chloride ion, bromide ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate, etc.). kA represents 0 or 1%; iA represents O or l.

R2A and R3A may be linked to each other to form a ring.

R2A%R3A%R4A is preferably a hydrogen atom or a substituted or unsubstituted lower alkyl group.

As the substituent for R and R%R, a hydroxy group, a carboxy group, a sulfo group, an amino group, etc. are preferable.

General formula (IA--2) General formula (IA-4') H In the formula, R5A is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an amino group, a substituted or unsubstituted lower alkyl group (preferably 7 to j% carbon atoms, particularly methyl, ethyl, and propyl groups), amino groups having alkyl groups (methylamino, ethylamino,
Represents a substituted or unsubstituted alkylthio group (dimethylamino group, diethylamino group, etc.).

Here, the substituents that R5A has include a hydroxy group,
Examples include a carboxy group, a sulfo group, an amino group, and an amino group having an alkyl group.

General formula (IIA) R-8-5-R6A In the formula, RI A is the same as RI A in general formula (IA), and R6A is synonymous with RI A. RI A and R6A
may be the same or different.

Among general formulas (IA), preferred are general formulas (II
A-/).

General formula (I[A-/) In the formula, R7A, R8A, 19 people are R2A, 1
3 people, synonymous with R4mu. hA, lcA, and z l A
are the same as hA, kA, and ZIA in the general formula (IA-/). iB represents O%l or -.

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

Here, the substituents from R to R include a hydroxy group,
These include carboxy groups, sulfo groups, amino groups, and lower alkyl groups.

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

General formula (IVA) where R14A, R15A, R16A F-i
They may be in the same or different ranges, and each represents a hydrogen atom or a lower alkyl group (for example, a methyl group, an ethyl group, etc., preferably having a carbon number of / to 3). kB represents an integer from / to j.

X I A represents an amide group which may have a substituent, a sulfo group, a hydroxy group, a carboxy group, or a hydrogen atom. The substituent may be a substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, hydroxyalkyl group, alkoxyalkyl group, carboxyalkyl group, etc.), and two alkyl groups may form m.

R%R%R may be linked to each other to form a ring. R14A +HR16A is preferably a hydrogen atom, methyl group or ethyl group, and X is preferably an amine group or dialkylamino group.

General formula (VA) where AIA is an n-valent aliphatic linking group, an aromatic linking group,
It is a heterocyclic linking group (when n = 1, Al4 represents a mere aliphatic group, aromatic group, or heterocyclic group). Twelve alkylene groups (eg trimethylene, hexamethylene, cyclohexylene, etc.) may be mentioned.

Examples of the aromatic linking group include arylene groups having 6 to 18 carbon atoms (eg, phenylene, naphthylene, etc.).

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

Here, the number of aliphatic linking groups, aromatic linking groups, and heterocyclic linking groups is usually one, but two or more may be linked, and the linking format may be direct or divalent linking groups (for example, -0 −
1-S-2R1^-3Ot-N-1 -1-C〇- or a linking group formed from these linking groups, and R20^ represents a lower alkyl group).

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

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

!-0-1-S-1 RlIA represents N- (RgIA represents a lower alkyl group (e.g. methyl group, ethyl group, etc.)), Rt't^, RIaA represents a substituted or unsubstituted lower alkyl It represents a group (e.g., methyl group, ethyl group, propyl group, isopropyl group, hemethyl group, etc.), and as a substituent, it represents a hydroxy group, a lower alkoxy group (e.g., methoxy group, methoxyethoxy group, hydroxyethoxy group, etc.). ), amino groups (e.g., unsubstituted amino group, dimethylamino group, N-hydroxyethyl-N
-methylamino group, etc.) are preferred. Here, when there are two or more substituents, they may be the same or different.

RI9^ represents a lower alkylene group having 1 to 5 carbon atoms (methylene, ethylene, trimethylene, methylmethylene, etc.), and Z2^ represents an anion (halide ion (chloride ion, bromide ion, etc.), nitrate ion, sulfate ion, p- toluenesulfonate, oxalate, etc.).

Also, RI'7^ and RIM^ are carbon atoms or heteroatoms (
For example, they may be linked via an oxygen atom, nitrogen atom, sulfur atom) to form a 5- or 6-membered heterocycle (for example, a pyrrolidine ring, a piperidine ring, a morpholine ring, a triazine ring, an imidazolidine ring, etc.) .

R1V^ (or RlmA) and A are connected via a carbon atom or a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom), and a 5- or 6-membered heterocycle (e.g., a hydroxyquinoline ring, a hydroxyindole ring, (isoindoline ring, etc.) may also be formed.

Furthermore, RIffA (or RIIA) and RIIA are connected via a carbon atom or a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom), and a 5- or 6-membered heterocyclic ring' (e.g., a piperidine ring, pyrrolidine ring, morpholine ring, etc.).

jlA is 0 or ISmA is 0 or 1, nA is 1.2 or 3, pA is 0 or 1, and qA is 0.1.2, or 3
represents.

General formula (VIA) R2Z^
A and kB are the same as XIA and kB in the general formula (rVA).

M! A is hydrogen atom, alkali metal atom, ammonia S
R''R1 RlKA represents a hydrogen atom or a lower alkyl group (having 1 to 5 carbon atoms and which may have a substituent).

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

(IA)-111 \N (CHz)z SH / (IA)-+21 (IA)-(31 (IA)-(41 (-J CIA>-(5) Hx H3 (Engineering A)-(6) ( (TJ )-(ts-N (A)-(+'Z) N-8(,:)1.
” 'N'ゝEdict 1 (zp') -7+= ) (Cause-(2◇) H (ffA) -(I) (IIA) -(ri(ffA) -e+ (ffA) -(41 (f [A) -(5) (IIA) -(ti) Crystal ([[A) -(7J (IIA) -(8) (ffA) -(9) (I[A) -(Io) niyu)- 811) (uA) - (I1) (Ii11A) - (I) (Box A) - (21 (E voice) - (31 (TIIA) - (4) (HA) - (5) (HA) - (6 (TVA) - (I1 (to 7) - (Machi (W8) - (61 (rg''A) - (7) (7'7A) - (3) (v-A) - (J)
(■8)-((LJ (VAI~(3n(VAI-(qノshi11□N(C)l, CH20H)27n") C112NCII2C112011 C1l.

ITA)-('A)
(VA)-(r
(V/λ) - (/7) (VA) - (/ I ) '2) J/) 2 co) (7A) - (''' ) (TA) - (24' ) (VA) - (Ji' (vA) - (24) (VIA) - (I) (VIA) - (2) (VIA) - (3) (VIA) - (41 (VIA) - + 5) (CH372N < Shi Mt)z
II Among the above bleach accelerators, particularly preferred compounds are I
A-2, IA-5, IA-13, IA-14, IA-1
5, IA-16, IA-19, [[A-111A-11
, VA-1, VIA-1 and VIA-2.

The amount of bleaching accelerator added is 0.000000000000000000 for 110000.
01g to 20g1, preferably 0.1g to 10g.

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

The concentration of the rehalogenating agent is from 0.1 to 5 mol, preferably from 0.5 to 3 mol per 11 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 phosphate,
Additives known to be commonly used in bleaching solutions, such as one or more inorganic acids, organic acids, and salts thereof, having pHM binding capacity, such as citric acid, sodium citrate, and tartaric acid, can be added.

The pH of the bath having bleaching ability of the present invention is set to 5.5 or less, preferably 5.3 to 2.0, most preferably 5.
．． It is 0 to 3.0. In a preferable pH range, there is particularly little bleaching edge blur and excellent desilvering performance.

The replenishment amount of the bath having bleaching ability of the present invention is 50 ml to 2000 ml per IM of light-sensitive material, preferably 100 mj! ~
There is 1000mffte.

In the present invention, after processing with a bath containing a photosensitive material, it is generally processed with a bath having fixing ability.

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

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

Fixing agents for baths having these fixing abilities include thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate; thiocyanates such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate; urea,
Thioether etc. can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.3 mol to 3 mol per 11 processing liquids.
It is 5 moles to 2 moles.

The fixing bath contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and bisulfite adducts of hydroxylamine, hydrazine, aldehyde compounds, such as acetaldehyde sodium bisulfite. be able to. Furthermore, various optical brighteners, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol, etc. can be contained, but in particular, as preservatives, it is possible to contain
It is preferable to use the sulfinic acid compounds described in No. 283831.

The replenishment amount of the bath with fixing ability is 300mA to 3000mJ per photosensitive material! is preferred, but more preferably 300mjl to 1000mjl! It is.

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

The shorter the total time of the desilvering step of the present invention, the more remarkable the effects of the present invention can be obtained. The preferred time is 1 minute to 4 minutes, more preferably 1 minute 30 seconds to 3 minutes. Also, the processing temperature is 2
The temperature is 5'' to 50°C, preferably 35°C to 45°C. In the preferred temperature range, the desilvering rate is greatly improved and the occurrence of staining after processing is effectively prevented.

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

A specific method for strengthening stirring is disclosed in Japanese Patent Application Laid-Open No. 62-18346.
No. 0, No. 62-183461, the method of impinging a jet of processing liquid on the emulsion surface of a photosensitive material, and the method of colliding a jet of a processing liquid on the emulsion surface of a photosensitive material, as described in JP-A No. 62-183-1.
No. 83461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the light-sensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. method, and a method of increasing the circulation flow rate of the entire treatment liquid. 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 bleaching agent and fixing agent into the emulsion film, and as a result increases the desilvering rate.

Further, the agitation improving means is more effective when a bleach accelerator is used, and can significantly increase the accelerating effect 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
257, No. 191258, and No. 191259. As described in JP-A-60-191257, such a conveying means is used to transfer from the front bath to the post bath. It is possible to significantly reduce the amount of processing liquid carried into the process, and it is highly effective in preventing the performance price of the processing liquid from increasing.This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

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.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotoluene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-(N~ethyl- N-(β-hydroxyethyl)aminocoaniline D-52-methyl-4-[N-ethyl-N-(β-hydroxyethyl)aminocoaniline D-64-amino-3-methyl-N-ethyl-N −(β
-(methanesulfonamido)ethyl]-aniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl- N=ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-phenylenediamine derivatives, Exemplified Compound D-5 is particularly preferred.

Further, these p-phenylenediamine derivatives may be salts such as sulfate, hydrochloride, sulfite, and p-)luenesulfonate. Preferably about 0.1 g to about 20 g,
More preferred is a concentration of about 0.5 g to about 10 g.

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

The preferred amount added is 0゜5g-1 per color developer IE.
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
Hydroxamic acids described in No. 9, hydrazines and hydrazides described in No. 61-170756, and hydrazides described in No. 61-188
Phenols described in No. 742 and No. 61-203253, α-hydroxyketones and α-aminoketones described in No. 61-188741, and/or No. 61-18
It is preferable to add various types of 11ff described in No.
No. 3, No. 61-166674, No. 61-165621
Monoamines described in No. 61-164515, No. 61-170789, and No. 61-168159, No. 61-173595, No. 61-164515,
Diamines described in No. 61-186560, etc., No. 61
-165621 and the polyamines described in No. 61-169789, the polyamines described in No. 61-188619, the nitroxy radicals described in No. 61-197760, No. 61-186561, and No. 61-19741.
It is preferable to use alcohols described in No. 9, oximes described in No. 61-198987, 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
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. It is preferable to use various buffering agents in order to maintain the above pi.

Specific examples of buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, trisodium phosphate, dipotassium phosphate, sodium borate, potassium borate, Sodium tetraborate (borax), potassium tetraborate, O-
Sodium hydroxybenzoate (sodium salicylate), potassium 0-hydroxybenzoate, 5-sulfo-2
-sodium hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0. 1 mole/
It is preferably 1 or more, particularly 0. 1 mol/1~
Particularly preferred is 0.4 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, organic acid compounds are preferred, such as aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids.

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

Nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic 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 Two or more of these chelating agents may be used as necessary. May be used together.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 1z
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 viewpoint of pollution, formulation properties, and prevention of color staining. Here, "substantially" means 2. m 1 or less,
Preferably, it means not containing it 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 No. 3,
813.247, p-phenylenediamine compounds shown in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, Kokko-Sho 44-30074, JP-A No. 56-156826 and JP-A No. 52-43429,
Quaternary ammonium salts represented by U.S. Patent No. 2.
No. 494.903, No. 3,128゜182, No. 4,2
No. 30,796, No. 3,253.919, Special Publication No. 1977
-11431, amine compounds described in U.S. Patent No. 2,482,546, U.S. Pat. Polyalkylene oxides shown in U.S. Pat. etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitroindazole, 5-nitroindazole,
Nitrogen-containing heterocyclic compounds such as 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, adenine can be cited as a representative example.

The color developer used in the present invention may contain a fluorescent whitening agent. Examples of the fluorescent whitening agent include 4゜4'-diamino-2,2'-disulfostilbene-based compounds. preferable. The amount added is θ~5 g/j! Preferably 0.1g~
4g/j! 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 45°C. The treatment time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes. The replenishment amount is preferably small, but is 100 to 1500 mJ, preferably 100 to 800 mJ, more preferably 100 to 800 mJ per photosensitive material.
ml to 400ml.

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 a black and white 1st IJI developer used for reversal processing of color photographic light-sensitive materials, or Those used for processing black and white photosensitive 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 1-phenyl-3-pyrazolidone, metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, 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 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;
Bactericidal agents and antifungal agents (for example, isothiazolones, organochlorine disinfectants, benzotriazole, etc.) that prevent the growth of various bacteria and algae, surfactants that prevent drying load and unevenness, and the like can be used. Or L, E.

West, “Water Qualit
y Cr1teria”, Photo.

Sci, and Eng, + vol, L 11
6. Compounds described on pages 344 to 359 (I965) 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.8For example, a solution having a buffering capacity of pH 3 to 6, a solution containing aldehyde (for example, formalin), etc. can be used. Can be done. The stabilizing solution contains ammonium compounds, Bi, Aj!, if necessary. metal compounds such as, fluorescent brighteners, chelating agents (e.g. 1-hydroxyethylidene-1,1-diphosphonic acid), bactericides,
A fungicide, a hardening agent, a surfactant, etc. can be used.

In addition, the water washing step and the stabilization step are preferably performed using a multi-stage countercurrent method, and the number of stages is preferably 2 to 4. The replenishment amount is 1 to 50 times the amount brought in from the previous bath per unit area, preferably 2 to 30 times. times, more preferably 2 to 15 times.

The filtrate used in these washing steps or stabilization steps includes tap water, as well as Ca
, water that has been deionized to have a Mgfi degree of 5■/It or less,
It is preferable to use water that has been sterilized with halogen, ultraviolet germicidal lamps, etc.

In each of the above-mentioned processing steps for photosensitive materials, when continuous processing is performed using an automatic processor, t! Shrinkage may occur, especially when the processing amount is small or the opening area of the processing solution is large. 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 is allowed to flow into a bath having a fixing ability, which is a pre-bath.

Next, the compound of general formula (I) used in the present invention will be explained.

Specific examples of the heterocyclic residue represented by Q in the general formula (2) include oxazole ring, thiazole ring, imidazole ring, selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, ba/tazole ring, Pyrimidine ring, theasia ring, triazine ring, thiadiazine ring, etc., or rings fused with other carbocycles or heterocycles, such as benzothiazole ring, benzotriazole ring, benzimidazole ring, benzoxazole ring, benzoselenazole ring, naphthoxazole ring , triazaindolizine ring, diazaindolizine ring, tetraazaindolizine ring, etc.

Particularly preferred among the mercapto heterocyclic compounds represented by the general formula (I) are -suji (II) and (I
ll) can be mentioned.

General formula Cf1) In the general formula (I[[) General formula CU), Y and Z are independently a nitrogen atom or CR (R is a hydrogen atom, a substituted or unsubstituted argyl group, or a substituted or unsubstituted aryl group) represents.

), R is -8o3M2, --C00M2, -OH
An organic residue substituted with at least one selected from the group consisting of , dodecyl group, octadecyl group, etc.), an aryl group having 6 to 20 carbon atoms (e.g. phenyl group, naphthyl group, etc.), and Ll is -5-1-〇-
represents a linking group selected from the group consisting of 1-N-1-CO-1-8O- and -5O2-, where n is O or l.

In addition to these alkyl groups and aryl groups, halogen atoms (F, CJ, Br, etc.), alkoxy groups (methoxy group, methoxyethoxy group, etc.), 71J-ruoxy groups (phenoxy group, etc.), alkyl groups (R is an aryl group) ), aryl group (when R2 is an alkyl group), amide group (acetamido group, benzoylamino group, etc.), carbamoyl group (mfl-substituted carbamoyl group, phenylcarbamoyl group, methylcarbamoyl group), sulfonamide group ( (methanesulfonamide group, phenylsulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), sulfonyl group (methylsulfonyl group, phenylsulfonyl group, etc.), sulfinyl group groups (such as methylsulfinyl and phenylsulfinyl groups), cyanogen groups, alkoxycarbonyl groups (such as methoxycarbonyl groups), aryloxycarbonyl groups (such as phenoxycarbonyl groups), and nitro groups. Good too.

Here, the substituents of R are -8o3M, -COOM.

When there are -OH and -NRR, they may be the same or different.

M means the same as that represented by general formula (I).

Next, in general formula (III), X represents a sulfur atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

L is -CONR, -NRCO, So□NR'-1-N
R802-1-OCO-1-COO-1-5-1-NR, -CO-1-SO-1-ocoo-1
-NRC0NR7-1-NRCoo -1-OCONR
- or -NR80NR7-, and R and R each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

R and M have the same meanings as those represented by general formulas (I) and (If), and n represents O or /.

Furthermore, as substituents for the alkyl group and aryl group represented by R%R%R and R, R
The same substituents mentioned above can be mentioned.

In the general formula, R is -803M and -COOM
Particularly preferred are those.

Specific examples of preferred compounds represented by general formula (I) used in the present invention are shown below.

CH2CH2CH25O3Na CH2CH20H CH2CH2So3Na ■ CH3 ■ (H3 The compound represented by the general formula (I) is known as sb, and can be synthesized by the method described in the following literature.

US Patent Tube 2. zrr,,zrr issue, the same λ,! ≠l,
22μ issue, special public Akihiro λ/, rg λ issue, JP 1973-
No. 10,732, British patent cylinder 1. λ7j, 70/issue,
D. A. Parginis et al., “Journal of Heterocyclic Chemistry 1”
t, al,, @Journalof Hetero
Cyclic Chemistry'') Volume 1J, No. 11 (Issue 7), 1 The Chemistry of Heterocyclic Chemistry'', Imidazole and Derivatives, Part■ ('The Chemi
Try of HeterocyclicChem
istry' lm1dazole andl)e
rivatives part l), jJA
~page 9, Chemical Abstraf) (Chemica
lAbstract),! r, 7ri 2j (I5'A
J), 3 ≠ pages, E, Hogarth, 'Journal of
Chemical Society (E, Hoggarth"Jou
rnal of Chemical 5ocie
ty") iito ~ 7 pages (/91 Hiro?), and S, R,
Saladler, W. Cal, 'Organic Functional Group Prevalence 1, Academic.
Press (S, R, 5audler, W, Karo,
'Organic Fancme onaJ QroupP
reparation-Academic Press
Company) J/J~j pages, (/l+Gr) M, C? M. Chamdon et al., Bruta/
・Société Chimique de France (Bul
letin de la 5ociete C
France), 723 (
/yj4(), D, A.

Shirley, D.W., Alley, Journal of the.
American Chemical Society (D, A.

5hirley, D. W., A11ey, J. Amer.

Chem, Soc,), ヱ9%44り22(/yj4(
) A, #Neil, W., Mertewald, Peritzchte (A.

Wohl, W., Marchwald, Ber.) (Journal of the German Chemical Society), Volume 2-! tt member (/IIri) Journal of American Kabakal Society (J,
Amer, Chem, Soc, ), ■, /jOko~i
Page o U.S. Patent No. 3,017,270, British Patent No. 2
4co, IT issue, Tokuko Akihirota t.

33≠ issue, Tokukai Shoj! -, ≠ No. 63, Advanced in Heterocyclic Chemistry (Advan
ced in Heterocyclic Chemi
stry),? , / 4 , t ~ J O ri (/ri t
r), West German Patent No. 2,716,707, The Chemistry of Heterocyclic Compounds, Ibadazole and Derivatives (The Chemi
Try of Heterocyclic Comp
ounds lm1dazole and ])e
organic synthesis), VOI/, 3114 pages, Organic Synthesis (Organic Synthesis)
t h -) N -r j Ber, 44 Aj (/P7A), Journal of the American Chemical Society (J
, Amer, Chem, Soc, ),! j, ko3ri0(
IP, 23) % open/close jo-r, 03≠ issue, same 3-
2! , 4 to 2, same j1-2/, 007, Tokko Shoda 0-λr, ≠ 2.

The compound represented by the general formula (I) is contained in the silver halide emulsion layer and the hydrophilic colloid layer (intermediate layer, surface protection layer, yellow filter layer, antihalation layer, etc.).

It is preferable to contain it in a silver halide emulsion layer or a layer adjacent thereto.

Further, the amount added is preferably /x10 ~ /X
/ 02, -l) I like 1xio - reference X10
, particularly preferably 5xto ~a x 1o-3y/m
It is.

The silver halides contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention are silver chloride, silver bromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide, and silver iodobromide.

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

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 70 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), Ori 17643 (
December 1978), pp. 22-23, “I.

Emulsion preparation
on and types)'1 and the same Nal 87
16 (November 1979), 648 pages, Graphic "Physics and Chemistry of Photography", published by Paul Montell (P, G
Ifkides, Chemic at Physi
quePhotographique Paul Mo
Ntel+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G.

F. Duffin, Photographic E.
Mulsion Chemistry (Focal P
(Ress, 1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L.

Zelilvan et al. Making an
dCoating PhotographicEmu
l! l1on, Focal Press+ 1964
), etc.).

U.S. Patent No. 3,574,628, U.S. Patent No. 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 1, Gutoff, Photographic Science and Engineering (Gutoff, PhotographicSc
ience and Engjneering), 1st
4S, pp. 248-257 (I970); U.S. Patent Nos. 4.434.226, 4,414.310, 4
, 433,048, 4.439,520 and British Patent No. 2.112.157.

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

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral enhancement. Additives used in such processes are subject to Research Disclosure 17
643 and 18716, and the relevant parts are summarized in the table below.

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

Additive type RDt7643 RDL8716
1 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity increasing agents Same as above 4 Brightening agents Page 24 Left to right columns 8 Dye image stabilizers Page 25 9 Hardeners Page 26 651
Page left 10 Binder Page 26 Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column Various color couplers can be used in the present invention, and specific examples thereof are given in the Research Disclosure (
RD) Na17643, described in the patent described in ■-C-G.

As a yellow coupler, for example, U.S. Patent Tube 3.93
3.501, 4,022,620, 4.3
No. 26,024, No. 4,401゜752, Special Publication No. 5
No. 8-10739, British Patent No. 1.425,020,
Same 1st. 476, 760, etc. are preferred.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
No. 0.619, No. 4,351°897, European Patent No. 73,636, U.S. Patent No. 3.061.432, No. 3,725.067, Research Disclosure Na 24220 (June 1984) month), Japanese Patent Application Publication No. 1983
-33552, Research Disclosure N12
4230 (June 1984), JP-A-60-43659
No. 4,500,630, U.S. Patent No. 4,540
．． Particularly preferred are those described in No. 654 and the like.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. 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'.

No. 895.826, No. 3.772,002, No. 3
．． No. 758,308, same No. 4. 334. No. 011,
No. 4,327,173, West German Patent Publication No. 3,329
．． 729, European Patent No. 121°365A, U.S. Patent No. 3,446.622, European Patent No. 4,333,999,
Preferred are those described in Patent No. 4,451,559, Patent No. 4,427,767, European Patent No. 161.626A, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure Arashi 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 coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2,125.
, No. 570, European Patent No. 96,570, West German Patent (Ko rA) No. 3. 234. The one described in No. 533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451.820, U.S. Pat.
It is described in No. 173, 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 RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097, LAQ;
No. 2,131.1819, Japanese Unexamined Patent Publication No. 15763/1983
No. 8 and No. 59-170840 are preferred.

In addition, examples of couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. , the multi-equivalent couplers described in JP-A No. 4,310,618, etc., the DIR redox compound releasing couplers described in JP-A-60-185950, etc., and the 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. etc. are listed.

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

Example -■ On a subbed cellulose triacetate film support,
A multilayer color photosensitive material was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/n (units). For silver halide, it indicates the coating amount in terms of silver. However, for sensitizing dyes, the coating amount in the same layer The coating amount is shown in moles per mole of halogenide.

(Sample) 1st layer; antihalation layer black colloidal silver 10.18 gelatin
0.40 2nd J1; Intermediate layer 2.5-di-t-pentadecylhydroquinone 0.1SEX-1
,0,07 EX-30,02 EX-12o,oa2 [J-10,OA [J-,20,01 [J-jO,10 HBS-/0.10
HBS-20,0 cogelatin / ottt Third layer (first red-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide t morch, average grain size o
, tμ, coefficient of variation with respect to particle size 0. /J) Silver θ,! ! Sensitizing dye I A, riX10' Sensitizing dye [1y, rxio-5 Sensitizing dye lit 3.1xio'
Sensitizing dye ■ 4t, O×1O-5EX-
2o, 3r.

HBS-/o, oozEX-
to o, oa.

Gelatin /, 20th layer (2nd layer)
No red-sensitive emulsion) Tabular silver iodobromide emulsion (silver iodide 10 molti, average grain size Q, 7μ, average aspect ratio J, J, average thickness 0.2μ)
) silver i,.

Sensitizing dye [1,/xIO' Sensitizing dye 1 /, Hiroshi x 1o-5 Sensitizing dye III 2,1X10-' Sensitizing dye ■ 3. oXio-5EX-20,≠
00 EX-30,010 EX-io o, oz gelatin /, JO j) - (third red-sensitive emulsion layer) Silver iodide emulsion (silver iodide it molar mass, average grain size /, 1
μ) Silver/, Aθ sensitized color cumulative rK
1.4'×70-5 sensitizing dye [1,≠×l0-
5 Sensitizing dye ■ Ko, Hiroxio' Sensitizing dye IV 3. /xio-5EX-J
o, 2≠0 EX-440, /λO HBS-10,22 HBS-20,10 Gelatin /・6j 6th layer (middle layer) EX j O,0hiro QHBS
-/0.0ko0EX-/ko
0,00≠gelatin
0.10 7th layer (first green-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 molt, average grain size 0)
．． 1μ, average aspect ratio 6. θ, average thickness o, is)
Silver Q, ≠O sensitizing dye 'J
, z, oXlo-5 sensitizing dye M
i, oXlo-' sensitizing dye ■ 3
．． lX10-'EX-40,21,0 EX-to, oko1 EX-70,030 EX-4o, o, 2j HBS-/0. /,00HBS
−≠ o, oi.

Gelatin 0 and 7' layers (first blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide tamorchi, average grain size 0)
．． 7μ, coefficient of variation regarding particle size 0. /I) Silver 0.10 Sensitizing color IAV x, tXio' Sensitizing dye Vi 7. (7X/(7-5 sensitizing dye ■ λ, tXio 'EX-+
o, ir.

EX-1o, oi.

EX-10,oor EX-70,0/koHBS-/0. /40HBS-
4' 0.001r gelatin
/, 10th P layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide lλ morch, average grain size i, o
μ) Silver /, Co-sensitized color cumulative V
3. ! X10-5 sensitizing dye■
r, oxlo-5 sensitizing dye ■ 3. O×
10-'EX-10,0t! EX-ii o, o
3゜EX-10,02 yo 1-I B S -i
o, ,2 jHBS-20,10 Gelatin 7.7≠Io-th layer (
Yellow filter layer) Yellow colloidal silver Silver O,0SEX-40
, Dr HBS-jo, o3 gelatin 0.2! 11th layer (
1st blue-sensitive emulsion layer) Tabular silver iodobromide emulsion (silver iodide 6 molt, average grain size 0)
．． 1μ, average ascent ratio is 67, average thickness o, i, t
) Silver 0.2≠sensitizing dye■
3. j×IO'EX-ta
o, rrEX-10, /2 HBS-10, Kot Gelatin /, 21 12th layer (
2nd blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide 10 molti, average grain size o, rμ, coefficient of variation regarding grain size 0.1t) silver 0.44
Yo sensitizing dye ■ λ, i×io-'EX-ta O9λQEX-/o
o, 0/zHBS-/
0. O! gelatin
73rd layer (third blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide ≠ morch, average grain size 3 μm)
) Silver 0.77 Sensitizing dye■ Ko, 2X10'EX-
TA O, KO 0HBS-10
, o7 gelati 7 o, ty 1st Hiro layer (
1st protective layer) Silver iodobromide emulsion (1 mol of silver iodide, average grain size 0.07
μ) Silver 0.2 [J-4LO+/ / '[J-10,/7 HBS-i O9riO gelatin i, o.

Seventh! N (No. 1 protective layer) Polymethyl acrylate particles (diameter approximately i3 μm) 0. lll5-70
．． /j S-20, Oj Gelatin 0.72 In addition to the above-mentioned components, a gelatin hardening agent H-/ and a surfactant were added to each layer.

-I l-2 J-3 N -CsLt EX-1 EX-201( ! (i) C-LOG! il1 EX-3 i1 3x4 d EX-5 H EX-5 EX-7 EX-8 EX-9 EX-10 i1 R-5CHCOOCH.

CH.

EX-11-Miss-1 but R-H EX-12 S-/S-,! HBS-1; Tricresyl phosphonate T (BS-
2, dibutyl phthalate 1 (BS-3; bis(2-ethylnixyl) phthalate) iBs-4 H-1 C11, -C! I -So, -CIl, -CONI
I - CIl yo'22ft (Cil=) 5sOs9(Cil:) xsO2fl
aC:E.

Samples 101 to 105 were prepared by adding the following amounts of antifoggants (comparative compound and compound of formula (I)) to the following layers in the above compositions.

Sample 101: Comparative compound A #102: #B Compound (I1) of general formula (I) 104:
# (I4)105: #
(28)〃106：〃(
I)〃107:〃 (7) Comparative compound A Comparative compound B
After IOCMS stepwise exposure was applied at 800'K, processing was performed using an automatic processor as follows. In order to demonstrate the effect of the present invention on processing performance, the bleaching solution was prepared by varying the type and amount of 1,3-diaminopropanetetraacetic acid ferric complex salt and the aminopolycarboxylic acid ferric complex salt used in combination, and further adjusting the pH.
Also changed.

Table 1 - Processing steps (temperature 38℃)
White 1 minute 00 seconds 81 5ml fixed 1 minute 15 seconds 8 j 33
mj stable ■ 20 seconds 471 - stable ■ 20 seconds 4j -■
20 4j! 33m1*: Photosensitive material 3
5 cabinets/- per width 1m length.

Note that drying was carried out at 65° C. for 1 minute.

In the above process, the stabilization step was a three-stage countercurrent system in which the liquid flowed in the order of ■-■-■.

The agitation of the automatic developing machine used for processing is based on the Japanese Patent Laid-Open No. 6
The jet stirring method is as described in Japanese Patent Application Laid-open No. 2-183460, and the conveying mechanism is a belt type conveying mechanism as described in Japanese Patent Application Laid-open No. 191257-1983.

(Color developer) Mother solution (g) Replenisher (g) Diethylenetriamine 5.0 6.0 Sodium sulfite pentaacetate 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.3 0.9 Iodide Potassium 1.2■ -Hydroxylamine sulfate 2.0 2.84-(N-ethyl-N-β
4.7 Add 5.3-hydroxyethylamino)-2-methylaniline sulfate solution 1. Office lady 1. OL
pH 10,0010,05 (Bleach solution) Mother liquor (g) Replenisher solution (g) Bleach accelerator 5 x 10-3 mol 7 x l
O1 amount ((II-A)-(I1) Ferric complex salt^ (listed in Table 2)) Listed in Table 2 1.1 times the amount on the left 1.3-Diaminobu ■Panetetraacetic acid 2nd Table-
2. 1.1 times the iron salt (I,3-DPTA) listed on the left.
-Fe) 1.3-diaminopropane 1.3-DPTA ie of 1.1 times tetraacetic acid shown on the left (mole ratio) Ammonium bromide 150.0 1?0.0
Ammonium nitrate 30.0 50.0 Ammonia water (27χ) 10.0ml
13.0+wl Vinegar III (98χ)
9.0ml 15.0m+1 Consists of ferric complex salt A
Aminopolycal (molar ratio) same as 1.1 times that of ferric complex A (molar ratio) Bonic acid pH adjustment Listed in Table 2 Listed on the left &su 0.3
Add low plants 11 1j! (
Fixer) Mother solution (g) Replenisher solution) l-Hydroxyethylidene-1,1-diphosphonic acid 10.0 11.5 Ethylenediaminetetraacetic acid di〇,5 0.7 Sodium salt Sodium sulfite 7.0 8.0 Bitonite Sodium sulfate 5.0 5.5Ammonium thiosulfate 240.0ml 1 260.0ml aqueous solution (70χ) Add water 1. OL 1.0L
pH6,76,6 (Stable liquid) Mother liquor, replenisher common formalin (37χ) 1.2m
15-chloro-2-methyl-4-6,0 mg isothiazolin-3-one 2-methyl-4-isothiazoline 3.0 mg 3-one surfactant 0.4 ethylene glycol 1.0 Add water
1.0L pH 5,0-7,0 After treatment, the amount of residual silver in the maximum density part of each sample was measured by fluorescent X-ray method, and the minimum density of yellow was measured with an Ezuku Light 310 model photographic densitometer. The results are shown in Table-2.

(Ferric complex salt A) 8-1 Ethylenediaminetetraacetic acid ferric complex salt A-2 Diethylenetriaminepentaacetic acid ferric complex salt A-3 Cyclohexanediaminetetraacetic acid ferric complex salt A-41,2-Propylenediaminetetraacetic acid ferric complex salt Iron complex salt table-2 (I) 1,3-DPTA4e:1,3-diaminopropanetetraacetic acid ferric salt table-2 (2) 1. 3-DPTA-Fe: 1,3-diaminopropanetetraacetic acid ferric complex salt As shown in Table 2, according to the present invention, residual silver is reduced to 5 μg/c+J or less, which is not a problem in practice, and The minimum yellow density due to bleaching blade yellowing can also be suppressed to a low level.

Example-2 On a subbed cellulose triacetate film support,
Sample 201, 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/m of silver for halogenated and colloid, and the amount expressed in g/rd for couplers, additives and gelatin. ,
In addition, for dyes with no exacerbation, halogenated 11W in the same layer
It is expressed as the number of moles per mole.

1st (antihalation layer) 1 black colloid ・ ・ 0.2 gelatin ・・・1. 3ExM-8
---0,06 UV-1...0. l UV-2...0.2 Solv-1-0゜0I Solv-2...-0,01 2nd layer (middle N) Fine grain silver bromide (average particle size 0.07μ)...0. 10 Gelatin...1.5UV-1...0,
06 UV-2...0,03 ExC-2...0.02 ExF-1...0,004 Solv-1-0,1 Solv-2...0. 09 Third layer (first red emulsion layer) Silver iodobromide emulsion (Ag 12 mol%, internal high Agl type, equivalent sphere diameter 0.3 μ, coefficient of variation of equivalent sphere diameter 29%, normal crystal, twin crystal mixed grains , diameter/thickness ratio 2.5) Kudzu π cloth jl amount ・ ・ ・ ・ ・ ・ 0. 4
Gelatin...0. 6ExS-
1-...1.0XIO-' ExS-2-...3. OXI O-' ExS-3-=txto-s ExC-3...0.06 ExC-4...0.06 ExC-7...0.04 ExC-2...0.03 Solv- 1-0,03 So 1v-3---0,012 4th store (second red-sensitive emulsion layer) Silver iodobromide emulsion (Ag+5 mol%, internal high Agl type, equivalent sphere diameter 0.11t, equivalent sphere Coefficient of variation of diameter 25%, normal crystal,
Twin mixed particles, diameter/thickness ratio 4) Coated steel amount...0,7 ExS-1... lXl0-'ExS-2...-3xlo-' Sn xS-3-txto-' Sn xC-3...0.24 ExC-4...0.24 ExC-7---0,04 ExC-2...0.04 Solv-1...0.15 Solv-3-0 ,02 No. 51Z (Third red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 110 mol%, internal high Agl type, sphere equivalent diameter 0.8 μ, coefficient of variation of sphere equivalent diameter 16%, normal crystal, mixed twin crystals) Particles, diameter/thickness ratio 1.3) Coated steel amount...1. 0 Gelatin...1. OF, x
S -1... I X 10-'E-xS-2
... 3X10-'ExS-3...-1
XIO-' ExC-5--・0.05 ExC-6...05l Solv-1-...0.01 Solv-2-0,05 6th Jii (intermediate layer) Gelatin...1.0Cpd-1
...0,03 Solv-1-0,05 7th layer (first green emulsion layer) Silver iodobromide emulsion (Ag + 2 mol%, internal high Agl type, equivalent sphere diameter 0.3μ, equivalent sphere diameter Coefficient of variation 28%, normal crystal, twinned mixed particles, diameter/thickness ratio 2.5) Coated steel amount...0.30 ExS-4...5XlO-' ExS-6...0. 3X10-' ExS-5... 2XlO-' Gelatin...1. OExM
-9-0,2 ExY -14...0.03 Snake X~1-8...0.03Sol
v-1--・0.5 8th layer (second green emulsion layer) Silver iodobromide emulsion (Ag 14 mol%, internal high Agr type, equivalent sphere diameter 0.6μ, coefficient of variation of equivalent sphere diameter 38% , normal crystal, twinned mixed particles, diameter/thickness ratio 4) Coating weight...0.4 ExS-4... 5X10-' ExS-5... 2XlO-' ExS-6... 0,3X10-' ExM-9-0,25 ExM-8・ ・ ・ 0. 03 ExM-10---0,015 ExY-14-=0.01 So 1v-1---0,2 97th! ! (Third green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 16 mol%, internal high Agl type, equivalent sphere diameter 1.0μ, coefficient of variation of equivalent sphere diameter 80%, normal crystal,
Twinned mixed particles, diameter/thickness ratio 1.2) Coated steel amount...0.85 Gelatin...1.0ExS-7
---3,5xto-'ExS-8---1,4XIO-' ExM-II ...0.01Ex
M -12...0.03 ExM-13...0.20 ExM-8...0.02 ExY -15-...0.02 Solv-1.=O120 So 1v-2...0 ．． 05 No. 10 sake (yellow filter layer) Gelatin...1. 2 Yellow colloid grudge...0.08Cpd-2...
・0. l 5olv-1-...0.3 11th layer (first blue emulsion) Silver iodobromide emulsion (Ag 14 mol%, high Agl type, equivalent sphere diameter 0.5 μ, coefficient of variation of equivalent sphere diameter 15% , octahedral particles) Coating i 11 ・ ・ ・ ・ ・ ・ 0 ,
4 Gelatin...1.0ExS-
9-=2xlO-' ExY-16-□ ・0. 9 ExY-14...0.07 Solv-1-0,2 121st (second blue emulsion layer) Silver iodobromide emulsion (Aglto mol%, internal high Agl type, equivalent sphere diameter 1.3μ, sphere Coefficient of variation of equivalent diameter 25%, normal crystal, twin crystal mixed grain, diameter/r!L ratio 4.5) Coated silver amount...0.5 Gelatin...0. 6ExS-
9...IX10-'ExY-16...0.
25 S'olv-1=0.07 13th store (1st protective layer) Gelatin ・ ・ ・
0.8UV-1・・・・0. l UV-2・・・0. 2 Solv-1-0,01 Solv-2-0,01 14th layer (2nd layer) Fine grain silver bromide (average particle size 0.07μ)...0.5 Gelatin...0.45 Polymethyl methacrylate particles (diameter 1.5μ)...042 H-1...0.4 Cpd-3...0.5 Cpd-4...0. 5 In addition to the above ingredients, a surfactant was added as a coating aid to each layer.
It was set to 1.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

UV-2 ・5olv-1 tricresyl phosphate・5olv-2 dibutyl phthalate・5olv-3 bis(2-ethylhexyl) phthalate E
xF-1 (n) C-H* xY-14 CHt xC-6 H OCHz CHt 5CHt C00HEx'C-7 CHt ExM-1゜ExY-16 Cpd-I Cpd-2x
S-2 xS-6 xS-7 xSr8 EXS-SoCHs■CH-5o□-CH! -CON H-CHHz
CHx -CH-5on -CHx -CONH-CH
zpd-4 Samples 201 to 205 were prepared by adding the following amounts of antifoggants (comparative compound and compound with binding margin <1) to the following layers in the above composition.

Sample 201: Comparative compound A '202: #B 〃203 Compound (I1) #204F of knee binding margin (I)
# (4)-205: #
(I8) The sample prepared as above was treated in the same manner as in Example-1, and the results are shown in Table-3.

1,3-DPTA4e: 1,3-diaminopropanetetraacetic acid ferric complex salt Similar to Example-1, according to the present invention,
Residual silver is reduced to 5μg/- or less, which is not a problem in practice,
Moreover, the minimum yellow density due to bleaching fog can be suppressed to a low level.

Example-3 In Example-1, the bleach accelerators added to the bleaching solution were sequentially changed to (IA)-(71, (IA)-(to), (IA)-4, and (IA)-Ql). As a result of processing in the same manner as in Example-1, substantially the same effects as in Example-1 were obtained.

Patent applicant: Fuji Photo Film Co., Ltd. February 63, 2015

Claims (1)

[Scope of Claims] A method of processing an exposed silver halide color photographic light-sensitive material with a solution having bleaching ability after color development, wherein the silver halide color photographic light-sensitive material is represented by the following general formula (I). The liquid containing at least one compound and having bleaching ability contains at least one ferric complex salt selected from the following compound group (A) as a bleaching agent and a ferric complex salt of 1,3-diaminopropanetetraacetic acid. Processing method for a silver halide color photographic light-sensitive material, characterized in that the molar ratio of the former to the latter is 3 or less and the pH is 5.5 or less Compound (A) A-1 Ethylenediaminetetraacetic acid secondary Iron complex salt A-2 Diethylenetriaminepentaacetic acid ferric complex salt A-3 Cyclohexanediaminetetraacetic acid ferric complex salt A-4 1,2-propylenediaminetetraacetic acid ferric complex salt General formula (I)Q-SM^1 (Formula Medium Q is -SO_3M^2, -COOM^2, -OH
and -NR^1R^2 represents a heterocyclic residue directly or indirectly bound to at least one selected from the group consisting of
M^1 and M^2 independently represent a hydrogen atom, an alkali metal, a quaternary ammonium, a quaternary phosphonium, and R^1,
R^2 independently represents a hydrogen atom or a substituted or unsubstituted alkyl group. )