JPH02105148A - Method for processing silver halide color photographic sensitive material and bleaching bath - Google Patents

Abstract

PURPOSE:To obtain the bleaching bath for the silver halide color photographic sensitive material which allows a rapid and stable low replenishment processing by incorporating a specific ferric complex salt of an org. acid as an oxidizing agent for bleaching image silver into the bleaching bath. CONSTITUTION:The ferric complex salt of the compd. expressed by formula I or formula II is incorporated into 50% of the ferric complex salt of the org. acid in the bleaching bath and at least 0.1mol/l acetic acid or acetate is incorporated into this bleaching bath; in addition, the pH is adjusted to 2.0 to 5.5. In formulas I, II, A1 to A4 denote -CH2OH, -COOM or -PO3M1M2; M, M1, M2 respectively denote a hydrogen atom, sodium atom, etc., potassium atom or ammonium group; X denotes 3 to 6C substd. or unsubstd. alkylene group. In formula II, n denotes 1 to 8 integer. The bleaching bath for the silver halide color photographic sensitive material which is improved in a desilvering property and bleach fogging and obviates the generation of silver sludge in spite of rapid and low replenishing is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides a method for processing silver halide color photographic light-sensitive materials (hereinafter also simply referred to as "photosensitive materials"), and is suitable for use in carrying out the processing method. More specifically, the present invention relates to a processing method and a bleaching solution that can perform sufficient desilvering in a short period of time, have less bleaching blade smudge, and generate less silver sludge.

[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 dichromate were 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 excellent in terms of bleaching blades for image silver, but there is a risk that they will decompose when exposed to light and produce cyanide ions and hexavalent chromium ions that are harmful to the human body. It has unfavorable properties in terms of pollution 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 complex salts are used as oxidizing agents as they have fewer pollution problems and meet the requirements of speeding up, simplifying, and reusing waste liquids. In recent years, treatment solutions have come to be used. However, treatment solutions using metal complex salts of organic acids are
Because the oxidizing power is slow, the image silver (
It has the disadvantage that the bleaching rate (oxidation rate) of silver (metallic silver) is slow. For example, iron(III) complex salt of ethylenediaminetetraacetate, which is considered to have a strong bleaching edge among aminopolycarboxylic acid metal complex salts, has been put into practical use as a bleach solution and a bleach-fix solution in some places, but silver bromide , high-sensitivity silver halide color photographic materials based on silver iodobromide emulsions, especially color papers for photography and non-color negative films for photography containing silver iodide as silver halide and containing a high silver content;
Color reversal films have the disadvantage that they lack bleaching blades and require a long time for the bleaching process.

In addition, in a development processing method in which a large amount of silver halide photographic light-sensitive material is continuously processed using an automatic processor, etc., the components of the processing solution are kept within a certain concentration range in order to avoid deterioration in the performance of the bleaching solution due to changes in component concentration. A means is needed to keep it safe. In recent years, from economic and pollution standpoints, proposals have been made for such methods, such as the so-called concentrated low replenishment method in which these replenishers are concentrated and refilled in small amounts, and another method in which a regenerant is added to the overflow fluid and used again as a replenisher. It has been done.

Particularly in bleaching solutions, organic acid ferrous complex salts formed by bleaching developed silver, such as iron(II) ethylenediaminetetraacetate! A method has been put into practical use in which the salt is oxidized and returned to ethylenediaminetetraacetic acid iron Cm)m salt, that is, an organic acid ferric complex salt, by aeration, and then a regenerant is added to make up for the missing components and used again as a replenisher. There is.

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. In addition, there is a strong need to reduce the stirrup area of a developing 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. As described above, when the concentration of color developer components in the bleaching solution increases, the proportion of reducing components such as the color developing agent and sulfite M salt that adheres to and mixes with the photosensitive material increases, and the bleaching reaction is suppressed. A more serious problem is that bleaching capri tends to occur.

In recent years, a technique using ferric complex salt of propylene diaminetetraacetic acid as a new bleaching agent has been known from Japanese Patent Application Laid-Open Nos. 63-65441, 63-141056, and 63-139348. However, although propylene diamine tetraacetic acid ferric complex salt has extremely excellent silver bleaching ability, it has been found that it has several drawbacks. One is that 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 ferrous.
This means that it is difficult to be oxidized to iron complex salts. As a result, the ferrous complex salts produced accumulate in the bleaching solution, resulting in leucoization of the dye and poor desilvering. Another drawback is that, due to its strong oxidizing power, it oxidizes the color developing agent during the bleaching process, causing indiscriminate coupling reactions, resulting in so-called bleaching edge blur.

It has been found that another drawback is that silver sludge tends to form in the bleaching solution. This is because silver halide (mostly silver bromide) is deposited in the bleaching solution, adhering to the inner walls of automatic processors and clogging filters.

These problems are accentuated by the recent trend of low replenishment or high reuse, and become increasingly serious problems.

[Purpose of the invention]

Therefore, the first object of the present invention is to provide a bleaching solution for silver halide color photographic materials and a processing method that enable rapid, stable and low replenishment processing.

Furthermore, the second objective is to provide a bleaching solution and processing method for silver halide color photographic materials that does not cause bleaching edge blur, has excellent desilvering properties, does not produce silver sludge, and can be processed stably over a long period of time. It is provided by.

[Structure of the invention]

The object of the present invention is to contain an organic acid ferric complex salt as an oxidizing agent for bleaching image silver;
0 mol% or more is a ferric complex salt of a compound represented by the following general formula [A] or [B], and at least 0.1 mol/%
1 of acetic acid or acetate, and has a pH of 2.0 to 5.
5, a bleaching solution for silver halide color photographic light-sensitive materials, and a method for processing silver halide color photographic light-sensitive materials, which involves immediately processing with a bleaching solution after color development, and subsequently processing with a geographical fluid having fixing ability. This is achieved by a method for processing silver halide color photographic materials using the bleaching solution as the solution.

[Specific structure of the invention]

Next, the compound represented by the general formula [Δ] will be explained in detail.

A, ~A4 may be the same or different, and -
ClI, Oll, -C00M or bar represents POsM+M*, and MlM and M each represent a hydrogen atom, a sodium atom, a potassium atom, or an ammonium group. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms (eg, trimethylene, tetramethylene, pentamethylene, etc.).

Examples of the substituent include a hydroxyl group and a lower alkyl group having 1 to 3 carbon atoms.

Below, the above formula Preferred specific examples of the compound represented by (A) are shown below.

(A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (A-7) (A-8) (A-9) (A-10) (A-11) (A-12) In addition to these compounds (A-1) to (A-12), these sodium salts, potassium salts, or ammonium salts 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 above compound examples, those particularly preferably used in the present invention are (A-1), (A-4), (A-7), and (A-9), and particularly preferred is (A-9).
-1) and (A-9).

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

A1-A4 have the same meanings as A and -A in the surface general formula (A), and n represents an integer of 1 to 8. B1 and B may be the same or different, and each represents a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms (eg, ethylene, trimethylene, tetramethylene, pentamethylene, etc.).

Examples of the substituent include a hydroxyl group and a lower alkyl group having 1 to 3 carbon atoms (methyl group, ethyl group, propyl group, etc.). Preferred specific examples of the compound represented by formula (B) are shown below.

(B-1) (In -2) (B-3) (B-4) (B-5) In addition to these compounds (B-1) to (B-7), these sodium salts, kalilim salts or Ammonium salts can likewise be used with preference.

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 above compounds, those particularly preferably used in the present invention are (B-1), (B-4) and (B-7).
Among these, particularly preferred is (B-1).

These ferric complex salts of compounds represented by formulas [A] and CB) are preferably used in an amount of at least 0.1 mol per 1Q of bleaching solution, more preferably 0.15 to 0. It is in the range of .60 mol/l, most preferably in the range of 0.2-0.5 mol/l.

The bleaching solution of the present invention contains a ferric complex salt of the compound represented by formula (A) or CB'l, and other ferric complex salts of aminopolycarboxylic acids (for example, ferric complex salts of ethylenediaminetetraacetic acid). , diethylenetriaminepentaacetic acid ferric complex salt, ■, 2-cyclohexanediaminetetraacetic acid ferric complex salt,
In the present invention, 50% (in terms of mole) of the organic acid ferric complex salt in the bleaching solution of the present invention can be used in combination with a ferric complex salt of glycol ether diamine tetraacetic acid, etc. It is essential that it is a ferric complex salt of a compound represented by (or CB), but from the viewpoint of better achieving the desired effects of the present invention, it is preferably 70% (in terms of mole) or more, and more preferably 80%. (on a molar basis) or more, particularly preferably 90% (on a molar basis) or more, and most preferably 95% (on a molar basis) or more (including 100%).

When the bleaching solution according to the present invention contains imidazole and its derivatives or at least one of the compounds represented by the following formulas (1) to (I), the desired effects of the present invention can be better achieved, and General formula (1) is more preferably used in the present invention because it also has the additional effect of improving precipitation caused by silver in a bleaching solution. In general formula (I), Q is a nitrogen-containing heterocycle (5° ~
(including those in which 6-membered unsaturated rings are condensed), R1 is a hydrogen atom, and R1 is a hydrogen atom with a carbon atom number of 1
~6 alkyl groups, cycloalkyl groups, aryl groups,
Represents a heterocyclic group (including those in which 5 to 6A unsaturated rings are condensed) or an amino group.

In general formula [11), R2 and R3 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 an - or n1-valent heterocyclic residue (including those in which 5- to 6-membered unsaturated rings are condensed), and X represents -51 = 0.
= NR", where R and R' are respectively R,
and synonymous with R1, X' is synonymous with Represents a 1 to 6 alkyl group, cycloalkyl group, aryl group, heterocyclic residue (including those in which 5 to 6 membered unsaturated rings are condensed) or an amino group, nl to n, and m l = ml each represents an integer of 1 to 6.

B represents an alkylene group having 1 to 6 carbon atoms, and R4 and R have the same meanings as R2 and R1, respectively. However, R4 and R6 may each represent -n-sz, or R2 and R1, R and R', and R4 and R 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.

General formula (nl) In the general formula (I[[), Ra and! C and C respectively represent 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, an aryl group, an alkenyl group, or B+S
Represents Zs. However, R, and R1 are combined to represent a ren group,
zl represents a hydrogen atom, an alkali gold atom, an ammonium group, an amino group, a nitrogen-containing heterocycle R/n represents an integer of 1 to 6.

General formula (IV) In general formula (TV), RI and R1 each represent an alkyl group or -(CH!)na
S O3''. (However, R1, is -(C1ll)
When "n, so,", a represents 0, and represents an alkyl group or l.) Ge represents an anion. n represents an integer from 1 to 6.

General formula (V) −+− In general formula (V), Q is a nitrogen-containing heterocycle (5 to 6
(including those with fused unsaturated or saturated rings)
represents a group of atoms necessary to form or represents an alkyl group. However, q' has the same meaning as Q.

General formula (Vl) In general formula (Vl), D , , D , , D , and , each represent a simple bond, an alkylene group having 1 to 8 carbon atoms, or a vinylene group, and Q ++ Q **
Qs and q are each 0. Represents l 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.

-Mathematical formula [■] RI2 R11RlI General formula [■] Nioiite, X, is -COOM', -0
1l.

-503M', -CONII2. -5OJI11.
-Nl+! , -511, -CN.

-COJt*,, -5O! Rta, -OR+i, -NR
+aRt7. -5R+s.

-5OJ+s, -NIICOR+a, -NH5O!
R+s, -0CORI@ or -5O! Represents R+a, Rrs Rrs RlI or a hydrogen atom, ■ and n are each 1 to 1
Represents an integer of 0. R+t, R12, Rtx, R14, R
II.

R17 and 1 each represent a hydrogen atom, a lower alkyl group, an anru group, or a lower alkyl group, and RII is -NR1@
Represents R11, -oR, or -3R0, R8゜ and R
lI each represents a hydrogen atom or a lower alkyl group, and R1! represents an atomic group necessary to combine with R11 to form a ring. R1° or Ro may be combined with R4 to form a ring. M' represents a hydrogen atom or a cation.

General formula [■] In the general formula [■], Ar represents a divalent aryl group or a divalent organic group combining an aryl group with an oxygen atom and/or an alkylene group, and B2 and B3 are
Each represents a lower alkylene group, Ro, R24, R□
and R1, each represents a hydroxy-substituted lower alkyl group, and X and y each represent 0 or l.

G' represents an anion, and 2 represents 0, 1 or 2.

In the general formula CI, R1 and R1° 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 R32
represents a hydrogen atom or a carboxy group.

Typical specific examples of the compounds represented by the above-mentioned formulas (1) to (I), imidazole, and its derivatives include
-32501, pages 17 to 39 (1-
1) to (I-10), (II-1) to (II-27),
(III-1) to (Ill-15), (IV-1)
~(IV-3), (V-1) ~(V-23), (Vl
-1) ~(Vl -17), (■-1) ~(■-15
), (■-1) ~ (■-7), (II-1) ~ (II
-5) and (A-1) to (A-8).

These compounds are generally used as bleach accelerators, and are hereinafter referred to as bleach accelerators of the present invention.

These bleach accelerators may be used alone or in combination with 211 or more, and good results are generally obtained when the amount added is in the range of about 0.01 to 100 g per 1Q of bleaching solution. However, in general, if the amount added is too small, the effect of promoting bleaching is small, and if the amount added is too large, precipitation may occur and contaminate the silver halide color photographic material being processed. 0.05-5 per 1Q of liquid
It is preferably 0 g, more preferably 0.05 to 15 g.

When adding a bleaching 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, etc. as necessary. It can also be dissolved and added using an organic solvent.

The bleaching solution of the present invention can be used at a pH of from 2 to 5.5, preferably from 3.0 to 5.0. The temperature of the treatment is 20°C to 45°C, preferably 25°C to 45°C.
The temperature is 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 contains boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
, In sodium carbonate, potassium bicarbonate, ammonium hydroxide, and the like can be contained alone or in combination of two or more kinds. Furthermore, various optical brighteners, antifoaming agents, surfactants, and antifungal agents can be contained.

Specific examples of the acetate of the present invention include sodium acetate, ammonium acetate, potassium acetate, triethanolammonium acetate, trimethylammonium acetate, and the like.

The acetate and acetic acid of the present invention are used in an amount of at least 0.1 mol, preferably 0.1 mol, per 1Q of bleaching solution.
It is in the range of 25 to 2.0 mol/l, more preferably 0
．． in the range 4 to 1.5 mol/l, most preferably 0
．． It is in the range of 5 to 1.2 mol/l.

The preferred replenishment amount of the bleaching solution according to the present invention is 1. 20+a (2 to 500
a12, particularly preferably 30m (! to 350m
m(2, more particularly preferably from 40IIIQ to 300■a, most preferably from 501IIQ to 250IIIQ).

In the method of 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 treatment 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 - Bleach - Bleach-fix - Wash with water (6) Color development - Bleach - Bleach-fix - 1st stability (7) Color development - Bleach - Bleach-fix - Stability (8) Color development - Bleach - Bleach-fix - 1st stability −
Second stabilization Among these steps (3), (4), (5)
.

(7) and (8) are preferred, especially (3) and (4).
).

(5) is preferred. 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 thiocyanate, and ammonium thiocyanate, thiourea, and thioether.

In addition to these fixing agents, fixing solutions and bleach-fixing solutions include ammonium sulfite, M potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite. D) I consisting of sulfites such as boric acid, borax, sodium hydroxide, potassium hydroxide A, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. It can contain one or more buffering agents.

Furthermore, alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride,
It is desirable to contain a large amount of a rehalogenating agent such as ammonium bromide. Also pl of borates, oxalates, acetates, carbonates, phosphates, etc.! Buffers, alkylamines, polyethylene oxides, and other substances known to be added to ordinary fixing solutions and bleach-fixing solutions can be added as appropriate.

The fixing agent is used in an amount of 0.1 mol or more per 1Q of geographical fluid, preferably 0.6 mol to 0.6 mol in terms of the desired effect of the present invention.
It is used in a range of 4 mol, particularly preferably in a range of 0.9 mol to 3.0 mol, particularly preferably in a range of 1.1 mol to 2.0 mol.

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, German Patent No. 2,3
31.220 specification), ion exchange method (Japanese Unexamined Patent Publication No. 5
1-17114, German patent 2,548.23
No. 7 Moe HJJ1! J) and metal substitution method (British patent 1
, 353.805) etc. can be effectively used.

It is particularly preferable to recover silver in-line from the tank solution, since the suitability for rapid processing becomes even better, but it is also possible to recover silver from the overflow waste solution and use it in (1).

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 m@12 or less per m@2 of light-sensitive material. Especially 1m of photosensitive material
20m per 2 (2-650m (2, especially 30m)
Good results are obtained when mQ ~ 400 m12.

Furthermore, when the fixing solution and bleach-fixing solution according to the present invention contain iodide (ammonium iodide, potassium iodide, sodium iodide, lithium iodide, etc.) O.1g/(2-10g/l), This further enhances the effects of the present invention.

Especially 0.3g/l to 5g/l1 Especially especially 0.5g
, l~3 g/(ls most preferably 0.8 g/
Good results are obtained when 1 to 2 g IQ.

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

- Formula (FA) [In the formula, R' and R'' each represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a nitrogen-containing heterocycle. n' represents 2 or 3.] General formula FA ), and the compound represented by formula (FA) is a general compound as described in U.S. Pat. No. 3,335.161 and U.S. Pat. No. 3,260.718. It can be synthesized using a conventional method.

Compound group (1? 13) V n -1 Thiourea FB-2 Ammonium iodide FB-3 Methylthiourea FB-4 Ammonium thiocyanate FD-5 Potassium thiocyanate FB-6 Sodium thiocyanate FB-7 Thiocyanocatechol These, The compound represented by formula (FA) and the compound of compound group (F B ) may be used alone or in combination of two or more. for example,
Thiourea and ammonium thiocyanate and ammonium iodide, thiourea and ammonium thiocyanate, (FA-1
2) and thiourea, (FA-12) and ammonium thiocyanate, (FA-12) 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 (FB
-4).

In addition, the amount of the compound represented by the formula (FA) and the compound of the compound group (F B) is 0 per geofluid IQ.
．． Good results are obtained in the range of 1g to 200g.

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

In the fixing solution and bleaching 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 stable sulfite adducts with the sulfite ion include compounds having an aldehyde group, compounds containing a cyclic hemiacetal, compounds having an α-dicarbonyl group, and compounds having a nitrile group. etc., but preferably general formula (A-1) ~
The compound represented by (A-11) is particularly preferably used.

Preferred specific examples other than the compounds represented by general formulas (Ad) to (A-11) are shown below.

General formula (A-11) A! , As, l'-s, and As represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a formyl group, an acyl group, or an alkenyl group. As an alkyl group having 1 to 6 carbon atoms,
Including straight chain or branched ones, such as methyl group, ethyl group, n-propyl group, 1so-propyl group, n-methyl group, n-/(rel g, 1so-barrel group, hexane group, isohexane group, etc.) and may be substituted, specifically formyl I & (e.g. formyl methyl,
2-formylethyl, etc.), amino IJs (e.g., aminomethyl, aminoethyl, etc.), hydroxyl groups (e.g., hydroxymethyl, 2-hydroxyethyl,
Substituents include substituents such as 2-hydroxypropyl, etc.), alkoxy groups (eg, methoxy, ethoxy, etc.), and halogen atoms (eg, chloromethyl, trichloromethyl, dibromomethyl, etc.).

Alkenyl groups include substituted and unsubstituted groups; unsubstituted groups include vinyl, 2-zuropenyl, etc., and substituted groups include, for example, 1゜2-dichloro.2
Examples include groups such as -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.

(Exemplary compound) 1+ C1h N+CIIJ "Cll0 I0C11
.

A O-II Formaldehyde sodium bisulfite A O-+2 Acetaldehyde sodium bisulfite A O-13 Propionaldehyde sodium bisulfite A O-14 Butyraldehyde sodium bisulfite AO
-21 Sodium succinic acid aldehyde bisulfite A O-22 Sodium glutaraldehyde bis bisulfite AO-23 β-Methylglutaraldehyde Sodium bis bisulfite A O-24 Sodium maleic acid dialdehyde bis bisulfite These sulfite addition compounds are Per IQ, 0-
It is preferably used in a range of 1 g to 80 g, more preferably in a range of 0.5 g to 40 g.

The total processing time of the bleaching solution and the processing solution (fixing solution or bleach-fixing solution) having 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 3 minutes and 20 seconds. Hereinafter, the desired effects of the present invention are best achieved when the duration is 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 in the range of 10 seconds to 2 minutes 40 seconds. It is particularly preferably in the range of 20 seconds to 2 minutes and 10 seconds.

In the geographic method of the present invention, it is preferable to apply forced liquid agitation to the bleach solution, fix solution, and bleach-fix solution. 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 Asahi Ri method High pressure spray treatment method is a discharge pressure of 0.1 kg/cm"
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/
Directly pour the processing liquid into the processing liquid by applying a pressure higher than co+',
This refers to a method of processing by spraying onto photosensitive materials, and generally a pressure pump or a liquid pump is used as the pressure source. Pressure pumps include plant jar pumps, gear pumps,
There are magnet pumps and cascade pumps, such as the 15-LPM type, 10-BFM type, and 20-manufactured by Sakiyama Seisakusho.
BFM type, 25-BFM type, etc. are known as examples.

As a liquid pump, for example, MD- manufactured by Ikki Co., Ltd.
30 type, MO-56 type, MDI-25 type, MDK-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 primarily determined by the flow rate (+2/+5 in) s spray pressure (Kg/cm”). Therefore,
In order to achieve sufficient effectiveness, a pressurizing device is required that can adjust the pressure in proportion to the number of spray nozzles. The most preferable pressure is 0.3 to 10 kg/cII! 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, the photosensitive material is vibrated by the bubbles ejected from its mouth, and the processing liquid is brought into effective contact with the front, back, and side surfaces of the photosensitive material. .

Corrosion-resistant materials such as hard PVC, polyethylene-coated stainless steel, and sintered metal are suitable for the sparger, and the diameter of the holes should be such that the diameter of the discharged air bubbles is 2 mm to 30 mm. , this from 5 mm to 15
Even better effects can be obtained if the thickness is set to millimeters. Air can be supplied using an air compressor, such as Hitachi's Bebicon (0.4KW, BU7TL), or an air pump, such as Ikki's air pump (Ap22).
Type 0), etc. The amount of air required is 2Q/min to 30Q/min per transport rack of an automatic developing machine, and more preferable results can be obtained with 5Q/min to 20a1min. 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.
Vibration width of photosensitive material due to bubbles is 0.2mm to 20m
Preferably, the amount of air or inert gas is delivered such that m.

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 liquid tank of an automatic processor and irradiates ultrasonic waves onto the photosensitive material to increase the efficiency of development promotion. . 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 1000K.
)1z is used, but especially 10-50KIlz
This 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.
28, V-411 type, etc. are generally used.

The method of installing the vibrator is to fix the vibrator to the upper part of the immersion processing tank of an automatic processor, and install it so that the vibrator is applied from the back side of the photosensitive material. The frequency of the vibrator is 100
-10000 times/min is preferred. The most preferred range is 5
00 to 6000 times/min. The amplitude of the photosensitive material to be processed is from 0.2-1 to 30 m5+, preferably from 1 mm to 20 m5+
It is sve. 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 when the processing tank is composed of multiple tanks, a preferable effect can be obtained by installing at least one vibrator in each processing tank.

In the present invention, the time for processing the silver halide color photographic light-sensitive material with the color developer is preferably 180 seconds or less, more preferably 150 seconds or less, even more preferably 2
It is in the range of 0 to 150 seconds, more preferably 30 to 120 seconds, and even more preferably 40 to 100 seconds.

In the present invention, by processing the above-mentioned silver halide color photographic light-sensitive material in the above-mentioned short time, surprisingly,
Not only can the effects of the present invention be achieved, but also the graininess of the resulting dye image can be improved.

Furthermore, in the method for processing a silver halide color photographic light-sensitive material of the present invention, the color developing solution preferably contains an aromatic primary amine color developing solution main ingredient in an amount of t, sx per 10 parts of the processing solution.
It is a color developing solution containing 70 or more 2.OX 10-' moles, and even more preferably 2.5X 10-' to 2X 10-'% L/Q(
1') A color developing solution containing at least one of the above developer main ingredients is preferred.

Most preferably, the content is in the range of 3XH1-' to lX10-' moles.

When such a color developing agent is used at a high concentration to activate the photographic light-sensitive material, an image with excellent sharpness and improved graininess can be obtained by short-time processing as described above.

This is particularly noticeable in magenta dye images.

Hereinafter, the color development vi! that can be preferably used in the present invention! , the liquid color developing agent will be explained.

The aromatic primary amine color developing agents used in the preferred color developing solution include known ones that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state.

Examples of aminophenol-based developers include 0-aminephenol, p-aminophenol, and 5-amino-2
-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl benzene, and the like.

In the present invention, the aromatic primary amine color developer that is particularly useful in the present invention is because it can better achieve the desired effect and improve the crystal precipitation on the inner wall of the color developer layer of an automatic processor. It is an aromatic primary amine color developer having an amino group having at least one water-soluble group, and particularly preferably a compound represented by the following formula (E).

- In formula (E), R1 represents a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and may have a substituent.

R8 and R3 represent a hydrogen atom, an alkyl group, or an aryl group, and these groups may have a substituent. At least one of R3 and R3 is a hydroxyl group,
an alkyl group substituted with a water-soluble group such as a carboxylic acid group, a sulfonic acid group, an amino group, a sulfonamide group, or
ut-io 1″'7R4.

This alkyl group may further have a substituent.

Note that t<' represents a hydrogen atom or an alkyl group, the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and p and q represent an integer of 1 to 5.

Next, the compounds represented by the above-mentioned formula (E) are listed (exemplary compounds): NH.

N.H.

(E-3) N.H.

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

(E-6) (E-7) (E-8) (E-9) (E-10) NH2 (E-11) N.H.

(E-12) N.H.

(E-13) N.H.

(E-14) N.H.

(E-15) N.H.

(E-16) These p-phenyl diamine derivatives represented by formula [■] can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, phosphate, p-)luene Sulfonates, sulfites, oxalates, benzenedisulfonates, etc. can be used.

In the present invention, p-7 represented by the above-mentioned formula (E)
Among the engineered nylene diamine derivatives, R2 and/or R
The effects of the present invention are particularly well exhibited when 3 is represented by ((C11ri40)eR' (p, q and R' are the same as defined above).

Preferred compounds for use in the color developer used in the present invention include sulfites, hydroxylamine, and development inhibitors. Examples of the sulfites include sodium sulfite, sodium hydrogen sulfite, potassium sulfite, potassium hydrogen sulfite, etc., and it is preferable to use them in the range of O0l~409/(2), more preferably in the range of 0.5~10g/(2). It is to be used in

The above hydroxylamine is used as a counterpoint to hydrochloride, sulfate, etc., and is preferably used in a range of 0.1 to 40 y/l, more preferably in a range of 0.5 to 10 g/l. Furthermore, development inhibitors preferably used in the above color developing solution include halides such as sodium bromide, potassium bromide, sodium iodide, and potassium iodide, as well as organic inhibitors, and the amount of these added is 0.005. ~20g
It is preferable to use it in the range of /l, more preferably 0. It is in the range of O1 to 5g/12.

Examples of the organic inhibitor preferably used in carrying out the present invention include nitrogen-containing heterocyclic compounds, compounds containing a mercapto group, aromatic compounds, onium compounds, and compounds having an iodine atom in a substituent. The following exemplified compounds specifically show these.

However, the compounds that can be used are not limited to the following compounds.

(Exemplary compounds) (Z-1) (Z-2) (Z-3)
(Z-4) (Z-5) (, Z-6) (Z-7) (Z-3>
(Z-9) (Z-10)
C2-11) (Z-12)
(Z -13) (Z -14)
(Z-Is)COOC=
H* (t) Furthermore, when carrying out the present invention, Japanese Patent Application No. 61/12781
The general formula [R
-1] to (R-Xlll) can be used, and by using the organic inhibitor in combination with the organic inhibitor described above in the present invention, the effects of the present invention can be more effectively achieved.

Further, the organic inhibitor in the present invention is as described above, but more specifically, it is described in the above-mentioned Japanese Patent Application No. 61-127.
(Z-1) to (Z-1) on pages 1 to 113 of the specification of No. 81
Z-3), (Z-6), (Z-111) to (Z-1
3), (Z-15) to (Z-17), (Z-19)
, (Z-22) to (Z-25), (Z-2'l),
(Z-31) ~ (Z-38), (Z-40), (Z
-41), (Z-43) to (Z-64) and (Z-
66) to (Z-73).

The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, and water softeners. Also, a thickening agent, a development accelerator, etc. can be optionally included.

Additives other than those mentioned above that may be added to the color developing solution include anti-staining agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, and the like.

The color developing solution of the present invention has a pH of 9 or more, particularly p)['l~
13 is preferred.

Furthermore, the processing temperature of the color developing solution is preferably 35°C or higher, particularly preferably a range of 38°C to 60°C, and most preferably 40°C, in order to better achieve the effects that meet the objectives of the present invention. ~50°C.

In addition to the above, there are no particular limitations on the processing method for the photographic material of the present invention, and any processing method can be applied.

In the photographic material according to the present invention, the silver iodide content in at least ljml of the silver halide-containing layer is 0.5 mol% or more, preferably in the range of 1 mol% to 15 mol%, more preferably 1 mol%. It ranges from .5 mol % to IO mol %.

The photosensitive material according to the present invention uses an internal development method (US Pat. No. 2,376.679) 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. 2.5'l12,243, No. 2,
590,970). 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 in combination, and the cyan couplers used in combination include those based on a naphthol or phenol structure and which form an indoaniline dye by coupling,
As a magenta coupler, 5-
Yellow couplers include benzoylacetanilide, bivallylacetanilide, and anruacetanilide structures having an active methylene ring, and those having a substituent at the coupling position. You can use any of the ones that don't. In this way, as the coupler, both a so-called 2-equivalent type coupler and a 4-equivalent type coupler can be applied.

In the present invention, the general formulas (C-A) to (C-C
) are preferably used, and specific examples of these cyan couplers include Japanese Patent Application No.
(C-1)-(C-46) described in specification W159 to page 173 of No. 33-32501 and 178 of the same specification
(C-51) to (C-11 described on page ~196)
8).

Next, examples of magenta couplers preferably used in the present invention include magenta couplers represented by the general formula (M-I) described on pages 197 to 207 of Japanese Patent Application No. 63-32051. Specific example compounds include (M-1) described on pages 208 to 227 of Japanese Patent Application No. 1983-32501.
~ (M-76), and the specification of Japanese Patent Application No. 61-9791,
No. described on pages 66 to 122, l = No
.

223 magenta coupler.

The silver halide color photographic light-sensitive material used in the present invention contains a compound (hereinafter referred to as
The desired effects of the present invention can be better achieved when containing an AR compound (referred to as an AR compound).

Preferably used BAR 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 32501 Specification 252
Examples include compounds (1) to (77) described on page 274.

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; Preferably, the emulsion is a silver halide emulsion containing silver halide grains having a silver iodide content higher than the silver iodide content of the outer edge phase of the grains.

In the processing method of the silver halide color photographic light-sensitive material of the present invention, it can be determined by the following method that the average silver iodide content of the grains is higher than the silver iodide content of the outer edge phase of the grains.

When the silver halide emulsion of the present invention contains silver halide grains having an average value of grain size/grain thickness of less than 5,
Average silver iodide content (J,
) and the silver iodide content (J2) on the grain surface determined by X-ray photoelectron spectroscopy, the relationship j; when Jl>Jx is satisfied.

The particle size referred to here is the diameter of the circumscribed circle of the surface where the projected area of the particle is maximum.

X-ray photoelectron spectroscopy will be explained.

Prior to measurement by X-ray photoelectron spectroscopy, the emulsion is pretreated as follows. First, a zolonase solution is added to the emulsion and stirred at 40° C. for 1 hour to decompose gelatin. Next, the emulsion particles are sedimented by centrifugation, and after removing the supernatant, an aqueous pronase solution is added and gelatin decomposition is performed again under the above conditions. This sample is centrifuged again, the supernatant liquid is removed, distilled water is added to redisperse the emulsion particles in the distilled water, the sample is centrifuged, and the supernatant liquid is removed. After repeating this water washing operation three times, the emulsion particles are redispersed in ethanol. This is applied thinly onto a mirror-polished silicon wafer to use as a measurement sample.

For measurements using X-ray photoelectron spectroscopy, the equipment P111 is used.
ESCA/SAM5 (type 30) is used, and X for excitation is used.
M9-Ka line, X-ray source voltage 15KV, X-ray source current 4
It is carried out under the conditions of 0 mA and pass energy of 50 eV.

Ag5d to determine the surface halide composition.

l3r3d, I3d3/2 electrons are detected.

The composition ratio is calculated by the relative sensitivity coefficient method using the refined intensity of each peak. Ag5d, Br5d.

13d3/2 relative sensitivity coefficient of 5.10゜0 respectively
．． 8+, /1. ', )92, the composition ratio can be given as the atomic percent at the 1112th position.

The silver halide emulsion used in the present invention has a grain size/
When particles having an average particle thickness of less than 5 are included, the particle size distribution is preferably monodisperse. A monodisperse silver halide emulsion is a monodisperse silver halide emulsion with an average grain size of γ centered around 120
% grain size range is 60% or more of the total silver halide grains yfLffi, preferably 70% or more, more preferably 80% or more.

Here, the average particle size Y is the frequency n of particles having particle size γ1
Define the particle size γi when the product niXγi3 of i and γi3 is maximum (3 significant figures, minimum digit is 5 to 40
people).

In the case of spherical silver halide grains, the grain size referred to here means the diameter thereof, and in the case of grains having shapes other than spherical, the diameter when its projected image is converted into a circular image of the same area.

The particle size can be obtained, for example, by photographing the particle with an electron microscope, magnifying it 10,000 to 50,000 times, and then calculating the particle diameter or projected area on the print (the number of particles measured). (There shall be 1,000 or more indiscriminately.) A particularly preferred highly monodispersed emulsion of the present invention is the distribution width defined by the average net diameter × 100 - distribution width (%) is 20% or less, more preferably 15% or less.

Here, the average particle size and particle size standard deviation shall be determined from 11 of the above definition.

When the silver halide emulsion used in the present invention is a tabular silver halide emulsion in which the average value of grain size/grain thickness is 5 or more, the average silver iodide content determined by the above-mentioned fluorescent X-ray analysis method (Jl) and the average value of the silver iodide content measured on silver halide crystals that are 80% or more away from the center in the grain diameter direction of the silver halide grains using the X-ray microanalysis method ( When comparing J3), the relationship Jl>Js is satisfied.

The X-ray microanalysis method will be explained.

Silver halide particles were dispersed in an electron microscope observation grid equipped with an energy-dispersive X-ray analyzer in an electron microscope, and the magnification was set so that one particle entered the field of view of a CRT by cooling with liquid nitrogen, and AgLσ was analyzed for a certain period of time.

The intensity of the IL (F line) is integrated.The silver iodide content can be calculated using the intensity ratio of ILα/AgLα and a calibration curve prepared in advance.

In tabular silver halide emulsions in which the average value of grain size/grain thickness is 5 or more, the average value of grain size/grain thickness is more preferably 6 or more and 100 or less, particularly preferably 7 or more and 50 or less.

In the silver halide emulsion according to the present invention in which the average value of grain size/grain thickness is less than 5, the silver iodide content (J,) on the grain surface as determined by X-ray photoelectron spectroscopy is 6 to 0 mol. is preferable, more preferably 5 to 0 mol%, particularly preferably 4 to 0.01 mol%.

In the tabular silver halide emulsion according to the present invention in which the average value of grain size/grain thickness is 5 or more, the distance from the center of the silver halide grains by 80% or more in the grain diameter direction is determined by the X-ray microanalysis method. The average value (J,) of the silver iodide content measured on the silver halide crystals is preferably 6 to 0 mol%, more preferably 5 to 0 mol%, particularly preferably It is 4 to 0.01 mol%. The average thickness of the tabular silver halide grains is 0.5-0. Old μl is preferred, particularly preferably 0.3 to 0.05 μl
It is. The average grain size of the silver halide grains contained in the tabular silver halide emulsion is preferably 0.5 to 30 .mu.m, more preferably 1.0 to 20 .mu.I.

The silver halide emulsion preferably used in the present invention and having an average value of grain size/grain thickness of less than 5 is preferably monodisperse, and is preferably of core/shell type. The tabular silver halide emulsion preferably used in the present invention and having an average value of grain size/grain thickness of 5 or more preferably has silver iodide localized in the center of the grains.

A core/shell type silver halide emulsion with an average value of grain size/grain thickness of less than 5 has a grain structure composed of two or more phases with different silver iodide contents. The phase having the highest content (referred to as the core) consists of silver halide grains other than the outermost layer (referred to as the shell).

The inner phase (core) having the highest silver iodide content may preferably have a silver iodide content of 6 to 40 mol%, more preferably 8 to 30 mol%, particularly preferably 10 to 20 mol%.
It is mole%. The silver iodide content of the outermost layer is preferably less than 6 mol%, more preferably 0 to 4.0 mol%.

The ratio of the shell portion of the core/shell type silver halide grains is preferably 10 to 80% by volume, and more preferably tL<l:
t15 to 70%, particularly preferably 20 to 60%.

In addition, the core portion accounts for 10 to 80% of the total particle volume.
%, more preferably 20 to 50%.

In the present invention, the content difference between the core portion with a high silver iodide content and the shell portion with a low silver iodide content of the silver halide grains may have a sharp boundary, or may have a continuous boundary that is not necessarily clear. It may be something that changes. Further, those having an intermediate phase between the core and the shell having a silver iodide content between the core and the shell are also preferably used.

In the case of core/shell type silver halide grains having the intermediate layer, the volume of the intermediate layer is preferably 5 to 60%, more preferably 20 to 55%, of the entire grain. The difference in silver iodide content between the shell and the intermediate layer and between the intermediate layer and the core is preferably 3 mol % or more, and the difference in silver iodide content between the shell and the core is preferably 6 mol % or more.

The core/shell type silver halide emulsion is preferably silver iodobromide, and its average silver iodide content is preferably 4 to 20 mol%, more preferably 5 to 15 mol%. Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

Core/shell type silver halide emulsion is disclosed in JP-A-59-177.
535, 130-138538, 59-52238
, No. 60-143331, No. C10-35726 and No. 60-258536.

When a core/shell type silver halide emulsion is grown starting from seed grains as in the method described in the Examples of JP-A-60-138538, the center of the grains may have a halogen composition region different from that of the core. sell.

In such cases, the halogen composition of the seed grains may be of any composition such as silver bromide, silver iodobromide, silver chloroiobromide, silver chlorobromide, silver chloride, etc., but if the silver iodide content is Silver iodobromide or silver bromide of 10 mol % or less is preferred.

The proportion of the seed grains in the total silver halide is 50% by volume.
% or less is preferable, and 10% or less is particularly preferable.

The distribution state of silver iodide in the above-mentioned core/shell type silver halide grains can be detected by various physical measurement methods. This can be investigated by measuring luminescence at low temperatures or using X-ray diffraction.

The core/shell type silver halide grains may be normal crystals such as cubes, tetradecahedrons, and octahedrons, may be composed of twin crystals, or may be a mixture of these, but it is preferable that they be normal crystals. preferable.

In a tabular silver halide emulsion in which the average value of grain size/grain thickness is 5 or more and silver iodide is localized in the center of the grain, the high iodine content phase in the center covers the entire grain volume. It is preferably 80% or less, particularly preferably 60% to 10%. The silver iodide content in the center is preferably 5 to 40 mol%, particularly 10 to 40 mol%.
30 mol% is preferred. The low iodine content phase (periphery) surrounding the high iodine content phase in the center has a silver iodide content of 0 to 10.
Preferably it consists of silver iodobromide in mole %, more preferably from 01 to 6.0 mole %.

A tabular silver halide emulsion in which silver iodide is localized in the center can be obtained by a known method such as that disclosed in JP-A-59-99433. In the method for processing a silver halide color photographic material of the present invention, the average silver iodide content of all the silver halide emulsions in the silver halide photographic material is preferably 0.1 to 15 mol%, More preferably 0.5 to 12 mol%, particularly preferably 1 to 6 mol%.

In the method for processing a silver halide color photographic material of the present invention, the average grain size of all the silver halide emulsions in the silver halide color photographic material is preferably 2.0 μm or less, more preferably 0.1 μm to 1 μm. .0 μm or less, particularly preferably 0.2 μm to 0.6 μm.

In the method for processing a silver halide color photographic material of the present invention, the total dry film thickness of all hydrophilic colloid layers of the silver halide color photographic material (hereinafter referred to as the film thickness on the emulsion side)
The lower limit of is determined by the silver halide emulsion, coupler, oil agent, additives, etc. contained, and the preferred film thickness on the emulsion surface is 5 μm = 18 μm, more preferably 10 μm.
-16 μm.

Further, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14 μm or less, and the distance from the emulsion layer to the lower end of the emulsion layer that is the next closest to the support is 14 μm or less.
It is preferably 0 μm or less.

As a method for thinning the color light-sensitive material of the present invention, there is a method of reducing the amount of hydrophilic colloid as a binder. The purpose is to retain minute oil droplets of coupler dissolved in silver halide and Takasu point solvent, to prevent increase in fog due to mechanical stress, and to prevent color turbidity due to diffusion of oxidized developing agent between layers. Because hydrophilic colloids are added, the amount can be reduced within a range that does not impair the purpose.

Another method for thinning the layer is to use highly chromogenic couplers.゛Another method for thinning the layer is to reduce the amount of high-temperature solvent;
Examples include a method of thinning the intermediate layer by adding a scavenger of an oxidized developing agent to the intermediate layer between layers having different color sensitivities.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the total amount of silver halide contained in the light-sensitive silver halide emulsion contained in all emulsion layers of the silver halide color photographic light-sensitive material is 6.5 g/ 1" or less, more preferably 2.5 to 6.0 g/s", more preferably 3.
0 to 5.5 g/@”1, particularly preferably 3.5 to 5.0
9/11”.

In the method for processing a silver halide color photographic light-sensitive material of the present invention, the total hydrophilic protective colloid layer coated on the emulsion layer side on the support of the silver halide color photographic light-sensitive material during development has a swollen film thickness when dried. The film thickness is preferably 180% to 350%, particularly preferably 200% to 300%.

Techniques for adjusting the swollen film thickness are well known to those skilled in the art, and can be carried out, for example, by appropriately selecting the amount and type of hardening agent.

As a hardening agent, aldehyde type, aziridine type (for example, PB Report 19,921, U.S. Patent 2,950.1)
No. 97, No. 2,964.404, No. 2,983.31
No. 1, Specifications of No. 3,271.175, Special Publication No. 1973
-40898 and JP-A-50-91315), inoxazole systems (for example, those described in U.S. Pat. No. 331,609), epoxy systems (
For example, US Patent No. 3,047,394, West German Patent No. 1,0
85,663, the specifications of British Patent No. 1,033,518, and those described in Japanese Patent Publication No. 48-35495),
Vinyl sulfone type (e.g. PB Revo-1-19,9
20, West German Patent No. 1,100,942, West German Patent No. 2,337,
No. 412, No. 2,545゜722, No. 2,635.5
No. 18, No. 2,742.308, No. 2,749゜26
No. 0, British Patent No. 1,251.091, Patent Application No. 1973-5
No. 4236, No. 48-110996, U.S. Patent No. 3,5
No. 39,644 and No. 3,490゜911), acryloyl type (for example, Japanese Patent Application No. 1973-
No. 27949, U.S. Pat. No. 3,640,720), carbodiimides (e.g., U.S. Pat. No. 2,938.892, U.S. Pat. No. 4,043.818, U.S. Pat. No. 4,061,499) Meisho, Special Publication 1977-387
15, Japanese Patent Application No. 49-15095), triazine type (for example, West German Patent No. 2,410.
No. 973, No. 2゜553.915, U.S. Patent No. 3,32
5.287, those described in JP-A-52-12722), polymer type (for example, British Patent No. 822
．． No. 061, U.S. Pat. No. 3,623.878, U.S. Patent No. 3.3
9G, No. 029, 3.22 (i, specifications of No. 234, Japanese Patent Publication No. 18578-18578, No. 18579, No. 47
-48896), other maleimide-based, acetylene-based, methanesulfonic acid ester-based,
(N-methylol type) hardening agents can be used alone or in combination. As a useful combination technology, for example, West German patent 2
．． No. 447.587, No. 2,505.746, No. 2,
514.245, specifications of U.S. Patent No. 4,047,957, U.S. Patent No. 3,832.181, U.S. Pat.
No. 52-127329, Special Publication No. 48-32364
Examples include combinations described in each publication of the issue.

In the present invention, the swollen film thickness during development is defined as the thickness after 3 minutes of immersion in the following solution kept at 38°C.

Solution for measuring degree of swelling 4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate 4.759 Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.59 Sodium bromide
1.3y Nitrilotriacetic acid trisodium salt (1 hydrated salt) 2.59 Potassium hydroxide 1.09 Add water to 1
Let it be Q.

The swelling film thickness can be measured, for example, by A. Green and G. I. B. Levenson, Journal of Photographic Science (J.

Photogr, Sci, ), 20.205 (197
2) Can be measured by the method described.

The dry film thickness in this specification means the film thickness measured at 23°C and 155% humidity control. In addition, for each film thickness, a cross section of the dried sample is photographed under magnification using a scanning electron microscope, and the film thickness of each layer is measured.

The above-mentioned total hydrophilic protective colloid layer includes at least one blue-sensitive, green-sensitive, and red-sensitive silver halide emulsion layer, as well as a protective layer coated as necessary;
It includes an antihalation layer, a yellow filter layer, an intermediate layer, etc.

The layer structure of the silver halide photosensitive material that can particularly exhibit the effects of the present invention is as follows: colloidal silver halation prevention P:! J (Intermediate layer) Red-sensitive layer (Intermediate layer)
Green-sensitive layer (intermediate layer) Colloidal silver yellow filter layer Blue-sensitive layer (intermediate layer) Coated with protective layer Furthermore, from the support, colloidal silver antihalation layer (intermediate layer) Red-sensitive layer (
Intermediate layer) Green sensitive layer (intermediate layer) Blue sensitive layer (intermediate WJ) Red sensitive NJ (intermediate layer) Green sensitive layer (colloidal silver yellow filter layer) Blue sensitive layer (intermediate layer) It has a layer structure coated with a protective layer. .

Note that the layers in parentheses may be omitted. It is preferable that each of the red-sensitive layer, green-sensitive layer and blue-sensitive layer is divided into a low-sensitivity layer and a high-sensitivity layer.

In addition, at least one of a red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer as described in Japanese Patent Publication No. 49-15495 is
A layer structure divided into two partial layers, a layer structure separated into a high-sensitivity emulsion layer unit and a low-sensitivity emulsion layer unit as described in Japanese Patent Application Laid-Open No. 51-49027, and West German Publication No. 2,622
．． No. 922, No. 2,622,923, No. 2,622.
No. 924, No. 2,704.826 and No. 2,704.
Examples include the layer structure described in No. 797.

Also, in the present invention, it is also possible to apply the layer configurations described in Japanese Patent Application Laid-Open Nos. 57-177551, 59-177552, and 59-180555.

These silver halide emulsions contain active gelatin: a sulfur sensitizer such as allylthiocarbamide, thiourea, cystine; a selenium sensitizer; a reduction sensitizer such as the first
tin salts, thiourea dioxide, polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiocyanate,
Sensitizers with water-soluble groups such as 3-methylbenzothiazolium chloride or ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate, and sodium chlorovaladate ( Depending on the amount, these types act as sensitizers or fog suppressants. It may also be chemically sensitized (eg, in combination with a selenium sensitizer).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before and during this chemical ripening,
Alternatively, after aging, at least one hydroxytetrazaindene and at least one nitrogen-containing hetero17-ring compound having a mercapto group may be added.

The silver halide used in the present invention is mixed with an appropriate sensitizing dye in a ratio of 5X 10-' to 3X 10-' per mole of silver halide in order to impart photosensitivity in the desired wavelength range.
It is also possible to optically sensitize by adding molar amount.

Various sensitizing dyes can be used, and one type or a combination of two or more types can be used. Examples of the sensitizing dyes advantageously used in the present invention include the following.

That is, as sensitizing dyes used in blue-sensitive silver halide emulsions, for example, West German Patent No. 929.080, U.S. Pat.
, No. 231,658, No. 2,493.748, No. 2,
503.776, 2,519.0 old number, 2,91
No. 2.329, No. 3,656.959, No. 3,672
, No. 897, No. 3,694.217, No. 4,025°349, No. 4,046,572, British Patent No. 1,24
2.588, Special Publication No. 44-14030, No. 52-2
Examples include those described in No. 4844 and the like.

Further, as sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.
No. 72,908, No. 2,739゜149, No. 2. '1
Representative examples thereof include cyanine dyes, melonanine dyes, and composite cyanine dyes as described in No. 45.763, British Patent No. 505.979, and the like. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent No. 2,269,234,
No. 2,270.378, No. 2,442゜710, No. 2,454.629, No. 2.77 (No. 3,280, etc.). Representative examples include U.S. Patent No. 2.213.995, U.S. Pat.
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in German Patent No. 929,080 and the like can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material according to the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary.

Typical particularly preferred spectral sensitization methods include, for example,
Japanese Patent Publication No. 43-493 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine
No. 6, No. 43-22884, No. 45-18433,
No. 47-37443, No. 4g-28293, No. 49
No.-6209, No. 53-12375, JP-A-52-2
No. 3931, No. 52-51932, No. 54-8011
No. 8, No. 5B-1539:26, No. 59-11136
46, No. 59-116647, and the like.

Further, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication Nos. 45-25831 and 47-
No. 11114, No. 47-25379, No. 48-384
No. 06, No. 48-38407, No. 54-34535, No. 55-1569, JP-A No. 50-33220, No. 50-38526, No. 51-107127, No. 51
-115820, 51-135528, 52-
Examples include No. 10.1916 and No. 52-104917.

Furthermore, regarding Ji19 combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example, Japanese Patent Publication Nos. 44-32753 and 4
No. 6-11627, JP-A-57-1483, and regarding merocyanine, for example, JP-B No. 48-3840.
No. 8, No. 48-41204, No. 50-40662,
JP 56-25728, JP 58-10753, JP 5L'11445, JP 59-116645, JP 50
-33828 etc. are mentioned.

Furthermore, regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publication No. 43-4932
No. 43-4933, No. 45-26470, No. 4
No. 6-18107, No. 47-874j, JP-A-59-
No. 114533, etc., and the method described in Japanese Patent Publication No. 6207/1983 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, methyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in Japanese Patent Publication No. 40659/1983 is prepared in advance. It is used by dissolving it in a hydrophilic organic solvent.

The addition may be made at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion.

The photographic constituent layer of the silver halide color photographic light-sensitive material according to the present invention contains a dye (A
The Al dye 11 includes oxonol dyes, hemioxonol dyes, merocyanine dyes, and azo dyes. Among them, oxonol dyes, hemioxonol dyes, merocyanine dyes, and the like are useful. Use? Examples of aluminum dyes include British Patent No. 584.60'1, British Patent No. 1,277.429,
JP-A-48-85130, 4'1)-QQ(320
No. 49-114420, No. 49-129537, No. 52108115, No. 59-25845, No. 5
9-111640, 59-111641, U.S. Patent No. 2,274.782, 2,533.472, 2,956.079, 3.125.448, 3
．． No. 148.187, No. 3.177.078, No. 3,
247.127, 3,260゜601, 3,5
No. 40.887, No. 3,575.704, No. 3;65
3゜905, 3,718.472, 4,070
, No. 352 can be mentioned.

These Al dyes are generally used at a concentration of 2 per mole of silver in the emulsion layer.
It is preferable to use X IQ-3 to 5X to-' moles.

Furthermore, in addition to DIR compounds, compounds that release development inhibitors during development can also be used in the present invention; for example, U.S. Pat.
No., West German Patent Application (OLS) 2,417.914
No., JP-A-52-15271, JP-A No. 53-9116,
Examples include those described in No. 59-123838 and No. 59-127038.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized form of a color developing agent to release a development inhibitor.

A typical example of such an IR compound is one in which a group is introduced into the active site of the coupler, forming a compound that has a development inhibiting effect when released from the active site.
l There are R couplers, such as British, YT'! J3'
,+,454, U.S. Pat. No. 3,227,554,
4,095°984, 4,149.88 (described in No. 3, etc.).

When the above DIR coupler undergoes a coupling reaction with an oxidized color developing agent, the coupler core forms a dye,
On the other hand, it has the property of releasing a development inhibitor. Moreover, in the present invention, U.S. Patent No. 3,652.345 and U.S. Pat.
Old name, No. 3,958.993, No. 3,961.959
No. 4,052.213, JP-A-53-11052
No. 9, No. 54-13333, No. 55-1 (31237
Also included are compounds which release a development inhibitor through a coupling reaction with an oxidized form of a color developing agent such as those described in No. 1, etc., and release a development inhibitor, but do not form a dye.

Furthermore, JP-A-54-145135 and JP-A-56-11
When reacted with oxidized color developing agents such as those described in No. 4946 and No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nucleophilic substitution reaction. Or so-called timing DI, which is a compound that releases a development inhibitor through an elimination reaction.
R compounds can also be used in the present invention.

Also, JP-A-58-100954, JP-A No. 58-16294
Timing DI in which a timing group as described above is bonded to a coupler core that produces a completely diffusible dye when reacted with an oxidized color developing agent described in No. 9.
R compounds can also be used.

The amount of the DIR compound contained in the photosensitive material is preferably in the range of 1 x 10-' mol to IOX 10-' mol per 1 mol of silver.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, and surfactants described in Research Disclosure No. 17643. , a plasticizer, a wetting agent, etc. can be used.

In the silver halide color photographic light-sensitive material used in the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, albumin, proteins such as tunosein, etc. , hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole,
Single or copolymer synthetic hydrophilic polymers such as polyacrylamide, etc. are included.

Examples of the support for the silver halide color photographic light-sensitive material (used in the present invention) include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support provided with a reflective layer or a reflective material, for example, Glass plate, cellulose acetate, cellulose nitrate or polyester film such as polyethylene terephthalate 1, polyamide filtrate 4, polycarbonate filtrate 1. JL, etc., and other ordinary transparent supports may be used.

The support C is appropriately selected depending on the intended use of the photosensitive material.

〔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 expressed in g per 1 m' 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 @l PFJ: Antihalation layer black colloidal silver...0.18 Ultraviolet absorber (UV
-1) ・0.20 colored coupler (CC
-1) ...0.05 colored coupler (CM
-2) ...0.06 high boiling point solvent (Oil-1
) ...0.20 gelatin
...1.5 1st Δ: Intermediate layer ultraviolet absorber (UV-1) ...0.0
1 high boiling point solvent (Oil-1) - 0.
01 Gelatin...1.2 3rd
Layer: Low sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (E+-1)...0.9t
t (F.m-2) - 0.6 Sensitizing dye (S-1)...2.2XlO-' (mol/silver 1 mol)
tt (S-2)...2.5XlO-'(
// )tt (S-3)...
0.5XlO-' (//) Anno J Blur (C'-4)...1.2//
(C'-2)...0.3 colored cyan coupler (CC-1)...0.05DIR compound (
D-1) ...0.002 High boiling point solvent (Oil-1) ...0.5 Gelatin
...1.2 4th layer: High sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (Em-3) ...2.0 Sensitizing dye (S-1) = 2.2X10-' (% le/ silver 1
mole) // (S-2)...2. OXIO
-'(tt) sensitizing dye (S-3) = 0.
1xlO-' (-t-le/silver 1 mole) Cyan coupler (C'-1)...0.20tt
(C”2) ...0.03//
(C'-3)...1.15 colored cyan coupler (CC-1)...0.015DIR
Compound (D-2) ・0.05 High boiling point solvent (Oil-1) ・=0.5 Gelatin ...1.3 5th layer: Intermediate layer gelatin ...0.5 6th layer: Low sensitivity green Sensitive emulsion layer Silver iodobromide emulsion (Em-1)...1.1 Sensitizing dye (S-4)...5XlO-' (mol/silver 1 mol)〃(S-5)...2xlO- '(tt
) Magenta coupler (M'-1)...0.4
5 color magenta coupler (CM-1)...0.0
5DIR compound (D-3)... Mouth.
O15// (D-4)
...0.020 high boiling point solvent (0 row 2)
...0.5 gelatin ...1
．． 0 7th layer: Intermediate layer gelatin...0.9 High boiling point solvent (Oil-1)...0.2 8th layer:
High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Elm-3)...1.2
Sensitizing dye (S-6)'・1.5XlO-' (mol/silver 1
mole) tt (S-7)-2,5X10-'(//
)tt (S -8)...0.7X10-'
(//') Magenta coupler (M'-2)
...0.08tt (M'-3)
...0.18 colored magenta coupler (CM-
2)...0.05 DIR compound (D-3)...0. O
11 High boiling solvent (Oil-3)...0.
5 Gelatin...1.3 9th layer: Yellow filter layer Yellow colloidal silver...0.12 Color stain inhibitor (SC-1)...0.1 High boiling point solvent (Oil3)...0. 1 gelatin
...0.8 1st θ layer: low sensitivity blue-sensitive emulsion layer silver iodobromide emulsion (E+-1) -., 0.30
tt (E m -2) ...0.2
5 Sensitizing dye (S-10)-7XlO-' (mol/silver 1 mol) Yellow coupler (Y-1)...0.
6/I (Y -2) ...0.2D
IR compound (D-2)...0. O1
1 High boiling solvent (Oil-3)...0.1
5 Gelatin...1.2 No. 11
Layer: High sensitivity blue sensitive emulsion layer Silver iodobromide emulsion (Em-4)...0.50
tt (Elm-1) ...0.22
Sensitizing dye (S-9)...1.3XlO-' (mol/silver 1 mol)tt (S-10)...3X10-'(I
I) Yellow coupler (Y-1)...
・0.36t> (Y −2) ・・
・0.12 high boiling point solvent (Oil-3) ・
...0.07 gelatin ...1
．． 2 12th layer: 1st protective layer Fine grain silver iodobromide emulsion...0.40 (average grain size 0.0877 m Ag+ 2.5 mol%) Ultraviolet absorber (UV-1)...0.1 Ott
(UV-2) ...0
．． 05 High boiling point solvent (Oil-1)...
0.1// (Oi Superintendent-4)
...0.1 formalin scavenger (us-1)...0,5//
(HS-2)...0.2 gelatin
...1.2 13th layer: 2nd protective layer surfactant (Su-1)"・0.005
Alkali-soluble matting agent...0. IO (average particle size 2μ) Cyan dye (^IC-1) ...0. Old magenta dye (^1tl) ...0.01
Slip agent (WAX-1) -0.04 Gelatin...0.7 In addition to the above composition, each layer includes a coating aid of 5u-2 and a dispersion aid of 5u.
-3, preservative DI-1, stabilizer 5tab-1, and antifoggant AF-1%AF-2 were added.

EIll-1 average grain size 0.46 μm, average silver iodide content 7.0 mol%, monodisperse surface paper silver iodide-containing emulsion Ea+-2 average grain size 0.32 μm 1 average silver iodide content 2
．． 5 mol%, monodisperse and uniform composition emulsion E+-3 average grain size 0.78μ, average silver iodide content 6.
0 mol %, monodisperse surface paper silver iodide-containing emulsion Em-4 average grain size 0.95 μm 1 average silver iodide content 7.
5 mol %, monodisperse surface-low silver iodide-containing emulsion E-11. Es+-33 and Es-4 are Japanese Patent Application Publication No. 60-1
It is a silver iodobromide emulsion mainly composed of octahedrons and has a multilayer structure adjusted with reference to the publications No. 38538 and No. 61-245151.

In addition, for Em-1 to E Kasumi-4, the average value of particle size/particle thickness is 1.0, and the width of particle distribution is 14%, 10%, 12%, and 12%, respectively. there were.

6 insects N white-I S-2 C'-3 C'-4 M'-1 CQ M-1 2H8 rccH2-CH302CH2) 5ccHzsOz
(CH2)2] :N(CH: ):5O3KW, to X-1 IC-1 A IM-1 Stab-I AF-1D 1-
1 all-1O1l 2 H Oihi3 Oil 4 After subjecting the film sample thus prepared to live exposure using a camera, a running test was conducted under the following conditions.

However, stabilization treatment is performed using a two-tank counter current.
The stabilization liquid was replenished into the final tank, and the overflow flowed into the previous tank. Furthermore, a portion of the overflow (275 mQ/m'') from the stabilizing tank following the constant R tank was poured into the fixing tank.

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

Potassium carbonate 30g Sodium hydrogen oxide 2.5g Potassium sulfite 3.0g Thorium bromide
1.2g potassium iodide
1.2mg hydroxylamine sulfate
2.5g Sodium chloride 0
．． 6g4-amino-3-methyl-N-ethyl-N-(β
-Hydroxylethyl) Aniline sulfate 4.6 g diethylenetriaminepentaacetic acid M3, 0 g Potassium hydroxide 1.2 g Water was added to make up to 1Q, and potassium hydroxide or 20% sulfuric acid was used to make polo
, adjusted to 01.

The composition of the color developer replenisher used is as follows.

Potassium carbonate 40g Sodium bicarbonate 3g Potassium sulfite
7g sodium bromide
0.5g hydroxylamine sulfate
3.1g 4-amino-3-methyl-N-ethyl-N-(β-hydroxylethyl) aniline sulfate 6.0g diethylentriaminepentaacetic acid 3.0g potassium hydroxide 2g Add water to make 1Q, potassium hydroxide Or adjust the pH to 10.12 using 20% sulfuric acid.

The composition of the bleaching solution used is as follows.

Organic acid ferric complex salt (listed in Table 1) 0.32 mol ethylenediaminetetraacetic acid disodium 10 g ammonium bromide 100 g glacial acetic acid
(Listed in Table 1) Ammonium acid feed
Add 40 g of water to make 1Q, and adjust the pH appropriately as shown in Table 1 using aqueous ammonia.

The composition of the bleach replenishment solution used is as follows.

Organic acid ferric rust salt (a in Table 1) 0.35 mol ethylenediaminetetraacetic acid disodium g Ammonium bromide 120 g Ammonium nitrate 50 g Ice vinegar @
21 m Q Add water and lQ
Then, adjust the pH of the bleach tank liquid as shown in Table 1 of 911 as appropriate using aqueous ammonia or glacial acetic acid.

The compositions of the fixer and fixer replenisher used are as follows.

Ammonium thiosulfate 200 g Anhydrous sodium bisulfite 20 g Sodium metabisulfite 4.0 g Disodium ethylenediaminetetraacetate 1.0 g Add water to make 700 ml, and adjust to pH 6.5 using glacial acetic acid and aqueous ammonia.

The compositions of the stabilizing solution and stabilizing replenisher used are as follows.

5-chloro-2-methyl-4-isothiazolin-3-one 0.05g2-
Methyl-4-inchazolin-3-one 0.02g
2.5 g of sodium formaldehyde bisulfite and water were added to obtain IQ, and the pH was adjusted to 7.0 using potassium hydroxide and 50% sulfuric acid.

The running process was carried out in an automatic processor until the bleach tank was replenished with twice the capacity of the bleach replenisher.

After the running process was completed, the amount of residual tR in the unexposed magenta tin and highest density areas of the processed film sample was measured.

Furthermore, the occurrence of silver sludge in the bleaching tank of the automatic processor was observed.

The results are summarized in Table 1.

1, EDT^ Fe is ferric ammonium ethylenediaminetetraacetate, NTA-Fe is ferric ammonium nitrilotriacetate, CyDTA-Fe is ferric ammonium 1,2-cyclohexanediaminetetraacetate, EDTMP.
Fe is ethylene diamine tetramethylene phosphonic acid secondary
Iron ammonium, NTMP-Fe is ferric ammonium nitrilotrimethylenephosphonate, (A-1) Fe
It means the ferric ammonium salt of (A-1).

(A-4)・Fe, (A-7)・Fe and (A-9)-
Fe, (A-10)・Fe, (B-1)・Fe
, (B-4)・Fe and (B7)・Fe are similarly
(A-4), (8-7), (A-9), (A-
10), (B-1), (B-4) and (B-7).

Furthermore, in the table, (A l)・Fe/(A l)・Fe
+EDT^・Fe-3/10 is (A-1)・
Fe and EDT^.Fe are added as a mixture, which means that 3/10 of the total is (A-1).Fe on a molar basis.

Furthermore, in the table, ○ means no silver sludge is generated, Δ
The symbol "X" means that there is some occurrence of silver sludge, the symbol "X" means that the occurrence of silver sludge is clearly observed, and the greater the number of "X" means that the degree of occurrence is more significant.

According to Table 1 above, the organic acid ferric complex salt contains 50% or more of the total organic acid ferric complex salt of the compound represented by the general formula [A] or [B] of the present invention, and acetic acid 0.1
When the content is mol/l or more and pi is in the range of 2.0 to 5.5, there is little magenta fog in the unexposed area, the desilvering property is good, and there is no generation of silver sludge, and both performances are good. It can be seen that the results are also good.

However, if any one of the three items mentioned above deviates from the conditions, the performance of one of them will be poor and it cannot be put to practical use.

Example 2 Experiment No. 11 except that magenta couplers M'-2 and M'-3 in the film sample used in Example 11, l-13, were replaced with magenta couplers listed in Table 2 in the same molar amount. No! The same running process and evaluation as in -6 were performed.

The results are summarized in Table 2.

However, the magenta couplers shown in Table 2 used were those described in Japanese Patent Application No. 1983-32501, pages 208 to 227.

Table 2 R-4 ShiU R-5 Shiμ From Table 2 above, it is clear that the objective effects of the present invention can be better achieved by using the pyrazoloazole type magenta coupler represented by formula (M-1) above. I understand that.

Example 3 A vinyl chloride nozzle with a hole of 0.5 mm in diameter was installed in the bleaching tank and fixing tank of Example 11 Experiment No. 6, and a magnetic pump M D-1 was installed on the emulsion surface of the photosensitive material.
The experiment was conducted in the same manner except that the treatment liquid was sprayed using No. 5. As a result, the magenta density in the unexposed area is 0.
02, and the amount of residual silver decreased to 1/2.

Example 4 Example 1. In Experiment No. 1-38, the same experiment was conducted except that all the over 70-solution of the bleaching tank solution was poured into the fixing tank, which is the next processing step. As a result, the amount of residual silver is 0-1mg from 0.4+*g/100cm"
/ 100cm”.

Other performances were almost the same as in Example 11 Experiment No. 1-38.

Example 5 In Example 4, an experiment was conducted under the same conditions as Example 4 except that the flow of the overflow liquid from the stabilizing tank into the fixing tank was stopped.

As a result, the amount of residual silver was 0.1sg/100cm'',
0.3 mg/100 cffi”, which was slightly worse.

Other performances were the same as in Example 4.

Example 6 A practical test was conducted in the same manner as in Example 1 except that 1.5 g #l of the bleach accelerator shown in Table 3 was added to the bleach replenisher of Example 11 Experiment No. 1-5.

The results are summarized in Table 3.

However, the bleaching accelerator used is
The one published in the specification of No. 01, pages 17 to 39 was used.

The bleaching accelerator numbers in Table 3 are clearly indicated in the old Japanese Patent Application No. 63-325 Table 3 From the above Table 3, it can be seen that the effects of the present invention can be further enhanced by using specific bleaching accelerators in combination. It costs r1.

Example 7 The average silver iodide content of the silver iodobromide emulsions used in the third and fourth layers of the film samples used in Example 1, Experiment No. 1-6 was varied as shown in Table 4 above. , an experimental film sample was prepared. Example 11 using this sample
Experiment No. 1-(3) The treatment was carried out in the same manner as in Experiment No. 1-(3), and the cyan density of the unexposed area was measured.

The results are shown in Table 4.

Table 4 From Table 4 above, it can be seen that when the average silver iodide content is 0.5 mol % or more, the cyan bleaching blade blur becomes good.

Example 8 Cyan coupler C' used in Example 11 Experiment No. 1-0
Example 1 except that C'-2 and C'-3 were replaced with cyan couplers listed in Table 5 having the same mole as C'-2 and C'-3.
1. The same treatment as in Experiment No. 1-6 was performed (however, the bleaching treatment was for 35 seconds), and the cyan density and magenta density of the unexposed area of the film sample after the treatment were measured. Furthermore, the cyanide concentration at the highest concentration of the treated film sample was measured, and then 120 g of ferric ammonium ethylenediaminetetraacetate/
1 solution (p I + 6, 0) for 6 minutes to completely oxidize the leuco-cyan dye (Ieuco-cyan dye) to cyan dye, and the cyan dye concentration at the highest density area was measured again, and the difference was determined by calculation. . However, the cyan coupler used is disclosed in Japanese Patent Application No. 1983-32501.
Those described on pages 59 to 196 were used. Cyan couplers (C-1) to (C-96) in Table 5 are patent applications filed in 1986-3.
It has the same meaning as the cyan coupler number described in No. 2501, pages 159 to 196. The results are summarized in Table 5.

(Note 1) Japanese Patent Application No. 1983-32501, pages 159-196
As is clear from Table 5 above, the cyan coupler described on page
When cyan couplers represented by formulas (C-A) to (C-C) are used as cyan couplers, there is little bleaching edge blurring of cyan dyes despite rapid processing, and there is also little generation of leucocyan dyes. In good condition.

In addition, although the couplers of formulas (C-A) to (C-C) were used, the magenta capri in the unexposed area was almost the same as in Example 1, Experiment No. 1-6, and was good. Silver also improved by 20-30%.

(Effects of the Invention) According to the present invention, there is provided a bleaching solution for silver halide color photographic light-sensitive materials, which can be quickly and refilled at a low rate, has improved desilvering properties and bleaching edge blur, and does not generate silver sludge, and a processing solution. A method is provided.

Claims (2)

[Claims] (1) In a method for processing a silver halide color photographic light-sensitive material, which is immediately treated with a bleaching solution after color development and subsequently treated with a processing solution having fixing ability, the organic acid ferric acid in the bleaching solution is More than 50% of the complex salt has the following general formula [A
] or a ferric complex salt of the compound represented by [B],
A method for processing a silver halide color photographic material, characterized in that the bleaching solution contains at least 0.1 mol/l of acetic acid or acetate and has a pH of 2.0 to 5.5. 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 3 to 6 carbon atoms. ] General formula [B] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1 to A_4 may be the same or different, and -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, and n is 1
Represents an integer from ~8. Further, B_1 and B_2 each represent a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, and may be the same or different. ] (2) 50% or more of the organic acid ferric complex salt in the bleaching solution is a ferric complex salt of a compound represented by the following general formula [A] or [B], and furthermore, at least 0.1 mol/l of the organic acid ferric complex salt is A bleaching solution for silver halide color photographic materials, which contains acetic acid or acetate and has a pH of 2.0 to 5.5. 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 3 to 6 carbon atoms. ] General formula [B] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A_1 to A_4 may be the same or different, and -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, and n is 1
Represents an integer from ~8. Further, B_1 and B_2 each represent a substituted or unsubstituted alkylene group having 2 to 5 carbon atoms, and may be the same or different. ]