JPH012047A - Silver halide color photographic material processing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic materials. More specifically, the present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as "photosensitive materials") having rapid desilvering ability and stability of cyan dye images.

[Background of the Invention] Generally, in order to obtain a color image by processing an imagewise exposed light-sensitive material, after the color development process, the generated metallic silver is treated with a processing solution having bleaching ability, followed by washing with water, Processing processes such as water washing substitute stabilization and stabilization are also provided.

Bleaching solutions and bleach-fixing solutions are known as processing solutions having bleaching ability. When a bleaching solution is used, a step of fixing the silver halide with a fixing agent is usually added next to the bleaching step, but with a bleach-fixing solution, bleaching and fixing are performed in one step.

Processing solutions with bleaching ability for processing photosensitive materials include:
Inorganic oxidizing agents such as red blood salt monodichromate are widely used as oxidizing agents for bleaching image silver.

However, some serious drawbacks have been pointed out to the processing solutions of these S machines that have bleaching ability and contain oxidizing agents. However, there is a risk that it will be decomposed by light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body, which is an unfavorable property for preventing pollution. In addition, because these oxidizing agents have extremely strong oxidizing power, it is difficult to coexist with silver halide solubilizers (fixing agents) such as thiosulfates in the same processing solution, and these agents are not used in bleach-fixing baths. It is almost impossible to use oxidizing agents;
This makes it difficult to achieve the goal of speeding up and simplifying processing. Furthermore, treatment liquids containing these inorganic oxidizing agents have the disadvantage that it is difficult to reuse them without discarding the waste liquid after treatment.

On the other hand, organic acid gold f!
Processing solutions using complex salts as oxidizing agents have come to be used. However, the treatment solution using a heavy metal complex salt,
Due to the oxidizing power or slowness, the image silver (
For example, some iron(m) complex salts of ethylenediaminetetraacetate, which are considered to have the strongest bleaching edge among the metal complex salts, have a slow bleaching speed (oxidation speed) of metal silver). It is used in conjunction with a bleaching solution and thiosulfate, which is a bleach-fixing agent, to bleach-fix a color vapor using a silver chlorobromide emulsion, or it is used to bleach-fix a color vapor using a silver bromide or silver iodobromide emulsion. Light-sensitive materials, especially color negative films and color rehearsal films for photography that contain silver iodide as silver halide, lack a bleaching blade, and traces of image silver remain even after long processing, resulting in poor desilvering properties. becomes. This tendency is particularly noticeable in bleach-fix solutions in which the 8j-forming agent, thiosulfate, and sulfite coexist, since the redox potential decreases.

On the other hand, as a means to speed up the desilvering process, West German patent 85
No. 6,505 Mei ftE; Is there a known bleach-fix solution containing a ferric aminopolycarboxylic acid complex salt and a thiosulfate in one solution as described in IJ? When aminopolycarboxylic acid ferric complex salt coexists with thiosulfate, which has reducing power, the bleaching blade is significantly weakened, resulting in high sensitivity.

It is extremely difficult to sufficiently desilver a color photosensitive material for photographing with a high jl'l rl, and the situation is such that it cannot be put to practical use.

On the other hand, methods using two or more bleach-fixing baths have also been proposed. For example, JP-A-49-1113
Publication No. 1 (OLS-2,217,570) describes a method of replenishing the bleach-fixing regenerating solution in a countercurrent manner in a method of processing using a continuous bleach-fixing bath consisting of two or more baths. . According to this method, it is possible to reduce the amount of waste bleach-fix solution, but the regenerating solution has a higher concentration of herodanion ions eluted from color photographic materials than normal replenishing solutions, so it has a particularly high iodine content. When processing color light-sensitive materials with high densities, there is a problem that desilvering is not carried out sufficiently. Furthermore, in JP-A-58-105148, at least two bleach-fixing baths are provided, the bleach-fixing bath near the color developing bath mainly contains fixing components, and the bleach-fixing bath near the washing bath mainly contains bleaching components. A method is described in which the desilvering performance is improved by replenishing each and processing in a countercurrent manner. However, even in this method, the desilvering property is not sufficient and the density of cyan in particular decreases, resulting in the problem of so-called poor color recovery.

Furthermore, JP-A-51-75352 discloses a method for improving desilvering properties by replenishing a bleaching agent in a bath close to the color developing bath and a fixing agent in a bath close to a water washing bath, and processing in a self-flow method. is disclosed. However, this method is only effective to a certain degree in preventing poor recoloring, but is insufficient in terms of desilvering properties.

Furthermore, in JP-A No. 62-91951, there are two bleach-fixing baths, the redox potential of the first bath is higher than the redox potential of the second bath, and the redox potential of the second bath is +60.
By making it in the range of mV to -60+aV.

It is stated that it can be desilvered in a short time. However, in this method, it has been found that whether the bleach-fixing bath or a fresh solution is sufficient in terms of desilvering properties, or whether cyan recoloring properties or desilvering properties become problematic as a result of running or depending on the amount of processing.

[Problems to be Solved by the Invention] Accordingly, a first object of the present invention is to provide a desilvering method that can quickly accomplish desilvering in 1 minute. A second object of the present invention is to provide a desilvering method that can prevent cyan dye from becoming leuco.

[Structure of the Invention] Silver halide color copy J' of the present invention that achieves the above object
f The method for processing photosensitive materials includes the steps of bleaching and fixing silver halide color photographic JT photosensitive materials after color development.
The silver halide color photographic light-sensitive material has the following pattern hole [A
], [B] or [C] at least l! This is a step in which at least two or more continuous bleach-fix tanks are used in the bleach-fix treatment process using a self-flow system, and the silver concentration in the bleach-fix solution in the final tank of the bleach-fix tank is determined by controlling the silver concentration in the bleach-fix solution in the first tank. It is characterized by maintaining the silver concentration at 80% or less of the silver concentration in the bleach-fix solution.

General formula [A] General formula [B] In the formula, R5 represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Y is a group represented by (However, R2 is an alkyl group) , represents an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and R3 represents a hydrogen atom or a group represented by R2.R2 and R1 may be the same or different, and are bonded to each other. may form a 5- to 6-membered heterocycle),
Z represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.

-Crest hole [C] R11 is -CON11+J+s, -NllCOR,4,
-NlCOR'+a.

Nll5OJ+a, -N11CONR14R15 or -NIISO□NR14RI%.

1.2 is a monovalent group, R1ff is a substituent, X is a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developing agent, and 1. Il is O~3°RI4, n
+% is a hydrogen atom, an aromatic group, an aliphatic group, or a heterocyclic group,
R16 each represents an aromatic group, an aliphatic group, or a heterocyclic group, and when 1, 2, or 3, each R1ff may be the same or different, or may be combined with each other to form a ring, or R14 and 81 %, R82 and R11) R12 and X may be combined to form a ring. However, when it is 0, ■ is 0, and R11 is -CONIIRI? and RI7 represents an aromatic group.

[Function of the Invention] The present invention is a method for processing a photosensitive material containing a specific cyan coupler, in which the bleach-fixing tank used is a self-flow system with at least two or more consecutive bleach-fixing tanks, and the bleach-fixing tank in the final tank is The silver concentration of the fixing solution is maintained at 80% or less of the silver concentration of the bleach-fixing solution in the first tank, but according to the studies of the present inventors.

The desilvering speed largely depends on the silver concentration in the bleach-fixing solution, and the lower the silver concentration, the faster the desilvering speed.1For example, when processing the light-sensitive material of the present invention, the ratio of the total amount of replenisher to the capacity of the bleach-fix tank. (Hereinafter referred to as "R".

When the round (referred to as "round") ranges from 0 to 0.2R, silver accumulation is small and does not significantly affect the desilvering rate; however, as processing exceeds 0.2R, the silver concentration in the bleach-fix solution increases. , it affects the desilvering speed, and furthermore, the desilvering ability of the bleach-fix solution decreases because the color developing solution is brought in by the light-sensitive material, so one way to improve this is to replenish the silver concentration to lower the silver concentration. Increasing the amount causes many problems in terms of pollution and cost, which led to the completion of the treatment method of the present invention.

[Specific structure of the invention] The present invention will be explained in detail below.

Regarding the number of baths (tanks) in the bleach-fixing bath (tank) of the present invention, from the viewpoint of lowering the silver concentration and the amount of replenishment, the larger the number of baths (tanks), the greater the effect, but in practice, it is 2 to 4 baths. , preferably a two-tank configuration.

The silver concentration in the bleach-fix solution is determined by the amount of silver in the photosensitive material to be processed and the amount of bleach-fix solution refilled, or the silver concentration in the bleach-fix solution in the final tank is determined by the silver concentration in the bleach-fix solution in the first tank. 80 of
% or less, preferably 60% or more, more preferably 40%
By doing the following, the desilvering promoting effect of the present invention is further enhanced.
Written by J. The silver concentration in the final bath is 0 per 11 bleach-fix solutions.
．． The amount is preferably 0.07 mol or less, more preferably 0.03 mol or less.

In order to further enhance the effects of the present invention, a significant improvement effect can be obtained by controlling the iodide concentration in the bleach-fix solution. Specifically, the absolute iodide concentration in the first bath is 0.
．． The amount is preferably from 0.002 to 0.03 mol/l, more preferably from 0.003 to 0.02 mol/l. The iodide concentration is adjusted depending on the photosensitive material to be processed by adjusting the amount of bleach-fixing replenisher and the amount of retroactive (countercurrent) overflow.

In the countercurrent method of bleach-fixing solution in the present invention, in a method of processing in a continuous bleach-fixing bath consisting of two or more baths, the bleach-fixing solution replenisher is replenished from the final tank, and the countercurrent method is used to transfer the bleach-fixing solution to the previous tank. A method of sequential replenishment is preferable.

Examples of bleaching agents used in the bleach-fixing bath of the soft invention include iron (■), cobalt (■), chromium (■), and copper (II).
), etc. (e.g. ferricyanide)
, peracids, quinones, nitroso compounds; dichromate;
Organic complex salts of iron (m) or cobalt (III) (e.g., aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, complexes such as aminopolyphosphonic acid, phosphonocarboxylic acids, and organic phosphonic acids, or citric acid) Organic acids such as , tartaric acid and malic acid; persulfates; hydrogen peroxide: permanganates, etc. can be used.

The bleaching agent used in the bleach-fixing process according to the present invention is preferably an organic acid ferric complex salt, and a bleaching agent that forms an organic acid ferric complex salt is preferable.
The acids are preferably aminocarboxylic acid compounds and aminophosphonic acid compounds, and an amino compound having at least one carboxylic acid group and an amino compound having at least one phosphonic acid group, respectively, are preferably used. more preferably, the following general formulas [11 and [2
] This is a compound represented by

General formula [11 General formula [2] In the formula, E is a substituted or unsubstituted alkylene group.

Represents a cycloalkylene group, a phenylene group, -n,, 50RssOnsa-, -RssZR-s-, Z represents >N455-As, >N-A3,
R, 5, ~ l1ss represents a substituted or unsubstituted alkylene group, A, ~, is a hydrogen atom, -011, -COOM
, -POffM2, and M represents a hydrogen atom or an alkali totally bent atom.

Next, preferred specific examples of the compounds represented by these general formulas [1] and [2] are listed below.

[Exemplary Compounds] [1-1] Ethylenediaminetetraacetic acid [1-2] Diethylenetriaminepentaacetic acid [1-3] Ethylenecyamine-N-(β-hydroxyethyl)-N, N', N'-
1-Triacetic acid [1-4]propylenediaminetetraacetic acid [
1-5] 1-lyethylenetetraminehexaacetic acid [1-6
] Cyclohexanediaminetetraacetic acid.

[1-7]1,2-diaminopropanetetraacetic acid [1-
8] 1.3-diaminopropan-2-ol-2-tetraacetic acid [1-9]ethyl ethercyamine tetraacetic acid [1-1
0] Glycol ether diamine tetraacetic acid [1-11] Ethylenediamine tetrapropionic acid [1-12] Phenylenecyamine tetraacetic acid [1-13]
] Ethylenediaminetetraacetic acid disodium salt [1-14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [1-15] Ethylenediaminetetraacetic acid tetrasodium salt m [1-16] Diethylenetriaminepentaacetic acid pentasodium salt [1-17] Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetic acid sodium salt [1-18] Propylenediamine tetraacetic acid sodium salt [1-19] Ethylenediamine tetramethylene phosphonic acid [1-2Q] Cyclohexane Diaminetetraacetic acid sodium salt [1-213 diethylenetriamine pentamethylene phosphonic acid [1-22 cocyclohexanecyamine tetramethylene phosphonic acid [2-1] nitrilotriacetic acid [2-2] iminodiacetic acid [2-3] hydroxyethyliminodi Acetic acid [2-4] Nitrilotripropionic acid [2-5] Nitrilotrimethylenephosphonic acid [2-6]
Iminodimethylenephosphonic acid [2-7] Hydroxyethyliminodimethylenephosphonic acid [2-8] Nitrilotriacetic acid trisodium salt Among these aminocarboxylic acid compounds and aminophosphonic acid compounds, the points of effect aimed at by the present invention are Among the compounds that are particularly preferably used are:

(1-1), (1-2), (1-4), (1-5).

(1-7), (1-8), (1-10), (1-
19).

Examples include (2-1), (2-3), and (2-5).

Especially among these aminocarboxylic acid compounds and aminophosphonic acid compounds, only one molecule of free acid (hydroxide)! Those with a molecular weight of 300 or higher are particularly preferably used because of their good fixing performance, such as (
1-2), (1-4).

(1-7) and (1-10) are mentioned as particularly preferred compounds.

The ferric complex salt of an a-acid according to the present invention can be a free acid (hydroxide), a sodium salt, a potassium salt, an alkali metal salt equivalent to lithium, or an ammonium salt, or a water-soluble amine salt such as a triethanolamine salt. Preferably, potassium salt, sodium salt and ammonium salt are used. At least one type of these ferric complex salts may be used, but two or more types may be used in combination.

Iron (m) j! As the salt, one or more ready-made complex salts may be used, or #(■) salts (e.g. ferric sulfate, ferric chloride) may be used.
Iron, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc.) and a chelating agent (aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.) are reacted in a solution to form ferric ions. When forming a complex salt in a solution, one or both of the ferric salt and the chelating agent may be used in combination of two or more types. It may be used in an amount greater than the stoichiometric amount, and may also contain metal ions other than iron such as cobalt and copper, complex salts thereof, or hydrogen peroxide.

Persulfates that can be used in the present invention include alkali metal persulfates such as potassium persulfate and sodium persulfate, and ammonium persulfate.

The amount of U0 agent per processing bath 11 having bleach-fixing ability is generally 0.2 to 2 mol, preferably 0.25 to 2 mol.
1.0 mol, particularly preferably 0.30~! , 0 mol. If the content of the bleaching agent is 0.25 mol or less, it tends to affect the recoloring property, and in terms of stable recoloring property, 0.25 mol or more, especially 0.30 mol or more is required as a tπ whitening agent.

As mentioned above, the bleach-fixing bath of the present invention contains, as a bleaching agent,
Ferric ion complexes of aminopolycarboxylic acids, aminopolyphosphonic acids, phosphonocarboxylic acids, and organic phosphonic acids are preferably used, and furthermore, free chelating agents other than the ferric ion complexes of the above-mentioned chelating agents are ferric ion complexes. It is used for stabilizing the complex, but according to the study conducted by the present inventors, it was found that if the content exceeds 7.5 mol% based on the ferric ion complex, the recoloring property tends to deteriorate. . Therefore, the free chelating agent is 7.5 mol% relative to the ferric ion complex.
Below, preferably 5 mol% or less is preferable for the present invention.

The preferable pn range of the bleach-fixing bath of the present invention is 0.5 to 9.0 in the case of ferric ion complex salts, especially aminopolycarboxylic acids, aminopolyphosphonic acids, phosphocarboxylic acids, organic phosphonic acid complexes, etc. In case of iron ion complex salt 4.
It is 0 to 8.5. In the case of a supersulfurized salt, it is preferable that 911 is in the range of 1 to 8.5 at a concentration of 0.1 to 2 mol/l.

In addition, the bleach-fixing solution according to the present invention includes the following general X, c
When containing at least one of the compounds represented by I1 to [lX], the desired effects of the present invention are better achieved,
Since it also has the additional effect of reducing precipitation caused by silver in the white fixer, it is more preferably used in the present invention.

- Monana [II Lower R3 [In the formula, Q represents an atomic group essential for forming a nitrogen-containing heterocycle (including 5 to 6 negative unsaturated rings or fused rings), and R3 is Hydrogen atom, alkyl group having 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic group (5 to 6
(including those with fused unsaturated rings), or an amino group. ]General Monna II] [In the formula, R1 and R1 are each a hydrogen atom, an alkyl group having I to 6 carbon atoms, a hydroquine group, a carboquino group,
Amino group, acyl group having 1 to 3 carbon atoms, aryl group,
Or represents an alkenyl group.

A represents an or n1-valent heterocyclic residue (including those in which 5-6H unsaturated rings are condensed), and X is =S, =0 or =N
R''. Here, R and R' are synonymous with R2 and R1, respectively, X' is synonymous with X, Z is a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic 9A group, an alkyl group, where R'' represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (a group in which 5- to 6-membered unsaturated rings are fused) ) or an amino group, n 1 ”'
-n@ and m+""m5 each represent an integer from 1 to 6.

and R5 may each represent -B-SZ, and R7 and R1, R and R', and R4 and R6 may each be bonded to form a ring.

Note that the compound represented by the formula also includes ethanolated compounds and salts thereof. ] General formula [II[] [wherein R8 and R9 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxyne group,
Amino group, acyl group having i to 3 carbon atoms, aryl group,
represents an alkenyl group or -B, -, Zl represents a hydrogen atom or an alkali metal atom, and an/ represents -S-B, -Y. 17 represents an integer of 1 to 6\ General formula [IV] [In the formula, Rs and R8 represent each, R1 (1 is an alkyl group or -(CHt)n*5
Represents O3e. (However, Rte is -(CHt)ns S
When it is O or e, g represents 0, and when it is an alkyl group, it represents I. ) G (1 represents an anion. ns represents an integer of 1 to 6.) General formula [V] [In the formula, Q is a nitrogen-containing heterocycle (5 to 6M unsaturated rings or saturated rings fused together) Represents the atomic group necessary to form a hydrogen atom (including those with a carbon atom), where Ro is a hydrogen atom and Q' is synonymous with Q. 8 represents an alkylene group or a vinylene group, and Q+, qtlQl and q4 each represent 0.1 or 2.Also, the ring formed with the sulfur atom may be further condensed with a 5- to 6-membered saturated or unsaturated ring. Good.] General formula [■CORte Rte Rte [In the formula, x2 is -COOM', -OH.

-305M', C0NHt, SO*NHt.

NHt, -8H, -C1'J, -COtR+s.

-SO snow R+s, -OR+*, N R+sRI?
.

SR1@, -5O3R1@, NHCORI@.

-NH5OtR1m, -0COR++ or -S Ot
RI @ represents, Y represents a hydrogen atom, mo and n each represent 1-10
represents an integer. RIlt R(*+ Rlas RI!
+R+ and Ro each represent a hydrogen atom, a lower alkyl group, an acyl group, or a K''kyl group % R1m is -NR1°R21, -0Rl
t or -SR□, R1゜ and R, .1 each represent a hydrogen□ atom or a lower alkyl group, R- is Rlm
Represents the atomic group necessary to combine with to form a ring.

R1° or Rt+ may be combined with R2 to form a ring. M' represents a hydrogen atom or a cation. ] General formula [■
] (II)x ((H・)z (II)y where Ar
represents a divalent aryl group or a divalent organic group combining an aryl group with an oxygen atom and/or an alkylene group, B and R3 each represent a lower alkylene group, rL , , R, , Rls and R1 each represent a hydroxy-substituted lower alkylene group, and X and y are each O or! represents. G' represents an anion, 2 is O
, I or 2. ] General formula [IX] 3t [In the formula, R2 and R2° each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, R represents a hydrogen atom or an alkyl group, and nsl represents a hydrogen atom or Represents a carboxy group. Ko.

The compounds represented by the general formulas [1] to [IX] that are preferably used in the Lee invention are compounds that are generally used as bleach accelerators, and are hereinafter referred to as the bleach accelerators of the present invention.

Typical specific examples of the bleaching accelerators of the present invention represented by the above-mentioned patterns [11 to [IX] include, but are not limited to, the following.

Exemplary compound ([-3) (1-4)([
-5) ([-6)CItCH
tCOOH (n-1) L) f-C-C-Nll.

S ([+-2) (II-3) ((I-4) (II-5) (■-6) +1. N-C3NIINIICS-NH.

(II-7) +1J-C3NII (CIt) JIICS-Nll.

(It-8) (tl-9) ([[-10) ([1-1t) (II-12) (II-13) (■-14) (■-15) ([r-16) (II -17) (II-18) (II-19) (■-20) (n-21) (II-22) (■-24) (II-25) (■-26) CU-21) (Ill- 1) (+[
-2) (Ul-3)
(lIt-4) (ill-5)
(ffl-6) (ill-7)
(III-8) (fl-9)
(, ■-10) (m-11) (III-12) ([[l-13) ([[l-14) ([1-15) (V-1) (V-2)
(V-3) (V-4)
CHa5C1ltO
I[(V-6) (V-7)
(V-8) (V-9) (
V-10) ' (V-11
)L (V-12) (V-13)(
V-14) (V-15) (V-16) (V-18) (V-19) (V-20
)(V-21)(V-2
2) (V-23) nYI+ H (Vr-t) (Vl-2)
(Vl-1) (Vl-4) (■-
5) (V[-6) (Vl-7)
(V[-8) (V[-9
) (VI-1o) (Vl publication 1)
(V[-12)0■ (Vl-13) (VI-14)
(Vl-15)Ctl-16)
(■-17) (vn-1 (■-2) (■-3) (■-4) (■-5) (■-6) (■-7) ('711-8) ('711-9 ) (■-10) (■-11) (■-12) (Vl[-1:1) 113C11□(:tlJCII□CIItCONH□
Ctl, 3 (■-14) 113C112CII□N II CII□C11□0
11(■-15) 113c112clI□NCII□C112011C2
11゜(■-1) C11J(CIIyCIltoll)z(■-2) (■-3) C)IJ(CLCLOH)t (■-4)4 CIbNII(CHtCIItOH) 2CH*NCC
H, CIl, OH).

(IK-1) (IX-2) (IX
-3), (IK-4)(
IX-5) In addition to the bleaching accelerator of the present invention exemplified above,
Exemplary compounds No., I-2, I-4 to 7゜I-9-- described on pages 51 to 115 of Specification No. 263568
13, l-16~21. I-2:l, ■ -24,
I-26, 27, I-30~36, ■-38, rl
-2~5゜H-7 to 10, ■-12~ZO1■-22N
25, ll-27, ■-29-33. ■-35, 36,
n-38~41.11-4:l, ■-45~55, ■-
57-60, ll-62-64, ■-67-71.11
-73~79. ll-81~84, ll-86~99,
■-tot, toz, ll-104~110, I
I-112 to 119゜ll-121 124. ll
-126, H-128~144, rI-146゜■-1
48-155, II-Isfu, m-4, m-6
~8゜m-10, 11, m-13, m-15~18, ■
-20, m-22, lll-23, m-25, l1l-
27, lll-29~32゜m-35,36,■-3,
IV-4, V-3~6, V-8~14. V-16~3
8, V-40~42, V-44~46, 66 to V-48
, V-68~70. V-72~74, ■-1F~79,
V-81, 82, V-84~ 100. V-10
2-tOa, v-tto, V-112, 113, V-1
16 to 119°V-121~123. V-125~1
:10, V-1:12~+114, V-145~+6
2. V-164~174, V-176-111
4, VI-4, VT-7, VI-10, VT-12
, Vl-1:l.

VT-16, VI-19, Vl-21, VI-22, ■
-25, V't-27-34, -36, VII-3
, VI[-6, ■-13, ■-19, ■-20, etc. can be similarly used.

These bleach accelerators may be used alone or in combination of two or more, and good results are generally obtained when the amount added is in the range of about 0.01 to 100 g per liter of bleach-fix solution. However, in general, if the amount added is too small, the effect of promoting bleaching will be small, and if the amount added is too large, precipitation may occur and contaminate the photosensitive material being processed. The amount is preferably from 0.05 to 50 g, more preferably from 0.05 to ISg per 11 of the blank fixer.

When adding a bleach accelerator, it may be added and dissolved as is, but it is common to dissolve it in water, alkali, organic acid, etc. before adding it, and if necessary, add methanol, ethanol, y It can also be dissolved and added using an organic solution such as setone.

As the bleach-fixing solution according to the present invention, the organic acid iron (
It is preferable to use a solution containing a II[) complex salt as a bleaching agent, a silver halide fixing agent, and, if necessary, a peracid m-salt. In addition, organic acid iron (
m) A bleaching liquid containing a small amount of a halogen compound such as potassium bromide in addition to a complex salt bleach and the above-mentioned silver halide fixing agent, or conversely a composition containing a large amount of a halogen compound such as potassium bromide. A bleach-fix solution consisting of
Furthermore, a special bleach-fixing agent having a composition consisting of a combination of a 1:1 organic acid iron (m) complex, a bleaching agent, and a large amount of a halogen compound such as potassium bromide can also be used. In addition to potassium bromide, the halogen compounds mentioned above include hydrochloric acid,
Hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

The silver halide fixing agent to be included in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, potassium thiocyanate, ammonium thiosulfate, which is used in ordinary fixing processing. thiosulfates, potassium thiocyanate, sodium thiocyanate.

Typical examples include thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and the like. These fixatives are 5g/9. The above amounts can be used within the range that can be dissolved.

The bleach-fix solution contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate,
A pH buffering agent consisting of various salts such as ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants may be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, nitroalcohol, nitrile m11! Stabilizers such as, organic solvents such as methanol, dimethyl sulfonamide, dimethyl sulfoxide, etc. may be included as appropriate.

In the processing method of the present invention, is it preferable to perform one-color development followed by bleach-fixing? After bleach-fixing, washing with water may be performed, or stabilizing processing may be performed without washing with water, or washing with water may be performed. However, stabilization treatment may be performed thereafter.

Furthermore, before the color development of the present invention, black and white development, fogging, stopping +
It is optional to use the steps such as L. and washing with water, that is, the commonly used treatment steps.

In the present invention, the bleach-fixing processing time is suitably within 6 minutes and 30 seconds, preferably within 5 minutes, from the viewpoint of speed. In this case, the processing time of the first bath is preferably 20 seconds to 4 minutes in order to sufficiently dissolve the silver halide in the first bath, but it is preferable in the present invention that the processing time of the first bath is approximately 50% or more. This is preferable because it achieves the following effects.

Next, the cyan coupler used in the red-sensitive silver halide emulsion layer of the light-sensitive material according to the present invention will be explained.

The cyan coupler of the present invention can be represented by the above formula [A], [B] or formula [C].

First, the -mathematical formula [A] and -mathematical formula [B] will be explained. In the formula, Y is a group represented by: Here, R1 and R2 are each an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (such as methyl, ethyl, E-butyl, dodecyl, etc.), an alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms (
allyl group, heptadecenyl group, etc.), cycloalkyl group,
Preferably those with 5 to 7 negative rings (e.g. cyclohexyl, etc.), aryl groups (e.g. phenyl, tolyl, naphthyl, etc.), heterocyclic groups, preferably containing 1 to 4 nitrogen atoms, oxygen atoms or sulfur atoms. 5-membered to 6-membered negative ring group (
For example, furyl group, thienyl group, benzothiazolyl group, etc.)
R3 represents a hydrogen atom or a group represented by R2, R2 and l(3 may be combined with each other to form a 5-6 negative heterocycle. For example, an alkyl group having 1 to 10 carbon atoms (eg, methyl, i-propyl, i-butyl, thi-butyl, t-octyl, etc.), an aryl group (eg, phenyl).

naphthyl, etc.), halogen atoms (fluorine, chlorine, bromine, etc.)
, cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.), sulfamoyl groups (methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl groups (
For example, methanesulfonyl, p-toluenesulfonyl, etc.)
, fluorosulfonyl group, carbamoyl group (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.), oxycarbonyl group (e.g. ethoxycarbonyl, phenoxycarbonyl, etc.), acyl group (e.g. acetyl, benzoyl, etc.), heterocycle (e.g. pyridyl group, pyrazolyl group, etc.) ), alkoxy groups, aryloxy groups, acyloxy groups, etc.

In the general formula [A] and -numerical formula [B], R.

represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by formulas [A] and -formula [B] and the cyan dye formed from the cyan coupler, preferably having 4 to 4 carbon atoms. 0 which is an alkyl group, aryl group, alkenyl group, cycloalkyl group or heterocyclic group of 30
For example, straight-chain or branched alkyl groups (e.g. t-butyl,
n-octyl.

(t-octyl, n-dodecyl, etc.), 5Q or 6-membered heterocyclic groups, and the like.

In the general formulas [A] and -numerical formulas [B], 2 represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized color developing agent.
(bromine, fluorine, etc.), 21-substituted or unsubstituted alkoxy group,
Examples include aryloxy groups, heterocyclic oxy groups, acyloxy groups, carbamoyloxy groups, sulfonyloxy groups, alkylthio groups, arylthio groups, heterocyclic thio groups, and sulfonamide groups.More specific examples include U.S. Pat. No. 741,563, JP-A-47-37425,
Tokuko Sho 48-. No. 36J194, JP-A-50-1013
No. 5, No. 50-117422, 1st issue 50-1: 1044
No. 1, No. 5t-toaait, No. 50-120343
No. 52-18315, No. 53-105226,
No. 54-14736, No. 54-48237, No. 55
-32071, 55-65957, 56-19
No. 38, No. 56-12643, No. 56-271117
No. 59-146050, No. 59-166956, No. 60-24547, No. 60-35731, No. 6
Examples include those described in No. 0-37557.

In the present invention, a cyan coupler represented by the general formula [D] is preferred.

General formula [D] B1 In the general formula [D], R4 is a 21-substituted, unsubstituted aryl group (especially preferably a phenyl group). When the aryl group has this substituent, the substituent is 5o2R
, + , halogen atoms (fluorine, salt, lead, bromine, etc.),
-CF, , -No□, -CN, -COR, , -
At least one substituent selected from COOR5, -3O20R1, is included.

Here, R5 is an alkyl group, preferably having 1 to 2 carbon atoms
0 alkyl groups (e.g. methyl, ethyl, L-phthyl,
dodecyl groups, etc.), alkenyl groups preferably having 2 carbon atoms
~20 alkenyl groups (allyl group, heptadecenyl group, etc.), cycloalkyl groups, preferably those with 5- to 7-membered rings (
R6 represents a hydrogen atom or a group represented by R5.

A preferable compound of the cyan coupler of the present invention represented by the general formula [D] is R4 is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro,
5O2R7 (nt is an alkyl group), halogen atom,
A compound that is trifluoromethyl.

In general formula [D], Z and Ro are each 17 general formula [A]
and [B] have the same meaning.

A preferred example of the ballast group represented by R1 is a group represented by the following formula [E].

-Formula [E] (Rv)K In the formula, J represents an oxygen atom, a sulfur atom, or a sulfonyl group, and K represents an integer from θ to 4. or l, and when K is 2 or more, two or more 8 may be the same or different <, Ra is a straight chain or branched chain having 1 to 20 carbon atoms, and aryl 2! represents a substituted alkylene group such as R
9 represents a monovalent group, preferably a hydrogen atom, a halogen atom (e.g. chromium, bromine), an alkyl group, preferably a linear or branched alkyl group having 1 to 20 carbon atoms (e.g. methyl, di-methyl, -pentyl, octyl, dodecyl, pentadecyl, benzyl, phenethyl, etc.)
, an aryl group (e.g. phenyl group), a multicyclic group (e.g. a nitrogen-containing heterocyclic group), an alkoxy group, preferably a straight chain or branched alkoxy group having 1 to 2 o carbon atoms (e.g. methoxy, ethoxy, butyloxy) , octyloxy, decyloxy, dodecyloxy, etc.), acyloxy group (e.g. phenoxy group), hydroxy group, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy group, benzoyloxy group), carboxy, an alkyloxycarbonyl group, preferably a linear or branched alkylcarbonyl group having carbon a1 to 2°, preferably a phenoxycarbonyl group, an alkylthio group;

Preferably an acyl group having from Al to 20 carbon atoms, preferably a straight chain or branched alkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably a straight chain or branched alkylcarboamyl group having 1 to 2 degrees of carbon atoms. , a benzenecarboxamide group, a sulfonamide group, preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms, or a benzenesulfonamide group, a carbamoyl group, preferably a carbon number 1
-20 linear or branched alkylaminocarbonyl group or phenylaminocarbonyl group, sulfamoyl group, preferably C1-20 linear or branched alkylaminosulfonyl group, phenylaminosulfonyl group, etc.

Next, specific examples of compounds of the cyan coupler of the present invention represented by the general formula [A] or [B] will be shown, but the invention is not limited thereto.

Margin below [Exemplary compounds] 4Hg (t)OsHly OH C■.

p Oh.

0-! 5 H (t)CsHlt 0H.

L C,H.

ρl 068! .

4H9 l t 0, Hl.

C-37 nIJ H -4l U4 Myo-υ2NH (t)c4ug H OCH20H200H.

Next, the above-mentioned formula [C] will be explained.

- Each branch represented by RI2 to RIT in formula [C] includes those having a substituent.

Rts is an aliphatic group having 1 to 30 carbon atoms, and an aliphatic group having 6 to 30 carbon atoms.
30 aromatic group, a heterocyclic group having 1 to 30 carbon atoms is preferable, and R14 and Rts are hydrogen atoms and Flys
Those listed as preferred are preferred.

R12 is a hydrogen atom bonded to Nil directly or via NH, Co or S02, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 primary primes, and a heterocyclic group having 1 to 0 carbon atoms. , OR+a, -COR+a-PO-+0R
tO)2, -P(leR2o)t, -COJto,
-5OJzo - or -3OJR*o (R
ts, R19 and R20 are respectively the above "14 +
"I! and Ls, R1, and RI9 may be combined to form a heterocycle)" is preferred.

R17 is preferably an aromatic group having 6 to 30 carbon atoms, and representative examples of substituents for R1 include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group,
Cyano group, aromatic group, heterocyclic group, carbonamide group,
Sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group,
Examples include an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, an imide group, an aliphatic group, and an aliphatic oxycarbonyl group. When substituted with a plurality of substituents, the plurality of substituents may be bonded to each other to form a ring, such as a dioxymethylene group.

Representative examples of RI:I include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, and a carbamoyl group.

Sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group.

Examples include an aliphatic thio group, an aromatic thio group, an aliphatic sulfonyl group, an aromatic sulfonyl group, a sulfamoylamino group, a nitro group, and an imide group.

The number of carbon atoms contained in this 1lti is preferably 0 to 30.

Examples of cyclic R13 when -=2 include a dioxymethylene group.

When the sentence is l, R11 is particularly preferably -CONR+J+s, ■ is preferably 0, and R12 is directly bonded to NH -COR+a, -C00R20, -3OJto, -C
ONR18R19,5OJRI-Rts is particularly preferred, and even more preferred is one GOOR that binds directly to Nll.
,,, -COR,a, -3OJ*.

Among others, -COOR. is most preferred.

Also included in the present invention are those that form dimers or more multimers via R++-RIz, X.

- Among formula [C], it is preferable that the value is 0.

A specific example of the coupler represented by the general formula [C] is JP-A-60
-237448, 61. -153640, 61
-145557, 62-85242, 48-1
No. 5529, No. 50-117422, No. 52-18:
IIs No. 52-90932, No. 53-52423
No. 54-48237, No. 54-66129, r
i7155-3207i, rib 55-65957, rib 5s-toszzs.

56-+9:1a, 56-12643, 5
No. 6-27147.

No. 56-126812, No. 58-. 95:146 and U.S. Pat. No. 3,488,193, etc.
It can be synthesized by the methods described in these.

To add a coupler to a light-sensitive material, depending on the physical properties (for example, solubility) of the coupler, a water-insoluble, high-boiling organic melt may be used. □Oil-in-water emulsion dispersion method.

Various methods can be used, including an alkali dispersion method in which the material is added as an alkaline solution, a latex dispersion method, and a solid dispersion method in which it is directly added as a fine solid.

The amount of coupler added is usually t per mole of silver halide.
ox io mol to 1.0 mol, preferably 5.0 x I
n''3 moles to 11.Ox 10-' moles.

Next, typical examples of the coupler represented by the general formula [C] will be shown, but the present invention is not limited thereto.

[Exemplary compounds] CI3CONH CIIaSOJH C-55 C-56 C1slb, 1SOJH H 0■ H C1H60CONH C, Il, 0CONH ,H,OCONH blgubsnrI C-750H IJII H -5O C,H,0CONH x: y -60: 40 (molar ratio) N

65 to N-
'00Q口cy'+
'Ideoo
OcoI 0mouthCHzCHtSCHtCIItCOtHCo , +1 CH*CHJH8OtCHs rθ CO,,H CaH+s Ca1ls CIl, CHs l0LI OOH OOH 0C■tCOMHCIJ'5 Cool( OOH CO,U (mol (ratio) Next, some supplementary information regarding the photosensitive material related to the present invention. explain.

The photosensitive material according to the present invention uses an internal development method (U.S. Pat. No. 2,375,579) in which a coupler is contained in the photosensitive material.
No. 2,801,171), as well as external development methods in which the coupler is contained in the developer (U.S. Pat.
No. 52,718, No. 2,592,243, No. 2.59
0,970), and any couplers generally known in the art can be used. For example, cyan couplers other than those of the present invention may be used in combination; Cyan couplers used in combination include those based on a naphthol or phenol structure and which form indoaniline dyes by coupling; magenta couplers include those having a 5-pyrazolone ring with an active methylene group as a backbone structure and pyrazole azole-based couplers. As yellow couplers, those having a benzoylacetanilide, bivalylacetanilide, or acylacedoanilite structure having an active methylene ring, with or without a substituent at the coupling position, can be used. In this way, as a coupler,
Both 2-equivalent type couplers and 4-equivalent type couplers can be applied.

The silver halide emulsion that can be used in the present invention includes any conventional halogen emulsion such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. It may be silver iodide, preferably silver iodobromide containing 0.5 mol % or more of silver iodide.

Further, a tabular silver halide emulsion or a core/shell emulsion may be used. In addition, as protective colloids for these silver halides, in addition to natural products such as gelatin, various synthetically obtained colloids can be used. The silver halide emulsion may contain conventional photographic additives such as stabilizers, sensitizers, hardeners, sensitizing dyes, and surfactants.

The photosensitive materials used in the present invention include color negative films, color vapors, color reversal films, color reversal papers, and other photosensitive materials that are applicable to processing systems that have a single color development process (including activator treatment) and a bleach-fixing process. You can use all of them, but color negative film for engraving is the most preferable.

In the color developing solution of the present invention, it is preferable to use a p-phenylenediamine color developing agent, which is generally used in the form of a salt, such as a hydrochloride or a sulfate, since it is more stable than a free state. . Further, the p-phelenediamine color developing agent is generally used in a concentration of about 0.5 g to about 30 g for the color developing solution 11.

In the present invention, a particularly useful p-phenylenediamine color developing agent is an aromatic primary amine color developing agent having at least one water-soluble amino group, and is particularly preferably represented by the following general formula [4]. The compound shown is

General formula [Myo] In the formula, R64 represents a water atom, a halogen atom, or an alkyl group, and this alkyl group is a linear or branched carbon number of 1 to 5.
represents an alkyl group, which may have a substituent. R6
, and R6G represent a hydrogen atom, an alkyl group or an aryl group, or these groups may have a substituent, and in the case of an alkyl group, an aryl group or a substituted alkyl group is preferred, and 86% and 116g. At least one is an alkyl group or +(C
Il□+0-)-867. This alkyl group may further have a substituent.

In addition, R67 represents a hydrogen atom or an alkyl group, and this alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and r represents an integer of 1 to 5.

Next, typical examples of the compound represented by the general formula [)tllll will be listed, but the invention is not limited thereto.

[Exemplary compounds]

(E-1) NH2 (H-2) NH2 (E-3) rslF summer.

(B-4) (E-5) N.H.

(E-6) (E-7) (E-8) N! (2 (E-9) N.H.

(E-10) N.H.

(E-11) N.H.

(E-12) (B-13) NH2 (E-14) NH2 (H-15) NH2 (B-16) N.H.

These p-phenylenediamine derivatives represented by the general formula [)flV] can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, and It is also possible to use acid salts, penzel disulfonates, and the like. In the present invention,
Among these p-phenylenediamine derivatives represented by the general formula, I? ss and/or R66 or 11□+O+Rat (t, , and R6? have the same meanings as above), the effects of the present invention are particularly well achieved.

[Effects of the Invention] According to the present invention, it is possible to provide a desilvering treatment method that can quickly and sufficiently achieve desilvering, and can also prevent leucoization of cyan dye. .

[Examples] Hereinafter, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto. Incidentally, the amount added is per 100 crn' unless otherwise specified.

Example 1 The following layers were sequentially disposed on a triacetyl cellulose film support to prepare samples No. 1. However, the amount of coated silver is 80mg/100cm'', and the dry film thickness is 2
5#L was honored.

Layer 1: A dispersion of 0.8 g of black colloidal silver, which is highly absorbent to light in the wavelength range of 400 to 7001 by reducing silver nitrate with hydroquinone as a reducing agent, is prepared in 3 g of gelatin, and an antihalation layer is applied. did.

Layer 2: Middle layer made of gelatin.

Layer 3 - 1.5 g of low-sensitivity red-sensitive silver iodobromide emulsion (Ag
l; 7 mol%), 1.6 g of gelatin and 0.8
5g of cyan coupler C-28 of the invention, 0,030g
1-hydroxy-4-[4-(1-hydroxy-8-
acetamido-3,6-cisulfo-2-naphthylazo)
phenoxy]-N-[δ-(2,4-di-amylphenoxy)butyl]-2-naphthamide disodium (hereinafter referred to as colored cyan coupler (CC-1))
A low-sensitivity red-sensitive silver halide emulsion layer containing 0.4 g of tricresyl phosphate (hereinafter referred to as TCP) dissolved therein.

Layer 4...-1,: 1 g of highly sensitive red-sensitive silver iodobromide emulsion (
Agl: 6 mol%), 1. ] g of gelatin and 0.0 g of gelatin.
28g cyan coupler (C-28), 0.020
g of colored cyan coupler (CC-1) dissolved in 0
, a highly sensitive blue-sensitive silver halide emulsion layer containing 17 g of TCP.

Layer 5: LO4g of di-n-butyl phthalate (hereinafter referred to as "fouling inhibitor (HQ-1)") in which 0.08g of 2.5-di was dissolved in mono-octylhydroquinone (hereinafter referred to as antifouling agent (HQ-1)).
DBP) and 1.2 g of gelatin.

W 6-1.6g of low-sensitivity green-sensitive silver iodobromide emulsion (Ag
l; 6 mol%), 1.7 g of gelatin and 0.32
g of 1-(2,4,6-)-lichlorophenyl)-3-
[:1-(2,4-di-t-amylphenoxyacetamide)benzenamide]-5-pyrazolone (hereinafter).

Magenta coupler (referred to as M-1)), 0.20g of 4
,4-methylenebis-11-(2,4,6-)lichlorophenyl)-3-[:1-(2,4-di-monoamylphenoxyacetamide)benzenamide 1-5-pyrazolone (hereinafter referred to as magenta coupler ( (referred to as M-2)),
0.066 g of 1-(2,4,6-dolichlorophenyl)-4-(1-naphthylazo)-3-(2-chloro-5
-octadecenylsuccinimide anilino)-5-pyrazolone (hereinafter referred to as colored magenta coupler (CM-1)
0.3 g of TCP in which three types of couplers (referred to as
A low-sensitivity green-sensitive silver halide emulsion layer containing.

Layer 7 - 1.5 g of high-sensitivity green-sensitive silver iodobromide emulsion (Agl
:8 mol%), 1.9 g of gelatin and 0.1O
g of magenta coupler (M-1), 0.098 g of 7 zenta coupler (M-2).

0.049g colored magenta coupler (CM-1)
A high-sensitivity green-sensitive silver halide emulsion layer containing 0.12 g of TCP dissolved in TCP.

Layer 8: Yellow filter layer containing 0.2 g of yellow colloid #, 0.11 g of DBP in which 0.2 g of antifouling agent (HQ-1) was dissolved, and 2.1 g of gelatin.

Layer 9...-0.95 g of low-sensitivity blue-sensitive silver iodobromide emulsion (
Agl; 7 mol%), 1.9 g of gelatin and 1.8
4 g of α-[4-(1-benzyl-2-phenyluco,
5-dioxo-1,2,4-triaplichel)】-α
- Contains 0.93 g of DBP in which pivaloyl-2-chloro-5-[γ-(2,4-di-amylphenoxy)butanamide]acetanilide (hereinafter referred to as yellow coupler (Y-1)) is dissolved. Low-speed blue-sensitive silver halide emulsion layer.

Layer lO...-1.2 g of highly sensitive blue-sensitive silver iodobromide emulsion (
Agl; 6%), 2.0g gelatin and 0
．． 0 in which 46g of yellow coupler (Y-1) was dissolved,
High-speed blue-sensitive silver halide emulsion layer containing 23 g of DBP.

Layer 11: Second protective layer made of gelatin.

W! 12 - First protective layer containing 2.3g gelatin.

These samples were cut into pieces and treated according to the first step using a 4M type light source according to a conventional method.

Processing process 1 (comparative process) Processing process Processing temperature Processing time Replenishment hanging wheel 1, color development 37.8°C 3 minutes 15 seconds 55 m12, bleach constant i 37.8°C 5 minutes 34.5 m 3, water
Washing 2 minutes lO seconds 4, stable 30-34
°C 1 minute 5 seconds 34.5 m15, dry Book: 24 shots per book Processing step 2 (processing of the present invention) Processing process Processing temperature Processing time Replenishment amount 1 ri 6 color development 37.8°C 3 minutes 15 seconds 55 ts cross 2, bleach fixing ■ 37.8℃ 3 minutes -3, bleach fixing ■
37.8℃ 2 minutes 34.501J14, water
Washing 2 minutes lO seconds 5, stable 30-34
℃ 1 minute 5 seconds: 14.5m sentence6. Dry explosion: 24 shots per shot
More supplemented.

The following color developing solution, bleach-fixing solution, and stabilizing solution were used.

[Color developing solution] [Bleach-fixing solution] [Stabilizing solution] After the light-sensitive material was subjected to 0.3R processing according to the above processing steps, the amount of silver was adjusted to be as shown in Table 1. Silver was added as silver bromide.

Next, the light-sensitive material sample was processed according to the above procedure, and the amount of residual #i (mg/drn') in the highest density part of the processed sample was measured by fluorescent X-ray method. In addition, the cyan dye concentration (
Transmission density) was measured using Sakura Photoelectric Densitometer PD-65 (manufactured by Konishiroku Photo Industry Co., Ltd.), and then using this value, the same sample was measured according to a conventional method.

The color restoration rate was calculated by setting the minimum cyan dye concentration after treatment with a 3% red blood salt solution for 3 minutes at room temperature as 100.

The results are summarized in Table 1.

Table 1 As is clear from the results in Table 1, when the bleach-fixing bath is one tank (sample No. 1), and even if it is a two-tank self-flow system,
When the silver concentration in the first tank is low (Sample No. 2.:l), the amount of residual silver is large and the rate of color recovery cannot be said to be high. The reason why both the desilvering property and the color restoration rate are low even though the processing time is longer is probably because a large amount of the color developer or the color developer is brought into the first tank of the bleach-fixing bath.

Example 2 Using the bleach-fix solution used in Example 1 and further using silver powder, 20 g of ferrous complex salt was produced, and sample No. of Example 1,
I adjusted ¥A so that the amount of silver was 5. Further, the evaluation was carried out in the same manner as in Example 1, except that the cyan couplers in layers 3 and 4 in the light-sensitive material were changed (equimolar amounts) as shown in Table 2.

The results are shown in Table 2.

Table 2 Comparative coupler 1 Comparative coupler 2 I2 As is clear from the results in Table 2, even if about 20 g of ferrous complex salt is produced, the color recovery rate is high by using the coupler of the present invention, and it has a good effect on desilvering properties. It turns out that there are no negative effects.

When ferric ammonium salt of ethylenediaminetetraacetate was also investigated, almost the same results were obtained.

Example 3 The bleaching agent and free chelating agent of the bleach-fix solution of the present invention used in Example 1 were as shown in Table 3, the same treatment as in Example 1 was carried out, and KI was further added as shown in Table 3. , Example 1
The same evaluation was conducted. However, the amount of silver in the bleach-fix solution of the present invention was the amount described in Sample No. 4.

The results are shown in Table 3.

As is clear from Table 3, in order to improve both the desilvering property and the recoloring rate, it is preferable that the bleaching agent be 0.25 mol or more, and the free chelating agent relative to the bleach be 7.0 mol% or less. Furthermore, Kl in the first layer is used as a means to improve desilvering properties.
It can be seen that it is good if the Kl of the second layer is 50% or less.

Applicant Roku Konishi Photo Industry Co., Ltd. Agent Patent attorney Nobuaki Sakaguchi (and one other person) Tewanine City J, E-j-shi (Voluntary) April 5, 1986

Claims (1)

[Claims] (1) After color development of the silver halide color photographic light-sensitive material,
In the bleach-fixing step, the silver halide color photographic light-sensitive material is treated with the following general formula [A], [B] or [C].
The bleach-fix treatment step is a step in which at least two consecutive bleach-fix tanks are used in a countercurrent manner, and the bleach-fix solution in the final tank of the bleach-fix tank contains at least one cyan coupler represented by A method for processing a silver halide color photographic light-sensitive material, characterized in that the silver concentration in the bleach-fix solution in the first bath is maintained at 80% or less of the silver concentration in the bleach-fix solution. General formula [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [B] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In the formula, R_1 is an alkyl group, alkenyl group, cycloalkyl group, aryl group, or heterocycle Y is a group represented by ▲There are numerical formulas, chemical formulas, tables, etc.▼ (However, R_2 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group, or heterocyclic group, and R_3 is a hydrogen atom. or represents a group represented by R_2, R_2 and R_3 may be the same or different, and may be bonded to each other to form a 5- to 6-membered heterocycle), Z is a hydrogen atom or an aromatic group. Represents a group that can be separated by a coupling reaction with an oxidized product of a primary amine color developing agent. General formula [C] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_1_1 is -CONR_1_4R_1_5, -NHC
OR_1_4, -NHCOOR_1_6, -NHSO_
2R_1_6, -NHCONR_1_4R_1_5 or -NHSO_2NR_1_4R_1_5, R_1_2 is a monovalent group, R_1_3 is a substituent, X is a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developing agent, l is 0 or 1, m is 0-3, R_1_4, R_1_5
is a hydrogen atom, an aromatic group, an aliphatic group, or a heterocyclic group, R_
1_6 each represents an aromatic group, an aliphatic group, or a heterocyclic group, and when m is 2 or 3, each R_1_3 may be the same or different, or may be bonded to each other to form a ring, and R_1
_4 and R_1_5, R_1_2 and R_1_3, R_1_
2 and X may be combined to form a ring, provided that when l is 0, m is 0, R_1_1 is -CONHR_1_7, and R_1_7 represents an aromatic group.