JPH02103040A - Bleaching bath for silver halide color photographic sensitive material and method for processing the silver halide color photographic sensitive material using said bleaching bath - Google Patents

Abstract

PURPOSE:To retard generation of a leuco dye in a bleaching bath and to enable rapid processing of a silver halide color photographic sensitive material by mixing a specified ferric complex salt and a specified amt. of a nitrate with a bleaching bath. CONSTITUTION:A bleaching bath contains a ferric complex salt of a compd. expressed by the formula I as ferric complex salt of an org. acid, and 0.2-2.0 mole/liter nitrate (e.g. NH4NO3). In the formula I, each A1-A4 is -CH2OH, -COOM, etc.; M is H, Na, etc.; X is a 2-5C (substituted) alkylene. A compd. expressed by the formula II is usable as the compd. expressed by the formula I. A sensitive material contg. a cyan coupler expressed by the formula III, etc. is preferred to be processed with the bleaching bath. In the formula III, R1 is an alkyl or aryl group; Y is -SO2R1, -CON(-R1)R2, etc.; R2 is H, or R1; Z is H or an eliminable group.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a bleaching solution for silver halide color photographic materials and a method for processing silver halide color photographic materials using the bleaching solution. The present invention relates to a bleaching solution for silver halide color photographic materials that produces less dye and can be rapidly processed, and a method for processing silver halide color photographic materials using the bleaching solution.

[Background of the invention]

Processing of light-sensitive materials basically consists of two steps: color development and desilvering, and desilvering consists of bleaching and fixing steps or bleach-fixing steps. In addition to this, rinsing treatment, stabilization treatment, etc. are added as additional treatment steps.

The processing solution with bleaching ability used in the desilvering process of photosensitive materials contains red blood salt, red blood salt, etc. as an oxidizing agent to bleach the image silver.
Inorganic oxidizing agents such as dichromates are widely used.

However, several serious drawbacks have been pointed out to processing solutions containing these inorganic oxidizing agents and having bleaching ability. For example, red blood salt and dichromate are relatively superior in terms of bleaching blades for image silver, but they can decompose when exposed to light and generate cyanide ions and hexavalent chromium ions that are harmful to the human body, causing pollution. It has properties that are unfavorable in terms of prevention. 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, metal complex salts of organic acids, such as aminopolycarboxylic acid metal rust salts, are used as oxidizing agents, as they have fewer pollution problems and meet the requirements of speeding up and simplifying treatment, and allowing waste liquid to be reused. In recent years, treatment solutions have come to be used. However, processing solutions using metal complex salts of organic acids have the disadvantage that the bleaching rate (oxidation rate) of the image silver (metallic silver) formed in the development process is slow due to its slow oxidizing power. There is.

For example, iron ethylenediaminetetraacetate (Il
l) Complex salts have been put to practical use in some areas as bleaching solutions and bleach-fixing solutions, but they are also used in high-sensitivity silver halide color photographic light-sensitive materials containing silver bromide and silver iodobromide emulsions, especially as silver halide. Photographic color papers, photographic color opaque films, and color reversal films that contain silver iodide and have a high silver content have the disadvantage that bleaching blades are insufficient and the bleaching process takes a long time.

In addition, in the development method in which a large amount of photosensitive material is continuously processed using an automatic processor, etc., in order to avoid deterioration of the performance of the bleaching solution due to changes in the concentration of the components, it is necessary to keep the components of the processing solution within a constant concentration range. A means is necessary.

In recent years, as such a method, a so-called concentrated low replenishment method has been proposed, in which the replenisher is concentrated and refilled in small quantities, and a method in which a regenerating agent is added to the overflow fluid and used again as a replenisher has been proposed in recent years from the viewpoint of economy and pollution. It's coming.

In particular, in a bleaching solution, an organic acid ferrous complex salt produced by bleaching developed silver, such as an ethylenediaminetetraacetic acid iron (II) complex salt, is converted into an ethylenediaminetetraacetate iron (Ill) complex salt, that is, an organic acid ferric complex salt, by aeration. A method has been put into practical use in which the liquid is oxidized back to water, a regenerating agent is added to supplement the missing components, and the liquid is used again as a replenisher.

However, in recent years, so-called compact laboratories (also known as mini-labs) have emerged in order to shorten the processing time of silver halide color photographic materials and reduce collection and delivery costs. There is a strong need to reduce the installation area of the machine, and recycling processing is not desirable because it requires complicated labor and management, and also requires processing space.

Therefore, it is preferable to use a concentrated low replenishment method that performs low replenishment without performing regeneration processing, but if the amount of replenishment of the bleaching solution is extremely reduced, the concentration of color developer components brought into the bleaching solution will increase.
In addition, it becomes more susceptible to the effects of concentration due to evaporation, and the accumulation of color developer components increases more and more. In this way, when the concentration of color developer components in the bleaching solution increases, the mixing ratio of color developing agents and sulfites, which are reducing components, increases, and this increases the concentration of ferrous complex salts, which causes the leuco dye to increase. This is a drawback that tends to occur.

In recent years, propylene diaminetetraacetic acid dichloromethane has become a new bleaching agent.
Techniques using iron complex salts are disclosed in JP-A-63-65441, JP-A-63-141056, and JP-A-63-1.
It has been known from the specification of No. 39348. However, although propylene diamine tetraacetic acid ferric complex salt has extremely excellent silver bleaching ability, it has been found that it has one major drawback. This is because the ferrous complex salts produced by the bleaching reaction of silver and the reducing components brought in by the photosensitive materials mentioned above are extremely difficult to oxidize into ferric complex salts. As a result, the ferrous complex salts produced accumulate in the bleaching solution, resulting in leucoization of the dye and poor desilvering.

Particularly in the case of low replenishment, which is a recent trend as described above, this drawback is accentuated and becomes an increasingly serious problem.

The above-mentioned drawbacks also become a big problem for bander-type automatic developing machines (also called hanging-type automatic developing machines), which have a large amount of carryover.

[Purpose of the invention]

Therefore, the first object of the present invention is to provide a bleaching solution for silver halide color photographic light-sensitive materials that generates less leuco dye, has good desilvering properties, and can be processed quickly, and a processing method using the bleaching solution. be. A second object of the present invention is to provide a bleaching solution for silver halide color photographic materials that can be refilled at low levels and is economical and environmentally friendly, and a processing method using the bleaching solution.

A third object is to provide a bleaching solution for silver halide color photographic materials that can be used in hanger-type automatic processors with a large amount of carryover and can provide rapid processing, and a processing method using the bleaching solution. .

[Structure of the invention]

As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the organic acid ferric complex salt in the bleaching solution for silver halide color photographic light-sensitive materials is substantially the same as the compound represented by the following formula CA). It is a diiron complex salt and contains 0.2 to 2.0 mol/nitrate.
A bleaching solution for silver halide color photographic light-sensitive materials characterized by containing l, and the following formula (C-A), (:C
- When a silver halide color photographic light-sensitive material containing at least one of the cyan couplers represented by B'l and (C-C) is prepared, the organic acid ferric complex salt in the bleaching solution is substantially of the following general formula [A]. A compound represented by 0.2 to 2 nitrate
．． It has been found that the above object can be achieved by a method for processing silver halide color photographic materials, which is characterized by processing with a bleaching solution containing 0 mol/l.

General formula (A) In the formula, AI to A may each be the same or different,
-CfL2011. -COOM also 1; t-PO3MIM
Represents 2.

M, M, and M2 each represent a hydrogen atom, a sodium atom, a potassium atom, or an ammonium group. X has 2 or more carbon atoms
5 represents a substituted or unsubstituted alkylene group.

The total number of carbon atoms including branched moieties may be 3 or more. ), 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.

In the formula, R represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Y is a group represented by -C0NHCOR2 or 100Nl5OJz (however, R2 is an alkyl group, alkenyl group,
It represents a cycloalkyl group, an aryl group or a heterocyclic group, and R3 represents a hydrogen atom or a group represented by R2. R
2 and Rj may be the same or different, and combine with each other to form a 5- to 6-membered heterocyclic group, and R1 is -CONR*
Rs, -NHCOOR -NHCOOR6, -N1 (S
o□R1, N) ICONRaRa or -NHSOzNR
*Ra and R2 are monovalent groups, R1 substituents, X is a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developing agent, Q is 0 or 1,011 or 0 to 3, R4 and R6
is a hydrogen atom, an aromatic group, an aliphatic group, or a heterocyclic group, R
, represents an aromatic group, an aliphatic group, or a heterocyclic group, respectively;
When m is 2 or 3, each R3 may be the same or different,
They may be combined with each other to form a ring, or R4 and R1, R
3 and R3, and R7 and X may be combined to form a ring. However, when Q is O, m is 0 and R.

is -CONHR, and R2 represents an aromatic group.

[Specific structure of the invention]

Next, the compound represented by the general formula (A) will be explained in detail.

In general formula (A), the substituent of the alkylene group represented by X includes, for example, a hydroxy group, and examples of the alkylene group include propylene, trimethylene, 2
-hydroxytrimethylene, tetramethylene, 2-methyltrimethylene, 2-dimethyltrimethylene and the like. Preferred specific examples of the compound represented by the general formula [A] are shown below.

(A-1) (A-3) (A-4) (A-5) (A-6) (A-2) (A (A-8) (A-9) These (A-1) to ( In addition to the compound A-9), sodium salts, potassium salts, or ammonium salts of these compounds can be similarly preferably used.

From the viewpoint of the desired effect and solubility of the present invention, ammonium salts of these ferric complex salts are preferably used.

Among the examples of compound compounds, those particularly preferably used in the present invention are (A-1), (A-4), and (A-7).
), (A-9), particularly preferred ones are (
A-1).

The ferric complex salt of the compound represented by formula [A] is preferably used in an amount of at least 0.1 mol, more preferably in the range of 0.15 mol to 0.6 mol, per bleaching solution IQ;
More particularly preferred is a range of 0.20 mol to 0.5 mol.

The bleaching solution of the present invention includes ferric complex salts of the compound represented by the general formula [A], other ferric complex salts of aminopolycarboxylic acids (for example, ferric complex salts of ethylenediaminetetraacetic acid, ferric complex salts of diethylenetriariminepentaacetate, diiron complex salt, 1,2-cyclohexanediaminetetraacetic acid ferric complex salt, glycol ether diamine tetraacetic acid ferric complex salt, etc.).

The term "ferric complex salt of a compound substantially represented by the following general formula [A]" as used in the present invention refers to a ferric complex salt of a compound represented by the general formula [A] contained in the bleaching solution of the present invention. Concentration of complex salt (
content) is 70% (%) of the total organic acid ferric complex salts in the bleaching solution.
(in terms of mole) or more. In order to better achieve the desired effects of the present invention, the above content is 80% (
molar equivalent) or more, more preferably 9 or more, and more particularly preferably 9
0% (in terms of mole) or more, most preferably 95% (
(in terms of moles).

Specific examples of nitrates in the present invention include liulium nitrate, sodium nitrate, ammonium nitrate, and lithium nitrate, and also include those in which nitric acid is added to a bleaching solution to form a nitrate in the solution.

These nitrates are used in the bleaching solution in a range of 0.2 to 2.0 mol/l, preferably 0.4 to 1.5 mol/l.
more preferably 0.6 to 1.2 mol/l
is within the range of

In addition, the bleaching solution of the present invention has a pH of
2 to 5.5 is preferable, more preferably 3.0 to 5.0
is within the range of

Furthermore, when the bleaching solution of the present invention contains 0.2 mol/l or more of acetic acid or acetate, there is little occurrence of bleaching blade blurring,
The desired effects of the present invention are also better achieved. Especially 0.
Good when used in the range of 4 to 2.0 mol/l,
Most preferably, the above effects are particularly good when used in the range of 0.6 to 1.5 mol/l. Examples of the acetate include sodium acetate, potassium acetate, ammonium acetate, and the like.

When the bleaching solution according to the present invention contains imidazole or a derivative thereof, or at least one of the compounds represented by formulas CI) to (ff) below, the desired effects of the present invention can be better achieved, and further, It also has the additional effect of improving precipitation caused by silver in the bleaching solution, so it is more preferably used in the present invention.

In the general formula CI), Q represents an atomic group necessary to form a nitrogen-containing heterocycle (including one in which 5- to 6-membered unsaturated rings are condensed), and R1 is a hydrogen atom and the number of carbon atoms. 1-6
represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group (including those in which 5- to 6-membered unsaturated rings are condensed), or an amino group.

- In formula (n), R2 and R1 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group,
It represents a carboxyl group, an amino group, an acyl group having 1 to 3 carbon atoms, an aryl group, or an alkenyl group.

A represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, an aryl group, a heterocyclic residue (5
-6-membered unsaturated rings are condensed together) or an amino group, and n1 to n6 and m1 to m5 each represent an integer of 1 to 6.

B represents an alkylene group having 1 to 6 carbon atoms, or n3
represents a valent heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed), X = 51 = 0 and t2 = #NR"
represents. where R and R' are R2 and R3 respectively
, X' is the same as X, Z represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocyclic residue, an alkyl group, and R1 and R6 each represent the general formula (II). It has the same meaning as R2 and R3. However, R4
and R3 may each represent -B-3Z, or R3 and R3, R and R' R, and R6 may be bonded to each other to form a ring. Note that the compound represented by the formula also includes enolated products and salts thereof.

-Formula CII [) In the general formula (III), R and R7 are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, an amino group, an acyl group having 1 to 3 carbon atoms, Represents an aryl group, an alkenyl group, -B, -5-Z. However, R6 and R7 are combined to represent a ren group, zl represents a hydrogen atom, an alkali metal atom, an ammonium group, an amino group, a nitrogen-containing heterocycle, and Rlo
represents an alkyl group or -(CI(2)n, SO, θ) (However, when R1° is -(CIRn6so, 0, α represents 0, and when it is an alkyl group, represents 1).

GO represents an anion. n represents an integer from 1 to 6. ] General formula [v] R7 represents an integer of 1 to 6.

In the general formula [lV] [-formula [v], Ql is a nitrogen-containing heterocycle (5 to
R1 represents a hydrogen atom, -
In formula (IV), Ra! i and R9 each represent a group. However, G' has the same meaning as Ql.

Represents SO□RIII, Formula [■] Y2 is Dl, B2, D, and in the general formula [Vl],
each represents a simple bond, an alkylene group having 1 to 8 carbon atoms, or a vinylene group, and Qt, q2, q3 and q4 each represent 0, 1 or 2. Further, the ring formed together with the sulfur atom may be further condensed with a 5- to 6-membered saturated or unsaturated ring.

General formula [■] R11R14 In the general formula [■], X2 is -COOM' -1°SO, M' -CONH2, -5O2NH2, -
N) +2, -5H, -CN.

COJ+a, -3o2R,6, -OR, , -NR1
6RI7, -5R,4,5oJR,i-NtlCOR,
. , -NH5O□R1-COR, or a hydrogen atom, and I and n each represent an integer of 1-10. R,,,R,! , R13, R14, Ro, R17 and R1, each represent a hydrogen atom, a lower alkyl group, an acyl group, or R+a represents a lower alkyl group, and R5, -NR.

R2 represents R22 or -SR2□, R2° and R2° each represent a hydrogen atom or a lower alkyl group, and R2□ represents an atomic group necessary to form a ring by bonding with R1. R2o or R11 may be combined with Rlfi to form a ring. M' represents a hydrogen atom or a cation.

General formula [■] In the general formula [■], Ar represents a divalent organic group consisting of an arylene group or a combination of an arylene group and an oxygen atom and/or an alkylene group, and B2 and B each represent a lower alkylene group. represents R21, R2 R2
6 and R3 each represent a hydroxy-substituted lower alkyl group, and X and y each represent O or l. G' represents an anion, and 2 represents 0.1 or 2.

Mathematical formula (Iri) represents.

Representative specific examples of the compounds represented by formulas CI) to (I) and imidazole and derivatives thereof are disclosed in JP-A-63
-32501 specification, pages 17 to 39 (I-1
) ~ (■ ~ 10), (n-1) ~ (n-27), (■1
”) ~Cm-15), (rv-1) ~(IV-
3), (V-1) to (V-23), (Vl-1)-(
Vl -17), (■-1) ~ (■-15), (■-1
) ~ (■-7), (II-1) ~ (ff -5), (A
-1) to (A-8).

These compounds are generally used as bleach accelerators and have the formula (I
In N), R2, R and O each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group,
R31 represents a hydrogen atom or an alkyl group, and R12 represents a hydrogen atom or a carboxy group. These bleaching accelerators may be used alone or in combination of two or more, and the amount added is generally about 0 per l&lQ of bleaching. Good results are obtained in the range of .01-100g. However, in general, when the amount added is too small, the effect of promoting bleaching is small, and when the amount added is too large, precipitation may occur and contaminate the silver halide color photographic light-sensitive material being processed. The amount is preferably 0.05 to 50 g, more preferably 0.05 to 15 g per 1Q of bleaching solution.

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 add methanol, ethanol, acetone as necessary. It can also be added after being dissolved using an organic solvent such as.

The treatment temperature used is 20-45°C, preferably 25-42°C.

A halide such as ammonium bromide is usually added to the bleaching solution of the present invention.

The bleaching solution of the present invention includes boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
pH buffering agents consisting of various salts such as sodium bicarbonate, potassium bicarbonate, ammonium hydroxide, etc. may be used alone or in combination.
A combination of two or more types can be contained. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained.

The preferred replenishment amount of the bleaching solution according to the present invention is 20 m12 to 500 m2 per 1 m2 of silver halide color photographic light-sensitive material.
m4, particularly preferably 30m12 to 3501
I112, more particularly preferably 40 mQ to 300 m4, most preferably 50 mQ to 2
It is 50mQ.

In the present invention, from the viewpoint of rapid processing, it is preferable to process with a bleaching solution and then subsequently with a fixing solution or a bleach-fixing solution.

Preferred specific geographical steps of the treatment method according to the present invention are shown below.

(1) Color development - constant bleaching, one wash (2) color development - constant bleaching - first stable (3) color development - constant bleaching - first stable (4) color development - constant bleaching - first stable - first 2 stable (5
) Color development - bleaching - bleach-fixing - washing with water (6) color development - bleaching - bleaching - fixing - washing - stable (7) color development - bleaching - bleach-fixing - stable (8) color development - bleaching - bleach-fixing - first Stability - Second Stability Among these steps, among others (3), (4
), (5), (7) and (8) are preferred, and (3), (4) and (5) are particularly preferred. The most preferred is (3).

A so-called fixing agent is essential to the fixing solution and bleach-fixing solution according to the present invention.

As fixing agents, compounds which react with silver halides to form complex salts in aqueous solution, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate;
Examples include thiocyanate salts such as potassium thiocyanate, sodium 1-ram thiocyanate, and ammonium thiocyanate, thiourea, and thioether.

In addition to these fixers, fixers and bleach-fixers include ammonium sulfite, potassium sulfite, vLr11 ammonium bisulfite, potassium bisulfite, sodium bisulfite,
Sulfites such as ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, acetic acid A pH buffering agent consisting of various salts such as sodium and ammonium hydroxide may be contained alone or in combination.

Furthermore, alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride,
It is desirable to contain a large amount of a rehalokenizing agent such as ammonium bromide. In addition, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to normal fixers and bleach-fixers may be added as appropriate. can do.

The fixing agent is used in an amount of 0.1 mol or more per processing liquid IQ, preferably in the range of 0.6 to 4 mol/l, particularly preferably 0.9 to 3.0 mol, from the viewpoint of the desired effect of the present invention. /l
Particularly preferably from 1.1 to 2.0 mol/l
It is used within the range of .

In the present invention, in order to increase the activity of the bleach solution or bleach-fix solution, air or oxygen may be blown into the processing bath and processing replenisher storage tank as desired.
or a suitable oxidizing agent such as hydrogen peroxide, bromate,
Persulfates and the like may be added as appropriate.

When carrying out the method of the present invention, silver may be recovered from the fixer or bleach-fixer by known methods. For example, electrolysis method (described in French Painting Patent No. 2,299.667), precipitation method (described in JP-A-52-73037, Narrow-mouth Patent No. 2,3
31.220 specification), ion exchange method (Japanese Unexamined Patent Publication No. 5
1-17114, Narrow-mouth Patent No. 2,548,23
7) and metal substitution method (British Patent No. 1,353)
, No. 805) etc. can be effectively used.

It is particularly preferable to recover silver from the tank solution in-line, since the suitability for rapid processing becomes even better, but silver may also be recovered from the over-70 waste solution and recycled.

The fixing solution and bleach-fixing solution according to the present invention exhibit the desired effects of the present invention better when the replenishment amount thereof is 800 mC or less per m2 of light-sensitive material. In particular, 1 m' of photosensitive material
20-650m12. Especially especially 30-400
Good results are obtained when m+2.

Furthermore, when the fixing solution and bleach-fixing solution according to the present invention contain 0.1 to 10 g/12 of iodide (ammonium iodide, potassium iodide, sodium iodide, lithium iodide, etc.), the present invention to further promote the effects of

Patent 0.3-5 g/(1, especially special i: 0.5
Good results are obtained with -3 g IQ, most preferably between 0.8 and 2 g/l.

The fixing solution or bleach-fixing solution according to the present invention has the following formula (
The compound represented by F A) or the following compound group (F B)
When the compound represented by is added and used, the desired effects of the present invention are not only better achieved, but also when a small amount of light-sensitive material is processed over a long period of time using a fixing solution or a bleach-fixing solution. It is more preferably used in the present invention because it has the additional effect of generating extremely little sludge.

Formula CFA) In formula (FA), R' and R'' each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a nitrogen-containing heterocyclic group. n' represents 2 or 3.

Specific examples of the compound represented by general formula (FA) are shown below.

These compounds represented by formula (FA) are U.S. Pat.
, 335,161 and U.S. Pat. No. 3,260,7
It can be synthesized by a general method as described in the specification of No. 13.

Compound group CF B) FB river Thiourea FB-2 Methyl thio atom FB-3 Dimethyl thiourea FB-4 Ammonium thionate FB-5 Potassium thiocyanate FB-6 Sodium thionate FB-7 Ammonium iodide These, the above formula ( The compound represented by FA) and the compounds of the compound group (FB) may be used alone or in combination of two or more. Examples are thiourea, ammonium thiocyanate, and ammonium iodide.
Thiourea and ammonium thionate, (FA-1
2) and thiourea, (FA-12) and ammonium thiocyanate, (FAI2) and ammonium iodide, (FA
-12) and (FA-32), (FA-12) and (
F A-38) etc. are mentioned as preferred examples.

Among these, the most preferable ones are (FB-1) and (F
B-4).

In addition, the amount of the compound represented by formula (FA) and the compound of compound group (FB) is 0.000.
Good results are obtained in the range of 1 to 200 g.

In particular, the range of 0.2 to 100 g is preferable, and the range of 0.5 to 100 g is particularly preferable.
A range of 50g is particularly preferred.

In the fixing solution and bleach-fixing solution according to the present invention, sulfite adducts are preferably used from the viewpoint of the desired effects of the present invention.

Examples of compounds that form a stable sulfite adduct with the sulfite ion include compounds having an aldehyde group, compounds containing a cyclic hemiacetal, compounds having an a-dicarbonyl group, and compounds having a nitrile group. Preferably, the following formula (A-I
) to (A-〇) are particularly preferably used.

lma body.

General formula CA-1) In general formulas (A-I) and (A-11), A 2,
A3, A4 and A represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group or an alkenyl group. The alkyl group having 1 to 6 carbon atoms includes straight chain or branched ones, such as methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, n-barrel group, 1so-barrel group. group, hexane group, isohexane group, etc., and may be substituted. Specifically, formyl group (for example, each layer of formylmethyl, 2-formylethyl, etc.), ami7 group (for example, aminomethyl, aminoethyl, etc.) ), hydroxyl groups (e.g., hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, etc. layers), alkoxy groups (e.g., methoxy, ethoxy, etc. layers), halogen atoms (e.g., chloromethyl, trichloromethyl, dibromomethyl, etc.) substituents such as (each layer) and the like.

The alkenyl group includes substituted and unsubstituted groups, and the unsubstituted groups include vinyl, 2-propenyl, etc., and the substituted groups include, for example, l.

Examples include groups such as 2-cyclo2-carboxyvinyl and 2-phenylvinyl.

Specific examples of compounds that form stable sulfite adducts with the sulfite ion are described below, but the present invention is not limited thereto.

1+1 C113-N (CI+2 chill.

! e CI+.

AO Formaldehyde Sodium bisulfite Acetaldehyde Sodium bisulfite Propionaldehyde Sodium bisulfite A O-14 Butyraldehyde Sodium bisulfite AO
-21 Succinic aldehyde Sodium bisulfite AO-22 Glutaraldehyde Sodium bisulfite AO-23 β-Methylglutaraldehyde Sodium bisbisulfite AO-24 Maleic acid dialdehyde Sodium bisulfite These sulfite addition compounds are ,0.
It is preferably used in a range of 1 to 80 g, more preferably in a range of 0.5 to 40 g.

The total processing time of the bleaching solution and the processing solution (fixing solution or bleach-fixing solution) having a fixing ability according to the present invention is preferably 3 minutes and 45 seconds or less, and the total time is more preferably 20 seconds to
The desired effects of the present invention are well achieved when the time is 3 minutes and 20 seconds or less, particularly preferably from 40 seconds to 3 minutes, particularly preferably from 60 seconds to 2 minutes and 40 seconds.

Further, the bleaching time can be arbitrarily selected within the range of the above-mentioned total time, but from the viewpoint of the desired effect of the present invention, it is particularly preferably 1 minute and 30 seconds or less, particularly 10 seconds to 70 seconds, particularly 2 minutes or less.
0 seconds to 55 seconds is preferable. The processing time of the processing liquid having fixing ability can be arbitrarily selected, but from the viewpoint of the desired effect of the present invention, it is preferably 3 minutes 10 seconds or less, and particularly preferably,
It is in the range of 10 seconds to 2 minutes and 40 seconds, particularly preferably in the range of 20 seconds to 2 minutes and 10 seconds.

In the processing method of the present invention, it is preferable to subject the bleaching solution, fixing solution, and bleach-fixing solution to forced liquid stirring. The reason for this is not only to better achieve the desired effects of the present invention, but also from the viewpoint of suitability for rapid processing.

Forced liquid stirring here means forcibly stirring the liquid by adding a stirring means, instead of the usual diffusion movement of the liquid.

Examples of forced stirring means include the following methods.

1. High pressure spray treatment method or spray stirring method 2. Air bubbling treatment method 3. Ultrasonic oscillation treatment method 4. Vibration treatment method High-pressure spray treatment method has a discharge pressure of 0.1 kg/am”
Refers to a method in which processing is performed by spraying a processing liquid directly onto the photosensitive material from a spray nozzle under a pressure above
The spray stirring method is a discharge pressure of 0.1 kg/
This refers to a method in which processing is performed by spraying a processing solution directly onto the photosensitive material in the processing solution by applying a pressure greater than 1.0 am", and generally a pressure pump or a liquid pump is used as the pressure source. There are jar pumps, gear pumps, magnet pumps, and cascade pumps, such as the 15-LPM type, 10-BFM type, and 20-BF manufactured by Ohin Seisakusho.
M type, 25-BFM type, etc. are known as examples.

In addition, as a liquid pump, for example, In-3 manufactured by Iwaki Co., Ltd.
0 type, MO-56 type, MD) l-25 type, MDX-32
There is a type.

On the other hand, there are various types of nozzles and spray nozzles, such as straight type, fan type, circular type, full surface type, and annular type. The impact force of the spray is mainly caused by the flow rate C01 min) and the spray pressure (
Therefore, a pressurizing device that can adjust the pressure in proportion to the number of spray nozzles is required to fully demonstrate the effect.The most preferable pressure is 0.3 to 10 kg/cm". If it is smaller than this, no effect will be obtained, and if it is too large, it may scratch or damage the photosensitive material.

Next, the air bubbling treatment method involves installing a sparger at the bottom of the lower conveyance roller in the treatment liquid tank.
In this method, air or inert gas is sent to the photosensitive material, and the photosensitive material is vibrated by the bubbles ejected from its mouth, and the top, back, and side surfaces of the photosensitive material are brought into effective contact with the geographical fluid.

Suitable materials for the sparger include corrosion-resistant materials such as hard PVC, polyethylene-coated stainless steel, and sintered metal. 501
An even better effect can be obtained by changing the length from 111 to 15+mm. An air compressor, such as Hitachi Bebicon (0.4KW, B
υ7TL) and an air pump, such as an air pump manufactured by Ikki (Ap220 type). The amount of air is 2Q/min to 30Q per transport rack of automatic processing machine.
/min, and more favorable results can be obtained with 5Q/min to 20Q1 min. The amount of air or inert gas must be adjusted depending on the size of the processing liquid tank and the amount of photosensitive material, but the vibration width of the photosensitive material due to air bubbles is 0.2
Preferably, the amount of air or inert gas is delivered from mm to 20 mm.

Next, the ultrasonic oscillation processing method is a method in which an ultrasonic oscillator is installed in the bottom or side wall space of the processing solution tank of an automatic processor and irradiates ultrasonic waves onto the photosensitive material to increase the efficiency of development promotion. be. As the ultrasonic oscillator, for example, a magnetostrictive nickel vibrator (horn type), a magnetostrictive barium titanate vibrator (holder type), etc. manufactured by Ultrasound Kogyo Co., Ltd. are used.

The transducer frequency of the ultrasonic oscillator is 5 to 10011
KHz is used, especially lO~50KH
z is preferable in terms of the desired effect of the present invention and damage to the equipment of the automatic processor. Ultrasonic waves can be irradiated onto photosensitive materials by direct irradiation or indirect irradiation by installing a reflector, but since ultrasonic waves attenuate in proportion to the irradiation distance, direct irradiation is not recommended. It is preferable to let The irradiation time is preferably at least 1 second or more. In the case of partial irradiation, it may be applied at any of the early, middle, and late stages of the treatment process.

Furthermore, the vibration processing method is a method in which vibration is applied to the photosensitive material between the upper roller and the lower roller in the processing liquid tank of an automatic processor to effectively perform immersion processing. As a vibrator for the vibration source, for example, V- made by Shindo Denki Co., Ltd.
2B, I+-48W, etc. are commonly used. The vibrator is installed by fixing a pie break to the top of the immersion processing tank of an automatic processor and installing the vibrator so that it is applied from the back side of the photosensitive material. The frequency of the vibrator is 100 to 100
00 times/min is preferred. The most preferred range is 500-6
000 times/min.

The amplitude of the photosensitive material to be processed is 0.2 to 30 ma+, preferably 1 to 20 nlffl. If it is lower than this, there is no effect, and if it is too large, the photosensitive material may be damaged.

The number of vibrators to be installed varies depending on the size of the automatic processor, but if the processing tank is composed of multiple tanks, a preferable effect can be obtained by installing at least one vibrator in each processing tank.

Next, general formulas (C-A) to (C
The coupler represented by -C) will be explained in detail.

First, the above formula (C-A) and formula (C-B) will be explained. In these formulas, Y is C0NHC
It is a group represented by OR2 or 100NH30J2.

Here, R1 and R2 are each an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, L-
butyl, dodenyl groups, etc.), alkenyl groups, preferably alkenyl groups having 2 to 20 carbon atoms (allyl groups, heptadecenyl groups, etc.), cycloalkyl groups, preferably 5- to 7-membered rings (for example, cyclohexyl, etc.), Aryl groups (e.g., phenyl, tolyl, naphthyl, etc.), heterocyclic groups, preferably 5- to 6-membered ring groups containing 1 to 4 nitrogen atoms, oxygen atoms, or sulfur atoms (e.g., furyl, thienyl, benzothiazolyl group, etc.). R3 represents a hydrogen atom or a group represented by R2. R2 and R3 may be combined with each other to form a 5- to 6-membered heterocycle. In addition,
Any substituent can be introduced into R1 and R2,
For example, alkyl groups having 1 to 10 carbon atoms (e.g., methyl, isopropyl, isobutyl, [-butyl, t-octyl, etc.), aryl groups (e.g., phenyl, naphthyl, etc.), halogen atoms (7), chlorine, bromine, etc. ), cyano, nitro, sulfonamide groups (e.g. methanesulfonamide, butanesulfonamide, p-toluenesulfonamide, etc.)
, sulfamoyl group (methylsulfamoyl, phenylsulfamoyl, etc.), sulfonyl group (e.g. methanesulfonyl, p-toluenesulfonyl, etc.), fluorosulfonyl group, carbomoyl group (e.g. dimethylcarbamoyl, phenylcarbamoyl, etc.) Examples include carbonyl groups (for example, ethoxycarbonyl, phenodicarbonyl, etc.), acyl groups (for example, acetyl, benzoyl, etc.), petero rings (for example, pyridyl groups, pyrazolyl groups, etc.), alkoxy groups, aryloxy groups, acyloxy groups, etc. .

In the general formula (C-A) and -numerical formula (C-B), R3
represents a ballast group necessary for imparting diffusion resistance to the cyan coupler represented by the general formula (C-A) and the numerical formula (C-B) and the cyan dye formed from the cyan coupler. Preferred are alkyl groups, aryl groups, alkenyl groups, cycloalkyl groups, or heterocyclic groups having 4 to 30 carbon atoms. For example, a straight-chain or branched alkyl group (e.g. t-
butyl, n-octyl, t-octyl, n-dodecyl, etc.), 5-membered or 6-membered heterocyclic groups, and the like.

In formulas [C-A) and (C-B), Z represents a hydrogen atom or a group that can be separated during a coupling reaction with an oxidized product of an N-hydroxyalkyl-substituted diamine derivative color developing agent.

For example, halogen atoms (e.g. chlorine, bromine, fluorine, etc.)
, substituted or unsubstituted alkoxy group, aryloxy group,
Examples include a heterocyclic oxy group, an acyloxy group, a carbomoyl oxine group, a sulfonyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfonamide group, and more specific examples include U.S. Pat. 56
No. 3, JP-A No. 47-37425, JP-A No. 48-368
No. 94, JP-A-50-10135, JP-A No. 5011742
No. 2, No. 50-130441, No. 51-108841
No. 50-120343, No. 52-18315,
No. 53-105226, No. 54-48237, No. 5
No. 5-32071, No. 55-65957, No. 5619
No. 38, No. 56-12643, No. 56-27147, No. 59-146050, No. 59-166956,
No. 60-24547, No. 60-35731, No. 60
-37557 etc. can be mentioned. In the present invention, a cyan coupler represented by the general formula [CD] is preferred.

In the general formula (CD), R4 is a substituted or unsubstituted aryl group (especially preferably a phenyl group). When the aryl group has a substituent, the substituent is -
502R halogen atom (fluorine, chlorine, bromine, etc.), -
Included are CF3, -N02, -CN, -COR6.

Here, %Rs is an alkyl group, preferably having 1 to 20 carbon atoms.
an alkyl group (e.g. methyl, ethyl, 1-butyl, dodecyl, etc.), an alkenyl group preferably having 2 to 2 carbon atoms.
20 alkenyl groups (allyl group, heptadecenyl group, etc.)
, represents a cycloalkyl group, preferably a 5- to 7-membered ring (e.g., cyclohexyl, etc.) or an aryl group (e.g., phenyl, tolyl, naphthyl, etc.), and R8 is a hydrogen atom or a group represented by R3. .

In a preferred compound of the cyan coupler of the present invention represented by the general formula (CD), R is a substituted or unsubstituted phenyl group, and the substituent to the phenyl group is cyano, nitro,
-5OJy (Rr is an alkyl group), a halogen atom, and trifluoromethyl.

In formula (C-D), 2 and R1 are each - formula (C-
It has the same meaning as A) and (C-B). A preferable example of the ballast group represented by R1 is the following formula (C-E
).

- In the formula (C-E), J represents an oxygen atom, a sulfur atom, or a sulfonyl group, k represents an integer from O to 4, Q represents 0 or 1, and when k is 2 or more, two or more are present. R to do
9 may be the same or different, R1 has 1 to 2 carbon atoms
0 represents a linear or branched chain, and a substituted alkylene group such as an aryl group, R represents a hydrogen atom or a -valent group, preferably a hydrogen atom or a halogen atom (e.g. chlorine, nitrogen)
, an alkyl group, preferably a straight chain or branched carbon number 1-2
0 alkyl groups (e.g. 6 groups such as methyl, [-butyl, t-pentyl, t-octyl, dodecyl, pentadecyl, benzyl, 7-enethyl, etc.), aryl groups (e.g. phenyl group), heterocyclic groups (e.g. nitrogen-containing central ring group), an alkoxy group, preferably a linear or branched alkoxy group having 1 to 20 carbon atoms (e.g. 6 groups such as methoxy, ethoxy, t-butyloxy, octyloxy, decyloxy, dodecyloxy), aryloxy group (e.g. phenoxy group), hydroxy group, acyloxy group, preferably alkylcarbonyloxy group, arylcarbonyloxy group (
For example, acetoxy group, benzoyloxy group), carboxy group, alkyloxycarbonyl group, preferably a straight chain or branched alkylcarbonyl group having 1 to 20 carbon atoms, preferably a phenoxycarbonyl group, an alkylthio group, preferably 1 to 20 carbon atoms an acyl group, preferably a linear or branched alkylcarbonyl group having 1 to 20 carbon atoms, an acylamino group, preferably a linear or branched alkylcarboxamide group having 1 to 20 carbon atoms, a benzenecarboxamide group,
Sulfonamide group, preferably a linear or branched alkylsulfonamide group having 1 to 20 carbon atoms or benzenesulfonamide group, carbamoyl group, preferably 1 to 2 carbon atoms
0 straight-chain or branched alkylaminocarbonyl group, phenylaminocarbonyl group, sulfamoyl group, preferably a straight-chain or branched alkylaminosulfonyl group or phenylaminosulfonyl group having 1 to 20 carbon atoms.

Next, specific examples of the cyan coupler of the present invention represented by the general formula (C-A) or [:C-B) will be shown, and this [exemplary compound] C L; 2H.

C-33 C-41 Shi4fl! ≧υ31Nt1 Next, general formula (CC) will be explained.

- The four groups represented by R2-R7 in formula (C-C) include those having substituents.

R6 is an aliphatic group having 1 to 30 carbon atoms, and 6 to 3 carbon atoms;
0 aromatic group and a heterocyclic group having 1 to 3 carbon atoms are preferred, and R1 and R6 are preferably hydrogen atoms, and those listed as preferred for R6 are preferred.

Directly as R2 or -N)l--Co- or 502
Hydrogen atom bonded to -Ni1- through -, carbon number 1-
30 aspiration group, aromatic group having 6 to 30 carbon atoms, RIG,
or -5OxOR+o (Rs, Rs and RIO are the same as defined in R6 and R6 above, respectively, and R8 and R may be combined to form a heterocycle) is preferred.

R7 is preferably an aromatic group having 6 to 30 carbon atoms,
Representative examples of substituents for R2 include a halogen atom, a hydroquine group, an amino group, a carboxyl group, a sulfonic acid group, a noano group, an aromatic group, a heterocyclic group, a carbonamide group, a sulfonamide group, a carbamoyl group, a sulfimoyl group, Urey l' group, acyl group, acyloxy group, aliphatic oxy7
group, aromatic oxy/group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide residue, aliphatic group, aliphatic oxycarbonyl group Examples include groups.

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 RJ include halogen atoms, hydroxy groups, amino groups, carboxyl groups, sulfonic acid groups, V ano groups, aromatic groups, heterocyclic groups, carbonamide groups, sulfonamide groups, carbamoyl groups, sulfamoyl groups, and ureido groups. , acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group, aromatic sulfonyl group, sul7amoylamino group, nitro group, imide residue, etc. I can name +7
) R, I preferably contain 0 to 30 carbon atoms. m=
An example of cyclic R1 when 2 is a dioxymethylene group.

When Q is 1, R1 is particularly preferably 100NR4R5, nl is preferably 0, and R2 is directly bonded to -Nl (-COR,, -C0R1,, -5O2R,, -CON
R,R,, -So, NRJ, are particularly preferred, and even more preferred is -COOR+o1-C, which is directly bonded to -NH.
ORa, 5O2R+ o Te, especially 100OR
, , is most preferred.

Also included in the present invention are those that form a dimer or more multimer through R1 to R1 and X.

- Among formulas (C-C), the case where Q=0 is preferred.

Specific examples of couplers represented by general formula (C-C) include JP-A-60-237448, JP-A No. 61-153640, Im
No. 61-145557, No. 62-85242, No. 4
No. 8-15529, No. 60-117422, No. 52-
No. 18315, No. 52-90932, No. 53-524
No. 23, No. 54-48237, No. 54-66129, No. 55-32071, No. 55-65957, No. 5
No. 5-105226, No. 56-1938, No. 56-1
No. 2643, No. 56-27147, No. 56-1268
No. 32, No. 58-95346 and U.S. Patent No. 3,448
, No. 193, etc., and can be synthesized by the methods described therein.

To add the cyan coupler of the present invention into a light-sensitive material,
Depending on the physical properties of the coupler (e.g. solubility), oil-in-water emulsion dispersion using a water-insoluble high-boiling organic solvent, alkaline dispersion adding as an alkaline solution, latex dispersion, direct addition as a fine solid, etc. Various methods can be used, such as a solid dispersion method.

The amount of the ./uncoupler of the present invention added is usually 1.0% per mole of silver halide. OX 10-' mol - 1,0 mol, preferably 5. OX 10 bow moles ~8. OX is in the range of 10-' moles.

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

[Example compound 1 C ll N 1'l14 Shi12H2s 0■ 0■ x:y 60:40 (molar ratio) CH2CH25CH2CH2Co2H υ CH2CH2NH30□CH.

CHzCHzSCHC+□825 o 2H 12H25 C-116 IQH21 OOH OOH OOH υ, then H2 to H2SO2, 2H2°゜679
No. 2,801.171), as well as external development methods in which the coupler is contained in the developer (U.S.
No. 52,718, No. 2,592,423, No. 2,59
0,970). Moreover, any couplers generally known in the art can be used.

For example, cyan couplers other than those of the present invention may be used, and cyan couplers used in combination include those based on a naphthol or phenol structure and which form an indoaniline dye by coupling; Coupling is carried out using those having a 5-pyrazolone ring having an active methylene group as a backbone structure or pyrazoleazole type, and yellow couplers having a benzoylacetanilide, bivalylacetanilide, or acylacedoanilide structure having an active methylene ring. Both those with and without substituents can be used. Thus, as the coupler, both the so-called 2-equivalent type coupler and the 4-equivalent type coupler can be applied.

Next, the magenta coupler preferably used in the present invention is disclosed in Japanese Patent Application No. 197-32051.
Examples include magenta couplers represented by the general formula (M-1) described on pages 207 to 207, and specific examples of these magenta couplers include those described on pages 208 to 227 of the specification of the old Japanese Patent Application No. 1983-325. CM-1) ~ [M2O3 and Japanese Patent Application No. 61-9791, pages 66-122 t
Examples include magenta couplers No. 1, No. 1-No., and No. 223.

The silver halide color photographic light-sensitive material used in the present invention has at least one silver halide emulsion layer containing a compound (hereinafter referred to as BAR) which reacts with an oxidized form of a coloring agent to release a bleaching accelerator.
The objective effects of the present invention can be better achieved when the compound contains

Preferably used BΔR compounds include those disclosed in Japanese Patent Application No. 1983.
-32501 specification, pages 233 to 252, compounds represented by the general formulas (BAR-A) and (BAR-B) are mentioned, and specific examples of these BAR compounds include Japanese Patent Application No. 63-32501. Specification page 252-2
Examples include compounds (1) to (77) described on page 74.

In the light-sensitive material according to the present invention, the silver iodide content of at least one of the silver halide-containing layers is preferably 0.5 mol% or more, more preferably 1 to 15 mol%, and particularly preferably. is in the range of 1.5 to 10 mol%.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the silver halide emulsion used is silver halide grains composed of two or more phases having different silver iodide contents; A silver halide emulsion containing silver halide grains having a silver iodide content higher than the silver iodide content of the external phase of the grains is preferred.

〔Example〕

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 In all Examples, the amount added in the silver halide photographic light-sensitive material is 9 per Lm'' unless otherwise specified.

In addition, silver halide and colloidal silver are shown in terms of silver.

Sample 1 of a multilayer color photographic element was prepared by sequentially forming each layer having the composition shown below on a triacetyl cellulose film support from the support side.

Sample-1 (comparison) 1st layer: Antihalation layer Black colloidal silver...0.18 Ultraviolet absorber (UV-1) -0,20 colored coupler = (CC-1)...0.05 colored coupler (CM-2) ...0.05 High boiling point solvent (Oil-1) ...0.20 Gelatin ...1.2 Second layer: Intermediate layer ultraviolet absorber (IIV-1) -0.01 High boiling point solvent (Oil-1) ...0.01 Gelatin ...1.2 Third layer: low sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Ell-1) ...0.
9 silver iodobromide emulsion (Em-2) Sensitizing dye (S-1)...2.5XIO sensitizing dye (S-
2) -2,5XlO Sensitizing dye (S-3)...0.5X10 Uncoupler (C'-4) / Uncoupler (C'-2) Colored cyan coupler CCC DIR compound CD-1) High boiling point solvent ( Oil-1) Gelatin 1st layer: High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (E+n-3) Sensitizing dye (S-1)...2.0X10 sensitizing dye (S-
2)...2, 0X10 sensitizing dye (S-3)...
・0.1XlO cyan coupler (C'-1) Cyan coupler (C'-2) Cyan coupler (C'-3) Colored cyan coupler (CO DIR compound (D-2)...1.8 4 (mol/ 1 mol of silver) 4 (mol/1 mol of silver) 4 (mol/1 mol of silver) ...0.15 ...0.03 ...1.20 1) ...0.015 ...0. O5...0.3 4 (mol/1 mole of silver) 1 (mol/1 mole of silver) 1 (mol/1 mole of silver)...1.2...0.1 ■)...0. 05 ...0.002 ...0.5 ...1,4 5th layer: 6th layer: 7th layer: 8th layer: High boiling point solvent (Oil-1) ...0.5
Gelatin...1.3 Intermediate layer gelatin...0.5 Low sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Em-1)...0.8 Sensitizing dye (S-4)...5X10 -' (mol/silver 1 mol) Sensitizing dye (S-5)...lXl0-' (mol/silver 1 mol)
mole) magenta coupler (M-1)...0
．． 5 color magenta coupler (CM-1)...0.
05DIR compound (D-3)...0
．． 015DIR compound (D-4)...
・0.020 high boiling point solvent (Oil-2)
...0.5 gelatin ...0
．． 9 Intermediate layer gelatin...0.7 High boiling point solvent (Oil-1)...0.2 High sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Ea+-3)...1.0
Sensitizing dye (S-6) ・1.5X10-' (mol/silver 1 mol) Sensitizing dye (s-7)...2.5X1O sensitizing dye (
S-8)...0.5XlO magenta coupler (T2) Magenta coupler CM-3) Colored magenta coupler IR compound (El-3) High boiling point solvent (Oil-3) Gelatin 9th layer: Yellow filter layer Yellow colloid Silver stain inhibitor (SC-1) High boiling point solvent (Oil-3) Gelatin 10th layer: Low sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Eln-1) Silver iodobromide emulsion (Em-2) Sensitization Dye (S-10)...7X10 Yellow coupler (Y-1) Yellow coupler (Y-2) 4 (mol/silver 1 mol) 4 (mol/silver 1 mol)...0.06...0 .18 - (CM-2) ...0.05 ...0.01 ...0.5 ...1.0 ...0.1 ...0.1 ...0.1 ...0.8 ...0.20 ...0.20 4 (mol/1 mole of silver) ...0.6 ...0,12 11th layer: 12th layer: DIR compound (D- 2) ...0. O
11 High boiling solvent (Oil-3)...0.
15 Gelatin...1.0 High sensitivity blue-sensitive emulsion layer Silver iodobromide emulsion (Em-4)...0.40
Silver iodobromide emulsion (Em-1)...0.15
Sensitizing dye (S-9) ...lXl0-' (mol/silver 1 mol) Sensitizing dye (S-10) -3XlO-' (mol/silver 1 mol) Yellow coupler (Y-1)
・・0.36 yellow coupler (Y-2) ・
・・0.06 high boiling point solvent (Oil-3)
・・・0.07 gelatin ・・・
1.1 First protective layer fine grain silver iodobromide emulsion...0.2 (average grain size 0.08μra Agl 2 mol%) ultraviolet absorber (UV-1) -0.10 ultraviolet absorber (
UV-2) -0.05 High boiling point solvent (Oil
-1) ...0.1 high boiling point solvent (Oil
-4) ...0.1 formalin scavenger (HS-1) ...0.5 formalin scavenger (HS-2) ...0.2 gelatin
...1.0 Thirteenth layer: second protective layer surfactant (Su-1) -0,005 Alkali-soluble matting agent ...0. IO (average particle size 2μII+) Cyan dye (AIC-1) ...0.0
05 Magenta dye (AIM-1)...0
．． Ol swell agent (WAX-1) -0,
04 Gelatin...0.8 Furthermore,
In addition to the above composition, each layer contains coating aid 5u-2, dispersion aid 5u-3, hardening agents H-1 and H-2, preservative D11,
Stabilizer 5tab-1x Antifoggant AF-1% AF-2
was added.

Em-1 average grain size 0.46 μm, average silver iodide content 7.
5%, monodisperse surface paper silver iodide-containing emulsion Em-2 average grain size 0.32 μm, average silver iodide content 2.
0%, monodisperse and uniform composition emulsion En+-3 average grain size 0.78 μm, average silver iodide content 6
．． 0%, monodisperse surface low silver iodide content emulsion En-4 average grain size 0.95 μm, average silver iodide content 8.
Emulsions Em-1, Em-3 and Em-4 containing 0%, monodisperse surface paper silver iodide are disclosed in JP-A-60-13
It is a silver iodobromide emulsion mainly composed of octahedrons and has a multilayer structure adjusted with reference to publications No. 8538 and No. 61-245151. Also, Em-1-Em-4 are all
The average value of particle size/particle thickness is 1.0, and the width of particle size distribution (variation system) is 14%, 110%, 12%, and 12%, respectively (C1lz)xso," (Cll□) ,s(h"・(C2H6)3NH" (C1lz)+ri0* (CI+2)4SO,e ・(C2Hs)iNI+"C'C' M-1 ■ Q C2H.

IC IM-1 tab-1 F-1 [(CHI-C11502C11□)3CCH2S02
(C112)21□N(CI2)zsOJCC00CH
z(CFxCF2)JH.

AX I il ■ i1 H Oi+ il 4 The sample thus prepared was subjected to wenge exposure using white light, and then subjected to the following development treatment.

Processing process for comparison Processing time Processing temperature Color development (1 tank) 3 minutes 15 seconds 38°C bleaching
(ll) 40 seconds 38°C fixation (tt)
1 minute 20 seconds 38°C stabilization (3 tank case) 1 minute 38°C drying (40°C~8
0°C) for 45 seconds The composition of the color developing solution used is as follows.

Color developer Potassium carbonate 25g Sodium bicarbonate 2.0g Potassium sulfite 5g Sodium bromide
1.25g potassium iodide
1.2mg hydroxylamine sulfate
3.0g Sodium chloride 0
．． 6g diethylenetriaminepentaacetic acid 3.0g
4-Amino-3-methyl-N-ethyl-N-(β-hydroxylethyl) Aniline sulfate 4.6g Potassium hydroxide 1.2g Add water to I
Q and pH using potassium hydroxide or 20% sulfuric acid.
Adjust to 10,00.

Bleach liquid Organic acid ferric complex salt Listed in Table 1 Ethylenediamine disodium acetate 10g Ammonium bromide
150g glacial acetic acid
40g color development
300m (2 nitrate) Add water as shown in Table 1 to obtain IQ, and adjust to pH 4.5 using aqueous ammonia or glacial acetic acid.

Fixer ammonium thiosulfate 200g ammonium sulfite 26g thiourea
5g disodium elendiaminetetraacetate 0.5g 50mQ of the above bleaching solution Add water to 11
2 and adjust the pH to 6.5 using acetic acid and aqueous ammonia.

Stabilizing liquid formaldehyde (37% solution) 2m (15
-Chloro-2-methyl-4-isothiazolin-3-one 0.05g Emulgen 81
0 1 raQ Formaldehyde bisulfite adduct sodium Add 2g water and IQ
The pH was adjusted to 7.0 with aqueous ammonia and 50% sulfuric acid.

As shown in Table 1 below, experiments were conducted by changing the organic acid ferric complex salt and nitrate in the bleaching solution and the fixing solution, respectively.

However, the bleaching solution and fixing solution were stored at 38° C. for 7 days in a sealed container, and then developed according to the processing steps described above.

The highest density transmitted red light density of the processed film sample was measured using a photodensitometer PDA-65A (manufactured by Konica Corp.).

Furthermore, the amount of residual silver in the highest concentration area was determined by fluorescent X-ray method.
DTA-Fe is ferric ammonium ethylenediaminetetraacetate, NTA-Fe is ferric ammonium nitrilotriacetate, CyDTA-Fe is ferric ammonium 1,2-cyclohexanediaminetetraacetate, and (AI)・Fe
, (A-4)・Fe, (A-5)・Fe, (
A6)・Fe, (A9)・Fe are (A-
1), (A4), (A-5), (A-6), (A-9)
means the ferric ammonium salt of

As is clear from Table 1 above, when the specific organic acid ferric complex salt of the present invention is used in the bleaching solution and the nitrate is used in a specific concentration range, the generation of leuco dye is small and the amount of residual silver is extremely small. It can be seen that the condition is good.

Example 2 The organic acid ferric complex salt in the bleaching solution used in Example 11 Experiment No. l-5 was changed as shown in Table 2, and the others were as in Example fII.
The experiment was conducted in the same manner as in I. However, as the ferric organic acid, a mixture of (A-1).Fe and EDTA-Fe was used in a total amount of 0.3 mol/l.

From Table 2, 7 of the organic acid ferric Ha used in the bleaching solution of the present invention.
It can be seen that the effects of the present invention are achieved when 0 mol % or more is the ferric complex salt of the compound represented by formula [A].

Example 3 The same experiment as in Example 1 was conducted except that the amount of acetic acid added to the bleach solution used in Example 1, Experiment No. 1-5 was changed as shown in Table 3. However, the pH was adjusted appropriately using ammonia solution. At the same time, the dye density in the unexposed area of the processed sample was measured. The results are summarized in Table 3.

From Table 3 above, it can be seen that by using the bleaching solution of the present invention in combination with acetic acid, not only the effects of the present invention can be favorably achieved, but also the unexposed area fogging can be improved.

Example 4 A vinyl chloride nozzle with a hole of 0.5 mm in diameter was installed in the bleaching tank and fixing tank of Experiment No. 1-5 in Example 1, and an Iwaki Magnent Pump M was installed on the emulsion surface of the photosensitive material.
The experiment was conducted in the same manner except that D-15 was used to spray the treatment liquid.

As a result, the amount of leuco dye and the amount of residual silver were reduced to 1/2.

Example 5 The pH of the bleaching solution of Experiment No. 1-5 in Example 1 was determined from Table 4 above.
An experiment was conducted in the same manner as in Example 1 except for the following changes.

From Table 4 above, it can be seen that the bleaching solution of the present invention exhibits the effects of the present invention better in a pH range of 2 to 5.5.

Example 6 Cyan coupler C used in Example 2, Experiment No. 2-5
Example 2 except that C'-2 and C'-3 were replaced with cyan couplers listed in Table 5 having the same mole as C'-2 and C10.
An experiment similar to Experiment No. 2-5 was conducted (however, the bleaching time was 40 seconds), and the Noan density in the unexposed area and the amount of residual silver in the highest density area of the processed film sample were measured. moreover,
Measure the cyan density at the highest density part of the processed film sample,
Next, the mixture was treated with a 120 g/l solution of ferric ammonium ethylenediaminetetraacetate (PL+6.0) for 6 minutes to completely oxidize the leuco-cyan dye (1euco-cyan dye) to cyan dye, and the difference was calculated by calculating t.
;.

The results are summarized in Table 5.

R-6 R As is clear from Table 5 above, when cyan couplers represented by the general formulas [C-A] to (C-C) are used as cyan couplers, some residue remains despite rapid processing. The silver content and bleaching edge blur are small, and the generation of leucocyan dye is also small, making it good.

Example 7 A running process was performed using the color negative film and processing solution prepared in Experiment No. 1-5 of Example 1, and the following replenisher.

The composition of the color developing solution used is as follows.

Color developer Potassium carbonate 35g Sodium bicarbonate 3g Potassium sulfite
7g sodium bromide
0.2g hydroxylamine sulfate
3.5g4-amino-3-methyl-N-ethyl-N=
(β-Hydroxylethyl) Aniline sulfate 6.3g Potassium hydroxide 2g Add water to make IQ, and adjust to pH 10 using potassium hydroxide or 20% sulfuric acid.
,20.

Bleach replenisher (A-1) - Fe (same meaning as in Table 1) 0.4 mol ethylenediamine disodium acetate 2 g ammonium bromide
178g glacial acetic acid
45g ammonium nitrate
Add 10 ml of brine to make IQ, and adjust to pH 3.6 using aqueous ammonia or glacial acetic acid.

Fixer replenisher Ammonium thiosulfate 200g Anhydrous sodium bisulfite 15g Sodium metabisulfite 3g Thielenediamine disodium tetraacetate 0.8g Thiourea 5g Add water to make IQ.
Adjust the pH to 6.5.

The stabilizing solution used in Example 1 was used as the stabilizing replenisher.

The processing steps, processing time, processing, and replenishment amount of the running processing were as follows.

(The replenishment amount is the value per 1 m2 of photosensitive material.) However, the fixing tank [or 2 tanks counter current (45 seconds, 2 tanks)]
I went there.

However, the automatic developing machine used was a modified bunker type color film processor model HM-55S manufactured by Noritsu Koki Co., Ltd.

The running process was continued for 40 days until the bleach replenisher was replenished in an amount twice the capacity of the bleach tank.

When the maximum density transmitted red light density (D maxR) and the amount of residual silver of the film sample after the running treatment were measured in the same manner as in Example 1, there was almost no generation of leuco dye and no residual silver was observed.

〔Effect of the invention〕

The bleaching solution of the present invention can be used as a bleaching solution for silver halide color photographic light-sensitive materials, as it generates little leuco dye, has good desilvering properties, can be processed quickly, and can be refilled in a low amount. It is a bleaching solution with excellent economical efficiency and pollution resistance, and it can also be used in hanger-type automatic processors with a large amount of carryover, as it does not generate leuco dyes or reduce desilvering performance due to contamination with color developer. This allows for rapid processing.

Furthermore, according to the method of the present invention, it is possible to obtain not only the effects of the above-mentioned bleaching solution but also the effect of reducing bleach blade blur.

Claims (2)

[Claims] (1) The organic acid ferric complex salt in the bleaching solution for silver halide color photographic light-sensitive materials is substantially the ferric complex salt of the compound represented by the following general formula [A], and the nitrate content is 0.2 to 2 A bleaching solution for silver halide color photographic materials, characterized in that it contains .0 mol/l. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1 to A_4 may be the same or different, -CH_2OH, -COOM or -PO_3M_
Represents 1M_2. M, M_1 and M_2 each represent a hydrogen atom, a sodium atom, a potassium atom or an ammonium group. X represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, and the total number of carbon atoms including branched moieties is 3 or more. ] (2) The following general formulas [C-A], [C-B] and [C-C
] A silver halide color photographic light-sensitive material containing at least one cyan coupler represented by the formula [A] is prepared when the organic acid ferric complex salt in the bleaching solution is substantially represented by the general formula [A] according to claim (1).
1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing a silver halide color photographic material with a bleaching solution containing 0.2 to 2.0 mol/l of nitrate. General formula [C-A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [C-B] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 is an alkyl group, an alkenyl group, a cycloalkyl group, Represents an aryl group or a heterocyclic group, and Y is ▲Mathematical formula, chemical formula, table, etc.▼, ▲Mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, -CONHCOR_2 or -CONHSO_2R_2
(However, R_2 represents an alkyl group, alkenyl group, cycloalkyl group, aryl group, or heterocyclic group, and R_3 represents a hydrogen atom or a group represented by R_2. (Also, they may be different, and may be bonded to each other to form a 5- to 6-membered heterocyclic group.) Represents a group that can leave. ] General formula [C-C] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [R_1 is -CONR_4R_5, -NHCOR_4,
-NHCOOR_6, -NHSO_2R_6, -NHC
ONR_4R_5 or -NHSO_2NR_4R_5, R_2 represents a monovalent group, R_3 represents a substituent,
represents a hydrogen atom or a group that leaves by reaction with an oxidized aromatic primary amine developing agent, l is 0 or 1, and m is 0 to
3, R_4 and R_5 each represent a hydrogen atom, aromatic group, aliphatic group, or heterocyclic group, R_6 represents an aromatic group, aliphatic group, or heterocyclic group, and when m is 2 or 3, each R_3 may be the same or different, may combine with each other to form a ring, or R_4 and R_5, R_2 and R_
3. R_2 and X may be combined to form a ring. however,
When l is 0, m is 0, R_1 is -CONHR_7, and R_7 represents an aromatic group. ]